SPE 137268

The Development and Application of A Novel Free-damage Fracturing Fluid

(pH<2)
Jin Zhang; Yan Zhang; China University of Petroleum; Yongfu Wu; Missouri University of Science and Technology;
Xiuqing He; Xinzhu Zhang; Oil Field, Heilongjiang China

Copyright 2010, Society of Petroleum Engineers

This paper was prepared for presentation at the Abu Dhabi International Petroleum Exhibition & Conference held in Abu Dhabi, UAE,1–4 November 2010.

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
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Abstract
At present, water-based fracturing fluid systems are mainly polymer (macromolecule) and visco-elastic surfactant
(micromolecule). Because of polymer properties and incomplete gelout, the damage to matrices and conductivity
of artificial fractures will be inevitable. The surfactant-based fracturing fluid system is a micro-molecule system
not to damage artificial fractures. However, it is difficult to eliminate the damages from rock debris moving and
clay swelling in formation. A novel free-damage fracturing fluid system (FDFF), a cationic surfactant derived
from a long chain fatty acid, has been developed and applied in Daqing oil field. FDFF can crosslink in a wide
range from a strong acid to a weak acid, and its performance inherits the properties of traditional VES. Because its
molecules can be crosslinked in acid, the fracturing process is simultaneously an acidizing process. The pollution
to the vicinity of well, therefore, is cleaned out. Meanwhile, the damages of particle motion and plastic strain of
the formation near cracks are alleviated so that the high permeability zone around artificial cracks is created. The
damages induced by a fracturing treatment are completely removed. The rheology, leakoff, capacity of carrying
proppant, and conductivity of FDFF together with its case studies are demonstrated in this paper.

1. Introduction
The function of fracturing fluid is to create fracture and carry proppant. The goal that engineers pursue is how to
control crack height and maximize crack length, decrease treatment pressure, eliminate damages of fracturing
fluid to formation. Driven by the above purposes, the properties of fracturing liquid are improved unceasingly.
Since the fracturing liquid is injected into formation at high pressure, it is possible to induce physical and
chemical reactions in the formation. The reactions will do harm to the formation. In other hands, the hydraulic
fracturing is a complicated process and the structures of the fractures created by it are completely different. Some
are three-dimensional reticulates cellar structure (see Fig. 1) [1]. At the situation, it is very difficult for the
fracturing fluid to flow back along the injected path, even if there are no chemical and physical reactions between
the fracturing fluid and formation. The fracturing fluid kept in the fractures and the formation near the fractures
will occupy oil/gas paths so that. The results of the damages will decrease the effect of increasing production.
Navarrete and co-workers report that there exist three damage regions when fracturing fluid leak off asshown in
Fig. 2. [2]
1. Outer of filter cake
It is formed at the surface of cracks by the deposit of condensation of fracturing fluid and that of filtration reagent.
It is an advantage factor because it decreases fluid-loss during operation. At production, however, it is a barrier of
fluid seepage of underground. Combined with residue and formation debris, it is a damage to flow conductivity of
cracks.
2 SPE 137268

2. Inner of filter cake

The tiny particles produced by hydraulic fracturing and the macromolecular in fracturing fluids block up the pore-
throats in the invaded zone. [3]

3. Invasion of filtration fluid

When fracturing fluid is leaked off, the clay minerals of formation are swollen. They move at random and block
up the cracks.

According to Fig. 2 and the process of fracturing treatment, the properties of fracturing fluid should be satisfied
with: (1) less fluid-loss; 2) high suspension capacity; (3) low friction; (4) good thermal staility and shearing
stability; (5) no damage to permeability of the formation and the conductivity of artificial cracks; (6) clean up
completely after fracturing treatments.

Fig. 1 Complex fracture morphology Fig. 2 Damage mechanism of fracturing fluid

Water-based polymer fluid system with crosslinkers (i.e., borate, Ti, Zr) is still the most widely used fracturing fluid
system in the present fracturing operation due to its low cost. Because of the properties of polymers, it is difficult to
avoid “fish eyes” during preparing solution. Furthermore, whatever gel breaker is enjoyed, it is possible that gelout is
imperfect. New deposit is generated. Permeability and flow conductivity of fractures near wellbore is damaged by
blocking up pores from moving rock debris.

2. The design idea of FDFF and its implementation

2.1 Viscosity elastic surfactant (VES) fluid
The properties of surfactuants depend on the size of the head, tail length, and configuration of the tail, surface
charges, ionic strength and environment temperature. VES fracturing fluid with no dregs, registered as the name
of ClearFRAC by Schlumberger company, was first succeeded in hydraulic fracturing in 1997 [4]. With a few
years development, it has been applied to acid treating, acid fracturing, precipitating, sand controlling, fluid loss
decreasing and so on [5]. In 2005, Schlumberger has applied successfully VES to foam fracturing fluids by carbon
dioxide. At the same time, a new kind of high temperature VES, working at 150°C, was developed by
Schlumberger.

VES is salt solution of cationics of quaternary ammonium with long chain fatty acid. Micellar solution is formed
among surfactant molecule as salt serves as its gegenions. Micellae twist each other and form cellar structure.
They make the solution high viscosity and high elasticity which determines carry proppants. Oil wet organisms,
such as gas and oil, fall into micellae and make long chain micellae to be swollen until they decomposes into
small spherical micellae and turn into low viscosity aqueous solution. If micellae are diluted by formation water,
long chain interaction of VES is weakened and long chains break up into spherical micellae. Therefore the of
SPE 137268 3

viscosity of VES fracturing liquid will be reduced dramatically when it mixes formation water, crude oil or gases
in formation.

The application of VES fracturing liquid has changed the view to the function of fracturing fluid in treatment. It
can carry proppants at low viscosity, control the heights of fractures and increase the lengths of fractures [6]. The
studies of real-time monitor of pressure and flowback indicate that by using the no damage and low viscosity
fracturing liquid, the lengths of fractures are increased effectively even if little fracturing liquid and proppants are
applied. Another advantage of VES is that it lowers friction so that the coiled tube can be enjoyed in hydraulic
fracturing [7]. The test of the conductivity in pack-sand tubes shows that 90% permeability is retained. It is far
higher than that of cross-link polymer fracturing liquid.

Results of in-situ experiments exhibit that VES fracturing liquid, compared with traditional polymer fracturing
liquid, has 85% fluid efficiency and keeps complete flow conductivity in proppant pack.[8] It needs a few additives
and it is easy to be prepared in the field. It even can be gelled by sea water. Because all micellea participate in
establishing three dimensional cellar structures, the fluid with lower viscosity but with higher elasticity (G’>G”)
can carry proppants more effectively. The height of fractures can be controlled and the length of fractures can be
propagated longer. Thus, few proppants can be carried, however, with that of polymer fracturing fluid, the same
propped fracture length can be obtained. With the low friction of fracturing fluid, different formations can be
treated selectively by using continuous oil tubes. Furthermore, VES fracturing liquid can be pumped with lower
pressure because of its smaller friction. Thus fracturing operation time and flowback can be shorted dramatically.

Although VES fracturing fluid can greatly decrease the damage to the conductivity of cracks and effectively
control heights of cracks, moving tiny particals induced in fracturing treatment and fracture propagation will
plugged the effective pores of formation. [9] Moreover, cracks propagation will cause high stress and plastic
deformation of the zone near cracks, so that permeabilities at near cracks will be damaged permanently. Because
of the reasons, there exist the lower permeability zones between propped cracks and the matrices near cracks.
Stimulation can’t be achieved effectively.

2.2 Technologies of acid fracturing and acid treating

Acid fracturing is a fracturing technology without proppants. The length of artificial fracture created with acid
fracturing is decided by the overall effect of acid reaction rate and acid filtration rate from fracture to formation.
Stimulation technology with acid fracturing and acidizing is applied widely in oil field. [8] However, there are
some defects on field application of these stimulations. Acidizing can be performed generally for near wellbores
and the radius is about 3-5 m. For acid fracturing, it is difficult to control the loss of acidizing fluid and its
reaction rate with formation. Moreover, the depth of penetration of acid liquid is limited. The acid fracturing
liquid is leaked off seriously in some acid fracturing wells. The lengths of cracks by acid corrosion are not so long
that they can link up fissures of far wells. With production, the effective stress of formation will increase and the
corroded cracks not propped will close up quickly and lose its affectivity.

2.3 The design idea of FDFF and its implementation

At present, the main stimulation methods for low permeability oil and gas fields are hydraulic fracturing, acid
fracturing and acidizing, which have been widely studied and applied. However, each stimulation method has its
own merits and demerits. Thus the stimulation target can’t be achieved if only one method is applied, especially
for tight oil and gas reservoirs. The surfactants were screened carefully in order that it viscosifies in acid solution
and turns into viscoelastic fluid. Because the fluid system is composed of surfactants without any polymers, it has
all of the advantages of VES fracturing liquid: low viscosity, high elasticity, low friction, high carrier and no
breaker. Furthermore, the system is acid. It can acidify formation. Secondary damage of fracturing to formation is
cleared also.

The purpose of acid fracturing or acidizing is to increase penetrating distance of reservoir and delay the reaction
rate between acid and formation. Variable viscosity acids can achieve these purposes. During acid fracturing and
acidizing, acid concentration changes and the temperature of working fluid rises with the temperature of
formation. Increasing viscosity of working fluid by variation of temperature, pH and counter-ion can decrease its
4 SPE 137268

reaction rate with formation. And fluid loss can be reduced. Thus the penetrating distance will be prolonged.[10]
Naturally, it is necessary to make acid fracturing fluid of anionic surfactants have the properties of variable
viscosity acids. During creating fractures with pad fluid, the pollution of near wellbore and secondary damage
from fracturing work can be removed. Thus the complete fracture configuration, the path of carrier fluid, can be
created. At the same time, microfractures are blocked off. The loss of working liquid will decrease. Fissures and
pores of far wellbores can be linked.

2.4 Performance of FDFF system

At present, acid fracturing fluid of cationic surfactant has been synthetised in our laboratory. Its performance is
being evaluated.

250
10℃
15℃
200 20℃
60℃
Viscosity ( mPa.s)

150

100

50

0 5 10 15 20

Concentration of acid(%)

Fig 3. Viscosity and concentration of acid of fracturing fluid of free damage

at different temperatures (viscosity, concentration of acid)

Fig. 3 shows the relation curves between viscosity and concentration of acid at different temperatures. From the
figure, it can be found: (1) The liquid viscosity increases along with the concentration of acid. the position of
maximum value of liquid viscosity is at about 10% concentration of acid, then decline gradually. (2) The liquid
viscosity increases along with the temperature decrease. The higher temperature, the lower viscosity. Viscosity of
the fracturing fluid is sensitive to temperature.
The proportion of fracturing fluid of free damage in Fig. 4 is: 10.0% HCl, 3.0% KCl, 6.0% surfactant and +1.0%
YH-2.
The proportion of fracturing fluid of free damage in Fig. 5 is: 10.0% HCl, 3.0% KCl, 10.0% CH3OH, 6.0%
surfactant and 1.0% YH-2.
SPE 137268 5

200

180

Viscosity ( mPa.s)
160

140

120

100
20 40 60 80 100 120 140
Time( min)

Fig. 4 Viscosity and shear time relation of the fracturing fluid of free damage (25℃, 170 s-1)

140

120

100
Viscosity ( mPa.s)

80

60

40

20

0
20 40 60 80 100 120

Time( min)

Fig. 5 Viscosity and shear time relation of fracturing fluid of free damage (60°C, 170 s-1)

It can be seen from Fig. 4 and Fig. 5 that: (1)The systems have good shearing resistance. The liquid viscosity
decreases a little along with the shearing, then remain stable. (2) Sensitive to temperature. (3) Alcohol can reduce
viscosity of the liquid. The systems satisfy the requirement of carrying proppants. The apparent viscosity is higher
than 30 mPa·s.
6 SPE 137268

200 90

180 Viscosity
80
160
temperature

140 70

temperature,℃
Viscosity,mPa.s
120
60
100
50
80

60 40

40
30
20

0 20
0 20 40 60 80 100 120

Time, min

Fig 6. The rheological curve of FDFF (170 s-1)

Because the systems are acid, acid will corrode operating tools and strings. Under the conditions of high
temperature, high pressure and dynamic injecting acid, the corrosion will be more serious. Corroded product,
ferrous ion, will change to gel of ferric hydroxide which is tiny grains with 1.8 μm diameter. They can block up
pores of gas producing formation. It has an effect on the stimulation. In order to solve corrosion problems,
corrosion inhibitors of medium-high temperature have been evaluated and selected. According to SY/T5405-96,
industry criterion of China National Petroleum Corporation, some experiments are performed and shown in Table
1. Used steel chips at temperature of 60 °C, each experiment lasts 4 hours at static states.

Table 1. Corrosion Speed of Corrosion Inhibitors at Static States

Corrosion Concentration Concentration of Corrosion Speed

Inhibitor (wt.%) HCl (wt.%) (g/m2·hr)

0.5 10 0.97
ZX01
1.0 10 0.83

1.0 10 8.61
API
2.0 10 3.98

MP 2.0 10 27.22

HY01 2.0 10 1.76

The table shows that the selected corrosion inhibitors meet the industry criterion, < 5 g/m2·hr. The corrosion speed
of ZX01 is far slower. And pitting corrosion doesn’t appear. It guarantees that fracturing fluid of free damage
shows no harm to operating tools and strings.
Compared with other technologies of acid fracturing or hydraulic fracturing, FDFF has the traits as follows:

1) Free damage VES fracturing liquid is of micro-molecule. All the advantages of VES have been inherited. It
can break viscosity automatically, when it mixes with oil, gas or water. After viscosity break, no deposit and
no damage to formation left. Using cationic surfactants, operators will be able to solve the problems
completely on the reduction of dimensions of pores of sandstone formation and wettability reversal of rock
surface.
SPE 137268 7

2) Excellent non-uniform leakoff rate and chemical retardation When the FDFF filtered into the formation
react with minerals of formation, the solution pH decreases and the brine concentration increases, too. As a
result, viscosity of the fluid is dramatically increased to 300 cp in order that the leak-off rate and chemical
retardation is improved obviously. In fracture acidizing treatments, such a high viscosity performance greatly
enhances the capacity of fracture propagation that the etching effective fracture length induced is more than
that of other fluids. During leaking off the surface near fracture, the live acid fluid is easy to filter into high
permeability zones and generate a lot of high permeability wormholes. Meanwhile, the pH of the fluid
decreases further and its viscosity will increase continuously. The higher the permeability of the matrices is,
the more numbers of wormholes. The non-uniform leakoff rate in acid fracturing progress will be created
obviously so that the loss rate in high permeability zones will be lowered.
3) Low friction and low treatment pressure Because thickening agent is surfactant, its friction is only one fifth
of water or half of guar gum. The treatment pressure can be reduced to 10 Mpa for a well with a depth of
2000 m.
4) Shearing resistance and long-term conductivity Micellae of VES is a self-assembly structure. The micellae
can be broken under shearing force, and they can be crosslinked after the shearing force is removed. Thus the
fracturing liquid will have strong capacity carrying proppant before its viscosity is broken. The proppant can
be laid down uniformly in the cracks induced by hydraulic fracturing and acid treating. It will keep the flow
conductivity for a long time.

FDFF can remove the pollution to the vicinity of wells and acidify matrices of near cracks. Because fracturing
liquid is surfactant, its viscosity can be broken automatically and no deposit left in formation when it mixes with
oil, gas or water. The force on flowback of fracturing liquid, cleaning out other pollutions from formation and
cracks, will increase because of the chemical reactions between the fracturing fluid and the formation.

3. Case studies
This FDFF has been successfully applied in Daqing oil field with depth 1500 m and temperature 60 °C. A volume
of 23m3 proppant was successfully pumped into the formation with the maximal proppant concentration
exceeding 250 kg/m3. The production data is in Table 2.
Table 2 Results of field tests of acid-fracturing

Production Oil production(t/day) Water production (t/day)

Before 1.28 1.6

After 3.03 9.45

The oil production before the fracturing is 1.28 t/day, and it increased to 3.03 t/day after the FDFF used. Also, the
production of gross liquid(oil and water) is as five times as it before. The FDFF can not only readily carry
proppant but also react with the carbonate formation to eliminate the formation damage and connect the natual
fracture. In this way, it can maximize the drainage area and the stimulation reservoir volume, which has been
proved to benefit the well productivity.

4. Conclusions
• Developing a novel hydraulic fracturing fluid system is necessary to oil industry. Today, most of fracturing
fluid systems is cross-link polymer in alkali solution. The new system can cross-link in acid (pH < 2) solution
with excellent characteristics as described in this paper.

• Combining the hydraulic fracturing and the acidizing in one process. At present, acidizing and hydraulic
fracturing with proppant have been performed separately. Proppant fracturing cannot be performed during
acid treating or acid fracturing. Acidizing cannot be done during hydraulic fracturing. FDFF integrates the
two main stimulation models together so that such a hydraulic fracturing inherits almost all advantages
hydraulic fracturing and acidizing and avoids their disadvantages. The process of hydraulic fracturing will
company with the process of acidizing simultaneously. Hydraulic fracturing creates a high permeability zone
near the fracture propped not just an artificial fracture. The pollution to the vicinity of wells is removed also.
8 SPE 137268

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