Journal of Petroleum Science and Engineering 179 (2019) 675–683

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Journal of Petroleum Science and Engineering

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

Mechanism of formation of chromium acetate(Cr3+)/ phenol-formaldehyde T

resin prepolymer(PRP) complex and its compound cross-linking reaction
with polymer for conformance control
Lei Zhanga, Feipeng Wub,∗, Chunsheng Pub
a
Department of Petroleum Engineering, China University of Geosciences (Wuhan), Wuhan 430074, China
b
College of Petroleum Engineering, China University of Petroleum (East China), Tsingdao 266580, China

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

Keywords: For the heterogeneous oil reservoir with high water cut, the conformance control by using polymer gels is good
Oil production for increasing oil production and decreasing excessive water. However, facing the current situation of low oil
Polymer gel prices, how to improve the exploitation efficiency and reduce the production cost in the maximum extent are still
Conformance control drawing the attention of petroleum engineers. Therefore, it is necessary to further study the polymer gels to
Chromium acetate
achieve this purpose. Among the polymer gels, the polymer/Cr3+ system and polymer/phenolic-formaldehyde
Phenol-formaldehyde
compounds system are the most common used, which are suitable for the low temperature reservoir and high
temperature reservoir, respectively. Based on the properties of each other, the combination of Cr3+ and phenol-
formaldehyde resin prepolymer (PRP) as a type of cross-linking agent can not only improve the thermal stability
of polymer/Cr3+ gel, but also enable polymer/PRP gel to be applied to low-medium temperature reservoirs,
which can further improve the application effect of polymer gels. However, the mechanism of compound cross-
linking reaction of Cr3+-PRP and polymer is still unclear. In this paper, the properties of Cr3+-PRP solution is
first tested and then the process of crosslinking reaction of Cr3+-PRP and polymer is study. In the Cr3+-PRP
solution, a new polynuclear olation complex ion of chromium (Cr3+-PRP complex) is formed, of which the
properties is different from PRP solution or chromium acetate solution. The cross-linking reaction of Cr3+-PRP
complex and polymer is compound. During the compound reaction at the temperature of 45 °C, the reaction of
Cr3+ and polymer has an impact on that of PRP and polymer, so that the reaction of Cr3+-PRP complex and
polymer is different from the superposition of the two reaction processes of Cr3+/polymer system and PRP/
polymer system. The formed Cr3+-PRP complex can resist salt to 70,000 mg/L. The experimental results can
provide a theoretical guidance for the high efficient practical application of conformance control by using
polymer/Cr3+ system or polymer/phenolic-formaldehyde compounds system.

1. Introduction
During oilfield development by water flooding for decades, ex-
cessive water production is becoming a serious problem that not only
reduces the crude oil production but also increases the cost of invest-
ment for waste water treatment (Li et al., 2016; Mi et al., 2016; Wang
and Tand, 1986; Xiaoping et al., 2013; Zhao et al., 2017). Especially in
China oilfields with the continental sedimentation, the high water cut
of oil well is a common phenomenon due to the heterogeneity of oil
layer, such as Daqing oilfield and Shengli oilfield (Cui et al., 2014;
Wang et al., 2009; Xie et al., 2019; Zhou et al., 2017). Therefore, to
treat the excessive water production, many techniques have been pro-
posed and applied to the mature oilfield. However, until now, the
conformance control technology by using polymer gels are still the most
commonly used to enhance oil recovery and reduce excessive water
production because of its low cost and easy operation (Hakiki et al.,
2015a; Zhang et al., 2015a, 2016, 2017a, 2017b; Zhao et al., 2017b;
Wang et al., 2017).
Polymer gel is mainly composed of acrylamide (AM)-based polymer
and inorganic or organic cross-linker. Under the ground conditions,
polymer/cross-linker system is an aqueous solution with a low viscosity
and a strong flow capacity, which is called a gelant. In the reservoir, as
time goes by, this fluid-based system can gradually form a continuous,
three-dimensional (3D), solidlike network structure by the cross-linker
cross-linking the polymer, which is called a gel. Thus, the formed gel
can be used to achieve the conformance control of heterogeneous

∗
Corresponding author.
E-mail address: upcwfp@163.com (F. Wu).

https://doi.org/10.1016/j.petrol.2019.04.097
Received 18 March 2019; Received in revised form 21 April 2019; Accepted 28 April 2019
Available online 01 May 2019
0920-4105/ © 2019 Elsevier B.V. All rights reserved.
L. Zhang, et al.
reservoirs (Zhu et al., 2017a). There have two main mechanisms for the
conformance control (Bai et al., 2015). One is flow diversion. The ge-
lant has a priority to enter and fill the water channels with a higher
permeability and then plug the water channel after gelation, which can
divert the subsequent injected water to the adjacent lower permeable
pore throats. The other is water permeability reduction. During sub-
sequent water flooding, the formed gel can be penetrated by the water.
However, due to a high cementing between the gel and the rock, a gel
film is formed on the wall of pore throats, which can decrease the
diameter of pore throats and reduce the permeability of the subsequent
injected water.
The inorganic cross-linker, such as Cr3+, Zr4+, Al3+, etc., reacts
with the carboxyl group of the polymer chain to generate the ionic bond
(Zhang et al., 2019a, 2019b). Among the inorganic cross-linking
polymer gels, the polymer and chromium acetate (Cr3+) system is the
most common due to its good adaptability (Vargas-Vasquez and
Romero-Zeró, 2008; Natarajan et al., 1998; Cordova et al., 2008;
Nguyen et al., 2004; Willhite et al., 2002). In aqueous solution, the
chromium ion goes through the process of complexation, hydrolysis,
olation, and further hydrolysis and olation to form a polynuclear ola-
tion complex ion in the water. Chromium acetate (Cr3+) is para-
magnetic and possesses a large, effective magnetic moment, which has
a trimetallic arrangement where six acetates bridge three metal ions
connect by a triply-bridging oxygen (Eshel and Bino, 2001, 2002; Eshel
et al., 2000; Lin et al., 2008). Thus, four carboxylate oxygens surround
each Cr3+, and water molecules act as the terminal ligands. The
structure of chromium acetate depends on the pH of the solution, and it
can be predominantly trimeric cyclic or tirmeric linear. The cross-
linking reaction of polymer and Cr3+ can be sorted into two types
(Wang et al., 2008). One is the intramolecular cross-linking reaction
that takes place in different chains within the same polymer molecules
when the concentration of polymer is low (usually < 1000 mg/L). In-
tramolecular cross-linking forms a “regional” network molecular
structure, so that the viscosity stays the same or even decreases after
gelation, observed in the colloidal dispersion gel and the linked
polymer solution. The other is the intermolecular cross-linking reaction
that takes place among the different polymer molecules when the
concentration of polymer is high (usually > 1000 mg/L). Inter-
molecular cross-linking reaction has a “local” network molecular
structure, which can result in an increase of the viscosity, such as in the
bulk gel. Because of a high reactivity between Cr3+ and carboxyl group
of the polymer, the formed polymer gel is susceptible to degradation
and syneresis under high temperature, so that the polymer/Cr3+ system
is suitable for low temperature reservoir.
The organic cross-linker, such as phenolic-formaldehyde com-
pounds, polyethylenimine, etc., reacts with the amide group of the
polymer chain to generate the covalent bond (Zhang et al., 2018; El-
Karsani et al., 2014; Chen et al., 2018). Among the organic cross-linking
polymer gels, the polymer and phenolic-formaldehyde compounds
system is the most common due to its low price and extensive raw
materials (Gu et al., 2018; Liu et al., 2017; Zhao et al., 2015). Due to its
carcinogenic feature, formaldehyde can be replaced by the lower toxi-
city chemicals. For example, hexamethylenetetramine (HMTA) can be
applied to replace formaldehyde to generate polymer gels. HMTA is a
product that can thermally break down to generate formaldehyde and
ammonia, thereby participate in the reaction. Phenolic compounds in-
clude phenol, catechol, resorcinol, hydroquinone (HQ), and so forth.
Due to the toxicity of phenol, phenol can be replaced by other com-
pounds. The process of cross-linking reaction of polymer and phenolic-
formaldehyde compounds is as follows: the first step is that phenolic
compounds reacts with formaldehyde to form a phenol-formaldehyde
resin prepolymer (PRP); the second step is that the hydroxyl groups
(−CH2OH) of PRP cross-link with the amide groups (−CONH2) of the
polymer (Fang et al., 2017; Zhu et al., 2017b, 2017c). However, since
the reaction of phenolic compounds with formaldehyde is insufficient
in the gelant solution, a part of phenolic compounds and the
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Journal of Petroleum Science and Engineering 179 (2019) 675–683
formaldehyde is wasted and the properties of the formed gel is also
poor. For this reason, in the majority of cases, the phenolic compound
and the formaldehyde are first directly mixed on the ground to form
PRP under certain conditions, and then PRP is used as a cross-linking
agent to be mixed with the polymer solution to form a gelant after
stirring uniformly. This method can improve the utilization of phenolic
compounds and formaldehyde, and the properties of the formed gel in
the reservoir are more excellent. This cross-link reaction is a type of
dehydration condensation reaction, which forms the C–N between the
polymer side chains and cross-linker system, thus, forms a stable net-
work structure. Polymer/PRP system appears to be very good candi-
dates for high temperature applications, which can exhibit excellent
stability at high temperature above 60 °C.
Based on the above analysis, it concludes that the combination of
Cr3+ and PRP as a type of cross-linking agent can not only improve the
thermal stability of polymer/Cr3+ gel, but also enable polymer/PRP gel
to be applied to low-medium temperature reservoirs, which can further
improve the application effect of conformance control by using polymer
gels in the heterogeneous reservoir with the low-medium temperature
(such as Daqing oilfield and Changqing oilfield with the temperature of
45 °C). The prerequisite for achieving this goal is to understand the
reaction multi-crosslinking mechanism of Cr3+-PRP and polymer. In
this respect, Zhang et al. (2015b) had studied the gelation behavior of a
high temperature resistant polymer gel system consisting of partially
hydrolyzed polyacrylamide (HPAM), chromium lactate (CrL), and
water-soluble phenol-formaldehyde resin (PRP). They concluded that
the gelation process of the gel system could be divided into four suc-
cessive steps: induction, first cross-linking with metal cross-linker,
secondary cross-linking with organic cross-linker, and stabilization
based on the results of rheological measurements. However, the ap-
plication of chromium lactate is rarely applied to practice in oilfield,
and the properties of chromium lactate are different from those of
chromium acetate. More importantly, it is not sufficient to investigate
the reaction process only by using the rheological measurements. Be-
sides, Jia et al. (2017), Jia and Chen, (2018) had studied the process of
non-isothermal gelation of fresh chromium acetate (Cr3+)-poly-
ethyleneimine (PEI)-polymer gel sealant. They found that the first ge-
lation reaction occurs between the polymer and Cr3+ at surface tem-
perature. However, the fresh chromium acetate is different from
chromium acetate complex and the properties of PEI is also different
from that of PRP. But besides these, the literature about reporting the
compound crosslinking mechanism of Cr3+-PRP and polymer is few.
Therefore, it is important and necessary to investigate the compound
crosslinking mechanism of Cr3+-PRP and polymer.
2. Experiment
2.1. Reagents and equipment
In the experiment, water samples with the different salinities are
prepared with the different concentrations of NaCl and deionized water,
which are used for preparing the gelants and other aqueous solutions.
An anti-high temperature and high salt polymer (KYPAM) is from
Beijing Hengju Chemical Group Corporation in China, which is syn-
thesized by the copolymerization of acrylamide (AM), 2-acrylamide-2-
tetradecyl ethyl sulfonic acid (AMC16S), and 2-acrylamide-2-methyl-
propanesulfonic acid (AMPS). Its molecular weight is 12 million g/mol
and its hydrolysis degree is 22%. KYPAM is a white solid powder, which
can form a homogeneous polymer aqueous solution under fully stirring
for 50 min when 2000 mg KYPAM is added to 100 mL deionized water.
Corresponding values of the viscosity of the KYPAM solution with the
concentration of 2000 mg/L under the different salinities at the tem-
perature of 45 °C are shown in Fig. 1. It can be observed that KYPAM
has good salt resistance. Even when the salinity is up to 100,000 mg/L,
the retention rate of the viscosity is still higher than 81%. This is be-
cause there have entanglement between molecules in the aqueous
L. Zhang, et al.
Fig. 1. Changes in the viscosities of KYPAM solution with the concentration of
2000 mg/L under the different salinities at the temperature of 45 °C.
solution to form a network structure, which can be shown in Fig. 2. The
entangled network structure can inhibit the curl of the polymer chain
during cation compressing the diffused electric double layer of the
polymer molecule (Hakiki et al., 2015b). Therefore, the viscosity of
KYPAM solution can maintain a high value under a higher salinity.
Phenolic resin prepolymer (PRP) is formed by prepolymerization of
formaldehyde and phenol (the molar ratio of formaldehyde and phenol
is 3:1) on condition that sodium hydroxide is as a catalyst, which is
obtained from Shandong Shida Oilfield Technical Services Co., Ltd. PRP
is a mixture of polycondensation polymer with the degree of poly-
merization of 2–10. Its structure is shown in Fig. 3a. Chromium acetate
solution is consisting of anhydrous sodium acetate and chromic
chloride hexahydrate in a proportion of 3:1 (mole ratio), which is also
from Shandong Shida Oilfield Technical Services Co., Ltd. The con-
centration of Cr3+ in the chromium acetate solution is 5 mg/mL. Ac-
cording to a 1:3 mol ratio of Cr3+ and CH3COO−, the coordinate
covalent bonds of chromium have been completely occupied by
CH3COO−, which can be shown in Fig. 3b.
Other equipment include a DV-III Brookfield viscometer, a UV2550
ultraviolet–visible spectrophotometer, a DSC823 differential scanning
calorimeter, a 90Plus PALS Zeta potential and particle size analyzer, a
Hitachi S-4800 scanning electron microscope (SEM) and a Nicolet 5700
fourier transform infrared (FTIR) spectrometric analyzer. The shear rate
of measuring viscosity is 7.34 s−1 at the temperature of 45 °C.
2.2. Experimental procedure
2.2.1. Testing the properties of Cr3+-PRP solution and PRP solution
By comparison of the properties of Cr3+-PRP solution and PRP so-
lution, the physico-chemical interaction between Cr3+ and PRP in the
Fig. 2. Microstructure of KYPAM (a: SEM image at the scale of 50 μm; b: SEM image at the scale of 10 μm).
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Journal of Petroleum Science and Engineering 179 (2019) 675–683
solution can be identified. The experimental steps are as follows: ① PRP
solution is prepared by adding 2000 mg/L PRP to the deionized water;
② The absorbance, particle size, Zeta potential, and chemical structure
of PRP in the solution are measured by UV–vis spectrophotometer, Zeta
potential and particle size analyzer and FTIR spectrometric analyzer,
respectively; ③ Cr3+-PRP solution is prepared by adding 20 mg/L Cr3+
to PRP solution; ④ The absorbance of Cr3+-PRP solution is measured
before and after the physico-chemical reaction by UV–vis spectro-
photometer(It can be considered that the reaction between Cr3+ and
PRP stops when the value of absorbance no longer change.); ⑤After the
properties of Cr3+-PRP solution remains stable, its particle size, Zeta
potential, and chemical structure are measured by Zeta potential and
particle size analyzer and FTIR spectrometric analyzer, respectively.
Thus, the values are recorded to evaluate the difference in properties of
Cr3+-PRP solution and PRP solution.
2.2.2. Bottle test of Cr3+-PRP and KYPAM system
Bottle test is an effective, practical method for the study of gelation
behaviors, which can be used for evaluate the influence of the para-
meters of cross-linker on the characteristics of gelatinization. The pro-
cedure of bottle tests consists of two parts. One is to adjust the con-
centration of Cr3+ while keeping the other parameters constant. The
other is to adjust the concentration of PRP while keeping the other
parameters constant. In the experiment, the prepared cross-linking
agents (consisting of Cr3+ and PRP) can be used for up to 1 days after
preparation. The prepared gelants with different concentrations of
cross-linking agent and KYPAM are shown in Table 1. The specific ex-
perimental steps are as follows: ①A series of the prepared gelants are
sealed in bottles and then placed in an incubator at the temperature of
45 °C; ②The change of the viscosity of each of the gelants with time is
measured by the viscometer at the same time intervals until the visc-
osity no longer change. In the experiment, the gelation time of the
gelant can be determined by the evolution of the apparent viscosity of
the gelant, which is shown in Fig. 4. Bai et al. (2015) had investigated
that the curve of apparent viscosity vs time can be divided into three
sub-curves: two sub-curves approximate to straight lines located at both
ends and an arc-like sub-curve located in the middle, the regression
lines of two ends sub-curves with different slopes can be achieved and
cross over at one point; the gelation time was defined as the time to
which the cross point corresponded. Thus, the relationship of viscosity
vs time of the gelants can be established.
2.2.3. Differential scanning calorimetry (DSC) measurement of the gelants
It is known that changes in heat during a chemical reaction can
characterize the process of the chemical reaction. Therefore, by com-
parison of the heat changes of Cr3+/KYPAM, PRP/KYPAM, and Cr3+-
PRP/KYPAM during the cross-linking reaction, the process of cross-
linking reaction of Cr3+-PRP/KYPAM can be analyzed, which can
provide a theoretical basis for controlling this reaction. Cr3+/KYPAM
gelant is consisting of 20 mg/L Cr3+ and 2000 mg/L KYPAM. PRP/
KYPAM gelant is consisting of 2000 mg/L PRP and 2000 mg/L KYPAM.
L. Zhang, et al.
Table 1
The detailed scheme of Cr3+/PRP/KYPAM systems.
No. KYPAM cross-linking agent
Cr3+
Part 1 1 2000 mg/L 10 mg/L
2 20 mg/L
3 30 mg/L
Part 2 4 2000 mg/L 20 mg/L
5 20 mg/L
6 20 mg/L
Fig. 4. Schematic of the gelation time determination (Bai et al., 2015).
Cr3+-PRP/KYPAM gelant is consisting of 20 mg/L Cr3+, 2000 mg/L
PRP, and 2000 mg/L KYPAM. The three gelants are prepared with the
deionized water. During each measurement, about 10 mg of gelant is
placed in a hermetic pan with a nitrogen purge rate of 50 cm3/min. And
an empty hermetic pan is set as a reference sample. All samples are
equilibrated at 25 °C for 5 min to remove the former thermal history.
The heating rates are 3 °C/min from 20 to 130 °C for all measurements.
2.2.4. Testing the properties of Cr3+-PRP and KYPAM system under the
different salinities
Presently, as is well-known, there have many influencing factors on
the characteristics of gelatinization under an oil reservoir environment
during water flooding, such as reservoir temperature, the properties
and salinity of the water, the size of porous media, etc. However, for
operations of conformance control technology on the ground, the sali-
nity of injection water is easy to be controlled and adjusted. Therefore,
we focus on investigating the influence of salinity on the gelatinization
between Cr3+-PRP system and KYPAM, which can provide an im-
portant theoretical basis for further understanding the reaction me-
chanism.
For Cr3+-PRP/KYPAM system, due to a good salt tolerance of
KYPAM, salinity mainly affects the properties of Cr3+-PRP system.
Therefore, the first step in the experiment is to investigate the changes
in the absorbance, particle size, Zeta potential of Cr3+-PRP system
(consisting of 20 mg/L Cr3+ and 2000 mg/L PRP) under the different
salinities to evaluate the effect of salinity on its properties. And then on
Journal of Petroleum Science and Engineering 179 (2019) 675–683
Fig. 3. Chemical structure of the crosslinking agent
(a: the structure of PRP with n = 2–8, b: the struc-
ture of chromium acetate complex in deionized
water).
this basis, the effect of salinity on the gelatinization between Cr3+-PRP
system and KYPAM is investigated. In the experiment, a series of Cr3+-
PRP/KYPAM gelants (consisting of 20 mg/L Cr3+, 2000 mg/L PRP, and
2000 mg/L KYPAM) are prepared with the different salinities water
PRP samples, respectively. Thus, all of the gelants are placed into an oven at
the temperature of 45 °C. The gelation time of each of the gelants is
2000 mg/L
measured according to the viscosity vs time curve. Until the viscosity of
2000 mg/L
2000 mg/L a gelant no longer change, its value can be used to characterize the
1000 mg/L strength of gelatinization.
2000 mg/L
3000 mg/L
3. Results and discussion
3.1. Complexation of Cr3+ and PRP
The comparison results of physical and chemical properties of Cr3+-
PRP system and PRP are shown in Fig. 5. Fig. 5a shows the changes in
the absorbance of the two. It can be observed that the absorbance of the
system after Cr3+ mixed with PRP is increased with time and then re-
mains stable at 120 min. At time zero, due to a considerably higher
concentration of PRP than that of Cr3+, the absorbance of Cr3+-PRP
mixture is consistent with that of PRP. Next, the absorbance of Cr3+-
PRP mixture starts to increase gradually, which shows that there may
be a physical-chemical reaction between Cr3+ and PRP. After 120min,
the absorbance of Cr3+-PRP mixture doesn't change with reaction time,
which shows that the Cr3+-PRP mixture becomes a stable product
(named “Cr3+-PRP complex”).
Fig. 5b shows the changes in the particle size of Cr3+-PRP complex
and PRP. It can be observed that the average particle size of Cr3+-PRP
complex is larger than that of PRP. Fig. 5c shows the changes in the Zeta
potential of the two. It can be observed that the Zeta potential of Cr3+-
PRP complex is higher than that of PRP. According to the results of
Fig. 5a, b, and c, it can conclude that a new chemical product can be
produced by adding the chromium acetate solution to the PRP solution.
It is known that the chromium acetate solution is a type of polynuclear
olation complex ion of chromium, of which the coordinate covalent
bonds have been occupied by CH3COO−. PRP is a low molecular weight
polymer that can be uniformly dispersed in water with a relatively large
hydrodynamic volume and solvation. Due to a higher activity of hy-
droxymethyl and phenolic hydroxyl of benzene ring than that of
CH3COO−, the polynuclear olation complex ion of chromium reopens
to go through the process of complexation and olation to form a new
polynuclear olation complex ion of chromium when the chromium
acetate is added to the PRP solution.
Fig. 5d shows the changes in the chemical structure of Cr3+-PRP
complex and PRP by using FTIR spectra. It can be observed that there
are obvious differences in the FTIR spectra between the two in spite
that the main skeletons of the two are both PRP. For PRP, 3600 cm−1 is
the characteristic absorption peak of hydrogen bond association of the
hydroxyl group; 1630 cm−1 is the characteristic absorption peak of
stretching and vibration of C=C; 1470 cm−1 is the characteristic ab-
sorption peak of methylene bridge –CH2- linked by ortho-para position;
1200 cm−1 is the characteristic absorption peak of stretching and vi-
bration of -C-O- of the phenol; 1000 cm−1 is the characteristic ab-
sorption peak of stretching and vibration of -C-O- of the hydroxymethyl
group; and 880 cm−1 is the characteristic absorption peak of out-of-
plane bending vibration of -CH- of the benzene ring. However, for Cr3+-
PRP complex, the shape of the peak of hydrogen bond association of the
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L. Zhang, et al.
Fig. 5. Changes in the physical and chemical properties of Cr3+-PRP system and PRP (a: changes in the absorbance; b: changes in the particle size; c: changes in the
Zeta potential; d: changes in the chemical structure).
hydroxyl group becomes wider and larger, and the intensity of the peak
is higher, which shows that the association of hydroxyl groups has been
changed. In addition, the shapes of the peaks of stretching and vibration
of -C-O- of the phenol and the hydroxymethyl group become sharper,
and the intensity of the peaks are also higher, which shows that -C-O- of
the phenol and the hydroxymethyl group have also been changed. From
the above analysis, it can be concluded that the infrared spectra of -O-
H, -C-O- and related groups have undergone significant changes due to
the complexation of PRP with chromium ions. It can be proved that PRP
does complex with chromium ions to produce a new substance (called
Cr3+-PRP complex).
The process of formation of Cr3+-PRP complex is shown in Fig. 6. It
can be observed that the coordinate covalent bonds of chromium have
been occupied by the hydroxyls of the PRP. Both R1 and R2 can be
Fig. 6. The process of formation of Cr3+-PRP complex.
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Journal of Petroleum Science and Engineering 179 (2019) 675–683
substitute for hydroxyl of PRP or acetate, which are decided by the
dissociation degree of the chromium acetate complex and the activation
of PRP.
3.2. Cross-linking reaction of Cr3+-PRP complex and KYPAM
3.2.1. Gelation behavior
The gelation behavior of Cr3+-PRP complex and KYPAM can be
shown by the changes in the viscosity of the gelant with time, which is
shown in Fig. 7. Fig. 7a shows that the gelation time is shortened and
the viscosity of the gelant is increased with the increase of the con-
centration of Cr3+ under the same other conditions. Fig. 7b shows that
the gelation time is basically unchanged and the viscosity of the gelant
is increased with the increase of the concentration of PRP under the
L. Zhang, et al.
Fig. 7. Changes in the gelation behavior of Cr3+-PRP complex and KYPAM (a: different concentrations of Cr3+; b: different concentrations of PRP).
same other conditions. Whether the concentration of Cr3+ or PRP in-
creases, the viscosity of the formed gel is increased. This is because both
Cr3+ and PRP can be taken as a crosslinking agent to cross-link with the
polymer. The higher the concentration of the crosslinking agent, the
more cross-linking points there have, so that the viscosity of the gel is
greater. However, the increase of the concentration of Cr3+ can reduce
the gelation time but that of PRP cannot. This indicates that the con-
centration of Cr3+ is the decisive factor for initiating the cross-linking
reaction at the temperature of 45 °C. Due to a higher activity, the ad-
dition of Cr3+ initiates the cross-linking reaction and then reduce the
activation energy of the reaction, thereby causing the PRP to participate
in the crosslinking reaction.
3.2.2. Process of cross-linking reaction
The DSC curves of Cr3+/KYPAM system, PRP/KYPAM system, and
Cr3+-PRP/KYPAM system are shown in Fig. 8. Fig. 8a and b shows that
all the three have an endothermic peak, which indicates that the three
cross-linking processes are an endothermic reaction. We already know
that Cr3+ is cross-linked with the carboxyl group of KYPAM and PRP is
cross-linked with the amide group of KYPAM. Suppose that the two
reactions are independent of each other for the Cr3+-PRP/KYPAM
system, the changes in reaction heat of Cr3+-PRP/KYPAM system can
be characterized by the superposition of curves in Fig. 8a. However,
Fig. 8b shows that the variation characteristics of DSC curve of the
Cr3+-PRP/KYPAM system is different from those of the superposition of
Cr3+/KYPAM system and PRP/KYPAM system. It shows that the pro-
cess of reaction of Cr3+-PRP complex and KYPAM is not a superposition
of the two reaction processes of Cr3+/KYPAM system and PRP/KYPAM
system. This indicates that there has an interaction between the cross-
linking reaction of Cr3+ and the carboxyl of KYPAM and the cross-
linking reaction of PRP and the amide group on KYPAM in the Cr3+-
PRP/KYPAM system. In addition, from Fig. 8b, it can be observed that
Fig. 8. DSC curves of the three gelants (a: Cr3+/KYPAM system and PRP/KYPAM system; b: Cr3+-PRP/KYPAM system).
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Journal of Petroleum Science and Engineering 179 (2019) 675–683
when the crosslinking reaction occurs, the exothermic rate of the Cr3+-
PRP/KYPAM system starts to be much higher than that of the Cr3+/
KYPAM system. This is because the occurrence of the cross-linking re-
action between Cr3+ and KYPAM can reduce the activation energy of
the whole system, and then initiate the cross-linking reaction between
PRP and KYPAM, which leads to an increase in the exothermic rate of
the whole system, even at a temperature of 45 °C(below 60 °C).
Therefore, it can be inferred that the process of reaction of Cr3+-PRP
complex with KYPAM can be divided into two steps: the first step is that
a part of Cr3+ released from the Cr3+-PRP complex can generate a
cross-linking reaction with KYPAM; the second step is the remaining
Cr3+ and all of the PRP from the Cr3+-PRP complex can simultaneously
crosslink with the KYPAM. The process of the reaction is shown in
Fig. 9, and finally a three dimensional space structure with a double
crosslink is formed.
3.2.3. Microstructure of cr3+-PRP/KYPAM gelant
Corresponding to the changes in viscosity of the gelant with time,
the structures of the gelant at two time points are analyzed, which are
shown in Fig. 10a–d. The three-dimensional network structure of the
gelant is improved and becomes more compact with the increase of
reaction time. Fig. 10a and b shows that the irregular mesh structure of
KYPAM has been replaced by the dendritic structure of the gelant after
reaction of 40 h. The main reason is that the cross-linking reaction
between Cr3+ and the carboxyl group of KYPAM predominates at this
cross-linking point. In the solution of Cr3+-PRP/KYPAM system, the
released Cr3+ from the complex is free to move around and then can be
evenly distributed in the solution. Thus, when it touches KYPAM, it can
reacts with KYPAM through the chemical bonds to form a structural
unit. However, the gel is not formed by these units with a simple
connection one by one but is formed by the combination of aggregates
and aggregates.
L. Zhang, et al.
Fig. 9. The process of the reaction of Cr3+-PRP complex and KYPAM.
At the beginning, the units are bound in pairs to become a dimers,
and then the dimers are combined each other to form an increasingly
larger structure. The growing of the dendritic structure is mainly due to
the existence of a shielding effect, of which the tip of the foremost
branch can most effectively capture the diffused particles. As the branch
grows, the volume of the aggregate increases. However, the process of
aggregation is carried out in a limited space in the experiment, the
aggregate will automatically terminate due to the space constraints
681
Journal of Petroleum Science and Engineering 179 (2019) 675–683
when it increases to a certain volume. And then another favorable re-
action point is selected and a new aggregation starts. Further, a den-
dritic structure is formed. Besides, the scanning range is narrowed to
observe the structural feature of the aggregates, which is shown in
Fig. 10b. The aggregates are closely packed by small particles with the
different sizes, which is caused by the cross-linking of Cr3+ with the
carboxyl group of polymer. A lot of pores are left in the aggregates due
to the drying of the bound water and free water.
Fig. 10. Microstructures of the gelant composed of
2000 mg/L KYPAM, 20 mg/L Cr3+, and 2000 mg/L
PRP under the different reaction times and the dif-
ferent scales (a: the reaction time of 40 h and the
scale of 50 μm; b: the reaction time of 40 h and the
scale of 10 μm; c: the reaction time of 60 h and the
scale of 50 μm; d: the reaction time of 60 h and the
scale of 10 μm).
L. Zhang, et al. Journal of Petroleum Science and Engineering 179 (2019) 675–683

Fig. 11. Changes in the properties of Cr3+-PRP complex with salinity (a: changes in the absorbance and the Zeta potential; b: changes in the particle size).

As the reaction proceeds, the PRP molecules begin to react with the
amide groups of KYPAM and gradually dominates, so that the three-
dimensional network structure is further formed and the dendritic
structure becomes denser, which are shown in Fig. 10c and d. Since the
PRP molecule is rigid and its size is much larger than that of Cr3+, the
formed network structure is more prominent in the spatial three-di-
mensional layer and the gel has a compact and uniform three-dimen-
sional space structure.

3.3. Effect of salinity on the properties of Cr3+-PRP/KYPAM system

3.3.1. Effect of salinity on the properties of Cr3+-PRP complex

The results of the effect of salinity on the properties of Cr3+-PRP
complex are shown in Fig. 11. Fig. 11a and b shows the changes in the
absorbance, Zeta potential, and particle size of Cr3+-PRP complex with
the salinity, respectively. In the range of 0–5000 mg/L NaCl, as the
concentration of NaCl increases, the amount of Na+ entering the dif-
fusion double layer of Cr3+-PRP complex increases, which results in a
decrease in the thickness of the electric double layer and a decrease in Fig. 12. Effect of salinity on the cross-linking reaction of Cr3+-PRP/KYPAM.
the Zeta potential. However, in this range, the number of aggregated
molecules does not change significantly, and the electrostatic repulsion
increases. This is because the ionic strength in the solution increases
is predominant between the aggregates. Due to the increase of charge
and the degree of dissociation of the Cr3+-PRP complex increases with
distribution around the aggregates and the compression of the electric
the salinity increases, so that the concentration of Cr3+ participating in
double layers, the aggregates are compressed and then the phenomenon
the step 1 of the crosslinking reaction increases. In addition, the gel
of reduction of the particle size occurs, which is shown in Fig. 11b.
strength is decreased as the salinity increases. Since the molecular size
Since the particle size is reduced and the number of molecules remain
of the aggregates of Cr3+-PRP complex increases as the salinity in-
unchanged, the absorbance is reduced, which is shown in Fig. 11a.
creases, the number of molecules of the complex is decreased, and then
In the range of 5000–70000 mg/L NaCl, as the concentration of
the number of molecules involved in the crosslinking reaction can be
NaCl increases, the diffusion electric double layer of the Cr3+-PRP
correspondingly reduced. Nevertheless, the gel strength and cross-
complex is gradually compressed, and the Zeta Potential is gradually
linking time can still be in a suitable range to meet the application of
reduced, which is shown in Fig. 11a. As the Zeta potential of the
on-site construction of conformance control technology. However,
complex aggregate decreases and the repulsion energy decreases, the
when the salinity exceeds 70,000 mg/L, the gelatinization strength and
Cr3+-PRP complex aggregates further aggregate, and thus the mole-
gelation time are greatly reduced. This is because the structure of the
cular size gradually increases and the absorbance decreases, which can
Cr3+-PRP complex has been unstable.
be shown in Fig. 11a and b. Nonetheless, in this range, Zeta Potential,
molecular size and absorbance can maintain a suitable value. When the
4. Conclusions
salinity is higher than 70,000 mg/L, the aggregate of Cr3+-PRP complex
becomes unstable with the increase of NaCl concentration, the Zeta
(1) When the chromium acetate solution is mixed with the PRP solu-
potential is greatly reduced, the aggregation and flocculation of ag-
tion, a new polynuclear olation complex ion of chromium can be
gregate molecules are rapidly intensified, which is easy to form the
formed by the replacing CH3COO− with hydroxymethyl and phe-
large flocculates. So that there has also a greatly reduction in absor-
nolic hydroxyl of PRP.
bance. This indicates that the Cr3+-PRP complex can resist salt to
(2) During gelation, the cross-linking reaction first happens between
70,000 mg/L.
the released Cr3+ from the Cr3+/PRP complex and carboxyl group
of the polymer. The concentration of Cr3+ is the decisive factor for
3.3.2. Effect of salinity on cross-linking reaction
initiating the cross-linking reaction. The occurrence of the cross-
The characteristics of crosslinking reaction of Cr3+-PRP and KYPAM
linking reaction between Cr3+ and polymer can reduce the acti-
under different salinities are shown in Fig. 12. In the range of
vation energy of the whole system, and then initiate the cross-
0–70000 mg/L NaCl, the gelation time is shortened as the salinity

682
L. Zhang, et al.
linking reaction between PRP and polymer. Thus, the remaining
Cr3+ and all of the PRP crosslink with the polymer. After the double
crosslinking reaction is completed, the gel has a compact and uni-
form three-dimensional space structure.
(3) Salinity can affect the morphology and structure of the Cr3+-PRP
complex, and thus affects the crosslinking reaction of Cr3+-PRP
complex and KYPAM. The Cr3+-PRP/KYPAM system can resist salt
to 70,000 mg/L.
Notes
The authors declare no competing financial interest.
Acknowledgments
This study was supported by the Fundamental Research Funds for
the Central Universities (CUG 180612).
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.petrol.2019.04.097.
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