Journal of Petroleum Science and Engineering 187 (2020) 106734

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Journal of Petroleum Science and Engineering

journal homepage: http://www.elsevier.com/locate/petrol

A review of diverting agents for reservoir stimulation

Liqiang Zhao a, Xiang Chen a, Honglan Zou b, Pingli Liu a, *, Chong Liang a, b, Nanlin Zhang a, **,
Nianyin Li a, Zhifeng Luo a, Juan Du a
a
State Key Laboratory of Oil & Gas Reservoir Geology and Exploitation, Southwest Petroleum University, Chengdu, 610500, China
b
Research Institute of Petroleum Exploration and Development, CNPC, Beijing, 100083, China

A R T I C L E I N F O A B S T R A C T

Keywords: Compared with conventional fracturing and acidizing technology, temporary plugging and diverting stimulation
Reservoir stimulation technology (TPDST), which has been becoming more and more popular in many countries, can achieve diverting
Diverting agents re-fracturing for old wells and diversion acidizing in long interval, and increase stimulated reservoir volume
Temporary plugging mechanism
(SRV) in coal-bed methane (CBM) and shale reservoir. The diverting agent is used to plug temporarily the high
Materials
permeability layers or treated areas during acidizing, which causes the acid fluid to divert to the low perme­
Application conditions
ability layers or the untreated areas to achieve homogeneous acidizing. Besides, the technologies of hydraulic
fracturing and acid fracturing rely on diverting agent to block the old fractures, natural fractures or the just-
opened new fractures, forcing the fracturing fluid or acid to divert to create more new fractures, thereby
achieving volumetric fracturing or network acid fracturing. Based on the differences of the temporary plugging
mechanism, diverting agents can be categorized as chemical particle, fiber, gel, surfactant (including foam
diversion acids, emulsified diversion acids, and self-diverting acids), composite and phase-transition diverting
agents (including thermo-responsive diverting agent and liquid nitrogen). Researchers have summarized tem­
porary plugging mechanisms of different types, commonly used materials, performances, and appropriate
application conditions. After comparing and analyzing the advantages and disadvantages of various diverting
agents, the results have shown that thermo-responsive diverting agent for fracturing and self-diverting acid for
acidification have superior performance and accord with the likely future development trends in oil and gas
resource exploitation. Thus, great effort should be made to improve and optimize the performance of thermo-
responsive diverting agent and self-diverting acid.

1. Introduction process, chemical diverting method is more favored by oilfields.

Fracturing and acidizing, as the key technologies for conventional
oilfield stimulation and for the commercial development of unconven­
tional oil and gas resources, are of significant interest to oil companies
and governments (Li et al., 2014; Xu et al., 2018). However, conven­
tional fracturing and acidizing treatment cannot meet the requirements
of diverting re-fracturing for old wells and increasing SRV for the
development of unconventional oil and gas resources. In consequence,
temporary plugging and diverting stimulation technology (TPDST) have
been developed, which can be divided into two methods including
mechanical plugging method and chemical diverting method (Cohen
et al., 2010). As mechanical plugging has the characteristics of moving
string, long construction time, high costs, and complicated operation
Currently, chemical diverting agents has been applied to oilfields in
numerous countries around the world, such as the Las-Eganskoye
(Astafyev et al., 2016) and the Prirazlomnoe oilfields in Russia (Ser­
dyuk et al., 2016), offshore oilfields in Saudi Arabia (Mirza and Turton,
1995; Safwat et al., 2002), the Jujo-Tecominoacan oilfield in Mexico
(Martin et al., 2010), the Kashagan oilfield in Kazakhstan (Shi et al.,
2015), and major oilfields in China (Liu et al., 2013a; Luo et al., 2019;
Xue et al., 2019). Compared with conventional fracturing and acidizing,
after using diverting agents, the stimulation effect is significant. Based
on the application effects, many experts believe it is necessary to apply
diverting agents for reservoir stimulation (Leal Jauregui et al., 2010;
Verna�ez et al., 2016; Yang et al., 2019).
A variety of diverting agents have been developed, and they

* Corresponding author.
** Corresponding author.
E-mail addresses: liupingli@vip.163.com (P. Liu), nanlin_zhang@163.com (N. Zhang).

https://doi.org/10.1016/j.petrol.2019.106734
Received 8 July 2019; Received in revised form 26 October 2019; Accepted 21 November 2019
Available online 23 November 2019
0920-4105/© 2019 Elsevier B.V. All rights reserved.
L. Zhao et al.
generally face the following challenges: (1) Diverting agents are good
injection performance, and not limited by well type and completion
measures. (2) They have good compatibility with treatment solution and
carrying fluid. (3) The plugging layers, formed by diverting agents, are
quite compact to reduce fluid loss and improve plugging strength. (4)
After treatment, they can be decomposed artificially or degrade auto­
matically. Less residue and less damage to reservoirs are required. (5)
The raw materials, selected for the preparation of diverting agents, are
environmentally friendly materials. Meanwhile, they are non-toxic
products to ensure the safety of construction personnel.
The working principles of diverting agents in reservoir treatment are
as follows. Firstly, formation is fractured by high pressure fluid, and
fractures continuously propagate in the process of fracturing. Based on
the principle of minimum resistance, most of the acid flow to the high
permeability areas and then etches wormholes in acid treatment (Fig. 1
(b)). Secondly, diverting agents are carried by fluid (i.e. a solid diverting
agent) or independently pumped (i.e. a liquid diverting agent) to layers
(Xiong et al., 2018). Thirdly, based on the principle of minimum resis­
tance, diverting agents flow to high permeability areas (Fig. 1(b)),
natural fractures and pre-artificial fractures (Fig. 1(a)). Then, relying on
the effect of diverting agents, acid flow to low permeability areas to
achieve uniform distribution of acid (Fig. 1(b)), or fluid flow direction is
changed and then new fractures grow (Fig. 1(a)). In Fig. 1(a), numbers
represent the order in which fractures appear. The smaller the number,
the earlier the fractures appear. Inter-layer diverting occurs in the
different layers, while intra-layer diverting occurs in the same layer. In
Fig. 1(b), the arrows mean the acid flow direction, and the length of
arrows in the low permeability area mean acid quantity. Obviously, the
plugging strength of inter-layer diverting is greater than that of
intra-layer diverting. Finally, diverting agents can be decomposed
Fig. 1. Schematic diagram of chemical diverting method.
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Journal of Petroleum Science and Engineering 187 (2020) 106734
artificially or degrade automatically under the reservoir conditions, and
then flow back to ground. It causes less damage or even no damage to the
oil-bearing layer and makes full use of pre-artificial fractures, natural
fractures, or high permeability areas (Li et al., 2018; Qiao et al., 2014).
According to the differences of temporary plugging mechanisms,
chemical diverting agents can be divided into chemical particle, fiber,
gel, surfactant, composite and phase-transition diverting agents, as
shown in Fig. 2. This paper will give a review of the chemical diverting
agents in the following sections according to this classification.
2. Chemical particle
2.1. Temporary plugging mechanism
In this approach, chemical particles are pumped into the reservoir
through a fluid carrier and then form dense filter cakes by bridging
between large particles and filling with small particles. Nevertheless, for
fracture with larger width, the particles produce temporary plugging
mainly through sedimentation and accumulation (Liu et al., 2017). After
treatment, particles can be dissolved in oil, acid or formation water and
then flow back to the ground. For filter cakes formed by the bridging and
filling, the plugging effect depends on the matching relationship be­
tween particle size and pore, throat, or fracture width. Many researchers
have studied it and different matching principles have been proposed,
mainly including ideal filling theory (d1/2 theory), the d90 principle
(Hands et al., 1998), the 1/3 matching principle (Abrams, 1977), the
2/3 matching principle (Lou and Lou, 1992), and the 1/3–2/3 matching
principle (Xu et al., 2012) for pore reservoirs, as well as the 80%–100%
matching principle (Ye et al., 2005), and temporary plugging fractal
theory (Cui, 2002) applied to fracture reservoirs. Herein, the d1/2 theory,
L. Zhao et al.
Fig. 2. Classification of temporary plugging and diverting stimulation technology.
d90 principle and 1/3–2/3 matching principle are commonly used in
oilfields. Fig. 3(a) shows the bridging mechanism when the particle size
is 1/3 to 2/3 of the pore or throat size. There are larger gaps in filter
cakes formed by chemical particles of same size, as shown in Fig. 3(b).
Thus, in order to improve the plugging strength and reduce fluid
filtering loss, a measure, filling with particles of various size and
deformable particles (Fig. 3(b)), is used to reduce gaps (Brannon et al.,
2006).
2.2. Main materials and performances
According to the differences in removal media, chemical particle can
be subdivided into water-soluble, acid-soluble and oil-soluble agents (Li
et al., 2011). Currently, acid-soluble agents mainly comprise calcium
carbonate materials, which are suitable for use over a wide temperature
range, have high plugging strength (6 MPa) and have a dissolution
performance of about 95% in acid solution (Yan, 2012; Zhang et al.,
2016; Zhou and Su, 1992). Water-soluble agents can be applied at
different reservoir temperatures, and have medium plugging strength of
approximately 4.5 MPa. Those have a core penetration rate recovery
value of 93%, water solubility of 96% and temporary plugging rate of
98% (Jiang et al., 2017; Zhao et al., 2004). Oil-soluble agents are mainly
made of paraffin, rosin or resin, are suitable for temperatures up to 149
�
C (Babey et al., 2015), and have a plugging strength of up to 7 MPa.
They have a core penetration rate recovery value of 90% and the tem­
porary plugging rate of 95% (Li et al., 2018; Zhao et al., 2016b). When
reservoir temperature is higher than particle softening point tempera­
ture, solid particles begin to melt. When the reservoir stress is greater
than the compressive strength of particles, solid particles will be broken.
Hence, reservoir temperature and stress will affect the plugging effect.
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Journal of Petroleum Science and Engineering 187 (2020) 106734
2.3. Application conditions
Based on reservoir conditions and construction requirements, the
application conditions for chemical particle can be summarized as fol­
lows: (1) Higher plugging strength: Use different particle size combi­
nations to reduce gaps, resulting in smaller filtering losses. Most of the
particles have high compressive strength and the plugging strength can
reach 7 MPa (Yang et al., 2019; Zhao et al., 2018). (2) It has a wide
application temperature range: The preparation materials of diverting
agents are various, such as inorganic salts, resins, and paraffin, etc., and
the applicable temperature can reach 149 � C (Zhao et al., 2018b). (3)
Residue generation: Particle dissolution is affected by various features of
the reservoir and particles cannot be completely dissolved (Pei, 2017).
The remaining residue damages the reservoir, electric submersible
pumps and rod pumps, which limits its application for rod pump and
electric submersible pump production wells. (4) Poor adaptability of
well type: Due to the different dissolution medium, oil-soluble agents
generally are not used in water injection wells and gas wells.
Acid-soluble agents mostly are used during acidizing and acid frac­
turing. Water-soluble agents commonly are used in water injection
wells. (5) Poor injection properties: Particles have the same problems as
proppants with difficulty in injection, which can cause “sand plug” in the
wellbore or stratum. At the same time, the particles cannot be injected
into the micro-fractures and small pore throats (Babey et al., 2015; Yang,
2017). (6) Limitation of well completion method: The design of the
chemical particle size needs not only to consider the matching rela­
tionship with pore throats or fractures, but also the limitation of the well
completion method. That is, whether particles can pass through existing
well completion conditions (e.g. a screen pipe completion).
L. Zhao et al. Journal of Petroleum Science and Engineering 187 (2020) 106734

Fig. 3. Schematic diagram of the 1/3–2/3 bridging mechanism and measure to reducing gaps.

3. Fiber process (Fig. 4(b)). (3) The fiber layer compaction stage: The pressure
difference between front and back causes the fiber layer to be continu­
3.1. Temporary plugging mechanism ously compacted (Fig. 4(c)). In Fig. 4, v represents the filtration rate.
After the formation of the dense cake, the filtration rate v3 is approxi­
The fibers are softened in the carrier fluid and injected into the mately equal to 0. After stimulation, fibers can be dissolved in acid,
reservoir with the carrier fluid. The long and short fibers twine around alkaline solution or water and then flow back to the ground.
each other to form a three-dimensional network structure; that is, a
“filter cake (filter network)” structure (Yang et al., 2019). The formation
3.2. Main materials and performances
of an effective plugging layer goes through three stages: (1) The inner
filter cake formation stage: After fibers are pumped to the reservoir, that
Fibers utilized for this application mainly are plant fibers and their
flow first into the high permeability layer or the fractures, according to
modified products. The typical materials include polyester fiber, poly­
the principle of minimum resistance. The long fibers are captured as the
lactic acid fiber, and polypropylene fiber. The applicable temperature is
bridges at the pore throats or fractures. Under the displacement pres­
up to 135 � C. The core penetration rate recovery value can reach 96%
sure, the fibers are pushed into the pore throats or the inner fractures.
(Jiang et al., 2015; Quevedo et al., 2012). The plugging strength is
Different wall roughnesses and the drag resistance retain the fibers in
generally lower with the value of 0.4–3.5 MPa. Most fibers are only
place (Fig. 4(a)). (2) The outer filter cake formation stage: The captured
dissolved in acid with an acid solubility rate of 96%. Very few fibers can
long fibers, which act as bridges, and their accumulation increases with
be dissolved in water or alkaline solution with the dissolution rate of
the injection liquid process. At the same time, the ability of the rough
about 90% (Du et al., 2019; Ma et al., 2018; Zhao et al., 2014). Reservoir
crack walls to capture the short fibers is enhanced, and the fibers twine
pressure has little effect on fibers. With the increase of reservoir tem­
around each other and gradually form a fiber layer during the capture
perature, the plugging strength decreases rapidly, especially after it is

Fig. 4. Schematic diagram of the temporary plugging mechanism.

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L. Zhao et al. Journal of Petroleum Science and Engineering 187 (2020) 106734

higher than the application temperature of fibers (Hu, 2018). Increasing

the concentration of fibers can promote the plugging strength, but the
concentration is generally not more than 2%.

3.3. Application conditions

The following points should be noted when using fibers: (1) There is
little influence from salinity and they have a wide applicable tempera­
ture range. As fibers are synthesized above the ground, its performance
is stable, unlike that of polymers that are crosslinked underground,
which are affected by many factors in the reservoir. The fibers can be
used between 20–135 � C. (2) Compared with large size particles, fiber
injection is relatively straightforward. The fibers are softened and sus­
pended in the carrier liquid, and integrate with the carrier fluid. In
addition, fiber injection and its ability to pass through the well
completion are related to fiber length, concentration (generally not
more than 2%) and materials (Xue et al., 2015; Yang et al., 2013a, b). (3)
Fibers have a single dissolution medium and is often used for
acid-related reconstruction. As most of the fibers can be dissolved only
in acid solution, plugging removal with acid needs to be done after the
hydraulic fracturing reconstruction (Ma et al., 2018). (4) The plugging
strength is lower, and fibers are used in combination with other
diverting agents. Compared with chemical particles, the fiber filter cake
layer is more dense, lesser fluid filtering loss, and can effectively prevent
proppant reflux. Hence, fiber combination with other diverting agents
can be used in multiple fracturing (Che et al., 2018; Leal Jauregui et al.,
2011).

4. Gel

Fig. 5. Schematic diagram of gel temporary plugging mechanism (Wide pore

4.1. Temporary plugging mechanism
throats mean higher permeability. Based on the principle of minimum flow
resistance, the gel will first plugging high permeability areas.).
Gels achieve temporary plugging that relies on jelly-like volume
plugging (Fig. 5). Gels have two forms, of particle and fluid in the
4.3. Application conditions
ground condition (Wang et al., 2007). In the first case, gels form parti­
cles through cross-linking in ground, which is easier to store and
Although gels have two manifestations under the ground conditions,
transport. Gel particles are carried by fluid to pore throats or fractures,
they have similar temporary plugging mechanism in formation. The
and then, under the action of high temperature heating in reservoir,
following points should be noted in application: (1) Injection properties,
particles melt and cross-link again to form gel rubber plugs. Therefore,
well depth structure and well completion method: As the gel particles
the same problem exists between gel particles and chemical particles
melt in high temperature reservoirs and then cross link, gel particles
when passing through well completion conditions (e.g. a screen pipe
have the same problems as chemical particles in the injection process.
completion). The other case is that gel solution can be directly pumped
On the contrary, due to gel solution is always liquid before crosslinking,
to pore throats or fractures, and then cross-link under reservoir condi­
it can be injected into micro-fractures and micro-pores to form volume
tions to form gel rubber plugs. After the construction is completed, gel
plugging without the limitations due to well type or well completion
rubber plugs degrade automatically or are decomposed into small
method (Bai et al., 2013; Wang et al., 2017b). (2) Wide applicable
molecules under the action of a gel breaker, and then flow back to the
temperature range: Amide-5-phenyl-1,3-oxazole copolymer (APOC) gel,
surface (Imqam et al., 2016).
developed by Vega et al. (2008), can be used in ultra-high temperature
reservoirs at 220 � C with a system viscosity of 2672 mPa s (the shear
4.2. Main materials and performances rate is 170 s 1). (3) Effective reducing of fluid filtering loss: The gels
crosslink under high temperature conditions to form a jelly-like bulk
The gel rubber plugs are formed by polymer cross-linking. The main rubber plug, and the structure is dense with almost no fluid loss. (4) It is
materials include phenolic gel, acrylamide, and modified products (Jia difficult to control the breaking time and there are many residues: The
et al., 2010; Ren et al., 2014; Verna
�ez et al., 2016). The suitable tem­ gel breaker is mainly encapsulated in capsules. As the high temperature
perature range is 40–220 � C (Vega et al., 2008). Gel plugs have lower resistant system is generally stable, breaking the gel and gel degradation
compressive strength and salt tolerance. The degradation rate can reach are extremely difficult, and many residues remain in the formation. The
up to 95% under the action of the gel breaker. The core penetration rate residue in micro-fractures and micro-holes is almost impossible to re­
recovery value can reach 90%. The gelation time is controllable (from turn, resulting in the substantial secondary damage (Pei, 2017). (5) The
120 min to 12960 min) and the gel rubber plug viscosity can reach more cross-linking process and system stability are affected by various factors:
than 1500 mPa s (Wang et al., 2017b). Most of the main components of Reservoir salinity, temperature, and pH value have great influence on
conventional polymer gels are partially hydrolyzed polyacrylamide, the crosslinking and stability of the system. Most polymers have tem­
which is prone to thermal degradation or salt degradation under high perature and salt tolerance problems (Wang et al., 2017a).
temperature or high salinity environment. In addition, the bigger the
permeability gradient of reservoir is, the better the plugging effect of
gels is (Zhao et al., 2018b).

5
L. Zhao et al.
5. Surfactant
Foam diversion acids, emulsified diversion acids, and self-diverting
acids are classified as surfactant diverting agents, as they rely on a
surfactant to achieve foaming, foam stabilization, emulsification or
viscosity change. Because the self-diverting acid is the most commonly
used technology for acidizing of carbonate reservoirs, the characteristics
of self-diverting acid are emphasized.
5.1. Temporary plugging mechanism
The self-diverting acid system is generally a low viscosity fluid under
ground conditions. When self-diverting acid is pumped into the forma­
tion, the acid-rock reaction occurs, which causes the pH of the acid
system and the concentration of Ca2þ and Mg2þ ions to increase, etc.
When the temperature, pH value, or the concentration of Ca2þ and Mg2þ
ions reach a certain value, the viscosity of the acid solution system in­
creases rapidly (Fig. 6) (Zhou, 2006, 2011). Based on the principle of
minimum flow resistance, acid first will enter the high permeability
layer or near-well area. With the acid-rock reaction going on continu­
ously, the viscosity of the system increases, which makes the flow
resistance of acid into the area increase. Then, the acid is forced auto­
matically to flow into the low permeability or far-well area. Eventually,
the entire wellbore or the entire fracture is acidified. The high-viscosity
self-diverting acid degrades automatically as reservoir temperature
rises, or it is decomposed to reduce viscosity when directly contacting
hydrocarbons (Liu et al., 2013b; Verna �ez et al., 2016). As shown in
Fig. 6, the viscosity after degradation is close to that of clean water,
which is convenient to return to the surface and effectively protects the
reservoir.
5.2. Main materials and performances
The self-diverting acid system consists mainly of acid and visco­
elastic surfactant. Therein, the surfactants are cationic surfactants or
amphoteric surfactants (Alleman et al., 2003; Zeiler et al., 2006). A
typical system would include visco-elastic surfactant based
self-diverting acid (VES-SDA) (Al-Mutawa et al., 2003, 2005), synthesis
of amphoteric surfactant sinapic amido propyl betaine (SAPBET) (Zheng
et al., 2005), temperature-controlled deep-diverting acid (TCA) (Zhou
et al., 2011), pH-controlled self-diverting acid (DCA) (Shi et al., 2015;
Wilson, 2016), erucic acid amido propyl betaine and cationic amido
Fig. 6. Viscosity change mechanism of the self-diverting acid system (Shi et al., 2015; Yue et al., 2017).
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Journal of Petroleum Science and Engineering 187 (2020) 106734
propyl quaternary ammonium salt (Hanafy et al., 2016). The applicable
temperature can reach 135 � C. The system viscosity is determined by pH,
temperature, and Ca2þ and Mg2þ ion concentration. Before it increases,
the viscosity of the system is less than 30 mPa s, and after increasing can
be more than 600 mPa s. Under the action of hydrocarbon (kerosene),
brine or high temperature, the system degrades automatically and the
viscosity falls to less than 10 mPa s, which is convenient to enable it to
be returned to the surface and protect the reservoir (Yang et al., 2013a).
5.3. Application conditions
Foam diversion acids, emulsified diversion acids, and self-diverting
acids are widely used for the acidizing of carbonate reservoirs. How­
ever, foam diversion acids and emulsified diversion acids have the
characteristics of complex construction technology, large friction and
poor reliability of acid diversion (Chang et al., 2001). In addition,
temperature has great influence on foaming, foam stabilization, and
emulsification. Thus, foam diversion acids and emulsified diversion
acids are not suitable for high temperature deep wells with large
permeability variation (Shun et al., 2005; Tao et al., 2012). The appli­
cation conditions of self-diverting acids will be highlighted below.
For acidizing using self-diverting acids, the following application
conditions should be considered: (1) Applicable temperature and in­
jection properties: self-diverting acid system can be used for high tem­
perature reservoirs at 135 � C. The mixed system consists of viscoelastic
surfactants and the acid solution remains low viscosity fluid instead of
solid, which can be injected into fractures and pore throats of any scale
and can pass easily through any completion measures (Hanafy et al.,
2016). (2) Simple construction technology and effective reservoir pro­
tection: self-diverting acid is pumped directly into the reservoir and then
the viscosity of the system increases automatically. No additional
operation is required in matrix acidizing or acid fracture process. After
treatment, the high viscosity system degrades automatically or is
decomposed when contacting hydrocarbons. Then the viscosity of the
system is close to that of clean water, which is convenient to return to
the surface (Chang et al., 2001). (3) The plugging strength is lower and is
suitable for non-mandatory diverting: Viscoelastic surfactants rely on
their own viscosity increase to achieve temporary plugging. Therefore,
the plugging strength is lower. Compared with the requirements for
fracture diverting plugging strength, this approach is more suitable for
reservoir acidizing (Xue, 2017; Yue et al., 2017). (4) Surfactant devel­
opment from cation to amphoteric: As the clay minerals are negatively
L. Zhao et al.
charged, they adsorb cation surfactants, resulting in rock wettability
that reverses oil wetness, which increases the oil phase seepage resis­
tance. In order to avoid surfactant waste and wettability reversal, the
viscoelastic surfactant should be developed gradually towards being an
amphoteric surfactant.
6. Composite diverting agents
Composite diverting agents have been used widely in oilfields, which
are composed mainly of chemical particles, fibers, gels, and viscoelastic
surfactants. Composite diverting agents combine the advantages of
every single type of diverting agent. They can meet the reconstruction
technology requirements of various reservoirs when matching right
construction technologies. Typical composite diverting agents that have
been applied in the oilfield include fibers þ chemical particles (Fig. 7)
(Che et al., 2018), fibers þ self-diverting acid (Leal Jauregui et al., 2011;
Martin et al., 2010) and fibers þ chemical particles þ gels (Leal Jauregui
et al., 2010; Shi et al., 2015). Fig. 7 shows diverting re-fracturing for old
wells. Original fractures are plugged by composite agents of fibers and
chemical particles so that new fractures grow and propagation, which
can improve the connectivity between fractures and wellbore in the
near-well zone, and increase well productivity.
7. Phase-transition diverting agents
7.1. Thermo-responsive diverting agent
Zhao et al. (2016a, b; 2018a) first developed a thermo-responsive
diverting agent that was liquid under normal temperature conditions
and formed a solid-like supramolecular material under physical stimu­
lation (eg. temperature) or chemical stimulation (eg. phase-transition
regulator). After the diverting agent is injected into the fracture, the
liquid diverting agent becomes solid as the temperature rises to the
phase-transition temperature, which changes flow direction of frac­
turing fluid or acid and then new fractures are created. As the temper­
ature in the fracture rises further, the solid supramolecular material
becomes liquid again, as shown in Fig. 8. After the treatment is
completed, the liquid diverting agent is returned to the surface. A single
fracturing construction can generate various fracture passages, thereby
greatly improving single well productivity.
Pei (2017) have developed two thermo-responsive diverting agents,
DMF and PC410, with different phase-transition temperature. For DMF
system, when the temperature rises to 102 � C–104 � C, it takes about 30
min for liquid to completely transform into solid. When the temperature
is higher than 109 � C, the time for solid to completely transform into
liquid is about 45 min. For PC410 system, as shown in Fig. 8, when the
temperature rises to 90 � C–95 � C, the time for liquid to completely
transform into solid is about 60 min. When the temperature is higher
Fig. 7. Diverting mechanism of fibers þ chemical particles composite.
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Journal of Petroleum Science and Engineering 187 (2020) 106734
than 115 � C, it takes about 80 min for solid to completely transform into
liquid. In addition, they also developed the phase-transition regulator to
shorten the phase change time. Because the phase transformation of
liquid diverting agent is affected by temperature, it is quite significant to
accurately calculate the temperature field. Xian and Zhao (2018)
established a wellbore-fracture-formation temperature field model to
predict temperature changes during treatment.
Thermo-responsive diverting agents can enter holes, fractures, and
pores of different sizes to cause volume plugging. The approach is
suitable for various types of reservoir diverting reconstruction and meets
the requirements for different well completion measures, well structures
and reservoir conditions. The thermo-responsive diverting agents have
good injection properties and adjustable plugging strength. The tech­
nology has been applied in Huabei oilfield and in the Inner Mongolia
oilfield in China. The plugging pressure can reach 11 MPa. It achieves
multi-stage acid fracturing, and inter-layer diverting of hydraulic
fracturing.
7.2. Liquid nitrogen
There are a large number of natural micro-fractures in CBM reser­
voir. In order to improve single well productivity, it is necessary to plug
natural micro-fractures to reduce fluid loss and obtain multiple artificial
long fractures. Yang et al. (2018) proposed to freeze CBM reservoir
fractures using liquid nitrogen to achieve blocking. The technical prin­
ciple is: When water in the natural fractures is mixed with the ultra-cold
and eco-friendly liquid nitrogen, the water is converted rapidly into ice
to achieve the diverting of fracturing fluid. After treatment, the ice melts
automatically with the increase of formation temperature and that
removes blocking. Indoor test results have demonstrated that the break
pressure of coal samples using liquid nitrogen freezing was significantly
higher than that of a coal sample without any treatment. Additionally, it
generated one fracture, whereas a large number of micro-fractures
appeared in coal samples without any treatment.
8. Discussion and summary
In the review, the recent advances in diverting agents for reservoir
stimulation are presented. The following will discuss, analyze and
summarize the different diverting agents.
The temporary plugging mechanisms include primarily point, filter
cake (filter network), and volume plugging. Temporary plugging balls
belong to point plugging category. Chemical particles and fibers achieve
plugging by forming filter cake. Gels, self-diverting acids, and phase-
transition diverting agents all belong to the volume plugging category.
Solid-like or jelly-like volume plugging is formed by liquid in under­
ground through crosslinking or cooling, which has the characteristics of
low fluid filtering loss, adjustable plugging strength, and entering holes,
L. Zhao et al. Journal of Petroleum Science and Engineering 187 (2020) 106734

Fig. 8. The phase-transition process of thermo-responsive diverting agent (PC410).

fractures, and pores of different sizes. Hence, the most effective tem­
porary plugging mechanism is volume plugging.
According to the systematic investigation and objective analysis, the
characteristics of diverting agents are summarized in Table 1.
Table 1 shows that plugging strength of multi-particle size combi­
nations is greater than that of same size particle, which demonstrates
that multi-particle size combinations can effectively reduce gaps of filter
cakes, make filter cakes denser, and increase plugging strength. Besides,
because of the difficultly matching chemical particle size with pore or
fracture size, limited by completion measures, high cost, much residue
and affecting the work of oil pumps, the oilfield application frequency of
chemical particle has been decreasing.
Compared with other diverting agents, the plugging strength of fi­
bers is low. Fibers have a good temporary plugging effect in the case of
fractures with a small width. Nevertheless, for fractures with larger
width, the temporary plugging effect of fibers is not ideal. Hence, fiber is
often used in combination with other diverting agents to improve
plugging strength. In addition, displacement is properly reduced so that
fibers have enough time to catch and accumulate in the fractures. It is a
good way to improve the filling effect of plugging layers.
Gels are suitable for fracturing with millimeter fracture width.
Although gel cross-linking is affected by formation brine, the influence
can be separated by the process of injecting a slug first. Gels have the
highest applicable temperature, but it is difficult to degrade and causes
serious damage to the reservoir. Because of its volume plugging and not
limited by completion measures, the development of degradable gel will
be a good direction. It can start with the materials of the crosslinking
agent and breaker, and laying method of breaker.
Compared with foam diversion acid and emulsified diversion acid,
self-diverting acid has obvious advantages and is widely used in car­
bonate reservoir acidification. It is significant to develop self-diverting
acid with wider range of viscosity change, more variable viscosity fac­
tors and higher applicable temperature, which meets the development
needs of different lithologic reservoirs with high temperature or large
permeability difference.
The plugging strength of composite diverting agents is obviously
higher than that of single diverting agent. However, its construction
technology is complex and the failure rate is high. Although liquid ni­
trogen can effectively cool formation water to ice, the cost of liquid
nitrogen is high and the distribution of formation water in reservoirs is
demanding. Therefore, the technology can not be widely used in the
oilfield.
The thermo-responsive diverting agent is very sensitive to tempera­
ture. Hence, it is significant to accurate calculation of temperature field
change during construction. It demands that reservoir temperature
should be higher than phase change temperature to achieve effective
temporary plugging and plugging removal. Therefore, thermo-
responsive diverting agent can not be applied to low temperature res­
ervoirs, such as CBM reservoir.
In Table 1, according to the analysis of applicable temperature,
plugging strength, degradation, well completion, cost, and matching
stimulation measure, researchers hold the view that self-diverting acid

Table 1
Performances of diverting agents and matching stimulation measure.
Chemical diverting method Performances of diverting agents Matching stimulation measure

Application Plugging Is it affected by Reservoir damage

temperature (� C) strength completion? degree

chemical water-soluble �80 <5 MPa yes ** acidizing and fracturing

particle acid-soluble �120 �6 MPa **
oil-soluble �149 �7 MPa **
fiber �135 �4 MPa yes **
gel �220 5–54 MPa/m yes(gel particle); ***
no (gel solution)
surfactant foam diversion acid �120 – no * acidizing in medium-low
emulsified diversion �80 – no * temperature reservoir
acid
self-diverting acid �135 – no * acidizing in carbonate reservoir
composite fiber þ particle – �13 MPa yes ** fracturing
fiber þ particle þ gel – �16 MPa yes ***
fiber þ self-diverting �135 �21 MPa yes ** acidizing and acid fracturing
acid
multi-particle size combination – �10 MPa yes ** acidizing and fracturing
thermo-responsive diverting agent �90 122–234 MPa/ no * acidizing and fracturing
m
liquid nitrogen – – no * fracturing in CBM reservoir

Notes: “*” means almost no damage; “**” means slight damage; “***” means serious damage.

8
L. Zhao et al.
and thermo-responsive diverting agent are the most developing poten­
tial. For carbonate reservoir acidification, self-diverting acid is un­
doubtedly the best choice. Thermo-responsive diverting agent can be
used for acidizing and fracturing of any lithologic reservoirs.
9. Concluding remarks and future extended work
With the development of oil and gas resources towards high tem­
perature, high pressure, deep layer, and dense reservoirs, the future
research will develop a new knowledge in the area of temporary plug­
ging and diverting stimulation technology. By comparing and analyzing
the characteristics of the diverting agents, researchers can conclude that
self-diverting acid and thermo-responsive diverting agent are satisfac­
tory. Furthermore, the future extended work should aim to develop high
temperature resistant viscoelastic surfactant with ideal plugging
strength and thermo-responsive diverting agent with wider application
temperature range, which should have the characteristics of low cost
and environmental protection.
Acknowledgment
The authors thank everyone involved in creating this paper with
supervision, knowledge, guidance, and operational assets. The work of
authors was supported by National Major Science and Technology
Projects of China (2017ZX05030; 2016ZX05014; 2016ZX05052) and
National Natural Science Foundation of China (U1762107).
Nomenclature
TPDST temporary plugging and diverting stimulation technology
SRV stimulated reservoir volume
CBM coal-bed methane
APOC amide-5-phenyl-1,3-oxazole copolymer
VES-SDA visco-elastic surfactant based self-diverting acid
SAPBET synthesis of amphoteric surfactant sinapic amido propyl
betaine
TCA temperature-controlled deep-diverting acid
DCA pH-controlled self-diverting acid
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