Carbohydrate Polymers 240 (2020) 116321

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Carbohydrate Polymers
journal homepage: www.elsevier.com/locate/carbpol

A review on the recent development of cyclodextrin-based materials used in T

oilfield applications
Wenyue Tanga, Changjun Zoua,*, Chang Dab, Yixuan Caoa, Hong Penga
a
School of Chemistry and Chemical Engineering, Southwest Petroleum University, Chengdu, 610500, PR China
b
McKetta Department of Chemical Engineering, The University of Texas at Austin, Austin, 78712, United States

A R T I C LE I N FO A B S T R A C T

Keywords: Cyclodextrin has been studied for more than 120 years. Due to the special structure and selectivity of the
Cyclodextrin-based materials cyclodextrin cavity, native cyclodextrins, cyclodextrin derivatives and inclusion complexes have received ex-
Cyclodextrin polymers tensive attention and are widely used in medicine, food, the environment, cosmetics, chemical analysis, se-
Host-guest inclusion complexes paration technology, catalysts and other fields. Cyclodextrin-based materials have been applied to oilfields since
Oilfield application
the early 1980s and performed well in enhancing the performance of petroleum chemicals and improving the
Enhance oil recovery
efficiency of oil exploration. This review introduces the characteristics of cyclodextrin-based materials, including
cyclodextrin polymers, inclusion complexes and new cyclodextrin nanocomposites, and summarizes their ap-
plications in oilfields for the first time, such as retarded acid solution, enhanced oil recovery, clay stabilizers,
corrosion and scale inhibitors, wastewater treatment, etc. Meanwhile, the action mechanisms, major challenges
and development tendencies of cyclodextrin-based materials in oilfields are also comprehensively discussed.

1. Introduction
Over the past few decades, polymeric compounds have been widely
used in the petroleum field, such as drilling, cementing, acidizing and
fracturing. However, with the increasing harsh conditions of oil and gas
storage and the limitations of the structure and chemical properties of
conventional polymers, applications of ordinary polymers in oil and gas
exploitation and transportation are limited. Due to the challenges
mentioned above, traditional polymers have been modified with var-
ious functional groups and molecules to improve their thickening
ability, shear resistance, temperature resistance, salts resistance, etc.
Therefore, at present, research is mainly focused on the design, synth-
esis and characterization of novel types of macromolecular polymer
materials and composite materials, which have the advantages of a high
efficiency, sustainable development, good economic performance, and
competitive production methods.
Meanwhile due to their fascinating characteristics, such as a high
availability, facile synthesis, large-scale production and harmless
nature (Crini, 2005; Kurkov & Loftsson, 2013), cyclodextrins (CDs) and
their derivatives have attracted substantial attention and have enabled
wide applications in the practical fields of science and technology, in-
cluding pharmaceuticals, biomedicine, the food industry, analytical
chemistry, agriculture and environmental protection, etc. (Del Valle,
2004; Dodziuk, 2006; Szejtli, 1988). CDs have been widely studied over
the past 128 years and have been presented with an increasing fre-
quency in related reports and publications, the number of which
reached up to 18,430 in the five years from 2011 to 2015 (Crini et al.,
2018). The annual worldwide production of CDs exceeds 10,000 tons,
∼30 % of which is used in pharmaceuticals, ∼20 % is used in the food
industry, and the rest is used in a variety of consumer products
(Jansook, Ogawa, & Loftsson, 2018). In addition, with the development
of science and technology, cyclodextrin (CD) has performed well in the
fields of molecular imprinting techniques, molecular imaging and other
advanced technologies (Lai, Rogach, & Wong, 2017; Lay, Ni, Yu, &
Shen, 2016). The special structure of CDs allows them to properly in-
clude guest molecules and form host-guest inclusion complexes. Poly-
saccharide biopolymers, including guar gum, xanthan gum, cellulose
derivatives, scleroglucan, etc., are widely used in oilfields to improve
oil recovery due to their environmental friendliness and chemical sta-
bility (Pu, Shen, Wei, Yang, & Li, 2018). Thus, oil researchers and en-
gineers, both domestic and international, were inspired to introduce
CDs into the petroleum industry. The application of CDs in oilfields
started as early as at the beginning of the eighties. Shibanai et al. (1981)
and Horikoshi and Shibanai (1984) patented the use of CDs to extract
oil from oil sands. Numerous efforts have been expended on CDs, CD
derivatives and CD-based materials over the past few decades.
Many different types of CD derivatives based on native CDs have
been synthesized and developed. CDs are collectively known to be a

⁎
Corresponding author at: No. 8 Xindu Avenue, Xindu District, Chengdu, 610500, PR China.
E-mail address: changjunzou@126.com (C. Zou).

https://doi.org/10.1016/j.carbpol.2020.116321
Received 5 December 2019; Received in revised form 13 April 2020; Accepted 14 April 2020
Available online 23 April 2020
0144-8617/ © 2020 Elsevier Ltd. All rights reserved.
W. Tang, et al.
series of cyclic oligosaccharides produced by the enzymatic degradation
of starches using the enzyme cyclodextrin glycosyltransferase (CGTase),
and CDs usually contain 6–12 D-glucose units that link into a ring via α
-1,4-glucoside bonds (Chen, Huang, Li, & Liu, 2018). These toroidal
cyclodextrin molecules contain many hydroxy groups, all of which are
on the outside surface of the molecules, forming an external hydrophilic
surface and stable hydrophobic cavity (Hui, Raoov, Zain, Mohamad, &
Osman, 2017; Mura, 2014). The central cavity is lined with skeletal
carbons and the ethereal oxygen of the glucose residue. Due to these
structural characteristics, CD molecules, as receptors, form inclusion
complexes through selective combination with the appropriate hydro-
phobic molecules via noncovalent host-guest interactions in the internal
cavity. In addition, better performances are shown by CD derivatives
obtained by covalent modifications of the external surface than others
(Frömming & Szejtli, 1994; Rajewski & Stella, 1996). Therefore, more
attention has been paid to CD polymers and complexes to tap their
potential for oil exploration and transportation.
Currently, the academic and industrial fields at home and abroad
have shown great research interest in CD polymers, inclusion com-
plexes and other CD-based materials. Numerous reviews on CD-based
materials exist in the literature, especially in the fields of medical
technology, food engineering and environmental pollution treatment.
However, to our knowledge, the application of CD-based materials in
oilfields has not been reported in an individual review. In this review
article, we mainly focus on the advancement of CD polymers, inclusion
complexes and new cyclodextrin nanocomposites in oilfields, with a
special emphasis on their effectiveness, characteristics, and important
mechanisms in enhancing oil recovery (EOR). This review includes not
only our group’s efforts in this area but also other group’s relevant
works.
2. Native cyclodextrins and their properties
According to practical needs, the three most studied native CDs are
α-CD, β-CD, and γ-CD, which consist of six, seven, and eight α -(1,4)-
linked glycosyl units, respectively, and have hydrophobic interiors and
hydrophilic exteriors (Fig. 1 (A)) (Dass & Jessup, 2000; Sikder et al.,
2019). According to the results of X-ray crystal diffraction and infrared
spectrum and nuclear magnetic resonance spectrum analyses, it has
been indicated that every D-glucopyranose that constitutes a CD mole-
cule is in the chair conformation. The CD molecules have a round,
bottomless, truncated bowl-shaped structure, with C6 OH groups
Fig. 1. (A) Chemical structure of α, β, and γ-CD; (B) shape and characteristics of
CDs.
2
Carbohydrate Polymers 240 (2020) 116321
located at the rim of one side of the cavity (smaller open end, primary
OH-face), which are primary hydroxyls, and C2 and C3 OH groups on
the rim of the other side of the cavity (larger open end, secondary OH-
face), which are both secondary hydroxyls. The CD molecules are stif-
fened by hydrogen bonding between C2 and C3 OH groups, whose O (2)
⋯ O (3) hydrogen-bonding distances are 2.98Å , 2.88 Å and 2.82 Å in
α-, β- and γ-CDs, respectively, so the hydrogen bond strength follows
the order of α − CD< β − CD < γ − CD (Fig. 1(B)) (Saenger & Steiner,
1998; Saenger et al., 1998; Sikder et al., 2019). Research has shown
that the hydrogen bonding of α-CD molecules follows the pattern of C2
OH groups as the acceptor and C3 OH groups as the donor; on the
contrary, in the β- and γ-CD molecules, all the C2 OH groups are donors
and all the C3 OH groups are acceptors (Saenger et al., 1998). The
small-sized cavity pores of α -CD molecules can only contain guest
molecules of a smaller size, e.g., materials composed of smaller mole-
cules, which limit their scope of application. Furthermore, due to their
rigidity, α -CD molecules hydrolyze completely with difficulty. γ -CD
molecules are the most flexible of the three and are easily hydrolyzed
by α -amylases. γ -CD molecules have a relatively large open space,
which causes them to include larger volume molecules. The producer
Wacker Chemie has realized the industrial production of γ -CD, but its
production costs more than α -CD and β -CD. α-, β-, γ-CDs and CD
derivatives can not only be transformed into CD polymers but can also
form host-guest inclusion complexes with various ions, molecules and
polymers, including polycyclic aromatic hydrocarbons, aromatic deri-
vatives, volatile organic compounds, metals, dyes, etc. However, due to
their specific characteristics, such as appropriate cavity size, great
complexation ability and low cost, β -CD and its derivatives have re-
cently been significantly widely used in various industries (Szejtli,
1982, 1988). Note that the limited solubility in water (β − CD < <
α − CD < γ − CD ) (Saenger et al., 1998) and catalytic activity of β-CD
are great challenges, which means the native CD needs to be modified
to break its usage limits and to improve its chemical and physical
properties.
3. Cyclodextrin derivatives
3.1. Simple cyclodextrin derivatives
A variety of CD derivatives can be obtained through chemical re-
actions of the primary and secondary hydroxy groups on their surface,
such as amination, esterification or etherification, under the condition
of maintaining the basic macrocyclic framework of the natural CD
molecules (Liu & Zhang, 2011; Maeztu, Tardajos, & Gonzalez-Gaitano,
2010). The chemical structure and properties of CD derivatives are
different from the those of original CD molecules. This is because the
hydroxy groups have been modified with functionalities, including
amines, thiols, thiourea, azide ions, halide ions, etc., through an elec-
trophilic or nucleophilic reaction (Szejtli, 1998). In general, when the
native CDs are modified, the substitution of the hydroxyl groups on CDs
occur randomly, and the aqueous solubility of the resulting mixture
increases to over 500 mg/mL (Pitha, Milecki, Fales, Pannell, & Uekama,
1986). The random substitution of hydrophilic hydroxy groups pro-
motes the transformation of native CDs from crystalline solids into
physically stable amorphous mixtures. Attaching substituents to CDs
enhances not only their own solubility but also the solubility of their
inclusion complexes (Jansook et al., 2018). Moreover, due to their
cyclic structure, CDs and modified CDs cannot be easily degraded by
enzymes. Therefore, CDs and their derivatives have been widely used in
organic chemistry and polymer chemistry.
3.2. Cyclodextrin polymers
Various CD polymers have been synthesized through the poly-
merization of native CDs and methyl-cyclodextrin, caboxymethyl- β
-cyclodextrin, sulfobutylether- β -cyclodextrin, hydroxyethyl- β
W. Tang, et al.
-cyclodextrin, hydroxypropyl β -cyclodextrin, etc., and simple CD de-
rivatives as raw materials. CD polymers are types of functional mac-
romolecular compounds with one or more CD units formed by self-
polymerization, copolymerization or bonding to other polymers of CDs
and modified CDs, which can be roughly categorized into four main
groups: crosslinked CD polymers, linear CD polymers, immobilized CD
polymers, and hyperbranched CD polymers. The physicochemical
methods available to analyze the molecular structure of CD derivatives
and polymers include Fourier-transform infrared spectroscopy (FTIR),
NMR spectroscopy, ultraviolet-visible (UV–vis) spectroscopy, etc. The
molecular weight distribution of water-soluble polymers is character-
ized by LS and/or GPC, while their surface properties can be revealed
by microscopic methods, including scanning electron microscope
(SEM), transmission electron microscopy (TEM), etc. CD polymers have
both the cavity structure characteristics of a CD and the excellent me-
chanical strength and hardness, high molecular weight and good
thermal stability of a polymer. Therefore, CD polymers are utilized in
various fields, including the environment, food, medicine, cosmetic,
separation technology, catalysis, chemical analysis and so on.
4. More cyclodextrin-based materials
4.1. Cyclodextrin inclusion complexes
Their cavity structures make CD and CD derivatives form host-guest
inclusion complexes controlled by several noncovalent host-guest in-
teractions, including hydrogen bonding, hydrophobicity, electrostatic
forces, van der Waals forces, dispersive forces, dipole-dipole forces, etc.
(Fig. 2) (Auzély-Velty & Rinaudo, 2002; Chen & Jiang, 2011; Kfoury,
Landy, & Fourmentin, 2018; Weickenmeier, Wenz, & Huff, 1997). Ac-
cording to the literature mentioned above, the enhanced water solu-
bility and inclusion ability of CD derivatives provide abundant possi-
bilities for the formation of functional inclusion complexes. During the
inclusion complex formation process, covalent bonds do not break, and
no new covalent bonds are formed. Thus, the network structure can be
constructed through host-guest interactions. Nevertheless, it is im-
portant to note that the ability of CD molecules to bind guest molecules
varies with the size and polarity of the guest molecules. When the
binding constant Kf is higher, the host-guest inclusion complexes of CDs
are more efficiently and stably formed (Pu, Yang, Wei, & Yuan, 2016).
As molecular hosts, CDs can protect guest molecules entering their
barrel-shaped hydrophobic cavity to improve their thermal stability,
enhance their solubility, increase their oxidation resistance and mod-
ulate the release of the encapsulated compounds. The molecules en-
capsulated in CDs and free molecules in an aqueous environment are
always maintained in rapid equilibrium. CDs, CD derivatives and
Fig. 2. The formation/dissociation equilibrium of host-guest inclusion complexes.
3
Carbohydrate Polymers 240 (2020) 116321
polymers are all capable of including hydrophobic molecules in the
interior of CD cavities and binding to hydrophilic molecules on their
exterior. The hydrophobic molecules or some lipophilic moieties of
larger molecules are more likely to bind to the hydrophobic cavity of
CDs than hydrophilic molecules are. The inclusion process is driven by
the increased enthalpy and entropy as well as the release of water
molecules from the cavity into the bulk phase, which in turn, solubilizes
hydrophobic compounds in water (Hedges, 1998). Schmidt et al.
(Schmidt & Barner-Kowollik, 2017) summarized the dynamic molecular
structure design based on the host-guest inclusion associations of CD
and described the inclusion process in detail.
To study the formation and stability of CD host-guest inclusion
complexes, the Kf values need to be assessed. High-performance liquid
chromatography (HPLC), static headspace coupled to gas chromato-
graphy (SH-GC), UV–vis spectroscopy, nuclear magnetic resonance
(NMR) spectroscopy, fluorescence spectroscopy, isothermal titration
calorimetry (ITC), solubility studies, and total organic carbon (TOC) are
among the most frequently used methods to determine the Kf value of
CD inclusion complexes. Kfoury et al. (2018) summarized the char-
acterization methods and techniques of CD/volatile inclusion com-
plexes in detail.
4.2. New cyclodextrin nanocomposites
Nanoparticles have drawn extensive attention from both academic
and industrial fields due to their advantages of small size and high
surface area. Nanoparticles, including nano-SiO2, nano-TiO2, carbon
nanotubes, graphene oxide, etc., can be used as cores for the synthesis
of polymer molecules with multiple branched chains, which not only
ensures the appropriate size of polymers but also improves their rigidity
and toughness, making the network structure denser and stronger (Hu,
Ke, Zhao, Lu et al., 2018a, 2018b, Hu, Zou, & Zou, 2019). In addition,
magnetic nanoparticles, such as Fe3O4 nanoparticles, have various
physical advantages, including a large specific surface area, good sur-
face activity and excellent magnetism (Zhang, Li, Bao, Yang, & Wang,
2016). Magnetic nanoparticles can attach to other hydrophilic or
oleophilic materials to form oil-water separator materials, which can be
well controlled and recovered under the action of a magnetic field.
Modified nanoparticles and CD derivatives are combined by chemical
bonds and hydrogen bonds to form cyclodextrin-based nanocomposites.
The combination of nanoparticles and CDs imparts nanoparticles with
the inclusion ability and selective molecular recognition ability of CDs.
Therefore, the number of studies on the synthesis and applications of
CD-based nanocomposites has grown exponentially over the past few
decades. Currently, the main oilfield applications of CD-based nano-
composites are for enhancing oil recovery and wastewater treatment.
W. Tang, et al. Carbohydrate Polymers 240 (2020) 116321

Table 1
The summary of CD-based materials applied in oilfields.
Number CD derivatives Molecular structural formula Application field Ref.

CDM-1 β -CD-PBTCA retarded acid solution (Zou, Liao et al., 2011)

CDM-2 N-β-CD-HEDP retarded acid solution (Zou, Qin et al., 2014)

CDM-3 N-β-CD-PBTCA retarded acid solution (Qin et al., 2015)

CDM-4 AM/A-β-CD/AE EOR (Zou, Ge et al., 2012)

CDM-5 HCMPAM EOR (Zou et al., 2013)

CDM-6 P(AM/A-β-CD/DMAPMA-C) EOR (Li et al., 2015)

CDM-7 HAP-CED (HAP-4: CDE = 0.2: 0.95 wt EOR (Li et al., 2018)
%)

CDM-8 AM/AA/N-ADA/N-β-CD EOR (Pu, Yang et al., 2016)

CDM-9 HMPAM EOR (Pu, Du et al., 2016)

(continued on next page)

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W. Tang, et al. Carbohydrate Polymers 240 (2020) 116321

Table 1 (continued)

Number CD derivatives Molecular structural formula Application field Ref.

CDM-10 AA/AM/AMPS/MAH-β-CD EOR (He et al., 2014)

CDM-11 AM/AA/AOAB/N-β-CD EOR (Liu, Jiang, Gou, Ye, Feng et al., 2013)

CDM-12 AM/AA/AOAB/O-β-CD EOR (Liu, Jiang, Gou, Ye, Feng et al., 2013)

CDM-13 Poly-A EOR (Peng et al., 2019)

CDM-14 Poly-B EOR (Peng et al., 2019)

CDM-15 Poly-S, P(AM/ A-β -CD/NaAA) EOR (Zou, Wu et al., 2011; Zou, Zhao et al.,
2012)

CDM-16 AM/DMDAAC/Allyl-β-CD, P(AM/ A- EOR, corrosion (Yan et al., 2014; Zou, Zhao et al., 2011;
β -CD/DMDAAC), ACDPAM, inhibitor, flocculants Zou, Qin et al., 2014; Zou, Zhao et al.,
2012)

CDM-17 SAP system EOR (Wei, Romero-Zerón et al., 2014a, 2014b,

2015; Wei, 2015)

(continued on next page)

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W. Tang, et al. Carbohydrate Polymers 240 (2020) 116321

Table 1 (continued)

Number CD derivatives Molecular structural formula Application field Ref.

CDM-18 Nanocomposite AAMC-S1 EOR (Hu, Ke, Zhao, Yu et al., 2018b)

CDM-19 AAMC/silica hybrids EOR (Hu, Ke, Zhao, Lu et al., 2018a)

(continued on next page)

6
W. Tang, et al. Carbohydrate Polymers 240 (2020) 116321

Table 1 (continued)

Number CD derivatives Molecular structural formula Application field Ref.

CDM-20 AAMC/O-Mt nanocomposites EOR (Hu, Ke et al., 2019)

CDM-21 AM/NaAA/AMPS/XBH clay stabilizer (Liu, Jiang, Gou, Ye, Luo et al., 2013)

CDM-22 A-β-CD/AM/AA/DABPAC clay stabilizer (Qin et al., 2014)

CDM-23 P (A-β-CD/AM/ATMAC) clay stabilizer (Qian & Ai, 2016)

CDM-24 β-CD-chitosan corrosion inhibitor (Liu et al., 2015)

CDM-25 β-CD-PEG corrosion inhibitor, (Liu et al., 2016; Zou, Liu et al., 2014)
scale inhibitor

CDM-26 Poly (AM-co-A- β-CD-co- AE) polymer corrosion inhibitor (Zou, Tang et al., 2012)

(continued on next page)

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W. Tang, et al. Carbohydrate Polymers 240 (2020) 116321

Table 1 (continued)

Number CD derivatives Molecular structural formula Application field Ref.

CDM-27 β-MEA corrosion inhibitor, (Tang et al., 2017)

scale inhibitor

CDM-28 β-CD-MA-SSS scale inhibitor (Gu et al., 2013)

CDM-29 MA/AA/MA- β-CD/SHP scale inhibitor (Ma et al., 2018)

CDM-30 CA-β-CD oilfield wastewater (Liang & Zou, 2019)

treatment

CDM-31 MNP-CD-PBTCA oilfield wastewater (Lin & Zou, 2017)

treatment

CDM-32 LCMP-β-CD-ASWCNTs oilfield wastewater (Hu, Zou et al., 2019)

treatment

5. Application of cyclodextrin-based materials in oilfields
It is known that various kinds of macromolecular compounds are
frequently used in petroleum exploitation and transportation; therefore,
CD polymers have been introduced as oilfield chemicals. CDs, CD de-
rivatives and polymers form CD inclusion complexes through host and
guest inclusion associations, which can effectively optimize the per-
formance and effect of macromolecular compounds in the petroleum
industry and expand their application range. The resulting CD inclusion
complexes play an effective role in oilfields, and their specific appli-
cations in oilfields will be elaborated on in the following paragraphs.
Some selected examples of CD-based materials (known as CDM), in-
cluding simple derivatives, CD polymers and inclusion complexes, used
in oilfields are shown in a non-exhaustive list (Table 1).

8
W. Tang, et al.
5.1. Cyclodextrin inclusion complexes used in retarded acid solutions
Acidification is an effective well stimulation technique to remove
damage, restore or improve permeability and thus enhance the pro-
duction of oil and gas reservoirs by using an acid solution to dissolve
and corrode rock cementite, formation pores and the internal plugs of
fractures (Cohen, Ding, Quintard, & Bazin, 2008; Crowe, Masmonteil, &
Thomas, 1992; Kharisov, Folomeev, Sharifullin, Bulgakova, & Telin,
2012; Shafiq & Shuker, 2013). The efficiency of acidification mainly
depends on the depth of penetration of acid into the formation, and the
etched length of acid corrosion fractures depends on the amount of
acid, the reaction rate and acid fluid loss from the fractures into the
formation (Economides & Nolte, 2000). Common candidates for acid-
ification mainly include hydrochloric acid, hydrofluoric acid, formic
acid, acetic acid, sulfuric acid, carbonic acid, phosphoric acid, mud acid
(mixtures of hydrochloric acid and hydrofluoric acid), solid acid (the
acid that solidifies into particles, such as sulfamic acid), etc. In the
conventional acidizing operation, due to the fast speed that acid in-
teracts with rock, the penetration distance of acid is relatively short so
that formation fractures far from the bottom of the well cannot easily
contact fresh acid; thus, only the damage in the near-well area can be
eliminated. The acid penetration distance increases with the con-
centration of acid but also leads to serious sediment and emulsion
blockage, which results in difficulties of corrosion prevention. There-
fore, it is an important consideration to reduce the reaction rate of acid
and increase the penetration distance of acid corrosion fractures. The
common methods for reducing the acid reaction rate involve the in-
jection of an ahead fluid preceding the acid fluid and the acidification
of the deep formation with retarded acids (Economides & Nolte, 2000).
The construction time and cost can be reduced by using the appropriate
retarded acid. In the process of reservoir acidification, the retarded
acids commonly used at present include autogenous acid (potential
acid), gelled acid, emulsified acid, foam acid, chemically retarded acid,
etc. In practice, these conventional retarded acids can cause various
problems or imperfections; for example, their dissolving power of rocks
and retarding effect are limited, their desired effect is nearly absent at
higher temperatures, precipitation cannot be effectively restrained, and
so on. Most importantly, these systems have no capacity for self-reg-
ulating dissolution or self-inhibiting clay swelling in the process of acid
treatment, which work against reaching the maximum penetration
depth of the reservoir, and lack the ability to improve reservoir pro-
ductivity (Wenger, Davis, Evensen, Gormly, & Mankiewicz, 2004; Zou,
Qin, Yan, Zhou, & Luo, 2014).
CD cavities have the benefit and function of molecular recognition
and encapsulation, which can selectively include other molecules, ions
or even free radicals. For example, CDs can be enabled to encapsulate
salicylic acid, formic acid, acetic acid, organic phosphoric acid, etc. in
their interior cavity to form host and guest inclusion complexes (Aree,
Schulz, & Reck, 2003; Belyakova, Varvarin, Lyashenko, Khora, &
Oranskaya, 2007; Qin, Zou, Yan, Zhou, & Luo, 2015; Terekhova &
Obukhova, 2007). When the acid solution enters the oil reservoir, the
hydrophobic cavity of CDs is more easily recognized by oil molecules,
and the acid molecules in the CD inclusion complexes are replaced by
oil molecules, thus stimulating the release of acid molecules and the
formation of free molecules. As the oil reservoir depth increases, the
temperature, pressure, mass of oil molecules and other real reservoir
conditions may significantly influence the rate of CD inclusion com-
plexes to release guest molecules (acids), thus effectively adjusting the
rate of the acid and rock reaction. In addition to including acid mole-
cules in the cavity, CD derivatives possessing quaternary ammonium
groups on their exterior surface can not only carry the acid but also
effectively inhibit clay swelling.
2-Posphonobutane-1,2,4-tricarboxylic acid (PBTCA) has the struc-
tural characteristics of phosphoric acid and carboxylic acid, along with
a low phosphorus content, enabling it to have a slow releasing perfor-
mance and coordination. Zou, Liao, Zhang and Chen (2011) synthesized
9
Carbohydrate Polymers 240 (2020) 116321
the inclusion complex, β-cyclodextrin-2-posphonobutane-1,2,4-tri-
carboxylic acid (CDM-1, as shown in Table 1) and designed a hydro-
chloric acid (HCl)/ CDM-1/ ammonium hydrogen fluoride (NH4F.HF)-
retarded acid system. According to the results, the preferred molar ratio
of β-CD to PBTCA was 1:1, and the suitable reaction time was 12 h. The
organic phosphoric acid has strong hydrophilicity, which tends to keep
it away from the hydrophobic cavity of β-CD in the inclusion process.
On the other hand, the carbonyl groups of CDM-1 attempt to enter the
cavity via carbon chains. Most of the host-guest inclusion complexes
combine through intermolecular hydrogen bonds, but a polybasic acid,
such as PBTCA, forms intramolecular hydrogen bonds to combine with
the β-CD cavity so that the stability of the inclusion compound can be
improved (Csernák, Buvári-Barcza, Samu, & Barcza, 2005; Lisnyak,
Martynov, Baumer, Shishkin, & Gubskaya, 2007; Zou, Liao et al., 2011).
The formation of CD inclusion complexes is believed to be at a dynamic
equilibrium, so the Kf values of PBTCA/β-CD at different temperatures
(from 303.15 K to 323.15 K) were investigated, and the results showed
that the formation of CD inclusion complexes was an exothermic pro-
cess. As the thermal vibration of molecules increases with temperature,
this thermal vibration prevents the guest molecules from entering the
CD cavity, which likely causes the release of the guests from the in-
clusion complexes. According to the experimental results, the corrosion
rate of mud acid increased up to 17.2 % in 15 min, while the rates of
PBTCA and CDM-1 stayed as low as 7.3 % and 4.8 %, respectively,
indicating that the retarded acid system of CDM-1 could extend the
acidification time and distance and validates the premise of deep
acidification. When this retarded acid system is used, HCl dissolves
rocks in the near-wellbore region, and CDM-1 reaches deep formation.
The increasing stratum temperature and the competition with oil mo-
lecules stimulates the release of PBTCA molecules from the cavity. The
deep acid treatment was performed by dissolving rocks with HF
through the reaction between PBTCA and NH4F. HF.
It is important to note that although PBTCA molecules have elec-
trostatic stabilization, which can suspend the particles formed during
the acid reaction and prevent the formation of precipitation, but the
anti-swelling ability of these molecules under harsh conditions is lim-
ited. Therefore, Changjun Zou and Yibie Qin et al. (Qin et al., 2015;
Zou, Qin et al., 2014) improved the CD inclusion complexes by binding
quaternary ammonium salt cations on the surface and designed the
retarded acid systems CDM-2 (as shown in Table 1) and 2-O-(hydro-
xypropyl-N,N-dimethyloctadecylamine)-β-cyclodextrin-2-phosphono-
butane-1,2,4-tricarboxylic acid (CDM-3, as shown in Table 1), which
can also inhibit clay swelling. The structure of the CD complex was
characterized by UV–vis, FTIR and NMR. The authors found that, under
the same operating conditions, the anti-swelling efficiency of the acid
systems with quaternary ammonium salt cations, such as CDM-2 and
CDM-3, which with the acid system consisting of a physical mixture of
N-β-CD with (1-hydroxyethylene)-diphosphonic acid (HEDP) or PBTCA,
was improved significantly. The addition of CDs can effectively slow the
dissolution rate of an acid system, but the dissolution rates of the CDM-
2 and CDM-3 acid systems were slower than those of the acid system
consisting of the physical mixture (N-β-CD with HEDP or PBTCA). Fi-
nally, the dissolution rates of all acid systems based on the same organic
acid drop and converge after a period of time. The reaction mechanism
of these acid systems and rock is shown in Fig. 3. On the one hand, CD
inclusion complexes release organic phosphoric acid guest molecules at
a slow rate, which effectively reduces the reaction rate of acid-rock. On
the other hand, the quaternary ammonium salt cations and polar hy-
droxy groups on the surface of these CD inclusion complexes are fa-
vorable for the adsorption of the negatively charged clay surface. This
adsorption not only enables the formation of a dense protective layer on
the clay surface that can inhibit clay swelling but also promotes the clay
particles to be connected or bridged together, which can reduce the
migration of clay and form a clear acid channel (Anderson et al., 2010).
However, the current work mainly focuses on the retarded acid of
CDs or the CD derivatives-organic phosphoric acid system, while
W. Tang, et al.
Fig. 3. The reaction mechanism of acid systems and rock (Zou, Qin et al., 2014).
studies on CDs or the CD derivative inclusion of other organic acids are
relatively scarce. Therefore, the sustained-release effect of CDs or CD
derivatives for the inclusion of organic acids other than phosphoric acid
should be further studied and discussed in the future. Of course, it is
necessary to further study the inclusion, release and substitution re-
lationship among the CD hydrophobic cavity, acid and oil molecules.
5.2. Cyclodextrin-based materials for enhancing oil recovery
Among the current processes of petroleum exploitation worldwide,
chemical flooding, thermal flooding and miscible flooding are the main
methods used for EOR (Da, Alzobaidi et al., 2018a, 2018b). EOR
technologies mainly aim at improving the sweep coefficient and oil
displacement efficiency, among which chemical flooding is outstanding
and has increasingly drawn attention. Chemical flooding is a method
that benefits crude oil production. The idea of chemical flooding is to
change the physicochemical properties of the displacement fluid and
the three phase (displacement fluid - crude oil - rock minerals) interface
properties by adding chemical agents into the injecting water to dis-
place crude oil from the formation to the production well and to im-
prove oil recovery. Chemical flooding includes polymer flooding, sur-
factant flooding, alkali flooding and combinations of binary and ternary
flooding. This review mainly focuses on the applications of various
polymers, host-guest inclusions and nanocomposites involving CD to
improve oil recovery.
5.2.1. Cyclodextrin-based polymer flooding
Polymer flooding is simply a method of adding water-soluble
polymers to the injected water to increase the viscosity and the fluidity
ratio (Wassmuth, Arnold, Green, & Cameron, 2009). The injection of a
polymer solution with a high viscosity can greatly improve the sweep
efficiency of the oil reservoir, thus enhancing oil recovery. However,
with the constant deepening of oil exploitation, the reservoir conditions
have become increasingly complex and face challenges, including high-
temperature, high-permeability, and high-salinity conditions. Conven-
tional oil-displacement polymers, such as polyacrylamide (PAM) and
partially hydrolyzed polyacrylamide (HPAM), cannot satisfy the needs
of the actual production of oil. According to previous relevant studies,
the introduction of large groups and hydrophobic side groups can ef-
fectively improve the temperature and salt tolerance of polymers
(Kamal, Sultan, Al-Mubaiyedh, & Hussein, 2015; Wever, Picchioni, &
Broekhuis, 2011). On the one hand, the introduction of large groups can
increase the molecular chain rigidity and weaken the crimping effect of
the polymer molecules due to high-temperature dehydration and a high
salt charge shielding effect. On the other hand, through the cooperation
of hydrophobic association, hydrophobic side groups can be associated
with each other so that the polymer molecules in solution form a three-
dimensional network structure, which can improve the viscosity and
shear resistance of the polymer solution. Water-soluble polymers that
introduce a small number of hydrophobic groups onto the hydrophilic
10
Carbohydrate Polymers 240 (2020) 116321
macromolecule chain are called water-soluble hydrophobic association
polymers (WSHAP). CD molecules have certain inclusion associations
with hydrophobic groups, strong steric hindrance and good rigidity.
Therefore, traditional polymers can be modified and optimized by
coupling CD molecules with various functional monomers.
Zou, Ge, Zhao, Cui & Zhang (2012) synthesized a kind of β -CD and
methacrylic acid octyl phenols poly(ethylene oxide) ester (AE)-mod-
ified acrylamide terpolymer system (CDM-4, as shown in Table 1),
which presented a typical three-dimensional network structure through
SEM imaging. Through a series of comparative experiments, the authors
found that the CD-modified polymer solution possessed a better tem-
perature and salt tolerance than the unmodified polyacrylamide and
had a potential to be applied in high-temperature and high-miner-
alization reservoirs. The authors (Zou et al., 2013) also synthesized a β
-CD-functionalized hydrophobically associating acrylamide copolymer
(CDM-5, as shown in Table 1), and the numerous independent CD side
groups on the molecular chain of the copolymer resulted in great steric
hindrance; this structure hindered the rotation within the copolymer
molecular chain and thus improved the rigidity of the copolymer chain,
enabling it to have a superior temperature tolerance and shear re-
sistance. Moreover, lab-scale flooding experiments demonstrated that
CDM-5 performed more effectively than HPAM at the same con-
centration, and the oil recovery rate was significantly increased by
5.7–9.4 %. Li, Zou & Cui (2015) synthesized a new quaternary am-
monium salt, methyl acrylamide propyl dimethyl butyl ammonium
chloride, and coupled this new quaternary ammonium salt with allyl- β
-CD and acrylamide to synthesize a cationic acrylamide copolymer
(CDM-6, as shown in Table 1), aiming at applications in EOR. The re-
sults clearly indicated that CDM-6 was endowed with better salt toler-
ance than PAM, likely due to the shrinkage of the copolymer molecular
chain that was produced by the association between the metal ions and
the carboxyl groups on PAM, the steric hindrance of the allyl-β-CD, and
the enhanced electrostatic repulsion of copolymer chains produced by
the synergism between the metal cations and quaternary ammonium
ions. Meanwhile, CDM-6 showed a good flooding effect, as the oil re-
covery increased significantly from 6.91 % from PAM to 15.4 %. Li,
Shu, Luo & Ye (2018) analyzed the rheological properties, flow beha-
vior in porous media and the EOR performance of the supramolecular
system CDM-7 (as shown in Table 1) through rheological tests and sand
pack tests. This system was prepared by dissolving HAP-4 and CDE
powder in water (HAP-4: CDE = 0.2: 0.95 wt %) in which HAP-4 was a
water-soluble hydrophobically associating polymer and CDE was the
polymer synthesized from β -CD crosslinked with epichlorohydrin
(Renard, Barnathan, Deratani, & Sebille, 1997; Renard, Deratani, Volet,
& Sebille, 1997). Xi Li et al. reported that the CDM-7 polymer system
showed an efficient thickening ability and had strong viscoelasticity,
which could effectively improve the flow resistance of the reservoir; the
oil recovery ratio of CDM-7 flooding was 5.7 % and 24.5 % higher than
that of single HAP-4 and HPAM flooding, respectively, providing evi-
dence that the introduction of the β -CD functional monomer in the
W. Tang, et al.
polymer has the potential to improve heavy oil recovery.
In addition to the CD terpolymer mentioned above, other functional
monomers were also introduced on the basis of the CD terpolymer,
which can be chemically synthesized into CD tetracopolymers (from
CDM-8 to CDM-14), and further diversified and improved the perfor-
mance of the polymer. Pu, Yang et al. (2016) prepared the novel co-
polymer CDM-8 (as shown in Table 1) by acrylamide, acrylic acid, 6-
acrylamide-β-CD and acrylamide-adamantane for EOR. Pu’s research
group (Pu, Du, Liu, Li, & Huang, 2016) also successfully synthesized the
CD functionalized tetrapolymer CDM-9 (as shown in Table 1) using
acrylamide, acrylic acid, modified β-CD and N-phenethyl-methacryla-
mide. He, Xu, Wu, Luo & Chen (2014) synthesized and characterized
the amphiphilic copolymer CDM-10 (as shown in Table 1) with acrylic
acid, acrylamide, maleic anhydride-β-CD (MAH-β-CD) and 2-acryla-
mido-2-methyl propane sulfonic acid (AMPS) as functional monomers.
Liu, Jiang, Gou, Ye, Feng et al. (2013) prepared two novel water-soluble
copolymers, CDM-11 and CDM-12 (as shown in Table 1), based on
acrylamide, acrylic acid, 1-allyl-3-oil acyloxy imidazole-1-ammonium
bromide, mono-6-(allylamino)-β-CD and mono-2-O-(allyloxy-2-hy-
droxy-propyl)-β-CD. Peng et al. (2019) prepared two hydrophobic
polyacrylamide copolymers (CDM-13 and CDM-14, as shown in
Table 1) based on acrylamide, acrylic acid, modified β-CD and two
kinds of twin-tailed hydrophobic monomers. It was clearly observed
from SEM images that CDM-13 and CDM-14 possessed robust connected
skeletons and a strong spatial network structure. The temperature and
salt tolerance, shear resistance, and viscoelastic properties of these CD
tetrapolymers were evaluated, and the researchers found that the co-
polymer solutions exhibited excellent characteristics due to the in-
troduction of CDs and functional monomers. Laboratory core flood tests
were conducted to explore the ability of the CD copolymer for EOR, and
the results indicated that the oil recovery ratios of CDM-8, CDM-9,
CDM-10, CDM-11, CDM-12, CDM-13 and CDM-14 were enhanced to
8.58 %, 16.4 %, 14.8 %, 18.3 %, 12.5 %, 8.22 % and 8.56 %, respec-
tively, while that of HPAM was only 3.24 %. It is obvious that the oil
recovery ratio of the CD tetrapolymer was substantially higher than that
of the polymers without CDs.
5.2.2. Complexation of surfactant/ β-cyclodextrin for flooding
Surfactants are widely used for EOR to improve the oil displacement
efficiency and displace immobile oil trapped in porous rock by reducing
interfacial tension, wettability reversal, emulsification, solubilization,
and coalescence to form an oil belt. In reality, reservoir environments
are always complicated; thus, besides the above characteristics, the
suitable surfactant used for oil displacement needs to have excellent
thermal stability, strong salt tolerance, low mineral adsorption and
good economical practicality. If the surfactant heavily adsorbs onto the
reservoir rock surface through electrostatic attractions and interactions
via hydrogen bonding, the oil displacement will be significantly im-
peded and a large amount of waste of chemicals will be produce, which
are far from the optimal economic benefits of an EOR technology.
Therefore, the low adsorption of surfactants on the surface of the re-
servoir rock is necessary for feasible EOR applications. How to prevent
surfactants from being adsorbed on formation rocks has been ex-
tensively studied (Ma et al., 2013). Previous literature has reported that
the CD/surfactant host-guest inclusion complex is beneficial to increase
the critical micelle concentration and solubility of the surfactant, which
provides a research idea for petrochemical researchers (Valente &
Söderman, 2014).
Martín et al. (2020) studied the effect of the surfactant oligomeric
degree (the number of surfactant hydrophobic tails) on the stability of
the cyclodextrin-surfactant inclusion complex and claimed that as the
number of hydrophobic tails increased, all the tri- and tetrameric sur-
factants in the experiment formed a 1:1 inclusion complex with cyclo-
dextrins. Only when the hydrophobic tails are better integrated into the
cyclodextrin cavity will the host-guest interaction between surfactant
and cyclodextrin be stronger. Based on the complexation zone of the
11
Carbohydrate Polymers 240 (2020) 116321
hydrophobic cavity of β -CD, Sirinthip Kittisrisawai and Hassan Al-
hassawi et al. (Alhassawi & Romero-Zerón, 2015a, 2015b, 2015c;
Kittisrisawai & Romero-Zerón, 2015a, 2015b, 2015c) performed a dy-
namic and static adsorption analysis and proposed a novel method for
surfactant/ β -CD inclusion complexes to reduce the adsorption of the
surfactant on solid surfaces. The authors selected sodium dodecyl sul-
fate (SDS) as the target surfactant and evaluated the ability of surfac-
tant/ β -CD inclusion complexes to improve oil recovery through a
series of lab-scale core-flooding tests. The experimental results in-
dicated that the SDS/ β -CD inclusion complexes had a higher capacity
for oil displacement than the conventional surfactant flooding and
could effectively improve oil production from 40 % to 82 %. Dynamic
adsorption data showed the effectiveness of the surfactant/ β -CD in-
clusion complexes in reducing the adsorption of the surfactant (SDS)
onto solid surfaces (sandstone, shale, and kaolinite), ranging from 50 %
to 92 %. The static adsorption test showed that the surfactant/ β -CD
inclusion complexes effectively minimized the adsorption of the sur-
factant (SDS) onto solid surfaces (sandstone, shale, and kaolinite), with
the adsorption reduction ranging from 64 % to 79 %. The authors ex-
plained that this excellent performance was due to the special chemical
structure as the SDS/ β -CD inclusion complex can selectively self-as-
semble and release the surfactant and rapidly equilibrate with free
surfactant in the solution through the formation and breakage of non-
covalent bonds during the complexation process. According to the
above research results, the surfactant/ β -CD inclusion complex can
effectively reduce the amount of surfactant adsorbed on the solid-liquid
surfaces because the CD cavity can encapsulate the surfactant and then
provide a shielding effect that prevents the surfactant from adsorbing
onto the rock surface. However, in the oil-saturated region of porous
media, the CD cavity is more likely to bind to oil molecules due to its
strong hydrophobicity, so that the encapsulated surfactant may leave
the β -CD cavity and enter the formation pores to perform its own
functions.
5.2.3. Cyclodextrin-based surfactant/polymer binary system for flooding
Chemical compound flooding refers to the oil-displacement method
that combines two or more oil displacement components, which is more
effective than the single flooding method, mainly due to the synergistic
effect among polymers, surfactants and alkali in compound flooding. An
aqueous solution that dissolves polymers for oil displacement usually
has a good viscoelastic performance but cannot reduce the interfacial
tension in contact with oil, water and stone rocks. Therefore, surface-
active groups are introduced into the polymer agents to simultaneously
increase the viscosity of the aqueous solution and reduce the interfacial
tension, thus obtaining a better oil displacement system (Raffa,
Broekhuis, & Picchioni, 2016). It has been well-documented that many
water-soluble polymers can bind surfactant molecules through the in-
clusion associations of CD cavities on the molecular chain of the
polymer or through the combination with ionic surfactants via non-
bonding interactions to improve the physicochemical and rheological
properties of the baseline polymer (Wei, Romero-Zerón, & Rodrigue,
2015; Zou, Wu, Ma, & Lei, 2011).
Changjun Zou (Zou, Zhao et al., 2011; Zou, Wu et al., 2011; Zou,
Zhao, Ge, Lei, & Luo, 2012) et al. designed and synthesized the anionic
acrylamide polymer CDM-15 (as shown in Table 1), which a cavity
structure and a molecular recognition function, using allyl- β -CD, so-
dium acrylate and acrylamide monomers. They also synthesized a novel
water-soluble cationic polymer (CDM-16, as shown in Table 1) from
allyl- β -CD, acrylamide and dimethyl diallyl ammonium chloride.
Moreover, the ideal mechanism model for enhancing oil recovery by the
synergistic effect of this series of polymers with CD side-groups and
surfactants was established, which is shown in Fig. 4. The model shows
what happens when the inclusion complex composed of polymer and
surfactants is injected into the stratum. The CD cavity of the polymer is
very hydrophobic, so the polymer tends to interact with oil-phase
molecules. This interaction causes oil to replace the surfactants and
W. Tang, et al.
Fig. 4. The ideal model of synergic action between CD-polymer and surfactant flooding (Zou, Wu et al., 2011).
enters into the CD cavity, while the surfactant can be released into the
reservoir environment. Subsequently, surfactants in the reservoir re-
duce the interfacial tension of the oil-rock interface and remove crude
oil from the rock surface, which provides the theoretical basis for EOR.
From the results of rheological, interfacial tension and adsorption
measurements, the authors found that adding the CD molecule to the
acrylamide polymer could effectively increase the thickening ability of
the polymer and the viscosity of the polymer solution. The CD-polymer
had excellent rheological properties and could effectively reduce the
loss of surfactant caused by stratum absorption in the flooding process.
Meanwhile, by comparing and analyzing the application of β -CD-
modified anionic and cationic acrylamide polymers for EOR, the au-
thors found that anionic polymers were more conducive to reducing the
interfacial tension in the process of tertiary oil recovery, while cationic
polymers were more suitable for improving the oil recovery capacity of
high-temperature and high-mineralization oilfields.
In addition, Bing Wei et al. (Wei, Romero-Zerõn, & Rodrigue, 2014a;
Wei, Romero-Zerón, & Rodrigue, 2014b; Wei, 2015, 2015) presented a
self-assembling polymeric network system, CDM-17 (as shown in
Table 1), derived from a surfactant, β -CD and hydrophobically mod-
ified sulfonated polyacrylamide (HMSPAM). In this system, the hy-
drophobic tail of the surfactant molecules was partially encapsulated in
the β -CD cavity, and the polar head of the surfactant molecules was
connected to the xanthan gum side chain through nonbonding inter-
actions, such as van der Waals interactions and hydrogen bonding. The
assembly was in dynamic equilibrium, and the dissociation process was
relatively fast; therefore, it was concluded that the mechanical shear
had a significant impact on the viscoelasticity of the system. In general,
the network structure disintegrated and exhibited a viscoelastic beha-
vior similar to that of xanthan gum under high shear rates. The network
structure of the system reassembled and the viscoelasticity was restored
at lower shear rates. Due to the “interlocking” and synergistic effect, the
novel system CDM-17 provided advanced viscoelasticity and enhanced
surface activity and presented superior mechanical properties, thermal
stability and salt tolerance. The authors conducted a sand-pack flooding
test to study the flow behavior in the porous media of the developed
12
Carbohydrate Polymers 240 (2020) 116321
CDM-17 system under the simulated reservoir conditions (Pelican Lake
reservoir, Alberta, Canada). The results showed that this SAP system
had better fluidity compared to that of HMSPAM polymer flooding and
the potential of working as an in-situ permeability modifier. Moreover,
the SAP system could also improve heavy oil recovery by approximately
20 %, which showed its potential application prospects.
5.2.4. Nanocomposites of β -cyclodextrin-functionalized polymer for
flooding
Now, we know from the above description that the introduction of β
-CD into the copolymer skeleton can significantly improve its salt and
temperature tolerances, which ensures the application potential of CD-
polymer flooding for EOR. As nanomaterials show outstanding cap-
abilities in many fields, people have begun to try to incorporate in-
organic nanoparticles in the petroleum field, such as via the develop-
ment of polymer-nanoparticle composites to enhance the performance
of polymer flooding in oil recovery. Maurya and Mandal (2016) re-
ported that the addition of silica nanoparticles to a PAM solution could
increase the apparent viscosity of the solution and improve its rheolo-
gical behavior, which showed the promising prospect for its potential
applications in EOR. Zhu, Wei, Wang and Feng (2014) reported that the
introduction of silica nanoparticles could tune the rheological proper-
ties of the hydrophobically associated polyacrylamide (HPAHPAM)
solution; increase the viscosity, thermal stability and salt tolerance of
the prepared solution; and obtain an oil recovery higher than that of the
pure HAHPAM solution in the core flooding test. Previous research (Ji,
Zeng, Ke, & Pei, 2017; Kumar & Sharma, 2018) has found that the in-
troduction of silica nanoparticles to bulk polymers could improve the
mechanical, thermal, toughness, electric, rheological properties of the
polymers.
Therefore, Hu, Ke, Zhao, Lu et al. (2018a) (2018b) strived to com-
bine the advantages of β -CD and nanoparticles by using maleic-anhy-
dride-modified β -CD, AMPS and acrylamide as the monomer to form
the copolymer AAMC and then mixed it with a suspension of silica
nanoparticles to prepare the novel water-soluble nanocomposite ma-
terials CDM-18 and CDM-19, as shown in Table 1. The structural
W. Tang, et al.
morphologies of AAMC and CDM-18 nanocomposite were observed by
SEM and presented the typical three-dimensional spatial network
structure, including the connecting skeleton and multiple cavities. The
comparison showed that the structure of the materials with silica na-
noparticles was substantially more compact than that of materials
without silica nanoparticles. Various lab-scale performance tests
showed that desirable properties could be attributed to the introduction
of silica nanoparticles to AAMC, which endowed the polymer with ri-
gidity and endowed the sample with a thermal stability and shear re-
sistance that was better than those of the pure AAMC solution. This
improvement in performance could be attributed to the hydrogen bonds
between the bulk polymer and the silica nanoparticles that made the
spatial network structure of the polymer denser and stronger, which
provided steric hindrance and inhibited the coiling of polymer macro-
molecule chains at elevated temperatures. At the same time, the
polymer chains absorbed on the silica surface, which could promote the
formation of a hybrid network and prevent the reduction in electro-
static repulsions, showing great potential due to its viscosification
property and salt tolerance. In particular, compared to unmodified si-
lica nanoparticles, silica nanoparticles modified with silane coupling
agents improved the interfacial adhesion between the filler and
polymer matrix and showed better dispersion and compatibility with
the polymer. Displacement tests showed that the resistance factor (RF)
and residual resistance factor (RRF) of a CDM-18 solution were higher
than those of the pure polymer solution, which indicated the great
potential of the nanocomposite for EOR. In a sandstone core, the na-
nocomposite CDM-18 and pure polymer AAMC could increase oil re-
covery to 13.25 % and 7.12 %, respectively.
Subsequently, Hu, Ke et al. (2019) further explored the nano-
composite CDM-20 (as shown in Table 1), which was prepared by
AAMC and organo-modified montmorillonite (O-Mt) via in situ poly-
merization. It is interesting to note that montmorillonite has a natural
layered structure with a high in-plane strength, stiffness and aspect
ratio (the ratio of length to thickness). When montmorillonite layers are
dispersed in polymer matrices, strong interfacial interactions are gen-
erated between them, which can significantly improve the mechanical
properties, thermal stability and barrier properties of bulk polymers.
The results of FTIR and XRD patterns indicated that O-Mt layers were
present in the CDM-20 nanocomposite, the AAMC polymer chains were
intercalated into open spaces of O-Mt, and partially exfoliated O-Mt
layers were chaotically dispersed in the AAMC polymer matrix, as
shown in TEM pictures. The authors claimed that the introduction of O-
Mt at an appropriate amount could improve the thickening ability of
the bulk polymer, and due to the light cross-linking system formed by
the exfoliated O-Mt nanolayers, increase the molecular dimension and
hydrodynamic volume of the polymer, thus resulting in increasing
viscosity. On the contrary, excessive introduction of O-Mt could hinder
the growth of polymer chains, thus reducing viscosity. In addition, the
labyrinth or barrier effect from the high aspect ratio of O-Mt provided
resistance against thermal decomposition of the polymer material and
restricted the movement and destruction of polymer chains at high
temperatures, thereby improving the temperature resistance and long-
term thermal stability of the nanocomposite. The salt resistance and
shear resistance tests clearly indicated that the nanocomposite CDM-20
had a higher viscosity retention ratio than the pure polymer AAMC
since the O-Mt layers provided rigidity for the polymer structure and
made its spatial network denser and stronger, thus improving its shear
resistance. β-CD is relatively rigid, and its large steric hindrance makes
it difficult to compress the electric double layer (formed by eCOO− and
Na+) of the CD nanocomposite, which is beneficial for the β-CD cavity
to encapsulate the long-chain alkyl hydrophobic groups on the O-Mt
surface and thus improve the salt tolerance of the nanocomposite. On
the other hand, the exfoliated O-Mt nanolayers could limit the attack of
metal ions due to the barrier effect, thus improving the salt tolerance.
These results indicate that the nanocomposite CDM-20 has potential
applications in EOR.
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Carbohydrate Polymers 240 (2020) 116321
From the above investigation, it can be concluded that the appli-
cation of β -CD may lead to a significant breakthrough in EOR.
However, applications of CDs in alkali flooding have not been reported.
In the future, researchers should explore relevant aspects. Concurrently,
more effort should be devoted to studying the application of CDs in
combination with various nanomaterials.
5.3. Cyclodextrin derivatives and polymers as clay stabilizers
The clay particles and fines in reservoirs are usually of an average
size of only a few microns, which facilitates their bridging across
narrow passages and pore throats during external operations in wells.
Clays are generally composed of layered particles of silicon oxide and
aluminum oxide. The replacement of cations or breaking of particles
may destroy the balance of positive and negative charges in clays,
making clay particles become negatively charged and repel each other.
The migration and dispersion of clay particles is prone to block pore
space in rocks and can also significantly reduce their permeability (the
ability of soil or rock to allow fluid to pass under a certain differential
pressure, which is a measure of the ease with which fluids can flow
through a formation) and affect the productivity of the reservoir (Qin,
Zou, Yan, Liu, & Li, 2014). In addition, clays swell by absorbing water,
like montmorillonite, which increases in volume up to 600 %
(Economides & Nolte, 2000). If clay particles occupy the important pore
throats and passages, swelling clays will create an almost impermeable
barrier layer to block fluid flow, which can reduce oil and gas pro-
duction. Therefore, to inhibit clay from hydrating swelling, and fines
migration, chemical additives are introduced into the working fluid to
stabilize clay particles and fines by adsorbing on the mineral surface to
form a protective layer. Clay particles are negatively charged, so clay
stabilizers with positive charges are bound strongly to the surface of
clay particles through electrostatic attraction or ion exchanges. Thereby
stabilizers pin the clay layers together and forces clay to maintain a
tight or non-dispersed state. In particular, the hydrocarbon chain of a
polymer clay stabilizer extends outward from the particles, forming an
organic barrier that binds the clay and prevents the particles from
migrating or swelling. However, certain researchers have claimed that,
in some cases, if the molecular weight of the polymer stabilizers is too
large, they would block the pore space and induce a formation damage
(Himes, Vinson, & Simon, 1989; Qin et al., 2014). Therefore, it is of
great significance to develop economical and effective polymer clay
stabilizers with a low molecular weight to control the formation da-
mage.
CD and its derivatives are considered to be economical and harmless
host molecules that have hydrophobic cavities and hydrophilic sur-
faces. Many studies have shown that the introduction of β-CD to a
polymer can effectively combine their features to form excellent poly-
mers with unique properties (Liu, Jiang, Gou, Ye, Feng et al., 2013; Sun
et al., 2012). Liu, Jiang, Gou, Ye & Luo (2013) prepared a new poly-
amine clay stabilizer (CDM-21, as shown in Table 1) based on β -CD. β
-CD was modified to form modular β -CD (2-O-(allyloxy-2-hydroxy-
propyl)-β-cyclodextrin) and then copolymerized with other monomers
to synthesize a polymer containing many amine units. The wettability
of clay changed upon the addition of polyamines towards being more
water-wet, and the polyamines had a sufficient molecular length to
bridge clay particles together. However, it is noteworthy that the
polyamine-treated clay was in contact with brines, as polyamine would
lose its positivity and be washed away from clay. Under this situation,
clay is no longer stabilized. Therefore, polyamine clay stabilizers have
the disadvantages of a short life and high cost.
As mentioned in the acid solution above, the combination of CD
derivatives, quaternary ammonium salt cations and organic phosphoric
acid formed the retarded acid, which had the double efficacy of dis-
solving clay and inhibiting clay swelling. Unfortunately, their effect on
stabilizing clay was limited compared to that of professional clay sta-
bilizers. Therefore, Yibie Qin and Huijie Qian et al. (Qian & Ai, 2016;
W. Tang, et al.
Qin et al., 2014) modified allyl-β-CD, attached a number of quaternary
ammonium salt cations to its surface and, finally, prepared the novel
short-chain cationic polyquaternary amine clay stabilizers CDM-22 and
CDM-23 (as shown in Table 1). The structure of the cationic allyl-β-CD
polyquaternary amines was characterized by FTIR and 1H NMR. These
analyses indicated that the synthesized polymer successfully combined
various reaction monomers. The authors inferred that the weight-
average molecular weight of the polymer from the static light scattering
data was lower than that of the polymer without allyl-β-CD molecules.
The decrease in molecular weight resulted in the reduction in perme-
ability damage (the phenomenon of reservoir permeability decreased
after formation contact with a foreign fluid). Based on XRD and SEM
analyses of the crystalline interspace and surface morphology of mon-
tmorillonite samples before and after treatment with stabilizers and
pure water, it was found that the crystalline interspace of montmor-
illonite after being treated with stabilizers was close to that of the dried
samples. The samples treated with stabilizers had high crystallinity and
a large crystal size, which revealed a more packed structure on the
surface. Through linear swelling and core flood experiments, it was
found that the permeability damage rate (the change in the rate of
reservoir permeability before and after the formation contacts a foreign
k −k
fluid, defined by the equation of Dd = 0 k a × 100%, where Dd is the
0
permeability damage rate (%), k 0 is the initial permeability (mD), and
ka is the permeability after damage (mD)) and the permeability re-
covery rate (to characterize the effect of the manual operation of the
k sion.
reservoir, defined by the equation ξ = kb × 100%, where ξ is the per-
0
meability recovery rate, k 0 is the initial permeability (mD), and ka is the
permeability after recovery (mD)) of the polymer with β -CD were
maintained at 9.75 % and 95 %, respectively, indicating its excellent
anti-swelling efficiency and heat resistance. Therefore, these results
indicated that allyl-β-CD polyquaternary amine stabilizers can inhibit
clay swelling.
A possible clay stabilization mechanism of the β -CD polymer clay
stabilizer was preliminary discussed. The theoretical model is shown in
Fig. 5. Chemicals that inhibit clay swelling, dispersion, and migration
are based on charge neutralization/electrostatic attraction (Liu, Jiang,
Gou, Ye, Luo et al., 2013). These polymers contain a number of cationic
groups, polar hydroxy groups and amide groups. Clay in the formation
is negatively charged, so strong electrostatic adsorption and hydrogen
bonding adsorption occur between the two, which causes the polymer
to firmly attach to the clay surface and form a dense protective layer.
This attachment significantly inhibits clay swelling and prevents clay
migration by bridging particles together. Polyamine clay stabilizers
adsorb strongly on the clay surface with many amine attachment points
and then effectively neutralize the negative charge of the clay
(Economides & Nolte, 2000). In polyquaternary amine clay stabilizers,
the quaternary ammonium cationic molecular chain contains multiple
ammonium ions, which can form multipoint adsorption on the clay
Fig. 5. Schematic representation of interactions between β-CD polymer and
clay surfaces (Qin et al., 2014).
14
Carbohydrate Polymers 240 (2020) 116321
surface and a crisscross molecular adsorption film, thus enhancing the
strength of clay while promoting the close bond of clay particles (Qian
& Ai, 2016). In addition, the β -CD polymer possesses many hydro-
phobic cavities, similar to the formation of a natural waterproof seal, as
the surface of the clay particles is claimed to be covered by hydrophobic
parts (Fig. 5). This layer acts as a shield and is beneficial to preventing
water molecules from entering the crystal layer of clay, thus further
inhibiting the hydration and swelling of clay minerals (Qin et al., 2014).
Namely, the β -CD polymer clay stabilizer provides a double-protection
layer on the clay surface, which stabilizes the clay and fines through
charge neutralization, water wetting and polymer bridging.
The polymer clay stabilizer with a double-protection layer of CD
hydrophobic cavities has great development potential, but it is neces-
sary to study the influence of molecular weight on its stabilization and
explore the clay stabilization mechanism. In particular, it should be
noted that in the discussion of the previous mechanism, a large number
of CD cavities are closely distributed, with the hydrophilic outer sur-
faces covering each other. Therefore, the hydrophilic effect is wea-
kened, and the hydrophobic cavities play a role in preventing water
molecules from entering the clay crystal layer, thus enhancing the effect
of inhibiting clay hydration expansion. However, if CD cavities are not
concentrated to form a dense layer, the hydrophilic outer surface of the
CD cavity may play an important role, as the ability to prevent water
molecules from entering the clay crystal layer is reduced. These hy-
potheses require further experimental analysis and theoretical discus-
5.4. Ecofriendly cyclodextrin-based corrosion and scale inhibitors in
oilfields
In the process of oil exploitation, acidification and hydraulic frac-
turing are significant technology approaches to enhancing oil recovery.
Pipelines and production equipment in oilfields are mostly made of
steel, thus the resulting acidification of wastewater is highly corrosive
to them and makes the steel brittle and vulnerable to fracturing. At the
same time, metallic iron is corroded into ions by acid, which causes
damage to the formation under certain conditions. These consequences
not only threaten the safety of oilfield exploitation but also cause
economic losses. Therefore, corrosion inhibitors are always added in
acid solutions to prevent or slow the acid corrosion of the drill pipe,
tubing or any other metal equipment. In addition, the wastewater
produced by hydraulic fracturing is concentrated with inorganic ions
and the organic matrix, including calcium, barium, magnesium, sulfate,
carbonate, etc., which combine to form stable carbonate and sulfate
precipitations and are deposited as oilfield scale in the near-wellbore
reservoir, wellbore, tubing and casing, water injection equipment,
gathering pipelines, etc. (Lester et al., 2015). Serious scaling problems
cause pore blockage in the oil reservoir and smaller pipe diameters,
resulting in lower production and affecting the development effective-
ness of the oilfield (Reilly, Singer, Jefferson, & Eckstein, 2015).
Therefore, it is necessary to use scale inhibitors to effectively disperse
the insoluble inorganic salts in water and to prevent or mitigate in-
soluble inorganic salts from settling on the metal surface or forming
scale to maintain a high performance and the original structure of the
oil well and production equipment. Nitrogen and phosphorus com-
pounds can effectively delay the corrosion and control the growth of
scale, but these corrosion and scale inhibitors have a poor biode-
gradation in water and may lead to eutrophication (Tang, Li, Ye, Kou, &
Fu, 2017). Therefore, under the pressure of a worsening global ecolo-
gical environment, environment-friendly corrosion and scale inhibitors
have become a hotspot of research.
Based on the large number of active eOH groups on the β -CD
molecular surface and the unique truncated-cone-shaped cavity struc-
ture, researchers have devoted themselves to the development of green
corrosion inhibitors and scale inhibitors by taking advantage of the fact
that CD can selectively adsorb and encapsulate some organic and
W. Tang, et al.
inorganic molecules. Ashassi-Sorkhabi, Ghalebsaz-Jeddi, Hashemzadeh
& Jahani (2006) mentioned that CD molecules bind to the surface of an
active metal through oxygen heteroatoms to form an adsorption center,
which has the potential to become a corrosion inhibitor. Gu et al.
(2013) demonstrated that β -CD could strongly interact with Ca2+, thus
inhibiting the crystallization of calcium carbonate and the attachment
of scale on steel surfaces. However, the water solubility of natural CD is
relatively poor, so hydrophilic groups such as carboxyl and sulfonyl are
often introduced to increase the water solubility of β -CD, and also, the
applications of cyclodextrin copolymers in corrosion and scale inhibi-
tion need to be investigated.
Corrosion inhibitors are an important type of acid additive, which is
the most practical approach for corrosion protection in oil wells. At
present, the organic corrosion inhibitors heavily used in oilfields in-
clude aldehydes, organosulfur compounds, oxygen-containing com-
pounds, sulfonates, amines, pyridines, alkynols, Mannich bases, and so
on. Yuan Liu, Changjun Zou, Xueling Yan, Mingjin Tang et al. (Liu et al.,
2015; Liu, Zou, Li, Lin, & Chen, 2016; Tang et al., 2017; Yan, Zou, &
Qin, 2014; Zou, Liu et al., 2014; Zou, Tang, Tan, Xiao, & Hu, 2012)
synthesized a series of polymers (CDM-24, CDM-25, CDM-16, CDM-26,
CDM-27, as shown in Table 1) with one or more polar groups, including
sulfur, oxygen, nitrogen, etc., by the polymerization of β -CD and other
monomers and discussed the corrosion inhibition of carbon steel in an
acid solution (hydrochloric acid or sulfuric acid) and salt solution under
the action of these polymers. Their study indicated that the CD inhibitor
presented excellent corrosion inhibition, and its inhibition efficiency
was more than 90 %. It could be clearly concluded from the experi-
mental results that within a given range, the corrosion rate (corrosion
rate is the speed at which any metal in a specific environment dete-
riorates) affected by the polymer inhibitor decreased with the con-
centration, while the changes in the corrosion efficiency (corrosion
efficiency is the percentage of corrosion rate reduced in a certain period
of time) were the opposite. Corrosion of a metal by an acid solution is
electrochemical corrosion. Corrosion causes the anode on the metal
surface to be oxidized and dissolved, while hydrogen ions are reduced
at the cathode to generate hydrogen. Therefore, the action mechanism
of the corrosion inhibitor (Fig. 6), on one hand, was to share electron
Fig. 6. Proposed action mechanism of the corrosion inhibitor (Liu et al., 2015).
15
Carbohydrate Polymers 240 (2020) 116321
pairs with the metal surface, and the resulting chemical bonds could
suspend the oxidation reaction of the metal in this area; on the other
hand, through electrostatic attraction, the corrosion inhibitor adsorbed
on the cathode region, forming a protective film that could inhibit acid
corrosion of the metal. Organic compounds containing functional
groups with S, N, O and other heteroatoms could provide lone pair
electrons, which could establish coordinative interactions with the
metal to effectively inhibit metal corrosion (Çakmakci, Duran, Duran, &
Bereket, 2013; Hmamou et al., 2013; Puthalath, Surendranathan, &
Murthy, 2014). The secondary hydroxy groups provided by the CD
could form coordination bonds with the active metal to adsorb on the
metal surface. This layer could reduce the dissolution of the anodic
metal and the hydrogen evolution reactions through the oxygen het-
eroatom as the adsorption center, so CD derivatives are likely to be
potential corrosion inhibitors (Ashassi-Sorkhabi et al., 2006). In the
same way, S, N and other heteroatoms in CD polymer corrosion in-
hibitors act similar acts to O atoms. In addition, organic corrosion in-
hibitors can form a layer of a fully dense passive film on the metal
surface by the effect of film formation, which isolates or reduces the
contact area between the acid and metal to inhibit corrosion. The
higher concentration of the corrosion inhibitor, the thicker and wider
adsorption film and the better scale inhibition effect (Liu et al., 2015).
To further study the corrosion of metals in an acid or salt solution,
researchers characterized the surface morphology of carbon steel im-
mersed in a solution via SEM, and the results are shown in Fig. 7(A) and
(B). The SEM images show that in the absence of the CD corrosion in-
hibitor, the steel surface was rough and corroded severely with deep
localized pits. However, the addition of the CD corrosion inhibitor to
the solution resulted in considerably less damage to the carbon steel,
and the corrosion degree reduced obviously. These data further confirm
that the active sites of metal were covered by CD inhibitor molecules to
form a dense protective film, effectively inhibiting the corrosion process
of the metal in solution.
Recently, carboxylic acid and sulfonic acid polymer scale inhibitors
have been widely employed in oil wells to prevent scale formation.
Copolymers containing carboxy, anhydride, hydroxy and sulfonic acid
groups have obvious advantages in scale inhibition (Xing, Ma, & Chen,
W. Tang, et al. Carbohydrate Polymers 240 (2020) 116321

Fig. 7. (A) SEM surface morphology (A1, A2, A3, and A4) of carbon steel after immersion in a solution without a corrosion inhibitor (CDM-24, CDM-25, CDM-16, and
CDM-26); (B) SEM surface morphology (B1, B2, B3, and B4) of carbon steel after immersion in a solution with corrosion inhibitor (CDM-24, CDM-25, CDM-16, and
CDM-26) (Liu et al., 2015; Yan et al., 2014; Zou, Liu et al., 2014; Zou, Tang et al., 2012).

Fig. 8. TEM (C1, C2) and SEM (C3, C4) images of the CaCO3 crystal formed in the absence (C1, C3) and presence (C2, C4) of inhibitor CDM-28 (Bao et al., 2016; Gu
et al., 2013).

16
W. Tang, et al.
2005; Xiong, Zhou, & Wei, 2003). Xiaoxian Gu and Yufei Bao et al.
(Bao, Li, & Zhang, 2016; Gu et al., 2013) synthesized a terpolymer scale
inhibitor (CDM-28, as shown in Table 1) for use in high-temperature
and high-hardness water systems using free-radical polymerization with
β-CD, maleic anhydride and styrene sodium sulfonate as monomers and
ammonium persulfate as the initiator. Based on the orthogonal ex-
periment, the authors found that parameters such as the molar ratio of
monomers, reaction time, reaction temperature and initiator con-
centration all affected the scale inhibition performance. Under optimal
conditions, the inhibition efficiency of CDM-28 to calcium carbonate
and calcium phosphate scale both reached greater than 95 %. In ad-
dition, SEM and TEM tests showed the surface morphology of calcium
carbonate scale with and without the CD scale inhibitor CDM-28
(Fig. 8) and led to following observations: in the absence of an in-
hibitor, the CaCO3 deposits had a regular cubic shape with a glossy
scale surface and compact arrangement; in the presence of the inhibitor,
however, the CaCO3 deposits presented a dispersed granular structure,
and the scale surface was rough. The morphological changes indicated
that the CD scale inhibitor could not only effectively prevent the ac-
cumulation of CaCO3 scale but also lead to crystal lattice deformation
during the growth process. From the inhibition mechanism perspective,
the active groups, including carboxyl, acid anhydride, sulfonic acid
groups; CD cavity; etc., in the CDM-28 copolymer molecules bond with
Ca2+ in the solution to form chelates, which can adsorb on the scale
surface to weaken the mechanical strength of the scale and provide a
synergistic antiscale effect of the functional groups (Tantayakom,
Sreethawong, Fogler, De Moraes, & Chavadej, 2005). Concurrently, the
CD cavity in the scale inhibitor contains an abundance of hydroxy
groups, and the polyhydroxy structure increases the repulsive force
between scale crystals through the double layer interaction, dispersing
the grains and hindering the accumulation of scale. Moreover, the
carboxyl groups on the molecular chain of the scale inhibitor ionizes in
the medium environment, thus losing protons and becoming anions,
which can chelate with the scale cations and inhibit the precipitation.
Subsequently, Yuan Liu et al. (2016) modified natural β -CD with
polyethylene glycol to synthesize a copolymer green scale inhibitor,
polyethylene-glycol-modified β -cyclodextrin (CDM-25), and in-
vestigated its effect in preventing calcium carbonate deposition in the
oilfield flow backwater. It should be noted that in addition to studying
the scale inhibition efficiency and the scale inhibition mechanism, the
authors also discussed the compatibility between the treated waste-
water and formation water and applied CDM-25 to solve the scaling
problem for the flowback water in Shanxi shale gas shell. Ma, Zhang,
Zhao,& Yang (2018) synthesized the quadripolymer CDM-29 (as shown
in Table 1) for scale inhibition using maleic anhydride, acrylic acid,
maleic-anhydride-modified β -CD and sodium hypophosphite. This
scale inhibition material presented an excellent scale inhibition effect,
with scale inhibition rates of calcium sulfate, calcium carbonate and
silicon of 93.35 %, 88.92 % and 74.33 %, respectively, and thus showed
great potential to be used in high-hardness water systems.
The addition of CD made the polymer corrosion and scale inhibitor
more economical and environmentally friendly. However, limitations
and challenges still exist in the current research on CD corrosion and
scale inhibitors. For example, a single acid or salt solution is often used
to study the inhibitory effect of CD corrosion inhibitors, which is far
from the complexity of the actual environment. In addition, scale in-
hibition of a CD scale inhibitor mainly focuses on inhibiting calcium
carbonate scale, and there have been few studies on other types of scale.
Therefore, the research scope can be broadened to explore, e.g., the
effect of the CD corrosion inhibitor on metal corrosion in a complex
solution environment, as well as the effect of the CD scale inhibitor on
various types of scale.
17
Carbohydrate Polymers 240 (2020) 116321
5.5. Application of cyclodextrin polymers and inclusion complexes in
oilfield wastewater treatment
Although oil-gas field development and oil exploitation have
brought considerable benefits to the global economy, they have also
caused numerous environmental pollution problems all over the world.
In recent years, the frequent occurrence of oily wastewater discharges
and oil leakage accidents have prompted people to strengthen the re-
search on demulsification and oil-water separation, to meet increas-
ingly high requirements of production water discharge. When crude oil
flows through the narrow fractures in the formation, oil pipelines and
nozzles, or stirring actions caused by natural gas escaping, those can
produce an emulsion under the action of emulsifiers with mixtures of
oil, gas and water. The high viscosity of the emulsion usually results in
poor fluidity, which not only prevents the acid from flowing back into
the wellbore but also causes formation plugging around the well. In
oilfields, chemical agents such as flocculants and demulsifiers are added
to optimize the interfacial properties of the emulsion to prevent oil and
water from emulsification or to separate the emulsion so that plugging
and formation pollution could be avoided or impeded. The process of
demulsification usually involves two steps. The first step is flocculation,
in which the dispersed phase particles gather into clusters, while each
particle still exists. The flocculation process is reversible, which means
the aggregated particles can be separated from each other under an
external interference, and under the dynamic equilibrium of formation
and dissociation. The second step of emulsion destruction is coales-
cence. In this process, the flocculated particles aggregate to form large
droplets. Correspondingly, the number of droplets in the emulsion de-
creases over time, and finally, the emulsion is completely destroyed.
The coalescence process is not reversible.
As a typical flocculant, polyacrylamide and its derivatives are
widely used in wastewater treatments. Polyacrylamide flocculants with
a higher relative molecular mass are beneficial to flocculation and the
settlement of pollutants. Therefore, it is necessary to study the pre-
paration of some acrylamide polymers with macromolecular side
groups. In studies on host compounds, it has been confirmed that the
structure of a CD with a large proportion contributes to the improve-
ment of its inclusion effect (Liu, Jiang, Gou, Ye, Luo et al., 2013; Zou,
Zhao et al., 2012). Zou, Liang, Chen & Yan (2014) introduced the in-
clusion function of β -CD into an acrylamide polymer, characterized the
flocculent property of the cationic polyacrylamide flocculant (acryla-
mide/allyl- β -cyclodextrin/dimethyl diallyl ammonium chloride,
known as CDM-16), and discussed the flocculation mechanism. The
authors compared the flocculation effects of acrylamide polymers with
and without the β -CD side groups and claimed that the former was
more dramatic than the latter. This was because the positively charged
dimethyl diallyl ammonium chloride (DMDAAC) in the side chain of
CDM-16 could adsorb the negatively charged particles in wastewater
through electric neutralization, as well as the inclusion function of β
-CD. The detailed flocculation mechanism is shown in Fig. 9. First, the
polymers adsorb particles and molecules through the electrical neu-
tralization and the inclusion effect of the β -CD cavity. The other seg-
ment of the particles then continues to be adsorbed by another polymer
chain to form bridges, inducing the particles to gather into clumps. In
general, several polymer chains between adjacent particles form
bridges, which can help bring the particles closer together to form ag-
gregates and attach to multiple particles, thus setting foreign particles
and destabilizing the colloid. In addition, due to the cooperation be-
tween monomers, when β -CD is added to hydrophobically modified
polyacrylamide, the new system can effectively inhibit hydrophobic
groups from adsorbing at the oil-water interface, thus weakening the
role of hydrophobic groups in the emulsification of crude oil. Lu et al.
(2017) reported this phenomenon and provided theoretical guidance
for exploring the emulsification and de-emulsification mechanism of
emulsions stabilized by amphiphilic polymers, which are widely ap-
plied in tertiary oil recovery.
W. Tang, et al. Carbohydrate Polymers 240 (2020) 116321

Zhang et al. (2016) reported magnetic composite particles (M-CDs)

Fig. 9. The flocculation mechanism of the cationic polyacrylamide flocculant
(Zou, Zhao et al., 2012).
modified with CD, which effectively separated the oil phase from the
water phase in various types of emulsions, including O/W and W/O
emulsions. Moreover, the magnetic nanoparticles could be recycled and
reused, fully meeting the economic, green and environmental protec-
tion concepts advocated by the current industry. Though M-CDs are
hydrophilic, the CD cavity structure on their surface can intelligently
adsorb oil molecules to form the magnetic CD-oil inclusion complex (M-
ICs), which spontaneously alters the surface wettability of magnetic
particles and converts them into hydrophobic compounds. The inter-
action between magnetic nanoparticles and β-CD and the wettability
modification of M-CDs due to the formation of M-ICs are illustrated in
Fig. 10(A). M-ICs formed spontaneously through the self-assembly
process at the oil-water interface and further assembled into micro-
crystals, which were attached to the emulsified droplet surface to re-
duce the interfacial tension between oil and water, leading to the for-
mation of a stable emulsion (Mathapa & Paunov, 2013; Xu, Liu, &
Zhang, 2015). Under the loading of an external magnetic field, the
microcrystals on the droplet surface were broken due to the magnetic

Fig. 10. (A)The formation of M-CDs and M-ICs and the changes of wettability; (B)The mechanism of M-CDs in O/W and W/O emulsion (Zhang et al., 2016).

18
W. Tang, et al.
response, and the stability of the droplets was damaged, resulting in a
rapid separation of the oil and water phases. The mechanism of M-CDs
in O/W and W/O emulsions is shown in Fig. 10(B). Subsequently,
Sellamuthu Selva Dasarathan Elanchezhiyan et al. (Elanchezhiyan &
Meenakshi, 2017) synthesized a series of metal ion-incorporated chit-
osan/ β -CD composite materials. The metal ions (La3+, Zr4+, and
Ce3+) were appropriately modified with hydroxy groups and amine
groups in the CD-functionalized chitosan bulk molecules. The prepared
composites presented an excellent adsorption performance and can ef-
fectively remove oil molecules in oily wastewater by the hydrophobic
interaction and electrostatic attraction.
In addition, oilfield wastewater contains various kinds of re-
calcitrant and toxic pollutants, such as naphthenic acid, benzene,
phenols and other organic compounds. CDs and their derivatives have a
good inclusion ability to incorporate a wide variety of guest compounds
in aqueous solution. Therefore, CDs have the potential to adsorb pol-
lutants in oilfield wastewater. Nadia Morin-Crini and Gregorio Crini,
et al. (Morin-Crini & Crini, 2013; Morin-Crini, Winterton et al., 2018b)
summarized the synthesis, characterization and application of water
insoluble β-cyclodextrin-epichlorohydrin polymers and introduced
various mechanisms of how these CD polymers remove pollutants from
aqueous solution in detail, including inclusion interactions, association
interactions, electrostatic interactions, chelation, van der Waals, hy-
drogen bonding, ion exchange, etc., and the network structure of β-
cyclodextrin-epichlorohydrin polymer was also shown to benefit the
adsorption process. Mohamed, Wilson, Headley & Peru (2011) in-
troduced β-CD to diisocyanate monomers that contained aliphatic and
aromatic linker units to prepare a range of novel supramolecular sor-
bents and discussed the potential of separating naphthenic acids from
oil sand process water. The authors inferred that the inclusion binding
sites in the β-CD macrocycle played a major role in the sorption of
naphthenic acids from aqueous solution, and the noninclusion binding
sites of the linker monomers played a secondary role. Among the co-
polymers that contained aromatic groups and aliphatic groups, the
latter was reported as having a stronger sorption capacity for naph-
thenic acids. Liang & Zou (2019) prepared a water-insoluble supra-
molecular adsorbent, poly (β-cyclodextrin-citric acid) (CDM-30, as
shown in Table 1), with polyvinyl alcohol as the main chain and β-CD
as the side group, for the treatment of naphthenic acid in oil sand
process-affected water. The authors monitored the concentration
change of naphthenic acid in water and found that the maximum ad-
sorption quantity of CDM-30 was 193.42 mg ∙g−1, indicating that CDM-
30 had an excellent adsorption capacity and that the host-guest inter-
action of β-CD promoted the adsorption of naphthenic acid. Chen, Zou,
Li & Li (2016) reported the case of a carboxymethyl β-CD polymer
material assisting the UV-Fenton process to degrade phenolic pollutants
in drilling wastewater and showed satisfactory results, which could
accelerate the degradation of phenolic pollutants.
With the development of nanomaterials, researchers have become
inspired to combine nanoparticles with β-CD with the goal of obtaining
adsorption materials that have a better performance and can be used to
improve the efficiency of treating wastewater. Lin & Zou (2017) com-
bined Fe3O4 magnetic nanoparticles with the β-CD inclusion complex
containing organic phosphoric acid through a chemical method and
successfully prepared the magnetic composite CDM-31 (as shown in
Table 1). This composite was used as an adsorbent to remove Hg+ from
wastewater for the first time, and the maximum adsorption capacity
reached up to 77.59 mg g−1. Vinod Kumar Gupta et al. (2017) com-
bined β-CD with graphene oxide to synthesize a novel nanocomposite to
rapidly adsorb and eliminate noxious impurities in aqueous solution,
such as bisphenol-A, and reported the maximum adsorption capacity of
373.4 mg ∙g−1 under laboratory conditions. Ragavan & Rastogi (2017)
synthesized the β -CD-capped graphene-magnetite nanocomposite (G-
Fe3O4-BCD), which could not only selectively adsorb bisphenol-A in
water but also accelerate the separation of target harmful molecules
under external magnetic fields with high magnetization and
19
Carbohydrate Polymers 240 (2020) 116321
superparamagnetic properties, as well as reproducibility and reusa-
bility. Hu, Zou et al. (2019) successfully prepared a supramolecular
carbon nanofiber (CDM-32, as shown in Table 1) with a large specific
surface area by combining carbon nanotubes and linear a β -CD
polymer. The participation of β-CD enabled this nanocomposite to se-
lectively adsorb organic pollutants from wastewater, such as aniline,
estradiol, phenol, nitrophenol, benzene, toluene, and nitrobenzene, and
inorganic pollutants, including Hg2+, Pb2+, Co2+ and so on. In addi-
tion, the regeneration sorption and desorption experiments indicated
that CDM-32 had a good regeneration capacity and durability, and its
adsorption capacity for organic pollutants remained above 80 % after 7
cycles. In addition, Morin-Crini, Fourmentin, Fourmentin, Torri and
Crini (2018a) summarized the synthesis and adsorption properties of
the cyclodextrin-functionalized silica network. This review article
showed that research on silica-containing cyclodextrin has been de-
veloped over 25 years, and although the research on the adsorption of
various organic and inorganic pollutants has been relatively mature,
studies focusing on the combinations and applications of CD-nano-silica
particles are still limited. Of course, these studies all indicate that cy-
clodextrin nanomaterials have great potential to treat oilfield waste-
water.
The selective inclusion associations of the CD cavity have provided
CDs with great potential to be used for flocculation, demulsification and
the adsorption of harmful substances in oilfield wastewater. However,
currently, only a few kinds of products involving CDs have been syn-
thesized and studied, and only limited explanations on the adsorption
mechanism and working process of CD-nanocomposite formed by
combining CDs with nanoparticles have been reported. Therefore, more
target CD products need to be developed and further explored in order
to go beyond lab-scale results as soon as possible and to be applied in
the production field and everyday practice.
6. Conclusion and future perspectives
The literature has shown that CD-based materials, especially CD
polymers and host-guest inclusion complexes, play an important role in
the process of petroleum exploitation and exhibit great potential for
applications in oilfields. The hydrophobic cavity structure of CD mo-
lecules can form a natural waterproof layer and play a shielding role to
prevent clay from hydrating/swelling and fine particle from migrating
as a clay stabilizer. CD molecules have been introduced as corrosion
and scale inhibitors mainly due to the numerous hydroxy groups pro-
vided in their cavity, which can form coordination bonds with the ac-
tive metal through oxygen hybridized atoms as the adsorption center,
adsorb on the metal surface to form a fully dense passive film that re-
duces the contact opportunities between acid and metal, and effectively
minimize the degree of metal corrosion. On the other hand, the multi-
hydroxyl structure increases the repulsion between grains through the
double electric layer interaction, thus dispersing the grains and pre-
venting them from accumulating into crystal scale. The cavity of the CD
molecule has the function of molecular recognition and encapsulation,
which can selectively encapsulate various molecules, ions, free radicals,
etc. so that it can be used in oil production for retarded acid and sur-
factant flooding for EOR and wastewater treatment. At the same time,
the steric hindrance and inclusion of CD molecules endows polymers
with better rigidity, which effectively improves their temperature re-
sistance and shear resistance, thus significantly improving oil recovery
in polymer flooding.
The application of CD-based materials in oilfields has been studied
for more than a decade; however, various challenges and further re-
search directions still exist and should be addressed in future work.
Researchers should develop more types of CD-based materials and de-
vote more efforts to develop environmentally friendly methods for CDs
to modify bulk chemicals. Meanwhile, the selectivity of CD molecules
has not been fully utilized, especially for various kinds of harmful
substances in oilfield wastewater. In addition, based on the advantages
W. Tang, et al.
of nanomaterials, it is necessary to address the cooperation between
CDs and nanomaterials to further improve the properties of materials.
In the future, we expect to witness and develop more specific applica-
tions of CD derivatives in oilfields.
Declaration of Competing Interest
There are no conflicts to declare.
Acknowledgement
This work was supported by the National Natural Science
Foundation of China (21576225), Sichuan Province Science and
Technology Support Program (2019YFG0054) and Chinese Scholarship
council.
References
Alhassawi, H., & Romero-Zerón, L. (2015a). New surfactant delivery system for control-
ling surfactant adsorption onto solid surfaces. Part I: Static adsorption tests. The
Canadian Journal of Chemical Engineering, 93(7), 1188–1193. https://doi.org/10.
1002/cjce.22217.
Alhassawi, H., & Romero-Zerón, L. (2015b). Novel surfactant delivery system for con-
trolling surfactant adsorption onto solid surfaces. Part II: Dynamic adsorption tests.
The Canadian Journal of Chemical Engineering, 93(8), 1371–1379. https://doi.org/10.
1002/cjce.22231.
Alhassawi, H., & Romero-Zerón, L. (2015c). Novel surfactant delivery system for con-
trolling surfactant adsorption onto solid surfaces. Part III: Oil displacement tests. The
Canadian Journal of Chemical Engineering, 93(9), 1539–1546. https://doi.org/10.
1002/cjce.22239.
Anderson, R. L., Ratcliffe, I., Greenwell, H. C., Williams, P. A., Cliffe, S., & Coveney, P. V.
(2010). Clay swelling - A challenge in the oilfield. Earth-Science Reviews, 98, 201–216.
https://doi.org/10.1016/j.earscirev.2009.11.003.
Aree, T., Schulz, B., & Reck, G. (2003). Crystal structures of β-cyclodextrin complexes
with formic acid and acetic acid. Journal of Inclusion Phenomena, 47, 39–45. https://
doi.org/10.1023/B:JIPH.0000003923.92981.0f.
Ashassi-Sorkhabi, H., Ghalebsaz-Jeddi, N., Hashemzadeh, F., & Jahani, H. (2006).
Corrosion inhibition of carbon steel in hydrochloric acid by some polyethylene gly-
cols. Electrochimica Acta, 51(18), 3848–3854. https://doi.org/10.1016/j.electacta.
2005.11.002.
Auzély-Velty, R., & Rinaudo, M. (2002). New supramolecular assemblies of a cyclodex-
trin-grafted chitosan through specific complexation. Macromolecules, 35(21),
7955–7962. https://doi.org/10.1021/ma020664o.
Bao, Y., Li, M., & Zhang, Y. (2016). Research on the synthesis and scale inhibition per-
formance of a new terpolymer scale inhibitor. Water Science & Technology, 73(7),
1619–1627. https://doi.org/10.2166/wst.2015.635.
Belyakova, L. A., Varvarin, A. M., Lyashenko, D. Y., Khora, O. V., & Oranskaya, E. I.
(2007). Complexation in a β-cyclodextrin-salicylic acid system. Colloid Journal, 69(5),
546–551. https://doi.org/10.1134/S1061933X0705002X.
Çakmakci, I., Duran, B., Duran, M., & Bereket, G. (2013). Experimental and theoretical
studies on protective properties of poly(pyrrole-co-N-methyl pyrrole) coatings on
copper in chloride media. Corrosion Science, 69, 252–261. https://doi.org/10.1016/j.
corsci.2012.12.011.
Chen, G., & Jiang, M. (2011). Cyclodextrin-based inclusion complexation bridging su-
pramolecular chemistry and macromolecular self-assembly. Chemical Society Reviews,
40(5), 2254–2266. https://doi.org/10.1039/c0cs00153h.
Chen, W., Zou, C., Li, X., & Li, L. (2016). The treatment of phenolic contaminants from
shale gas drilling wastewater: A comparison with UV-Fenton and modified UV-Fenton
processes at neutral pH. RSC Advances, 6(93), 90682–90689. https://doi.org/10.
1039/c6ra18662a.
Chen, Y., Huang, F., Li, Z. T., & Liu, Y. (2018). Controllable macrocyclic supramolecular
assemblies in aqueous solution. Science China Chemistry, 61(8), 979–992. https://doi.
org/10.1007/s11426-018-9337-4.
Cohen, C. E., Ding, D., Quintard, M., & Bazin, B. (2008). From pore scale to wellbore
scale: Impact of geometry on wormhole growth in carbonate acidization. Chemical
Engineering Science, 63(12), 3088–3099. https://doi.org/10.1016/j.ces.2008.03.021.
Crini, G. (2005). Recent developments in polysaccharide-based materials used as ad-
sorbents in wastewater treatment. Progress in Polymer Science (Oxford), 30(1), 38–70.
https://doi.org/10.1016/j.progpolymsci.2004.11.002.
Crini, G., Fourmentin, S., Fenyvesi, É., Torri, G., Fourmentin, M., & Morin-Crini, N.
(2018). Cyclodextrins, from molecules to applications. Environmental Chemistry
Letters, 16(4), 1361–1375. https://doi.org/10.1007/s10311-018-0763-2.
Crowe, C., Masmonteil, J., & Thomas, R. (1992). Trends in matrix acidizing. Oilfield
Review, 4, 24–40.
Csernák, O., Buvári-Barcza, Á., Samu, J., & Barcza, L. (2005). Uncommon interactions of
aliphatic dicarboxylic acids with cyclodextrins. Journal of Inclusion Phenomena, 51(1),
59–63. https://doi.org/10.1007/s10847-004-5795-5.
Da, C., Alzobaidi, S., Jian, G., Zhang, L., Biswal, S. L., Hirasaki, G. J., et al. (Alzobaidi
et al., 2018a). Carbon dioxide/water foams stabilized with a zwitterionic surfactant
at temperatures up to 150 °C in high salinity brine. Journal of Petroleum Science &
20
Carbohydrate Polymers 240 (2020) 116321
Engineering, 166, 880–890. https://doi.org/10.1016/j.petrol.2018.03.071.
Da, C., Jian, G., Alzobaidi, S., Yang, J., Biswal, S. L., Hirasaki, G. J., et al. (Jian et al.,
2018b). Design of CO 2 -in-water foam stabilized with switchable amine surfactants
at high temperature in high-salinity brine and effect of oil [Research-article]. Energy
and Fuels, 32(12), 12259–12267. https://doi.org/10.1021/acs.energyfuels.8b02959.
Dass, C. R., & Jessup, W. (2000). Apolipoprotein A-I, cyclodextrins and liposomes as
potential drugs for the reversal of atherosclerosis. A review. The Journal of Pharmacy
and Pharmacology, 52(7), 731–761. https://doi.org/10.1211/0022357001774606.
Del Valle, E. M. M. (2004). Cyclodextrins and their uses: A review. Process Biochemistry,
39(9), 1033–1046. https://doi.org/10.1016/S0032-9592(03)00258-9.
Dodziuk, H. (2006). Cyclodextrins and their complexes: Chemistry, analytical methods, ap-
plications. Weinheim: Wiley-VCHhttps://doi.org/10.1002/3527608982 Chapter 1).
Economides, M. J., & Nolte, K. G. (2000). Reservoir stimulation (Third edition). America:
Wileyhttps://doi.org/10.1017/CBO9781107415324.004 Chapter10).
Elanchezhiyan, S. S. D., & Meenakshi, S. (2017). Facile fabrication of metal ions-in-
corporated chitosan/β-cyclodextrin composites for effective removal of oil from oily
wastewater. ChemistrySelect, 2(35), 11393–11401. https://doi.org/10.1002/slct.
201702147.
Frömming, K. H., & Szejtli, J. (1994). Cyclodextrins in pharmacy. Dordrecht:
Springerhttps://doi.org/10.1007/978-94-015-8277-3 Chapter 2).
Gu, X., Qiu, F., Zhou, X., Qi, J., Zhou, Y., Yang, D., et al. (2013). Synthesis and application
of terpolymer scale inhibitor in the presence of β-cyclodextrins. Journal of Petroleum
Science & Engineering, 109, 177–186. https://doi.org/10.1016/j.petrol.2013.08.021.
Gupta, V. K., Agarwal, S., Sadegh, H., Ali, G. A. M., Bharti, A. K., & Hamdy Makhlouf, A. S.
(2017). Facile route synthesis of novel graphene oxide-β-cyclodextrin nanocomposite
and its application as adsorbent for removal of toxic bisphenol A from the aqueous
phase. Journal of Molecular Liquids, 237, 466–472. https://doi.org/10.1016/j.molliq.
2017.04.113.
He, Y., Xu, Z. H., Wu, F., Luo, Z., & Chen, C. L. (2014). Synthesis and characterization of a
novel amphiphilic copolymer containing β-cyclodextrin. Colloid and Polymer Science,
292(7), 1725–1733. https://doi.org/10.1007/s00396-014-3235-7.
Hedges, A. R. (1998). Industrial applications of cyclodextrins. Chemical Reviews, 98(5),
2035–2044. https://doi.org/10.1021/cr970014w.
Himes, R. E., Vinson, E. F., & Simon, D. E. (1989). Clay stabilization in low-permeability
formations. SPE Production Operations Symposium. https://doi.org/10.2118/
18881-MS.
Hmamou, D. B., Salghi, R., Zarrouk, A., Aouad, M. R., Benali, O., Zarrok, H., et al. (2013).
Weight loss, electrochemical, quantum chemical calculation, and molecular dynamics
simulation studies on 2-(benzylthio)-1,4,5-triphenyl-1H-imidazole as an inhibitor for
carbon steel corrosion in hydrochloric acid. Industrial & Engineering Chemistry
Research, 52(40), 14315–14327. https://doi.org/10.1021/ie401034h.
Horikoshi, K., & Shibanai, I. (1984). Patent No. US4444647.
Hu, X., Ke, Y., Zhao, Y., Lu, S., Deng, Q., Yu, C., et al. (2019). Synthesis, characterization
and solution properties of β-cyclodextrin-functionalized polyacrylamide/montmor-
illonite nanocomposites. Colloids and Surfaces A: Physicochemical and Engineering
Aspects, 560, 336–343. https://doi.org/10.1016/j.colsurfa.2018.10.035.
Hu, X., Ke, Y., Zhao, Y., Lu, S., Yu, C., & Peng, F. (Ke, Zhao, Lu et al., 2018a). Synthesis
and characterization of a β-cyclodextrin modified polyacrylamide and its rheological
properties by hybriding with silica nanoparticles. Colloids and Surfaces A:
Physicochemical and Engineering Aspects, 548, 10–18. https://doi.org/10.1016/j.
colsurfa.2018.03.039.
Hu, X., Ke, Y., Zhao, Y., Yu, C., Lu, S., & Peng, F. (Ke, Zhao, Yu et al., 2018b). Preparation
and properties of nanocomposites of β-cyclodextrin-functionalized polyacrylamide
and its application for enhancing oil recovery. RSC Advances, 8(53), 30491–30501.
https://doi.org/10.1039/c8ra05120h.
Hu, X., Zou, C., & Zou, X. (2019). The formation of supramolecular carbon nanofiber via
amidation reaction on the surface of amino single walled carbon nanotubes for se-
lective adsorption organic pollutants. Journal of Colloid and Interface Science, 542,
112–122. https://doi.org/10.1016/j.jcis.2019.01.130.
Hui, B. Y., Raoov, M., Zain, N. N. M., Mohamad, S., & Osman, H. (2017). Combination of
cyclodextrin and ionic liquid in analytical chemistry: Current and future perspectives.
Critical Reviews in Analytical Chemistry, 47(5), 454–467. https://doi.org/10.1080/
10408347.2017.1320936.
Jansook, P., Ogawa, N., & Loftsson, T. (2018). Cyclodextrins: Structure, physicochemical
properties and pharmaceutical applications. International Journal of Pharmaceutics,
535(1–2), 272–284. https://doi.org/10.1016/j.ijpharm.2017.11.018.
Ji, J., Zeng, C., Ke, Y., & Pei, Y. (2017). Preparation of poly(acrylamide-co-acrylic acid)/
silica nanocomposite microspheres and their performance as a plugging material for
deep profile control. Journal of Applied Polymer Science, 134(46), 1–11. https://doi.
org/10.1002/app.45502.
Kamal, M. S., Sultan, A. S., Al-Mubaiyedh, U. A., & Hussein, I. A. (2015). Review on
polymer flooding: Rheology, adsorption, stability, and field applications of various
polymer systems. Polymer Reviews, 21(3), 1–40. https://doi.org/10.1080/15583724.
2014.982821.
Kfoury, M., Landy, D., & Fourmentin, S. (2018). Characterization of cyclodextrin/volatile
inclusion complexes: A review. Molecules, 23(5), 1204–1226. https://doi.org/10.
3390/molecules23051204.
Kharisov, R. Y., Folomeev, A. E., Sharifullin, A. R., Bulgakova, G. T., & Telin, A. G. (2012).
Integrated approach to acid treatment optimization in carbonate reservoirs. Energy
and Fuels, 26, 2621–2630. https://doi.org/10.1021/ef201388p.
Kittisrisawai, S., & Romero-Zerón, L. B. (2015a). Complexation of surfactant/β-cyclo-
dextrin to inhibit surfactant adsorption onto sand, kaolin, and shale for applications
in enhanced oil recovery processes. Part I: Static adsorption analysis. Journal of
Surfactants and Detergents, 18(4), 603–613. https://doi.org/10.1007/s11743-015-
1688-4.
Kittisrisawai, S., & Romero-Zerón, L. B. (2015b). Complexation of Surfactant/β-
W. Tang, et al.
cyclodextrin to inhibit surfactant adsorption onto sand, kaolin, and shale for appli-
cations in enhanced oil recovery processes. Part II: Dynamic adsorption analysis.
Journal of Surfactants and Detergents, 18(5), 783–795. https://doi.org/10.1007/
s11743-015-1703-9.
Kittisrisawai, S., & Romero-Zerón, L. B. (2015c). Complexation of surfactant/β-cyclo-
dextrin to inhibit surfactant adsorption onto sand, kaolin, and shale for applications
in enhanced oil recovery processes. Part III: Oil displacement evaluation. Journal of
Surfactants and Detergents, 18(5), 797–809. https://doi.org/10.1007/s11743-015-
1692-8.
Kumar, R. S., & Sharma, T. (2018). Stability and rheological properties of nanofluids
stabilized by SiO2 nanoparticles and SiO2-TiO2 nanocomposites for oilfield applica-
tions. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 539, 171–183.
https://doi.org/10.1016/j.colsurfa.2017.12.028.
Kurkov, S. V., & Loftsson, T. (2013). Cyclodextrins. International Journal of Pharmaceutics,
453, 167–180. https://doi.org/10.1201/b11653.
Lai, W. F., Rogach, A. L., & Wong, W. T. (2017). Chemistry and engineering of cyclo-
dextrins for molecular imaging. Chemical Society Reviews, 46(20), 6379–6419.
https://doi.org/10.1039/c7cs00040e.
Lay, S., Ni, X., Yu, H., & Shen, S. (2016). State-of-the-art applications of cyclodextrins as
functional monomers in molecular imprinting techniques: A review. Journal of
Separation Science, 39(12), 2321–2331. https://doi.org/10.1002/jssc.201600003.
Lester, Y., Ferrer, I., Thurman, E. M., Sitterley, K. A., Korak, J. A., Aiken, G., et al. (2015).
Characterization of hydraulic fracturing flowback water in Colorado: Implications for
water treatment. The Science of the Total Environment, 512, 637–644. https://doi.org/
10.1016/j.scitotenv.2015.01.043.
Li, X., Zou, C., & Cui, C. (2015). Synthesis and characterization of a novel β-cyclodextrin
modified cationic polyacrylamide and its application for enhancing oil recovery.
Starch/Staerke, 67(7–8), 673–682. https://doi.org/10.1002/star.201500022.
Li, X., Shu, Z., Luo, P., & Ye, Z. (2018). Associating Polymer Networks based on cyclo-
dextrin inclusion compounds for heavy oil recovery. Journal of Chemistry, 2018, 1–9.
https://doi.org/10.1155/2018/7218901.
Liang, H., & Zou, C. (2019). Adsorption of naphthenic acids from oil sand process-affected
water with water-insoluble poly(β-cyclodextrin-citric acid). The Canadian Journal of
Chemical Engineering, 97(6), 1894–1902. https://doi.org/10.1002/cjce.23452.
Lin, L., & Zou, C. (2017). Kinetic and thermodynamic study of magnetic separable β-
cyclodextrin inclusion complex with organic phosphoric acid applied to removal of
Hg2+. Journal of Chemical and Engineering Data, 62(2), 762–772. https://doi.org/10.
1021/acs.jced.6b00827.
Lisnyak, Y. V., Martynov, A. V., Baumer, V. N., Shishkin, O. V., & Gubskaya, A. V. (2007).
Crystal and molecular structure of β-cyclodextrin inclusion complex with succinic
acid. Journal of Inclusion Phenomena and Macrocyclic Chemistry, 58, 367–375. https://
doi.org/10.1007/s10847-006-9284-x.
Liu, Y., Zou, C., Yan, X., Xiao, R., Wang, T., & Li, M. (2015). B-cyclodextrin modified
natural chitosan as a green inhibitor for carbon steel in acid solutions. Industrial &
Engineering Chemistry Research, 54(21), 5664–5672. https://doi.org/10.1021/acs.
iecr.5b00930.
Liu, Y., Zou, C., Li, C., Lin, L., & Chen, W. (2016). Evaluation of β-cyclodextrin-poly-
ethylene glycol as green scale inhibitors for produced-water in shale gas well.
Desalination, 377, 28–33. https://doi.org/10.1016/j.desal.2015.09.007.
Liu, C., & Zhang, N. (2011). Nanoparticles in gene therapy: Principles, prospects, and
challenges. Progress in Molecular Biology and Translational Science, 104, 509–562.
https://doi.org/10.1016/B978-0-12-416020-0.00013-9.
Liu, X., Jiang, W., Gou, S., Ye, Z., Feng, M., Lai, N., et al. (2013). Synthesis and evaluation
of novel water-soluble copolymers based on acrylamide and modular β-cyclodextrin.
Carbohydrate Polymers, 96(1), 47–56. https://doi.org/10.1016/j.carbpol.2013.03.
053.
Liu, X., Jiang, W., Gou, S., Ye, Z., & Luo, C. (2013). Synthesis and clay stabilization of a
water-soluble copolymer based on acrylamide, modular β-cyclodextrin, and AMPS.
Journal of Applied Polymer Science, 128(5), 3398–3404. https://doi.org/10.1002/app.
38558.
Lu, Y., Kang, W., Jiang, J., Chen, J., Xu, D., Zhang, P., et al. (2017). Study on the sta-
bilization mechanism of crude oil emulsion with an amphiphilic polymer using the β-
cyclodextrin inclusion method. RSC Advances, 7(14), 8156–8166. https://doi.org/10.
1039/c6ra28528g.
Ma, K., Cui, L., Dong, Y., Wang, T., Da, C., Hirasaki, G. J., et al. (2013). Adsorption of
cationic and anionic surfactants on natural and synthetic carbonate materials. Journal
of Colloid and Interface Science, 408(1), 164–172. https://doi.org/10.1016/j.jcis.
2013.07.006.
Ma, X., Zhang, M., Zhao, M., & Yang, L. (2018). Synthesis of MA/AA/MA-β-CD/SHP
quadripolymer and its performance evaluation as scale inhibitor. Russian Journal of
Applied Chemistry, 91(8), 1322–1331. https://doi.org/10.1134/s1070427218080104.
Maeztu, R., Tardajos, G., & Gonzalez-Gaitano, G. (2010). Natural cyclodextrins as effi-
cient boosters of the chemiluminescence of luminol and isoluminol: Exploration of
potential applications. The Journal of Physical Chemistry B, 114, 2798–2806. https://
doi.org/10.1021/jp909707x.
Martín, V. I., López-Cornejo, P., López-López, M., Blanco-Arévalo, D., Moreno-Vargas, A.
J., Angulo, M., et al. (2020). Influence of the surfactant degree of oligomerization on
the formation of cyclodextrin: Surfactant inclusion complexes. Arabian Journal of
Chemistry, 13(1), 2318–2330. https://doi.org/10.1016/j.arabjc.2018.04.015.
Mathapa, B. G., & Paunov, V. N. (2013). Self-assembly of cyclodextrin-oil inclusion
complexes at the oil-water interface: A route to surfactant-free emulsions. Journal of
Materials Chemistry A, 1(36), 10836–10846. https://doi.org/10.1039/c3ta12108a.
Maurya, N. K., & Mandal, A. (2016). Studies on behavior of suspension of silica nano-
particle in aqueous polyacrylamide solution for application in enhanced oil recovery.
Petroleum Science and Technology, 34(5), 429–436. https://doi.org/10.1080/
10916466.2016.1145693.
21
Carbohydrate Polymers 240 (2020) 116321
Mohamed, M. H., Wilson, L. D., Headley, J. V., & Peru, K. M. (2011). Sequestration of
naphthenic acids from aqueous solution using β-cyclodextrin-based polyurethanes.
Journal of the Chemical Society Faraday Transactions, 13(3), 1112–1122. https://doi.
org/10.1039/c0cp00421a.
Morin-Crini, N., & Crini, G. (2013). Environmental applications of water-insoluble β-cy-
clodextrin- epichlorohydrin polymers. Progress in Polymer Science, 38(2), 344–368.
https://doi.org/10.1016/j.progpolymsci.2012.06.005.
Morin-Crini, N., Fourmentin, M., Fourmentin, S., Torri, G., & Crini, G. (Fourmentin et al.,
2018a). Synthesis of silica materials containing cyclodextrin and their applications in
wastewater treatment. Environmental Chemistry Letters, 17(2), 683–696. https://doi.
org/10.1007/s10311-018-00818-0.
Morin-Crini, N., Winterton, P., Fourmentin, S., Wilson, L. D., Fenyvesi, É., & Crini, G.
(Winterton et al., 2018b). Water-insoluble β-cyclodextrin–Epichlorohydrin polymers
for removal of pollutants from aqueous solutions by sorption processes using batch
studies: A review of inclusion mechanisms. Progress in Polymer Science, 78, 1–23.
https://doi.org/10.1016/j.progpolymsci.2017.07.004.
Mura, P. (2014). Analytical techniques for characterization of cyclodextrin complexes in
aqueous solution: A review. Journal of Pharmaceutical and Biomedical Analysis, 101,
238–250. https://doi.org/10.1016/j.jpba.2014.02.022.
Peng, C., Gou, S., Wu, Q., Zhou, L., Zhang, H., & Fei, Y. (2019). Modified acrylamide
copolymers based on β-cyclodextrin and twin-tail structures for enhanced oil re-
covery through host-guest interactions. New Journal of Chemistry, 43(14), 5363–5373.
https://doi.org/10.1039/c8nj06432f.
Pitha, J., Milecki, J., Fales, H., Pannell, L., & Uekama, K. (1986). Hydroxypropyl-β-cy-
clodextrin: Preparation and characterization; effects on solubility of drugs.
International Journal of Pharmaceutics, 29, 73–82. https://doi.org/10.1016/0378-
5173(86)90201-2.
Pu, W., Shen, C., Wei, B., Yang, Y., & Li, Y. (2018). A comprehensive review of poly-
saccharide biopolymers for enhanced oil recovery (EOR) from flask to field. Journal of
Industrial and Engineering Chemistry, 61, 1–11. https://doi.org/10.1016/j.jiec.2017.
12.034.
Pu, W., Du, D., Liu, R., Li, K., & Huang, T. (2016). Synthesis and evaluation of β-cyclo-
dextrin-functionalized hydrophobically associating polyacrylamide. RSC Advances,
6(98), 96006–96014. https://doi.org/10.1039/c6ra14209e.
Pu, W. F., Yang, Y., Wei, B., & Yuan, C. D. (2016). Potential of a β-cyclodextrin/ada-
mantane modified copolymer in enhancing oil recovery through host-guest interac-
tions. Industrial & Engineering Chemistry Research, 55(31), 8679–8689. https://doi.
org/10.1021/acs.iecr.6b01793.
Puthalath, R., Surendranathan, A. O., & Murthy, C. S. N. (2014). Protective performance
of furfuryl alcohol on 13Cr L80 steel against corrosion in hydrochloric acid solution.
Industrial & Engineering Chemistry Research, 53(1), 23–30. https://doi.org/10.1021/
ie4014716.
Qian, H., & Ai, Z. (2016). Preparation and clay stabilization properties of cationic acry-
lamide polymer containing β-cyclodextrin. Research on Chemical Intermediates, 42(5),
4387–4401. https://doi.org/10.1007/s11164-015-2282-0.
Qin, Y., Zou, C., Yan, X., Liu, Y., & Li, L. (2014). Performance of cationic β-cyclodextrin as
a clay stabilizer for use in enhanced oil recovery. Starch-Starke, 66(9–10), 795–801.
https://doi.org/10.1002/star.201400011.
Qin, Y., Zou, C., Yan, X., Zhou, L., & Luo, P. (2015). High performance acid composition
based on cationic β-cyclodextrin inclusion complexes for enhancing oil recovery.
Chemical Engineering Research and Design, 94(8), 301–306. https://doi.org/10.1016/j.
cherd.2014.07.031.
Raffa, P., Broekhuis, A. A., & Picchioni, F. (2016). Polymeric surfactants for enhanced oil
recovery: A review. Journal of Petroleum Science & Engineering, 145, 723–733. https://
doi.org/10.1016/j.petrol.2016.07.007.
Ragavan, K. V., & Rastogi, N. K. (2017). β-cyclodextrin capped graphene-magnetite na-
nocomposite for selective adsorption of bisphenol-A. Carbohydrate Polymers, 168,
129–137. https://doi.org/10.1016/j.carbpol.2017.03.045.
Rajewski, R. A., & Stella, V. J. (1996). Pharmaceutical applications of cyclodextrins. 2. In
vivo drug delivery. Journal of Pharmaceutical Sciences, 85(11), 1142–1168. https://
doi.org/10.1021/js960075u.
Reilly, D., Singer, D., Jefferson, A., & Eckstein, Y. (2015). Identification of local
groundwater pollution in northeastern Pennsylvania: Marcellus flowback or not?
Environmental Earth Sciences, 73(12), 8097–8109. https://doi.org/10.1007/s12665-
014-3968-0.
Renard, E., Barnathan, G., Deratani, A., & Sebille, B. (1997). Polycondensation of cy-
clodextrins with epichlorohydrin. Influence of reaction conditions on the polymer
structure. Macromolecular Symposia, 122, 229–234. https://doi.org/10.1002/masy.
19971220136.
Renard, E., Deratani, A., Volet, G., & Sebille, B. (1997). Preparation and characterization
of water soluble high molecular weight β-cyclodextrin-epichlorohydrin polymers.
European Polymer Journal, 33(1), 49–57. https://doi.org/10.1016/S0014-3057(96)
00123-1.
Saenger, W., & Steiner, T. (1998). Cyclodextrin inclusion complexes: Host-guest inter-
actions and hydrogen-bonding networks. Acta Crystallographica Section A, 54,
798–805. https://doi.org/10.1107/S0108767398010733.
Saenger, W., Jacob, J., Gessler, K., Steiner, T., Hoffmann, D., Sanbe, H., et al. (1998).
Structures of the common cyclodextrins and their larger analogues - beyond the
doughnut. Chemical Reviews, 98(5), 1787–1802. https://doi.org/10.1021/cr9700181.
Schmidt, B. V. K. J., & Barner-Kowollik, C. (2017). Dynamic macromolecular material
design—The versatility of cyclodextrin-based host-guest chemistry. Angewandte
Chemie - International Edition, 56(29), 8350–8369. https://doi.org/10.1002/anie.
201612150.
Shafiq, M. U., & Shuker, M. T. (2013). Finding suitable acid for acidizing of Low
permeable sandstone formation: A research. SPE/PAPG Annual Technical Conference.
https://doi.org/10.2118/169641-MS.
W. Tang, et al.
Shibanai, I., Horikoshi, K., Nakamura, K. (1981). Patent No. US4255249.
Sikder, M. T., Rahman, M. M., Jakariya, M., Hosokawa, T., Kurasaki, M., & Saito, T.
(2019). Remediation of water pollution with native cyclodextrins and modified cy-
clodextrins: A comparative overview and perspectives. Chemical Engineering Journal,
355, 920–941. https://doi.org/10.1016/j.cej.2018.08.218.
Sun, M., Luo, Y., Christie, P., Jia, Z., Li, Z., & Teng, Y. (2012). Methyl-β-cyclodextrin
enhanced biodegradation of polycyclic aromatic hydrocarbons and associated mi-
crobial activity in contaminated soil. Journal of the Environmental Sciences, 24,
926–933. https://doi.org/10.1016/S1001-0742(11)60865-6.
Szejtli, J. (1982). Cyclodextrins and their inclusion complexes (cyclodextrine und ihre
Einschlußkomplexe). Verlag der Ungarischen Akademie der Wissenschaften. Budapest:
Akadémiai Kiadó.
Szejtli, J. (1988). Cyclodextrin technology. Dordrecht: Springerhttps://doi.org/10.1007/
978-94-015-7797-7 Chapter 1).
Szejtli, J. (1998). Introduction and general overview of cyclodextrin chemistry. Chemical
Reviews, 98, 1743–1753. https://doi.org/10.1021/cr970022c.
Tang, M., Li, J., Ye, Z., Kou, Z., & Fu, L. (2017). A novel eco-friendly scale and corrosion
inhibitor modified by β-cyclodextrin. Australian Journal of Chemistry, 70(8), 933–942.
https://doi.org/10.1071/CH16720.
Tantayakom, V., Sreethawong, T., Fogler, H. S., De Moraes, F. F., & Chavadej, S. (2005).
Scale inhibition study by turbidity measurement. Journal of Colloid and Interface
Science, 284(1), 57–65. https://doi.org/10.1016/j.jcis.2004.10.007.
Terekhova, I. V., & Obukhova, N. A. (2007). Study on inclusion complex formation of m-
aminobenzoic acid with native and substituted β-cyclodextrins. Journal of Solution
Chemistry, 36, 1167–1176. https://doi.org/10.1007/s10953-007-9170-1.
Valente, A. J. M., & Söderman, O. (2014). The formation of host-guest complexes between
surfactants and cyclodextrins. Advances in Colloid and Interface Science, 205, 156–176.
https://doi.org/10.1016/j.cis.2013.08.001.
Wassmuth, F. R., Arnold, W., Green, K., & Cameron, N. (2009). Polymer flood application
to improve heavy oil recovery at East Bodo. Journal of Canadian Petroleum Technology,
48(2), 55–61. https://doi.org/10.2118/09-02-55.
Wei, B. (2015). β-cyclodextrin associated polymeric systems: Rheology, flow behavior in
porous media and enhanced heavy oil recovery performance. Carbohydrate Polymers,
134, 398–405. https://doi.org/10.1016/j.carbpol.2015.08.011.
Wei, B., Romero-Zerón, L., & Rodrigue, D. (2015). Improved viscoelasticity of xanthan
gum through self-association with surfactant: β-cyclodextrin inclusion complexes for
applications in enhanced oil recovery. Polymer Engineering and Science, 55(3),
523–532. https://doi.org/10.1002/pen.23912.
Wei, B., Romero-Zerón, L., & Rodrigue, D. (Romero-Zerón et al., 2014a). Novel self-as-
sembling polymeric system based on a hydrophobic modified copolymer:
Formulation, rheological characterization, and performance in enhanced heavy oil
recovery. Polymers for Advanced Technologies, 25(7), 732–741. https://doi.org/10.
1002/pat.3279.
Wei, B., Romero-Zerõn, L., & Rodrigue, D. (Romero-Zerõn et al., 2014b). Formulation of a
self-assembling polymeric network system for enhanced oil recovery applications.
Advances in Polymer Technology, 33(3), https://doi.org/10.1002/adv.21413.
Weickenmeier, M., Wenz, G., & Huff, J. (1997). Association thickener by host guest in-
teraction of a β-cyclodextrin polymer and a polymer with hydrophobic side-groups.
Macromolecular Rapid Communications, 18(12), 1117–1123. https://doi.org/10.1002/
marc.1997.030181216.
Wenger, L. M., Davis, C. L., Evensen, J. M., Gormly, J. R., & Mankiewicz, P. J. (2004).
Impact of modern deepwater drilling and testing fluids on geochemical evaluations.
Organic Geochemistry, 35(11–12), 1527–1536. https://doi.org/10.1016/j.
orggeochem.2004.07.001.
Wever, D. A. Z., Picchioni, F., & Broekhuis, A. A. (2011). Polymers for enhanced oil re-
covery: A paradigm for structure-property relationship in aqueous solution. Progress
22
Carbohydrate Polymers 240 (2020) 116321
in Polymer Science (Oxford), 36(11), 1558–1628. https://doi.org/10.1016/j.
progpolymsci.2011.05.006.
Xing, X., Ma, C., & Chen, Y. (2005). Mechanism of calcium carbonate scale deposition
under subcooled flow boiling conditions. Chinese Journal of Chemical Engineering,
13(4), 464–470.
Xiong, R. C., Zhou, Q., & Wei, G. (2003). Corrosion inhibition of a green scale inhibitor
polyepoxysuccinic acid. Chinese Chemical Letters, 14(9), 955–957.
Xu, H. N., Liu, H. H., & Zhang, L. (2015). Blocking and blending: Different assembly
models of cyclodextrin and sodium caseinate at the oil/water interface. Langmuir,
31(33), 9061–9069. https://doi.org/10.1021/acs.langmuir.5b02111.
Yan, X., Zou, C., & Qin, Y. (2014). A new sight of water-soluble polyacrylamide modified
by β-cyclodextrin as corrosion inhibitor for X70 steel. Starch/Staerke, 66(11–12),
968–975. https://doi.org/10.1002/star.201400063.
Zhang, J., Li, Y., Bao, M., Yang, X., & Wang, Z. (2016). Facile fabrication of cyclodextrin-
modified magnetic particles for effective demulsification from various types of
emulsions. Environmental Science & Technology, 50(16), 8809–8816. https://doi.org/
10.1021/acs.est.6b01941.
Zhu, D., Wei, L., Wang, B., & Feng, Y. (2014). Aqueous hybrids of silica nanoparticles and
hydrophobically associating hydrolyzed polyacrylamide used for EOR in high-tem-
perature and high-salinity reservoirs. Energies, 7(6), 3858–3871. https://doi.org/10.
3390/en7063858.
Zou, C., Zhao, P., Hu, X., Yan, X., Zhang, Y., Wang, X., et al. (2013). β-cyclodextrin-
functionalized hydrophobically associating acrylamide copolymer for enhanced oil
recovery. Energy and Fuels, 27(5), 2827–2834. https://doi.org/10.1021/ef302152t.
Zou, C., Ge, J., Zhao, P., Cui, C., & Zhang, L. (2012). B-cyclodextrin and methacrylic acid
octyl phenols poly(Ethylene oxide) ester modified acrylamide polymer for enhancing
oil recovery. Journal of Macromolecular Science Part A- Pure and Applied Chemistry,
49(2), 171–177. https://doi.org/10.1080/10601325.2012.642227.
Zou, C., Liang, M., Chen, X., & Yan, X. (2014). β-Cyclodextrin modified cationic acryla-
mide polymers for flocculating waste drilling fluids. Journal of Applied Polymer
Science, 131(9), 1–5. https://doi.org/10.1002/app.40197.
Zou, C. J., Liao, W. J., Zhang, L., & Chen, H. M. (2011). Study on acidizing effect of β-
cyclodextrin-PBTCA inclusion compound with sandstone. Journal of Petroleum Science
& Engineering, 77(2), 219–225. https://doi.org/10.1016/j.petrol.2011.03.010.
Zou, C., Liu, Y., Yan, X., Qin, Y., Wang, M., & Zhou, L. (2014). Synthesis of bridged β-
cyclodextrin-polyethylene glycol and evaluation of its inhibition performance in
oilfield wastewater. Materials Chemistry and Physics, 147(3), 521–527. https://doi.
org/10.1016/j.matchemphys.2014.05.025.
Zou, C., Qin, Y., Yan, X., Zhou, L., & Luo, P. (2014). Study on acidizing effect of cationic β-
cyclodextrin inclusion complex with sandstone for enhancing oil recovery. Industrial
& Engineering Chemistry Research, 53(33), 12901–12910. https://doi.org/10.1021/
ie501569d.
Zou, C., Tang, Q., Tan, N., Xiao, P., & Hu, X. (2012). Cyclodextrin and methacrylic acid
octyl phenols poly(ethylene oxide) ester-induced synergistic effect in a novel poly
(AM-co-A-β-CD-co-AE) polymer. Starch/Staerke, 64(4), 281–289. https://doi.org/10.
1002/star.201100139.
Zou, C., Wu, H., Ma, L., & Lei, Y. (2011). Preparation and application of a series of novel
anionic acrylamide polymers with cyclodextrin sides. Journal of Applied Polymer
Science, 119(2), 953–961. https://doi.org/10.1002/app.32793.
Zou, C., Zhao, P., Lei, Y., Ye, H., Yao, Y., Chen, M., et al. (2011). Preparation and per-
formance of a novel water-soluble cationic polymer containing β-cyclodextrin.
Chemical Engineering & Technology, 34(11), 1820–1826. https://doi.org/10.1002/
ceat.201100143.
Zou, C., Zhao, P., Ge, J., Lei, Y., & Luo, P. (2012). β-cyclodextrin modified anionic and
cationic acrylamide polymers for enhancing oil recovery. Carbohydrate Polymers,
87(1), 607–613. https://doi.org/10.1016/j.carbpol.2011.08.031.