SPE-188241-MS

pH-Responsive Supramolecular Gelling Agents Used in EOR and Their

Potential as Fracking Fluids

Cengiz Yegin, Incendium Technologies LLC; Cenk Temizel, Aera Energy; Yagmur Yegin and Mufrettin Murat Sari,
Texas A&M University; Bao Jia, University of Kansas; Mohamad Yousef Alklih, ADCO

Copyright 2017, Society of Petroleum Engineers

This paper was prepared for presentation at the Abu Dhabi International Petroleum Exhibition & Conference held in Abu Dhabi, UAE, 13-16 November 2017.

This paper was selected for presentation by an SPE program committee following review of information contained in an abstract submitted by the author(s). Contents
of the paper have not been reviewed by the Society of Petroleum Engineers and are subject to correction by the author(s). The material does not necessarily reflect
any position of the Society of Petroleum Engineers, its officers, or members. Electronic reproduction, distribution, or storage of any part of this paper without the written
consent of the Society of Petroleum Engineers is prohibited. Permission to reproduce in print is restricted to an abstract of not more than 300 words; illustrations may
not be copied. The abstract must contain conspicuous acknowledgment of SPE copyright.

Abstract
Hydraulic fracturing is an important method to recover shale oil and gas that has drastically increased
U.S. energy production in recent decades. Shales are low permeability formations where natural resources
are trapped, and require a well-planned hydraulic fracturing process and a highly developed fracturing
(fracking) fluid for efficient oil/gas recovery. In this study, a pH-responsive solution synthesized by
supramolecular assembly of maleic acid and an amino-amide in an aqueous media is described as a
potential fracking fluid owing to its mobility control, proppant carrying and settling capacities. Previous
investigations on this solution system had shown its large potential to replace displacement fluids in EOR
due to pH-tunable and reversible viscosity behavior.
The main working mechanism is that; the initial viscosity of injected solution is kept at moderate/high
values to easily transport proppants and easily inject the fluid; and then decreased when the solution reaches
a position near fissures for settling of proppants. It has been reported by rheology tests of the developed
fracking fluid, which consists of the supramolecular solution and proppants (silica sand), viscosity can be
changed about 1600 times from pH 3.8 to pH 8.3 in a reversible fashion at only 2 wt.% concentration. On the
other hand, sedimentation studies indicated that the sedimentation speed of the silica proppants decreased
around five orders of magnitude from pH 4 to pH 8, again in a reversible way. Furthermore, experimental
studies revealed that the developed supramolecular solutions have both reversible pH-responsive properties,
and tolerance against high salinities and elevated temperatures. Another outstanding property of these
supramolecular solutions is their self-healing feature which enables them to disassemble and reassemble
upon exposure to extreme shear stresses, while polymer viscosifying agents the fracking fluids degrade and
break up under similar conditions.
The supramolecular assembly system discussed in this study has a promising potential to become
next-generation fracking fluids with its outstanding properties including but not limited to pH-sensitivity,
reversible viscosity, high proppant transfer capacity, tolerance to high temperatures and salinity, self-healing
behavior, environmental friendliness and sustainability.
2 SPE-188241-MS

Introduction
Over the last decades, there has been increasing concerns regading the worldwide energy consumption since
it is expected to increase by 50% compared to the current consumption by the 2030. Meeting this growing
demands using only renewable resources will be difficult because the scale of any alternative energy sources
is far behind of the world’s future energy demands (Shamsijazeyi et al. 2014). At this point, alternative
energy options will come up in near future focusing on different types of oil containing mixtures in order
to compensate the world energy consumption. Contrary to the expanding demand for oil as a basic energy
source, world`s current crude oil reservoirs are limited and discoveries of new oil fields are declining over the
last years. Also, the oil industry has big drawbacks to improve well productivity because the conventional oil
recovery methods, mainly called as primary and secondary methods, are only based on the initial pressure of
the compressibilitiy (X. P. Li et al. 2009). The limited capacity of these methods (about 15-30% of the total
oil reserve) is insufficient to remove oil from reservoir completely and it is estimated that nearly 7.0x1012
barrels of oil global oilfields will be still remained even after using only primary and secondary methods
(Thomas 2008). Hence, the new techniques and studies targeting to improve oil recovery efficiency of this
huge amount of oil left in reservoirs after conventional methods has gained increasing intereset in recent
years.
Enhanced oil recovery (EOR) is one of the promising alternative techniques that target to improve
recovery efficiency. Main principle of EOR is injection of displacing fluid toward producing field and the
basic function of the fluid is to sweep oil through the well. Viscosity and density of the displacing fluid is
the most important design parameters and these directly affect the displacement efficiency. Although water
are generally used as displacing fluid, using bare water is not enough for efficient recovery, and hence, some
improvements regarding the solution viscosity is needed (Bera and Mandal 2015).
For an efficient oil recovery process, interfacial tension between water and oil should be minimized by
increasing viscosity and density of water via mixing with thickening agents or other substances to avoid
the exit of water through the producing, or fingering through oil (Chagas et al. 2004). There are several
chemicals used in EOR such as polymer coated nanoparticles (Shamsijazeyi et al. 2014), xantan gum and
hydrolyzed polyacrylamide (Jang et al. 2015), sodium oleate (X. P. Li et al. 2009), long-chain alcohols (Y.-
Y. Li et al. 2014) and some surfactants as microemulsions (Santanna et al. 2009).
Viscosity modifiers are promising alternatives among many others and they have undergone a tremendous
growth in EOR. Viscosity-modifier-containing aqueous solutions match better viscosity of oil reservoir and
sweeping efficiency can be boosted with increasing water viscosity (I. Chen et al. 2014). This technique
provides sweeping large amounts of displaced oil even in very small cracks and micropores that cannot be
otherwise recovered (Seright 2010). Until now, a wide variety of density and viscosity modifiers have been
utilized in oil recovery. For instances, the long chain subtances with high molecular weight such as water
soluble polymers and polysaccharids can be listed as the most commony used viscosity modifiers due to
not only their higher miscibility of hydrophilic groups, but also prominent hydrophobic nature and micelle
formation ability of hydrophobic groups that cause increase in viscosity (Chagas et al. 2004; Kjøniksen et
al. 2008; Taylor and Nasr-El-Din 1998). This increased viscosity results in the decrease in mobility ratio,
and hence, provides a higher areal and vertical volumetric sweep efficiency (Kjøniksen et al. 2008; Zerpa
et al. 2005).
However, injection of such a highly viscous water into oil well come up some problems such as lack of
viscosity adjustment even though using it can be thought as an important advantage to sweep higher amount
of oil. To overcome such drawbacks and injection limitations, and hence, to perform efficient EOR even in
harsh environments and challenging reservoirs, new chemical additives and materials are required.
Some polymer-based viscosity modifying agents are also added to fracking fluids like that in EOR. These
polymers can be exemplified with poly(acrylicacid), guar gum poly(acrylamide)-based polymers (Yegin
et al. 2016). Nevertheless, these polymers bring several issues such as break-up in presence of slats and
SPE-188241-MS 3

high temperature, and reduced fluid performance upon exposure to shear stresses during injection, and pore
blockage before flowback (Wever, Picchioni, and Broekhuis 2011). Supramolecular assembly solutions
can be alternatives to solve these issues. Unlike in the EOR, fracking fluids should have a high viscosity
to effectively deliver proppants to fissures during injection, and low viscosity during flowback to leave
the proppants in the fissures and enable to completely clean the residues in the fissures and the wellbore
(Willberg et al. 1997). The pH-responsive supramolecular assembly system described in this work is a
very promsing solution to be used in fracking fluids with its adjustable and reversible viscosity behavior.
Next sections will respectively include fracturing theory and design criteria, types of fracking fluids and
environmental issues faced, and several experimental results of the supramolecular assembly solutions.

Fracturing Theory and Design Criteria

Hydraulic fracturing plays a vital role to enable production from formations with unfavorable characteristics
like tight formations and unconventionals. Hydraulic fracturing design is an essential part of the fracturing
treatment. Design and simulation of the fracturing treatment give probable results of the treatment before
field application and provide us chance to optimize the treatment variables. Better understanding about
the process and the variables that affect the productivity of the treatment is the key to achieve economic
production rates. A successful fracture treatment should be effective in terms of engineering perspectives
but also should be economically acceptable.
For an effective fracture design, before the selection or determination of the design elements, having
accurate reservoir and well completion data plays a vital role. These data can be listed as porosity,
permeability of the formation, reservoir pressure, formation modulus, formation compressibility, Poisson’s
ratio, formation depth, in-situ stress state, formation temperature, reservoir fluid type, saturations, net
and gross pay thicknesses, formation lithology, well bore completion data, fracture fluids and proppants
(Fracture treatment design 2016). The most important element of these data is the in-situ stress state. The
magnitude of the fracture initiation pressure (breakdown pressure) is dominantly depends on the values
and the differences between the principal stresses, the tensile stress and the reservoir pressure. The fracture
orientation will lay normal to the minimum principle stress (Micheal Economides 1994). An ideal design
of a fracture treatment process is given by Brady et al. (Brady et al. 1992), shown in Fig. 1.
The selection of the fluid type, additives and proppants are exclusively depended on the formation rock
and fluid characteristics and what type of fracture is desired (Fig. 2). The pad volume and the proppant
volume are also important parameters in fracture design since they are determine the final propped fracture
penetration and conductivity (Acharya 1988). Proper selection of the fracturing fluid additives basically
depends on the formation characteristics. A general guideline for the fracturing fluid selection is provided
by (Gulbis and Hodge 2013).
4 SPE-188241-MS

Figure 1—Fracture treatment design workflow

SPE-188241-MS 5

Figure 2—General guideline for fracturing fluid selection (Gulbis and Hodge 2013). Further reading on the
topic can be found in Montgomery et al. and Gulbis & Hodge (Gulbis and Hodge 2013; Montgomery 2013).

Geomechanical Challenges in Hydraulic Fracturing Design

Geological setting, material and mechanical properties of rocks such as strength, hardness and moduli and
the local tectonic signature help engineers design a hydraulic fracturing job. To perform a fracturing job,
fluid is pumped at a designed injection pressure such that a tensile stress acts on the rocks and deforms the
rocks to create tensile fractures. In order to prevent these fractures from collapsing due to in situ compressive
stresses, proppants such as natural sand or ceramic materials are used. Stress is therefore a dominating
design factor and frequently a source of error/uncertainty. One of the biggest geomechanical challenges is to
evaluate the stress in a complex heterogeneous and anisotropic environment where the type of rocks, moduli,
porosity, permeability, strength etc is varying (Fox et al. 2013). Stress vs. Strain diagrams of heterogenous
environmental rocks are given in Fig. 3.

Figure 3—Stress-Strain Curves for a Heterogeneous environment for rocks with different brittleness and
moduli. This image is indicative of difficulty in estimating stresses in true reservoirs (Fox et al. 2013).

Fracture Design in Different Types of Rocks

Fracturing process needed to be effectively designed to improve the economics. Prior to the production,
reservoir simulations are generally performed to maximize the economics. Choosing the right fracturing
6 SPE-188241-MS

fluid and proppant are the keys of hydraulic fracture design that the choices are based on several important
parameters of the reservoir. The permeability of the reservoir is probably the most important factor of
choosing fracturing fluid. If the formation permeability is high, more viscous fracturing fluids need to be
injected because the leak-off rate is likely to be high; if the permeability is low, relatively less viscous fluids
need to be injected because the leak-off rate is likely to be low. The mineralogy also affects the choice
of fracturing fluid. If too much clay is present in the formation, the swelling will occur in the formation
blocking the path way in the porous media, reducing the permeability of porous media. Thus, fracturing
fluids that will not cause significant swelling should be considered. Parameters affecting the choice of the
proppant include the formation stress, natural fracture conductivity and the flowing bottom hole pressure
(BHP) operated. For formation with more stress, the choice of proppant will be more demanding.
Without a knowledge of the rock properties, a routine perforation clusters will be applied. Anisotropy,
stress and lateral heterogeneity information are very beneficial for the completion effectiveness. The
perforations can be placed more efficiently to cover more reservoir volume and increase the recovery factor.
Well completion is the period of preparing the well to produce oil and gas. This process includes running
and cementing the casing, perforating and placing packers, fracturing, and cleaning-up. Advancement in
the horizontal well completion technology improves the performance of horizontal multi-staged wells.
However, the determination of the best completion strategy is still very difficult because of the variations of
the pores pressure, oil and gas properties and rock mineralogy. Two main completion methods are usually
applied for the horizontal well with multi-stage fracture (Edwards et al. 2010). One is cementing casing
in the wellbore and use the technology of "plug and pef", where the coiled tubing (CT) and pump down
wireline are used to set the bridge guns. The other one is the open hole method with the multi-stage fracturing
system (OHMS) aimed to save the time and reduce the cost of multi-stage fracturing. In OHMS, the external
packers are used that sliding sleeve tools can generate ports between the packers without perforating the
casing. OHMS allow the operator to continuously pump without the drilling rig.
Completion quality is a measurement of the fracturing potential of the reservoir. Several reservoir
properties affect the completion quality. (1) The brittle index is the most important one that sometimes it
is used exchangeable with completion quality. However, it is not defined strictly. It is related with rock’s
Young’s modulus and Poisson’s ratio. Poisson's ratio describes the ability of rock to expand when the stress
is loaded in the perpendicular direction. As it is related to the expansion effect, it is closely related to the
closure stress of the formation. Young’s modulus describes the stiffness of the rock, soft or hard, brittle
or ductile. Brittle rocks are usually ideal targets for hydraulic fracturing with good completion quality.
Young’s modulus is classified as dynamic and static. Dynamic Young’s modulus is measured using the sonic
log. Static Young’s modulus is obtained in a deformation test in the laboratory. Static Young’s modulus
is more important for fracture design. (2) Strain describes the deformation degree of the rock that related
to the displacement of a particle and a reference length. (3) Tensile stress is also an important factor for
hydraulic fracture design. It is the limiting force that pulls a material to break (Zoback 2007). The pressure
needs to be over the tensile stress in the hydraulic fracturing operation. (4) Pore pressure is an important
consideration for hydraulic fracturing design and completion method choice. It refers to the pressure in the
pores of the reservoir. It is defined as normal pressured if it equals the hydrostatic pressure. It is defined
as underpressured if it is smaller than the hydrostatic pressure. It is defined as overpressured if it is larger
than the hydrostatic pressure. The organic matter maturation and uplifting can cause the overpressured
phenomenon which can be favorable for producing oil and gas. A typical fracturing process is shown in
Fig. 4.
SPE-188241-MS 7

Figure 4—Hydraulic Fracturing Process (www.propublica.org/special/hydraulic-fracturing-national n.d.)

Perforation Design, Gun Selection and Phasing

Perforation is generating holes in the casing after cementing. It provides the communication between
the wellbore and the formation. The shaped charges are frequently used to generate perforation through
the casing and the cement. Perforation is the key to successfully performing the hydraulic fracturing
process. A good perforation design is to minimize the pressure drop in the near wellbore region during the
fracturing treatment. Several parameters are important, including the diameter, depth, orientation (phasing)
and gun selection of the perforation. A good perforation design needs to be optimized to minimize the
injection pressure for the fracture initiation, and reduce the tortuosity of the generated fracture (preferred
fracture plane, PFP). Many gas wells and wells applied with small and hollow-carried or low-density
perforation guns have good cement. Fracture initiation will start from the perforation with the good cement.
Experiment results indicate that the 180° phasing perforation located within 30° of the PFP provides good
communication between the fracture and the perforation. If the perforation phasing decreases which means
the angle between the perforation and the fracture increases, the shot density of the gun will increase. For
instance, if the perforation phasing changes to 60°, the shot density should be three times larger than that
with the phasing of 180 degrees(Behrmann and Nolte 1999).

Fracturing Stages and Design

It is called a "frac stage" if the reservoir undergoes the hydraulic fracturing with one perforation well
completion, and "multistage frac" if with multipleperforation completion. The degree of the overlapping of
the stimulated fracture network can be evaluated through the microseismic data. The overlapping problem
is termed as stage isolation and stage overlap which measures the efficiency of the stimulation technology.
The volume of Stimulated Reservoir Volume (SRV) is estimated by the volume including all the event
density. It can be estimated as the summation of all the volume in each stage (Vsum) or the density volume
considering all the events as a whole (Vcom). The overlapping degree is called the excess overlap that it can
be calculated as:
8 SPE-188241-MS

Eq. 1

and the overlap degree at the stage i is estimated as:

Eq. 2

where Vi is the volume of the at the stage i.

A lower overlap degree indicates a higher stimulation efficiency and less critical issue of stage isolation.
Besides the microseismic data, other approaches, including the records of the fracturing fluids and
proppants, the pressure and temperature distributions and signals from the sonic sensors. It is a critical issue
to determine the optimum fracturing stages to improve the stimulation efficiency. For example, the Middle
Bakken and the Three Forks formations began to boost the oil production since 2008 that the stimulation
technology started to apply. The operating experiences show that the pumping rate, fracture stages, and
fracturing fluid and proppants volume are required to be optimized to achieve optimal stimulation. In
general hydraulic fracturing process, the microseismic data are provided by many oil service companies. The
microseismic data can provide the information including the fracture length, fracture height, fracture width,
fracture propagation and time lapse as well. The microseimic data show that there is a strong correlation
between the reservoir performance and natural fracture and the faults that it can be used to interpret the
complex correlations. Nowadays it is possible to monitor the microseismic data in real time. This means that
operators not only can monitor the production behavior of the reservoir, but also can adjust the fracturing
operations to obtain a better fracturing treatment, for instance, adjust the fracture stages.

Fracturing Fluid Types, Challenges & Environmental Concerns

Hydraulic fracturing technique is a very commonly used technique in oil industry. It can increase
the production of hydrocarbon by making a fracture network (M. Economides and Nolte 2000). This
technique works by increasing hydraulic conductivity of reservoirs and proliferating surface area to produce
hydrocarbons.
A huge increase in hydrocarbon productivity increased the oil and gas production by making the resources
available which were not available in the past. A hydraulic fracturing fluid can be easily injected into a
reservoir by convey high pressure to open a crack on the rocks. Desired features of the fracturing fluids:

• Safe

• Easy to transport proppant

• Low friction pressure

• Compatible with the reservoir

• Economical

• Easy to cleanup

There are different types of fracturing fluids currently used in industry. Water frac, linear gel, and
crosslinked gels are the most common fracturing fluids. They have different advantages and disadvantages.
Water frac are preferred to use in gas wells since it does not damage to the proppant pack. Even though
its low cost is an advantage, its low viscosity limits the usage due to the formation of small fracturing
width. Linear gel fracturing fluids consist of water, gelling agent, and bactericides. They may also include
some other additives such as surfactant, buffers, and clay control agent. Liner gel can open wider cracks as
compared to water fracs due to its medium viscosity. It is commonly used in both gas and oil industry since it
SPE-188241-MS 9

can damage to proppant pack. Crosslinked gels are composed of the same additives as linear gels. They also
include crosslinker additives to be able to improve the viscosity. Since their viscosity is high, they provide
some advantages such as improved proppant transport and opening wide cracks. Speed of the crosslinking
is important for crosslinked gels. If the speed of crosslinking is too fast then very high shear degradation
may occur. In addition, too slow crosslinking speed is not good since proppant may settle in wellbore. Their
higher damaging properties to the proppant pack have helped them to be preferred in oil wells.
Hydraulic fracturing fluids generally contain water, sand, and additives. In general, they include
crosslinkers, gels, surfactants, breakers, and friction reducers. Fracturing fluids additives are determined
depending on the purpose of use and increasing the productivity.
Water and sand are composed almost 99.5% of the fracturing fluids. Water is used as a carrier medium for
sand (proppant) and chemical additives. Sand helps flowing of the hydrocarbons by keeping the fractures
open. Chemical additives are important even though they occupy only small portion of the fracturing fluids.

Table 1—Additives used in fracturing fluids (Groundwater Protection Council 2009).

Even though it is an excellent technology to increase oil profits, there are some environmental concerns
regarding to this technology. Hydraulic fracturing fluids contain many types of chemical additives. These
additives may be dangerous to our health and environment. They may contaminate air, surface water,
and ground water. Perforation of protective layers may cause serious contamination of ground water. Any
accident related to handling, transportation, and storage may contaminate surface water with toxic chemicals
and damage to human health.

Supramolecular Assembly Solutions in Hydraulic Fracturing

Hydrocarbon recovery from low-permeability shales formarions is achieved by hydraulic fracturing
technique (Warplnskl and Laboratories 1991). To maximize the recovery, fissures are opened in shale
formations via perfolierating guns. Fracking fluid which consists of mainly water, proppants (sand) and
10 SPE-188241-MS

various chemicals, is pumped to the wellbore to further increase the opening of these fissures via hydraulic
pressure and presence of etching chemicals, and deliver the proppants to the very end points. Proppants
need to remain in the fissures to prevent them closing due to mechanical pressure subjected by earth
ground (Fig. 5a). Transfer of these proppants from the very beginning to the end points, i.e. the fissures, is
achieved in presence of gelling agents (viscosity modifiers), which are mainly polymers. These agents must
provide emough drag and lift force to prevent sedimentation of proppants in early stages of the injection
(Montgomery 2013). These gelling have several drawbacks that limit the well productivity including low
thermal tolerance and decomposition in presence of salts, shear degradation during injection, and formation
of residues during flowback, which would block the fissures and the wellbore. Smooth flow and proppant
transport during injection, and settling of proppants without formation of residues can be achieved via using
the pH-responsive supramolecular assembly solution with its reversible and adjustable viscosity (Fig. 5b).
Synthesis and production, rheological properties, proppant sedimentation tests, and application potential
and environmental compatibility of this solution will be given here.

Figure 5—(a) Schematic illustration of hydraulic fracturing. (b) Viscosity of the supramolecular
system can be adjusted at different altitudes to control the productivity of operation.

Fig. 6 shows the reactived of the pH responsive supramolecular assembly system. Stearic acid was
selected as one of the building blocks due to its sustainability and cost effectiveness (simply obtained
from cocoa butter), and undergone a condensation reaction with N-(3-(dimethylamino)propyl)stearamide,
which will be called amino-amide for the sake of simplicity (Chu and Feng 2009). The compound obtained
following the condensation reaction mixed and complexed with maleic acid in an aqueous medium via
ultrasonic dispersion. pH measurements have shown that basic and acidic conditions introduce very different
charge interactions between the compound and the maleic acid, which substantially alters rheological
properties of the solutions. Basic conditions (higher pH), results in formation of supramolecular structures,
higher density and high gelling strength due to strong charge interactions between the two reactants. On the
other hand, acidic conditions (low pH) weakens these interactions, which will reverse these properties, i.e.
the solution will become much less viscous. More details and chemical analysis of the synthesis reaction
was shown in a previous work (I.-C. Chen et al. 2014).
SPE-188241-MS 11

Figure 6—Stearic acid is a building block of the supramolecular system that is used for coupling with an amino-
amide. The complex compound reacts with maleic acid to form the supramolecular solution. Changing pH leads
to association and dissociation of the two building blocks, which govern the viscosity values of the system.

Viscosity vs. shear rate response of 2 wt.% supramolecular assembly solution at several pH values is
indicated in Fig. 7a. The viscosity of the solution inceased for all shear rates up to pH 8.3 and it showed
a decreasing behavior. Also, the viscosity decreases with increasing shear rate for a specific pH value that
is also is known as shear thinning behavior. It is seen that the effect of pH on viscosity is more apparent
in Fig. 7b, with the zero-frequency viscosity (µ0) values collected from the flow-sweep experiments (Fig.
7a) performed for each pH and concentration. µ0 reaches a peak for each concentration, and for a given
pH, the viscosity of the solution system increases. The adjustable viscosity can be ascribed to the charge
interactions between the maleic acid and the amino-amide where detailed discussion and can be found in
a previous work (I.-C. Chen et al. 2014).

Figure 7—(a) Flow sweep experiments of supramolecular solution at various pH values for 2 wt.% concentration, and
(b) zero frequency viscosity values obtained from flow sweep experiments at several concentrations (Yegin et al. 2016).

Oil reservoirs contain high concentrations of salt due to presence of brine-oil mixture. high Also, seawater
is used for an abundant source in hydraulic fracturing due to the need of large volumes of water. Thus,
an efficient fracking fluid must show high performance in presence of salt. It has been reported to date
that seawater mainly consists of NaCl at concentrations in the range of 3.2%-3.6% (Millero et al. 2008).
Flow sweep experiments obtained from the supramolecular solutions having various NaCl concentrations
were given in the previous work (Yegin et al. 2016). It was shown that the change in viscosity was very
low at several salt conentrations from low to moderate shear rates. As such, the viscous properties and
12 SPE-188241-MS

integrity of the solutions were still in a good shape, and no total break-up or degradation were observed
at salt concentrations up to 5 wt%. The developed supramolecular assembly system was very effective at
salinities much higher than seawater.
Deep shale formations have higher temperature than the ground due to geothermal gradient. As such,
it is important to investigate the properties of fracking fluids at elevated temperatures. Effect of the
temperature on viscosity of the supramolecular assembly solutions was measured in presence of silica
sand from room temperature to 120 °C as shown in Fig. 8a and verified that the viscosity decreased
at higher temperatures similar to most of the fracking fluids. (Yegin et al. 2016) Activation energy of
dissociation of the solution was determined to be near 51.5 kJ/mol from Arthenuis plots (Fig. 8b), which
was similar to that of bare supramolecular solution where the activation energy was around 52 kJ/mol (I.-
C. Chen et al. 2014). Compared to the activation energy levels of the conventional polymer viscosifying
agent, polyacrylamide (~16 kJ/mol), it was more than three times bigger in supramolecular solutions at
the same concentration, which indicates that the supramolecular solutions developed here is much more
durable against high temperatures. Considering that numerous reservoirs around the world including Alberta
(Canada), Chaoyang-gou (China) and El Reno (OK) operate at temperatures up to 90 °C (Gaillard, Thomas,
and Favero 2013; Samuel et al. 2000; Wenjun et al. 2010), these supramolecular solutions are responsive to
thermal effects and will likely show high performance at elevated temperatures in reservoirs.

Figure 8—(a) Flow sweep experiments of supramolecular assembly solutions at various temperatures for a pH and solution
concentration of 8.3 and 2.0 wt.%, respectively, and (b) Arrhenius plot with the data obtained from (a) (Yegin et al. 2016).

One significant task of fracking fluids is to suspend and deliver the proppants to the fissures. Hence, we
observed the proppant suspension ability of the supramolecular solution at several pH values, where the
visual results are shown in Fig. 9. It was confirmed that low pH gives rise to faster settling: approximately
10 seconds and 27 hours at pH 4 and 6, respectively. Higher pH values greatly enhanced the seetling time:
5 days at pH 8 and 2 days at pH 10. We claim that changing the pH of the solution from 4 to 8 enhanced
the sedimentation time from seconds to several days. Seetling velocity of the proppants were calculated
as 2.3x10-3 m/s, 2.4x10-7 m/s, 5.3x10-8 m/s and 1.3x10-7 m/s for pH 4, 6, 8 and 10, respectively. Fracking
fluids providing sedimentation speeds less than 8×10-5 m/s are considered to be perfect proppant suspenders
(Kruijf et al., 1993), and our supramolecular solution shows up to three orders of magnitude lower speed at
pH 8. Pumping of fracking fluids to wellbores and onset of hydrocarbon recovery take around a week for
deep shale formations. Hence, use of the supramolecular assembly solutions with extremely high settling
time as fracking fluids can be very beneficial to maintain the efficient transfer of the proppants from the
well inlet to the fissures.
SPE-188241-MS 13

Figure 9—Particle settling tests of supramolecular solutions at pH 4, 6, 8, and 10. The duration of complete settling of
sand particles (>95%) at pH 4, 6, 8, and 10 were around 10 s, 27 hrs, 5 days, and 2 days, respectively (Yegin et al. 2016).

High temperature sendimentation tests were also performed (at 200 °F) to examine the properties of
the solutions elevated temperatures and changes in the proppant carrying capacity. The sedimentation time
decreased at this temperature, and the highest settling time at this temperature was attained at pH 8, both of
which were expected. The solution with pH 8 still gave a reasonable sedimentation time, which can benefit
the high temperature reservoirs (see the previous work for more details (Yegin et al. 2016)).
The substantial decrease in the sedimentation time and increased stability of proppants can be ascribed to
enhanced viscosity at high pH and particle-netwoek interactions between the sand proppants and the network
formation in the solution. At first glance, it was considered that the viscosity was the only reason of proppant
stability. But, we seeked other factors once we observed large differences between the experimental settling
velocities and theoretical values after Stoke`s Law calculations. For fracturing fluids that contain wormlike
micelles, it was reported that decreased sedimentation velocity was due to presence of the microscale
networks (Wang et al. 2014). To confirm whether the same condition was valid for supramolecular solutions,
we took optical images of the proppants in the soluions with pH values of 4 and 8, as shown in Fig. 10a
and b, respectively. Environmental scanning electron microscopy results were also obtained for further
confirmation, which were reported elsewhere (Yegin et al. 2016). While the microscale network formation
was not observed at low pH, it was clearly observed at high pH, while the network size in our solutions was
much larger (0.5-1 µm) than those with wormlike micelles (10-20 nm). This network formation contributes
to reduction in the settling velocity by surrounding the proppants. Moreover, unlike charges of the silica
proppants and the network structures, which were determined via zeta potential measurements, lead to
electrostatic attraction (Fig. 10c), which reduced proppant settling.
Finally, the supramolecular system discussed above is a promising alternative to be used in hydraulic
fracturing due to its sustainability and environmental friendliness. Two main building blocks of the solution:
(1) stearic acid, is abundant in nature and can be obtained from cocoa butter, and (2) N,N-dimethyl-1, 3-
propanediamine is a biodegradable molecule that will not damage ground waters, and plant and soil life.
14 SPE-188241-MS

Figure 10—(a,b) Optical images obtained from supramolecular solutions at pH 4 and 8. (c) mechanism
of proppant suspension due to electrostatic interaction and network structure (Yegin et al. 2016).

Conclusions
This study presents a pH-responsive fracturing fluid solution produced via supramolecular assembly of
maleic acid and an amino amide in aqueous media. After the history and background of the fracking process
were given, working priciples and recent advances, and fracturing theory and propogation were discussed.
Additionally, design criteria of fractures and methods in creating efficient fractures were included. Then,
fracturing fluid types, challenges and issues faced in fracking operations and environmental issues regarding
the inclusion of fracking fluids were described. Furthermore, our supramolecular assembly solutions were
introduced, and experimental results obtained from these solutions in presence of 7 wt.% silica sand
were provided in detail, and compared to those of conventional fracking fluids. It was shown that the
supramolecular assembly system containing proppants worked very well at several concentrations, pH
values, temperatures, and salt concentrations. Also, it was shown that the viscosity of these solutions
could be changed reversible by pH variations and set to a certain values specific to the position of the
reservoir. While these solutions could be used at various temperatures and salimities with negligible loss
in their visocus properties, it indicated a high proppant transfer ability since the loaded proppants had an
extremely low settling velocity. Presence of salts did not substantially effect the viscous properties and
proppant suspension supramolecular fracturing fluid, which indicates that this solution system can already
mixed with sea water. Having reported these results, it can be claimed that the pH-tunable supramolecular
solution system in this study has a great potential to enhance proppant transport, reduce polymer blockage
and damage during flowback, and overcome the environmental issues owing to its sustainable nature,
environmental friendliness and high biodegradability.

Acknowledgement
The authors thank Essentium Materials LLC for their valuable support in completion of this work.

References
Acharya, Ruma. 1988. "Hydraulic-Fracture-Treatment Design Simulation." Journal of Petroleum Technology 40(2):
139–42.
Behrmann, L.a., and K.G. Nolte. 1999. "Perforating Requirements for Fracture Stimulations." In SPE Drilling &
Completion, Lafayette, LA: SPE, 18–19.
Bera, Achinta, and Ajay Mandal. 2015. "Microemulsions: A Novel Approach to Enhanced Oil Recovery: A Review."
Journal of Petroleum Exploration and Production Technology: 255–68.
Brady, Barry et al 1992. "Cracking Rock: Progress in Fracture Treatment Design." Oilfield Review 4(4): 4–17.
Chagas, B. S. et al 2004. "Evaluation of Hydrophobically Associated Polyacrylamide― containing Aqueous Fluids and
Their Potential Use in Petroleum Recovery." Journal of applied … 91: 3686–92.
Chen, I-cheng et al 2014. "Use of pH-Responsive Amphiphilic Systems as Displacement Fluids in Enhanced Oil
Recovery." SPE Journal 19(6): 1035–46.
SPE-188241-MS 15

Chen, I.-C., C. Yegin, M. Zhang, and M. Akbulut. 2014. "Use of pH-Responsive Amphiphilic Systems as Displacement
Fluids in Enhanced Oil Recovery." SPE Journal 19(6).
Chu, Zonglin, and Yujun Feng. 2009. "A Facile Route towards the Preparation of Ultra-Long-Chain Amidosulfobetaine
Surfactants." Synlett 20(16): 2655.
Economides, M., and K Nolte. 2000. Reservoir Stimulation. 3rd ed. NY and Chichester.
Economides, Micheal. 1994. Petroleum Production Systems.
Fox, A et al 2013. "Geomechanical Principles for Unconventional Reservoirs." Microseismic.com.
"Fracture Treatment Design." 2016.
Gaillard, N, A Thomas, and C Favero. 2013. "Novel Associative Acrylamide-Based Polymers for Proppant Transport in
Hydraulic Fracturing Fluids." In SPE International Symposium on Oilfield Chemistry, The Woodlands, Texas: Society
of Petroleum Engineers.
Groundwater Protection Council, U.S. DoE. 2009. Modern Shale Gas Development in the US: APrimer Modern Shale
Gas Development in the United States: A Primer.
Gulbis, Janet, and Richard Hodge. 2013. "Fracturing Fluid Chemistry and Proppants." In Reservoir Stimulation, , 1689–99.
Jang, Hee Yeon, Ke Zhang, Bo Hyun Chon, and Hyoung Jin Choi. 2015. "Enhanced Oil Recovery Performance and
Viscosity Characteristics of Polysaccharide Xanthan Gum Solution." Journal of Industrial and Engineering Chemistry
21: 741–45.
Kjøniksen, Anna Lena et al 2008. "Modified Polysaccharides for Use in Enhanced Oil Recovery Applications." European
Polymer Journal 44(4): 959–67.
Li, Xin Ping et al 2009. "New Type Flooding Systems in Enhanced Oil Recovery." Chinese Chemical Letters 20(10):
1251–54.
Li, Yue-Yang, Jin-Zhou Zhao, Wan-Fen Pu, and Tian-Hong Zhao. 2014. "Solutions of Long-Chain Alcohols and
Surfactants for Enhanced Oil Recovery in High-Temperature Low-Permeability Reservoirs." Chemistry and
Technology of Fuels and Oils 50(4): 327–36.
Millero, Frank J, Rainer Feistel, Daniel G Wright, and Trevor J Mcdougall. 2008. "The Composition of Standard Seawater
and the Definition of the Reference-Composition Salinity Scale." Deep-Sea Research I 55: 50–72.
Montgomery, Carl. 2013. "Fracturing Fluids." In Effective and Sustainable Hydraulic Fracturing, InTech, 3–25.
Samuel, Mathew et al 2000. "Viscoelastic Surfactant Fracturing Fluids: Applications in Low Permeability Reservoirs." In
SPE Rocky Mountain Regional/Low-Permeability Reservoirs Symposium and Exhibition, Denver, Colorado, Colorado:
Society of Petroleum Engineers.
Santanna, V. C. et al 2009. "Microemulsion Flooding for Enhanced Oil Recovery." Journal of Petroleum Science and
Engineering 66(3–4): 117–20.
Seright, Randall. 2010. "Potential for Polymer Flooding Reservoirs With Viscous Oils." SPE Reservoir Evaluation &
Engineering 13(August): 24–28.
Shamsijazeyi, Hadi et al 2014. "Polymer-Coated Nanoparticles for Enhanced Oil Recovery." Journal of Applied Polymer
Science 131(15): 1–13.
Taylor, Kevin C., and Hisham a. Nasr-El-Din. 1998. "Water-Soluble Hydrophobically Associating Polymers for Improved
Oil Recovery: A Literature Review." Journal of Petroleum Science and Engineering 19(3–4): 265–80.
Thomas, S. 2008. "Enhanced Oil Recovery-an Overview." Oil & Gas Science and Technology-Revue … 63(1): 9–19.
Wang, Shibin et al 2014. "A Study of Relation between Suspension Behavior and Microstructure and Viscoelastic
Property of Guar Gum Fracturing Fluid." Journal of Petroleum Science and Engineering 124: 432–35. http://
linkinghub.elsevier.com/retrieve/pii/S0920410514002927 (May 6, 2015).
Warplnskl, Norman R, and Sandia Natl Laboratories. 1991. "Hydraulic Fracturing in Tight, Fissured Media." Journal of
Petroleum Technology 43(2): 146–52.
Wenjun, Wang et al 2010. "Hydraulic Fracturing in Low Temperature Horizontal Wells." In SPE Oil and Gas India
Conference and Exhibition, Mumbai, India: Society of Petroleum Engineers.
Wever, D.A.Z., F. Picchioni, and A.A. Broekhuis. 2011. "Polymers for Enhanced Oil Recovery: A Paradigm for Structure–
property Relationship in Aqueous Solution." Progress in Polymer Science 36(11): 1558–1628.
Willberg, D. M. et al 1997. "Determination of the Effect of Formation Water on Fracture Fluid Cleanup Through Field
Testing in the East Texas Cotton Valley." In SPE Annual Technical Conference and Exhibition, San Antonio, Texas.
"Www.propublica.org/special/hydraulic-Fracturing-National."
Yegin, C., M. Zhang, J.V. Talari, and M. Akbulut. 2016. "Novel Hydraulic Fracturing Fluids with Improved Proppant
Carrying Capacity and pH-Adjustable Proppant Deposition Behavior." Journal of Petroleum Science and Engineering
145.
Zerpa, Luis E., Nestor V. Queipo, Salvador Pintos, and Jean-Louis Salager. 2005. "An Optimization Methodology of
Alkaline–surfactant–polymer Flooding Processes Using Field Scale Numerical Simulation and Multiple Surrogates."
Journal of Petroleum Science and Engineering 47(3–4): 197–208.