polymers

Article
Evaluation of Viscosity Changes and Rheological Properties
of Diutan Gum, Xanthan Gum, and Scleroglucan in
Extreme Reservoirs
Xin Gao 1,2,3 , Lixin Huang 2,3, *, Jianlong Xiu 2,3 , Lina Yi 3 and Yongheng Zhao 1,2,3

1 School of Engineering Science, University of Chinese Academy of Sciences, Beijing 100049, China;
[email protected] (X.G.); [email protected] (Y.Z.)
2 Institute of Porous Flow and Fluid Mechanics, Chinese Academy of Sciences, Langfang 065007, China;
[email protected]
3 State Key Laboratory of Enhanced Oil Recovery, PetroChina Research Institute of Petroleum
Exploration & Development, Beijing 100083, China; [email protected]
* Correspondence: [email protected]

Abstract: The chemically synthesized polymer polyacrylamide (HPAM) has achieved excellent
oil displacement in conventional reservoirs, but its oil displacement is poor in extreme reservoir
environments. To develop a biopolymer oil flooding agent suitable for extreme reservoir conditions,
the viscosity changes and rheological properties of three biopolymers, diutan gum, xanthan gum,
and scleroglucan, were studied under extreme reservoir conditions (high salt, high temperature,
strong acid, and alkali), and the effects of temperature, mineralization, pH, and other factors on
their viscosities and long-term stability were analyzed and compared. The results show that the
three biopolymers had the best viscosity-increasing ability at temperatures of 90 ◦ C and below. The
viscosity of the three biopolymers was 80.94 mPa·s, 11.57 mPa·s, and 59.83 mPa·s, respectively, when
the concentration was 1500 mg/L and the salinity 220 g/L. At the shear rate of 250 s−1 , 100 ◦ C~140 ◦ C,
scleroglucan had the best viscosification. At 140 ◦ C, the solution viscosity was 19.74 mPa·s, and
the retention rate could reach 118.27%. The results of the long-term stability study showed that
the solution viscosity of scleroglucan with a mineralization level of 220 mg/L was 89.54% viscosity
Citation: Gao, X.; Huang, L.; Xiu, J.; retention in 40 days, and the diutan gum could be stabilized for 10 days, with the viscosity maintained
Yi, L.; Zhao, Y. Evaluation of Viscosity at 90 mPa·s. All three biopolymers were highly acid- and alkali-resistant, with viscosity variations of
Changes and Rheological Properties less than 15% in the pH3~10 range. Rheological tests showed that the unique double-helix structure of
of Diutan Gum, Xanthan Gum, and diutan gum and the rigid triple-helix structure of scleroglucan caused them to have better viscoelastic
Scleroglucan in Extreme Reservoirs. properties than xanthan gum. Therefore, these two biopolymers, diutan gum, and scleroglucan, have
Polymers 2023, 15, 4338. https:// the potential for extreme reservoir oil displacement applications. It is recommended to use diutan
doi.org/10.3390/polym15214338
gum for oil displacement in reservoirs up to 90 ◦ C and scleroglucan for oil displacement in reservoirs
Academic Editor: Raluca between 100 ◦ C and 140 ◦ C.
Nicoleta Darie-Nita
Keywords: diutan gum; xanthan gum; scleroglucan; rheological behavior; extreme reservoir; long-term
Received: 8 October 2023
stability
Revised: 1 November 2023
Accepted: 1 November 2023
Published: 6 November 2023

1. Introduction
Microbial polysaccharide is a substance produced by microorganisms during growth
Copyright: © 2023 by the authors.
and metabolism. It is a novel biopolymer possessing the physical and chemical properties of
Licensee MDPI, Basel, Switzerland.
thickening, emulsification, stability, and gelation, along with biocompatibility, sustainability,
This article is an open access article
and environmentally friendly features. This renders it highly versatile and useful in a
distributed under the terms and
variety of areas, including in food, petroleum, cement, textiles, and cosmetics [1–4]. In
conditions of the Creative Commons
the petroleum industry, biopolymers are widely used in oilfield drilling fluids, fracturing
Attribution (CC BY) license (https://
creativecommons.org/licenses/by/
fluids, and profile control and water plugging [1]. Drilling fluid is a multifaceted mixture
4.0/).
consisting of solids, liquids, and chemical agents. Xanthan gum, guar gum, starch, and

Polymers 2023, 15, 4338. https://doi.org/10.3390/polym15214338 https://www.mdpi.com/journal/polymers

Polymers 2023, 15, 4338 2 of 18

cellulose derivatives are commonly used biological viscosifiers in drilling fluids due to their
good viscosity-increasing properties. However, under extreme high-temperature and high-
salt circumstances, the fluid’s weaknesses, including poor thermal stability, weak shear
capacity, and reduced viscosity-increasing ability, become more evident [1,5–8]. Hydraulic
fracturing technology is a commonly employed method for modifying reservoirs. The
effectiveness of the fracturing fluid is crucial to the success of the operation. Biopolymers,
such as guar gum, are added to the fracturing fluid as thickeners with retarding properties.
Enhancing the temperature resistance of guar gum is achievable by modifying its molecular
chain and grafting it with rigid agents. To broaden its application scope, common cross-
linking agents include borate, Ti4+ , Zr4+ , and Al3+ [9,10]. As oilfield water plugging agents,
biopolymers not only improve the water absorption profile and displacement effect of
water injection wells but also expand the effective layers and directions of oil wells, thereby
overall improving oil recovery. Biopolymers currently used for water plugging and profile
control include modified starch, modified cellulose, guar gum, xanthan gum, chitosan,
etc. However, the majority of biopolymer plugging agents are currently still undergoing
laboratory research and are only being produced in small batches [1].
Currently, the majority of oil fields in China have entered the tertiary oil recovery
stage [11,12], among which, polymer flooding is widely used because it produces more oil
than other chemically enhanced oil recovery methods and is environmentally friendly. The
reservoir environment becomes increasingly hostile as the depth of reservoir formation
deepens, the concentration of formed water ions increases, and oil displacement technolo-
gies to alter the acidity and alkalinity of the reservoir proliferate, such as CO2 flooding,
alkali flooding, and ternary composite flooding. At present, polymer flooding is being
developed from use in medium- and low-temperature oil reservoirs to application in high-
temperature and high-salt oil reservoirs. However, the conditions of high-temperature and
high-salt oil reservoirs are complex; the oil displacement mechanism needs to be deepened,
and the compatibility of the oil displacement system is poor. There is an urgent need
for temperature and salt resistance and adaptability to harsh reservoir environments in
polymer oil-displacing agents [13]. The polymer oil displacement system commonly used
in oilfields is based predominately on partially hydrolyzed polyacrylamide (HPAM) and its
modified products [14–18]. This system has an excellent oil displacement effect in low- and
medium-temperature and low- and medium-mineralization reservoirs, but is subject to the
influence of temperature, mineralization, and acidity and alkalinity, and the environment
is prone to pollution. The use of biopolymers to improve the apparent viscosity of the oil
displacement system and to expand the efficiency of the wave and the effect of the system is
not weaker compared with HPAM, and they can be degraded in a safe and environmentally
friendly way.
In recent years, numerous oil fields have implemented microbial-enhanced oil recov-
ery technology (MEOR) to meet the requirements of green and efficient development. This
technology has received attention owing to its eco-friendly attributes, superior applicability,
and cost-effectiveness [19–23]. Zhou Hongtao [13] explored the feasibility of diutan gum,
welan gum, and xanthan gum as new polymers for oil repulsion; Zhang Xifeng [24] investi-
gated the static and dynamic rheological properties of a welan gum aqueous solution at a
formation temperature of 40 ◦ C and the factors affecting them; Karl-Jan [25] investigated
the rheology of schizophyllan, scleroglucan, guar gum, and xanthan gum in brines at con-
centrations ranging from 10 to 2300 mg/L, temperature levels ranging from 25 to 70 ◦ C, and
total dissolved solids concentrations of 30,100 mg/L and 69,100 mg/L; and Lai Nanjun [26]
investigated the rheological properties and the recovery-enhancing ability of diutan gum,
xanthan gum, and konjac gum at a temperature of 130 ◦ C and a mineralization level of
223.07 mg/L. However, less research has been carried out on the viscosity enhancement,
rheological properties, and long-term stability of the three biopolymers, namely, diutan
gum, xanthan gum, and scleroglucan, under extreme reservoir conditions.
The main objective of this paper is to explicitly determine the viscosity changes and
rheological properties, as well as the oil drive potential, of diutan gum, xanthan gum, and
Polymers 2023, 15, 4338 3 of 18

scleroglucan solutions under extreme reservoir conditions (high salt, high temperature, strong
acid, and alkali). Therefore, the viscosity concentration relationship, steady-state rheological
shear properties, linear viscoelastic region LVR and oscillatory frequency scanning, tempera-
ture resistance, salt resistance, acid and alkali resistance, and long-term stability in extreme
environments were investigated in detail. These properties were compared with each other to
provide technical support for the construction of a polymer oil displacement system.

2. Materials and Methods

2.1. Experimental Materials
Diutan gum and scleroglucan concentrate were supplied by Hebei Xinhe Bio-Chemical
Co., LTD. (Xinhe County, China), while xanthan gum was supplied by Meihua Bio-
Technology Group Co., LTD. (Langfang, China). The diutan gum was a light-yellow
colloid (effective content of 2%, molecular weight 5.2 × 106 Da); the scleroglucan was a
milky-white colloid (effective content 2%, molecular weight 1.3 × 105 ~6 × 106 Da); and the
xanthan gum was a light-yellow powder solid (effective content 90%, molecular weight
2 × 106 Da).
The biopolymer solution was prepared with six kinds of simulated brine with different
salinity levels. The 220 g/L simulated brine was the mother liquor, and the remaining five
simulated brines were diluted from the mother liquor. Their compositions are shown in
Table 1. The simulated brine preparation water was distilled water, and sodium chloride,
calcium chloride, magnesium chloride hexahydrate, sodium hydroxide, and hydrochloric acid
reagent grades were purchased from China Sinopharm Chemical Reagent Co., Ltd. Unless
otherwise specified, the biopolymer solutions were prepared using 6 g /L simulated saline.

Table 1. Simulated brine composition.

Composition (g/L) Total Mineralization

NaCl CaCl2 MgCl2 ·6H2 O (g/L)
192.5 16.5 11 220
148.75 12.75 8.5 170
70 6 4 80
21.875 1.875 1.25 25
13.125 1.125 0.75 15
5.3 0.45 0.3 6

2.2. Solution Preparation

2.2.1. Preparation Method for Diutan Gum and Scleroglucan
At room temperature (25 ◦ C), an appropriate amount of biopolymer concentrate was
placed in a beaker, a small amount of simulated brine was added, and the solution was stirred
at 1000 r/min for 10 min. The remaining simulated brine was added to finalize the solution
and it was stirred for another 3 h until the biopolymer was sufficiently dissolved to obtain the
biopolymer solution with the target mass concentration. The preparation water not mentioned
in the test experiments was simulated brine with a total mineralization of 6 g/L.

2.2.2. Preparation Method for Xanthan Gum

The simulated brine was first made to form a vortex at 800 r/min, and then the xanthan
gum powder was added slowly along the wall of the vortex. After all the xanthan gum was
added, it was stirred at 800 r/min for 30 min, and then the speed was lowered to 600 r/min
for continuous stirring until dissolution was complete.
Before testing, the solution was left at room temperature for 12 h to fully swell and
mature, allowing internal air bubbles to be eliminated to prevent interference with later
performance measurement research.
Polymers 2023, 15, 4338 4 of 18

2.3. Experimental Instruments

The Thermo Fisher Scientific Haake rotation rheometer MARS 60, equipped with two
test systems, a CC41 DG/Ti-02210522 double-cylinder test system and PZ DG 38 Ti high-
temperature sealed test system, was from Thermo Fisher Company, Germany; the Brookfield
viscometer was from the Brookfield Company of the United States; the electric blast drying
oven was from Shanghai Yiheng Scientific Instrument Co., Ltd., Shanghai, China; the Electric
constant- temperature water bath, was from Shanghai Boxun Medical Biological Instrument
Corp, Shanghai, China; the pH meter was from Shanghai INESA Scientific Instrument Co, Ltd.,
Shanghai, China; the cantilever electric stirrer instrument was from Shanghai Lichenbangxi
Instrument Technology Co., Ltd., Shanghai, China; and the electronic balance was from
Shanghai Zhuojing Electronic Technology Co., Ltd., Shanghai, China.

2.4. Experimental Test Methods

2.4.1. Viscosity Increase Performance Test
The apparent viscosities of the three biopolymer solutions at different concentrations
were determined at 20 ◦ C and 90 ◦ C to examine the relationship between apparent viscosity
and solution concentration. Three biopolymer solutions with a concentration of 1500 mg/L
were prepared according to the method described in Section 2.1 using 6 g/L of simulated
brine under two conditions to determine the apparent viscosity of the three biopolymer
solutions as a function of temperature: (1) in a temperature range of 20–90 ◦ C with a
shear rate of 7.34 s−1 using a CC41 DG/Ti–02210522 double-cylinder test system; and
(2) in a temperature range of 70–150 ◦ C with a shear rate of 250 s−1 using a PZ DG
38 Ti high-temperature confinement test system. The six simulated brines above, with
different mineralizations, were used to formulate biopolymer solutions at a concentration
of 1500 mg/L according to the method described in Section 2.1, and the apparent viscosity
changes of biopolymer solutions with different mineralizations at different temperatures
were determined. Three biopolymer solutions with a concentration of 1500 mg/L were
prepared using 6 g/L of simulated brine, and the viscosity changes with the pH of the three
biopolymer solutions were determined in the pH range of 3–10, at a temperature of 90 ◦ C
and a shear rate of 7.34 s−1 .

2.4.2. Rheological Properties Tests

All rheological properties, including steady-state rheological shear, oscillation ampli-
tude sweep, and oscillation frequency sweep tests, were performed on a Haake rotational
rheometer Haake MARS 60, using a CC41 DG/Ti-02210522 double-cylinder test system
and a PZ DG 38 Ti high-temperature closed testing system. All the tests were repeated at
least three times, and the relative deviation was less than 0.05%.
1. Steady-state rheological shear performance test.
The steady-state rheology of three biopolymer solutions was tested to examine the rela-
tionship between apparent viscosity and shear rate. The shear rate range was 0.01~1000 s–1 ,
the temperature was 90 ◦ C, and the temperature deviation was controlled at ±0.1 ◦ C;
the polymer solution mass concentration was 1500 mg /L. The measured steady-state
rheological curve was fitted using the power-law function (1):

η v = k · γ n −1 (1)

In the formula, ηv is the apparent viscosity; k is the consistency factor; n is the power-
law index, which is dimensionless; and γ is the shear rate in s –1 .
2. Linear viscoelastic zone LVR and oscillation frequency scanning tests.
First, strain amplitude scanning was performed on the three biopolymer solutions
to determine the linear viscoelastic region LVR of the solution. The concentration of
the prepared solution was 1500 mg /L, the oscillation frequency was fixed at 1 Hz, the
temperature was 90 ◦ C, and the strain was from 0.01% to 100%; after determining the linear
 power-law index, which is dimensionless; and 𝛾 is the shear rate in s .
2. Linear viscoelastic zone LVR and oscillation frequency scanning tests.
First, strain amplitude scanning was performed on the three biopolymer solutions to
determine the linear viscoelastic region LVR of the solution. The concentration of the
prepared solution was 1500 mg /L, the oscillation frequency was fixed at 1 Hz, the
Polymers 2023, 15, 4338 5 of 18
temperature was 90 °C, and the strain was from 0.01% to 100%; after determining the
linear viscoelastic zone L VR of the solution, the solution was then subjected to an
oscillation frequency scan test, in which the shear stress was fixed, and the frequency scan
was performedviscoelastic
in the rangezone L VR of the
of 0.01–10.00 Hz solution,
at 90 °C. the solution was then subjected to an oscillation
frequency scan test, in which the shear stress was fixed, and the frequency scan was
2.4.3. Long-term performed in the range of
Stability Performance 0.01–10.00 Hz at 90 ◦ C.
Test
A 1500 mg/L
2.4.3.quantity
Long-Termof Stability
diutan gum and 400Test
Performance mL of scleroglucan biopolymer
solution, respectively, were added to 20 high-temperature-resistant glass bottles with a
A 1500 mg/L quantity of diutan gum and 400 mL of scleroglucan biopolymer solution,
volume of 12 mL, into which nitrogen was injected and sealed to remove the dissolved
respectively, were added to 20 high-temperature-resistant glass bottles with a volume of
oxygen in the solution and prevent oxygen oxidation of the solution from interfering with
12 mL, into which nitrogen was injected and sealed to remove the dissolved oxygen in the
the apparent viscosity
solution data. Then the
and prevent glassoxidation
oxygen bottles containing the biopolymer
of the solution solution
from interfering with the apparent
were placed into
viscosity data. Then the glass bottles containing the biopolymer solution to
a 100 °C constant temperature oven to age and taken out at intervals were placed into
determine the apparent
a 100 ◦ C viscosity.
constant temperature oven to age and taken out at intervals to determine the
apparent viscosity.
3. Results
3.1. Comparison3.ofResults
the Viscosity‐Increasing Properties of Three Biopolymers
3.1. Comparison Relationships
3.1.1. Viscosity Concentration of the Viscosity-Increasing Properties of Three Biopolymers
of Three Biopolymers
3.1.1. Viscosity Concentration Relationships of Three Biopolymers
The apparent viscosities of the three biopolymer solutions were measured at a shear
rate of 7.34 s−1 andThe apparent viscosities
temperatures of the90three
of 20 °C and °C. Asbiopolymer solutions
can be seen were1,measured
in Figure the at a shear
rate of 7.34 s −1 and temperatures of 20 ◦ C and 90 ◦ C. As can be seen in Figure 1, the
apparent viscosities of all three biopolymer solutions increased with the increase in
apparentbut
solution concentration, viscosities of all three
the apparent biopolymer
viscosities of the solutions
biopolymerincreased with
solutions the increase in solution
increased
concentration, but the apparent viscosities of the biopolymer
to different extents at different temperatures for different concentrations. For example, solutions increased
at to different
extents at different temperatures for different concentrations. For example, at 90 ◦ C, all three
90 °C, all three biopolymer solutions had a concentration of 2500 mg/L, and the apparent
viscosities werebiopolymer
223.8 mPa·s solutions had agum,
for diutan concentration
169.45 mPa·sof 2500
formg/L, and the apparent
scleroglucan, and 121.7viscosities were
223.8 mPa · s for diutan gum, 169.45 mPa · s for scleroglucan,
mPa·s for xanthan gum; the apparent viscosities of the diutan gum and scleroglucan and 121.7 mPa·s for xanthan
gum; the apparent viscosities of the diutan gum and scleroglucan solution were nearly
solution were nearly 1.84 times and 1.39 times that of xanthan gum, respectively. Figure 2
1.84 times and 1.39 times that of xanthan gum, respectively. Figure 2 is the change curve
is the change curve of the biopolymer solution concentration with apparent viscosity ◦at
of the biopolymer solution concentration with apparent viscosity at 90 C. To ensure the
90 °C. To ensure the solution has the same apparent viscosity (100 mPa·s), it is necessary
solution has the same apparent viscosity (100 mPa·s), it is necessary to add 1414 mg/L of
to add 1414 mg/L of diutan gum or 1725 mg/L of scleroglucan, while for xanthan gum, a
diutan gum or 1725 mg/L of scleroglucan, while for xanthan gum, a higher concentration is
higher concentration is needed and, under the same conditions, is necessary to achieve
needed and, under the same conditions, is necessary to achieve the same apparent viscosity,
the same apparent viscosity, which is about 2140 mg/L.
which is about 2140 mg/L.

(a) (b)
Figure 1. Variation in apparent viscosity of the biopolymer solution with concentration at 20 ◦ C (a),
and 90 ◦ C (b).

The diutan gum solution showed better viscosity thickening than the xanthan gum
and scleroglucan solutions. This was due to the high molecular weight of diutan gum,
the increase in the entanglement of the polymer chains at high concentrations, the corre-
sponding increase in apparent viscosity, and the formation of agglomerates at low shear
rates (7.34 s−1 ) by entangling the stretched molecules with each other, resulting in a greater
resistance to fluid flow and leading to a better viscosity enhancement effect. This is similar
to the findings of Xu [2], Holzwarth [27], and G.P. Mota [28].
Polymers 2023, 15, x FOR PEER REVIEW 6 of 19

Polymers 2023, 15, 4338 6 of 18

Figure 1. Variation in apparent viscosity of the biopolymer solution with concentration at 20 °C (a),
and 90 °C (b).

Figure
Figure 2.
2. Variation
Variation in
in the
the biopolymer
biopolymer solution ◦ C.
solution concentration with apparent viscosity at 90 °C.

3.1.2.The
Temperature
diutan gum Resistance
solution Performance
showed better Test
viscosity thickening than the xanthan gum
The solutionssolutions.
and scleroglucan of diutanThisgum,wasxanthan
due togum, andmolecular
the high scleroglucan wereofprepared
weight at a con-
diutan gum, the
centrationinof 1500
increase mg/L, and the apparent
the entanglement viscosity versus
of the polymer chains temperature curves of the three
at high concentrations, the
biopolymer solutions
corresponding increasewere measuredviscosity,
in apparent at a low shear
and rate (7.34 s−1 ) and
the formation a temperatureatrange
of agglomerates low
of 20–90 ◦ C, as shown
shear rates (7.34 s−1) byinentangling
Figure 3. It can
the be seen molecules
stretched that all three polymer
with solutions
each other, exhibited
resulting in a
greater resistance to fluid flow and leading to a better viscosity enhancement effect. with
thermal thinning behavior [29]: the apparent viscosity decreased to varying degrees This
increasing
is similar totemperature,
the findings with
of Xuthe
[2],apparent
Holzwarth viscosity of diutan
[27], and gum[28].
G.P. Mota and scleroglucan solu-
tions decreasing to a lesser extent, from 105.6 mPa·s and 96.28 mPa·s at the initial 20 ◦ C to
Polymers 2023, 15, x FOR PEER REVIEW mPa·s and 85.21
94.17 Temperature
3.1.2. 90 ◦ C, whereasTest
mPa·s at Performance
Resistance the apparent viscosity of xanthan 7 of
gum19 solution

decreased further, from 78.12 mPa ·s at the initial ◦

20 and 47.42 mPa·s atwere
C to scleroglucan ◦
90 C.prepared at a
The solutions of diutan gum, xanthan gum,
concentration of 1500 mg/L, and the apparent viscosity versus temperature curves of the
three biopolymer solutions were measured at a low shear rate (7.34 s−1) and a temperature
range of 20–90 °C, as shown in Figure 3. It can be seen that all three polymer solutions
exhibited thermal thinning behavior [29]: the apparent viscosity decreased to varying
degrees with increasing temperature, with the apparent viscosity of diutan gum and
scleroglucan solutions decreasing to a lesser extent, from 105.6 mPa·s and 96.28 mPa·s at
the initial 20 °C to 94.17 mPa·s and 85.21 mPa·s at 90 °C, whereas the apparent viscosity of
xanthan gum solution decreased further, from 78.12 mPa·s at the initial 20 °C to 47.42
mPa·s at 90 °C.

Figure
Figure3.3.Variation in in
Variation thethe
apparent viscosity
apparent of theof
viscosity biopolymer solutions
the biopolymer with temperature
solutions at a shear at a shear
with temperature
rate of 7.34 s−1.−1
rate of 7.34 s .
Figure 4 shows the apparent viscosity retention φ (φ, the ratio of apparent viscosity
Figure 4 shows the apparent viscosity retention ϕ (ϕ, the ratio of apparent viscosity at
at different temperatures to the initial apparent viscosity at 20 °C) of ◦the three biopolymer
different temperatures to the initial apparent viscosity at 20 C) of the three biopolymer
solutions at temperatures ranging from 20 to 90 °C and ◦ C at a shear rate of 7.34 s−1. The −1
apparent viscosity retention φ of diutan gum and scleroglucan solution changed slightly s . The
solutions at temperatures ranging from 20 to 90 and at a shear rate of 7.34
apparent
with viscosity
the increase retention ϕwhile
in temperature, of diutan gum and
the retention φ ofscleroglucan solutiongradually
xanthan gum solution changed slightly
with the increase
decreased and theindecrease
temperature, while Additionally,
was larger. the retention at
ϕ ofthexanthan gum solution
same temperature, thegradually
decreased
apparent and theretention
viscosity decrease was
φ of larger.
diutan gumAdditionally, at the
and scleroglucan same temperature,
solution the apparent
was always higher
than that of xanthan gum, and the apparent viscosity retention φ of the diutan gum and
scleroglucan solution were 89.18% and 88.50%, respectively, while that of the xanthan
gum solution was only 60.70% at the temperature of 90 °C.
 Figure 3. Variation in the apparent viscosity of the biopolymer solutions with temperature at a shear
rate of 7.34 s−1.

Figure 4 shows the apparent viscosity retention φ (φ, the ratio of apparent viscosity
at different temperatures to the initial apparent viscosity at 20 °C) of the three biopolymer
Polymers 2023, 15, 4338 solutions at temperatures ranging from 20 to 90 °C and at a shear rate of 7.34 s−1. The 7 of 18
apparent viscosity retention φ of diutan gum and scleroglucan solution changed slightly
with the increase in temperature, while the retention φ of xanthan gum solution gradually
decreased and the decrease was larger. Additionally, at the same temperature, the
viscosity retention ϕ of diutan gum and scleroglucan solution was always higher than that
apparent viscosity retention φ of diutan gum and scleroglucan solution was always higher
of xanthan
than that of gum,
xanthanand the and
gum, apparent viscosity
the apparent retention
viscosity ϕ of the
retention φ ofdiutan gumgum
the diutan and and
scleroglucan
solution were 89.18% and 88.50%, respectively, while that of the xanthan
scleroglucan solution were 89.18% and 88.50%, respectively, while that of the xanthangum solution was
only 60.70% at the temperature of 90 ◦ C.
gum solution was only 60.70% at the temperature of 90 °C.

Figure
Figure4.4.Apparent
Apparent viscosity retention
viscosity rate rate
retention (φ) of(ϕ)
biopolymer solutions
of biopolymer at different
solutions temperatures
at different temperatures
under a shear rate of 7.34 s−1. −1
under a shear rate of 7.34 s .
Under the above experimental conditions, the CC41 DG/ Ti-02210522 two-barrel test
Under the above experimental conditions, the CC41 DG/Ti-02210522 two-barrel test
system of the Haake Rheometer was used, and the temperature limit of this system was
system of the Haake Rheometer was used, and the temperature limit of this system was
90 ◦ C. For the higher temperature range, a Haake Rheometer PZ DG 38 Ti high-temperature
confinement test system was used. However, this test system is only suitable for high shear
rates (>170 s−1 ), so the apparent viscosity of the three biopolymer solutions was tested as a
function of temperature in the temperature range of 70–150 ◦ C and at a shear rate of 250 s−1 .
As shown in Figures 5 and 6, between 70 and 150 ◦ C, it can be seen that the apparent
viscosity of the diutan gum and xanthan gum solutions decreased significantly with in-
creasing temperature, while the apparent viscosity of the scleroglucan solution, on the other
hand, increased slightly. Compared with 70 ◦ C, at 150 ◦ C, the apparent viscosity retention
rates ϕ of diutan gum and xanthan gum solutions were only 44.83% and 19.3%, respectively,
while the scleroglucan solution had an apparent 118.27% viscosity retention rate, and was
still able to maintain a higher apparent viscosity under the ultra-high temperature.
It is clear that diutan gum and scleroglucan are less sensitive to temperature than
xanthan gum. Within 20–70 ◦ C, the apparent viscosity value and the degree of temperature
stability of the solutions of diutan gum and scleroglucan were always better than those of
xanthan gum, and as can be seen in Figures 5 and 6, at 100 ◦ C, the apparent viscosity of
diutan gum was 17.39 mPa·s and the apparent viscosity retention rate was 89.00%, but at
110 ◦ C, its apparent viscosity retention rate was only 67.40%, which was a large decrease. It
can be concluded that the diutan gum was tolerant to the 100 ◦ C high temperature. On the
other hand, the xanthan gum solution, with apparent viscosity retention rates of 74.80% and
57.32% at 100 ◦ C and 110 ◦ C, respectively, had poor temperature resistance. Meanwhile, the
apparent viscosity of scleroglucan increased with temperature in the range of 70–150 ◦ C,
proving that its temperature resistance was superior.
Commonly, the entanglement of biological macromolecules and the strength of poly-
mer networks are predominately formed by van der Waals forces and hydrogen bonds [30].
An increase in temperature accelerates the movement of molecules and distorts a large
number of hydrogen bonds, leading to a gradual loss of the second nearest-neighbor spatial
correlation and weakening the van der Waals forces and hydrogen bonds [2,31]. At high
temperatures, water molecules in the molecular chain escape easily due to the weakening
of hydrogen bonds and the thermal motion of the molecules.
 viscosity of the diutan gum and xanthan gum solutions decreased significantly with
increasing temperature, while the apparent viscosity of the scleroglucan solution, on the
other hand, increased slightly. Compared with 70 °C, at 150 °C, the apparent viscosity
retention rates φ of diutan gum and xanthan gum solutions were only 44.83% and 19.3%,
respectively, while the scleroglucan solution had an apparent 118.27% viscosity retention
Polymers 2023, 15, 4338 8 of 18
rate, and was still able to maintain a higher apparent viscosity under the ultra-high
temperature.

Figure 5. Variation
Variation in
inthe
theapparent
apparentviscosity
viscosityofof biopolymer
biopolymer solutions
solutions with
with temperature
temperature at aat a shear
shear rate
− 1 −1.
rate of 250
of 250 s . s −1.

Figure 6. Apparent
Figure 6. Apparent viscosity
viscosity retention
retention rate (φ) of
rate (ϕ) of biopolymer
biopolymer solutions
solutions at
at different
different temperatures
temperatures
under a shear rate of 250 s −11
−
−1
under a shear rate of 250 s . .

In the xanthan gum solution, the reticular structure existed at 20 ◦ C but had been de-
stroyed by 90 ◦ C. Water molecules adhering to the edges of the double helix detached from
the molecular chain, leading to a decrease in water retention. Meanwhile, xanthan gum
molecules underwent a conformational transition from an ordered double-helical structure
to a disordered helical structure in the process of temperature increase, weakening the
association between molecular chains, and the apparent viscosity gradually decreases [2,13].
Due to the rigidity of the molecular chain, the double-helix structure of diutan gum could
still maintain its conformation well at higher temperatures (≤100 ◦ C), and a large number
of water molecules were still tightly trapped in the double-helix structure due to the strong
internal force, so it had strong temperature resistance [2,28,29]. The molecular chain of
scleroglucan has a triple-helix structure in aqueous solution, and this structure, due to
the stabilization of intramolecular and intermolecular hydrogen bonding, results in scle-
roglucan exhibiting a strong stability over a wide range of temperatures (≤150 ◦ C) [32–35],
which is also approximate to the findings of Kalpakci [36] et al. Therefore, it can be con-
Polymers 2023, 15, 4338 9 of 18

cluded that diutan gum and scleroglucan solutions have better temperature resistance
compared with xanthan gum solutions.

3.1.3. Comparison of Salt Resistance of Three Biopolymers

To investigate the salt resistance of the three biopolymer solutions at different tempera-
tures, six simulated brines with different mineralizations were prepared for the formulation
of 1500 mg/L biopolymer solutions, and the changes in apparent viscosity with mineraliza-
tion were determined at 20 ◦ C, 55 ◦ C, and 90 ◦ C, as shown in Figures 7–9, with a shear
Polymers 2023, 15, x FOR PEER REVIEW
rate
10 of 19
of 7.34 s−1 . Moreover, Figure 10 shows the curve of viscosity retention ϕ of the biopolymer
solution as a function of mineralization at 90 ◦ C.

Figure 7. Variation in apparent viscosity of biopolymer solutions as a function of salinity at 20 ◦°C.

C.

Figure 8. Variation in apparent viscosity of biopolymer solutions as a function of salinity at 55 ◦°C.

C.

It can be seen that at these three temperatures, when the mineralization of the biopoly-
mer solution was increased from 6 g/L to 220 g/L, the apparent viscosity of the diutan
gum solution essentially remained high and unchanged, and the viscosity retention ϕ was
still maintained at 90.12% at 90 ◦ C. The apparent viscosity of the scleroglucan solution
decreased slightly, with a viscosity retention ϕ of 70.04% at 90 ◦ C. The apparent viscos-
ity of the xanthan gum solution decreased relatively significantly from 47.42 mPa·s to
11.57 mPa·s, with a viscosity retention ϕ of only 24.40% at 90 ◦ C.
Polymers 2023, 15, 4338 10 of 18

Figure 8. Variation in apparent viscosity of biopolymer solutions as a function of salinity at 55 °C.

Polymers 2023, 15, x FOR PEER REVIEW 11 of 19

90 ◦°C.
Figure 9. Variation in apparent viscosity of biopolymer solutions as a function of salinity at 90 C.

Figure
Figure 10.
10. Variation inviscosity
Variation in viscosityretention
retention rate
rate φ biopolymer
ϕ of of biopolymer solutions
solutions as a function
as a function at 90 ◦ C.
of salinity
of salinity at
90 °C.
Diutan gum and xanthan gum are polyelectrolytes, which are polyanions in aqueous
solution
It can [29,37,38].
be seen For that anionic
at thesepolyelectrolytes,
three temperatures, cationswhen(Na+the 2+ , and Mg2+ ) in the
, Camineralization of
simulated brine
biopolymer play two
solution wasmain negative
increased from roles:
6 g/L (1)toshielding
220 g/L,electrostatic
the apparent repulsion
viscositybetween
of the
chargedgum
diutan groups of macromolecules,
solution enablinghigh
essentially remained macromolecules
and unchanged, to adoptandmore compact
the viscosity
conformations;
retention φ was and (2) maintained
still densifying the at hydration
90.12% at layer 90 °C.around the biopolymer
The apparent molecules,
viscosity of the
thus reducingsolution
scleroglucan the apparent viscosity
decreased of diutan
slightly, with gum and xanthan
a viscosity retentiongum φ solutions
of 70.04%[2,29,39].
at 90 °C.
The side viscosity
The apparent chains ofofthe thediutan
xanthan gumgum molecules are entangled
solution decreased insidesignificantly
relatively the main chains,
from
and the shielding effect of inorganic cations is limited, which
47.42 mPa·s to 11.57 mPa·s, with a viscosity retention φ of only 24.40% at 90 °C. has no effect on the water
molecules
Diutanwrapped
gum andinxanthanthe coregumof thearedouble helix; on the
polyelectrolytes, otherare
which hand, xanthanin
polyanions gum has a
aqueous
disordered conformation in pure water or low-concentration simulated
solution [29,37,38]. For anionic polyelectrolytes, cations (Na+, Ca2+, and Mg2+) in the brine, and as the
mineralization
simulated brine level increases,
play two main xanthan gum starts
negative roles:to (1)
show an ordered
shielding conformation
electrostatic due to
repulsion
the charge shielding effect. Meanwhile, according to Long
between charged groups of macromolecules, enabling macromolecules to adopt more Xu‘s study [2], the presence of
inorganic salts did not change the viscoelastic properties of the
compact conformations; and (2) densifying the hydration layer around the biopolymer diutan gum, and the elastic
componentthus
molecules, was reducing
still dominant, while the
the apparent dynamic
viscosity modulus
of diutan gum of and
xanthan
xanthangumgum wassolutions
reduced,
which indicated
[2,29,39]. that the diutan gum solution had a better resistance to high salt.
Scleroglucan
The side chains is a of
non-ionic
the diutanwater-soluble
gum moleculesbiopolymer producedinside
are entangled by Sclerotium
the main rolfsii [40].
chains,
Due to its peculiar rigid triple-helix rod structure, the molecules
and the shielding effect of inorganic cations is limited, which has no effect on the waterin scleroglucan solutions
are virtually independent of the ionic environment, and thus, are insensitive to solution
molecules wrapped in the core of the double helix; on the other hand, xanthan gum has a
salinity [29,41].
disordered conformation in pure water or low-concentration simulated brine, and as the
mineralization level increases, xanthan gum starts to show an ordered conformation due
to the charge shielding effect. Meanwhile, according to Long Xu‘s study [2], the presence
of inorganic salts did not change the viscoelastic properties of the diutan gum, and the
elastic component was still dominant, while the dynamic modulus of xanthan gum was
Polymers 2023, 15, 4338 11 of 18

3.1.4. Comparisons of the Acid and Alkali Resistance of Three Biopolymers

Polymers 2023, 15, x FOR PEER REVIEW Most of reservoirs are in a neutral environment, but gas flooding in tertiary12oil of re-
19
covery, especially CO2 flooding, changes the reservoir’s acid-base environment, putting
the reservoir in an acidic environment, while some fields use alkali flooding or ternary
composite flooding, bringing the reservoir into an alkaline environment. Therefore, it is
Three biopolymer
essential to study the solutions were
effect of pH prepared with simulated
on the apparent viscositybrine
of thewith a salinitysolutions.
biopolymer of 6 g/L
at different pH levels.
Three biopolymer solutions were prepared with simulated brine with a salinity of 6 g/L at
The pH
different apparent
levels. viscosity of the biopolymer solutions changed with pH at 90 °C, as
shown Theinapparent
Figure 11. The apparent
viscosity viscosities solutions
of the biopolymer of the three biopolymer
changed with pH solutions were
at 90 ◦ C, as
almost unchanged in the pH range of 5–7, and the apparent viscosities
shown in Figure 11. The apparent viscosities of the three biopolymer solutions were almost of the three
biopolymer
unchanged in solutions
the pH decreased
range of 5–7,to different degrees in
and the apparent a more acidic
viscosities of the environment.
three biopolymer The
xanthan gum solution decreased to a large extent (19.05%), followed
solutions decreased to different degrees in a more acidic environment. The xanthan gum by diutan gum and
scleroglucan;
solution decreasedin antoalkaline environment,
a large extent (19.05%),the apparent
followed viscosity
by diutan gumof and
the scleroglucan;
scleroglucan
solution slightly
in an alkaline increased (up
environment, 8.34%), the
the apparent diutan ofgum
viscosity solution was solution
the scleroglucan stable, and the
slightly
apparent
increasedviscosity
(up 8.34%), of the
thexanthan
diutan gumgumsolution
solution was
slightly decreased,
stable, and the which
apparentwasviscosity
due to theof
destruction of the xanthan gum part of the intramolecular and intermolecular
the xanthan gum solution slightly decreased, which was due to the destruction of the hydrogen
bonding gum
xanthan by the partstrong
of thealkali [13,42]. However,
intramolecular the diutan hydrogen
and intermolecular gum molecules bonding were
by not
the
destroyed. The stability of scleroglucan’s acid-base resistance is due
strong alkali [13,42]. However, the diutan gum molecules were not destroyed. The stability to its non-ionic
properties and molecular
of scleroglucan’s acid-base rigidity. Thereisare
resistance duehydroxyl groups inproperties
to its non-ionic the glucose andunit, and the
molecular
triple-helix structure
rigidity. There is stabilized
are hydroxyl through
groups in theinterchain hydrogen
glucose unit, bonds,
and the so its structure
triple-helix structurewillis
not changethrough
stabilized due to the acid-base
interchain environment
hydrogen bonds,[35]. Diutan
so its gumwill
structure and notscleroglucan
change due solution
to the
viscosity
acid-basewas not very affected
environment by alkali
[35]. Diutan gum concentration.
and scleroglucan Thay can beviscosity
solution used in awaswidenotrange
very
of alkalibyconcentrations
affected and can
alkali concentration. Thay becan used in oil
be used in afields
wide to improve
range of alkalioilconcentrations
recovery by
compounding
and can be used with alkalis.
in oil fields to improve oil recovery by compounding with alkalis.

Figure 11. Variation

Figure 11. Variation in
in apparent viscosity of
apparent viscosity of biopolymer
biopolymer solutions
solutions with
with pH
pH at
at 90
90 ◦°C.
C.

3.2. Rheological
3.2. Rheological Properties
Properties of
of Three
Three Biopolymers
Biopolymers
3.2.1. Steady-State Rheological Shear Test
3.2.1. Steady-State Rheological Shear Test
Steady-state rheological
Steady-state rheological shear
shear tests
tests were performed on
were performed the biopolymer
on the biopolymer solutions,
solutions, and
and
Figure 12 shows the flow curves of the biopolymer solutions at a temperature of 90 ◦ C (with
Figure 12 shows the flow curves of the biopolymer solutions at a temperature of 90 °C
shear rates in the range of 0.01–1000 s−1 ), comparing the apparent viscosity of diutan gum,
(with shear rates in the range of 0.01–1000 s−1), comparing the apparent viscosity of diutan
xanthan gum, and scleroglucan solutions as a function of shear rate. It can be seen that at
gum, xanthan gum, and scleroglucan solutions as a function of shear rate. It can be seen
elevated temperatures, the apparent viscosities of all three biopolymer solutions decreased
that at elevated temperatures, the apparent viscosities of all three biopolymer solutions
with increases in shear rate and showed a strong shear thinning behavior, which was an
decreased with increases in shear rate and showed a strong shear thinning behavior,
obvious pseudoplastic fluid behavior. At the same time, the apparent viscosities of the
which was an obvious pseudoplastic fluid behavior. At the same time, the apparent
three biopolymer solutions did not differ greatly at high shear rates (greater than 100 s−1 ),
viscosities of the three biopolymer solutions did not differ greatly at high shear rates
and the apparent viscosities of the diutan gum and scleroglucan solutions were higher than
(greater than 100 s−1), and the apparent viscosities of the diutan gum and scleroglucan
solutions were higher than that of the xanthan gum solution at low shear rates (less than
100 s−1). This is due to the fact that this shear-thinning property is closely related to the
state of molecular aggregation or dispersion in the shear flow [43]. Biopolymer molecules
normally exist as aggregates at low shear rates, but when the shear rate increases, the
 themselves along the direction of flow. The result is a decrease in apparent viscosity, and
the molecular weights of diutan gum and scleroglucan are larger relative to those of
xanthan gum, which can exhibit higher viscosities at low shear rates [3,44].
Table 2 shows the parameters of the power-law model for the apparent viscosity
Polymers 2023, 15, 4338 versus the shear rate of diutan gum, xanthan gum, and scleroglucan solutions at 12 90of°C.
18
The power-law model fits well (R > 0.99) for the pseudoplastic behavior of xanthan gum,
2

diutan gum, and scleroglucan solutions in the range of shear rates from 0.01 to 1000 s−1,
and has
that of thebeen used numerous
xanthan gum solution timesatby lowother
shearresearchers
rates (lesstothan fit the
100 relationship
s−1 ). This is between
due to the the
apparent viscosity and shear rate of biopolymer solutions [2,28,39,41,45,46].
fact that this shear-thinning property is closely related to the state of molecular aggregation As shown in
Table
or 2, the in
dispersion power rate flow
the shear exponent n of all three
[43]. Biopolymer was less
molecules than 1,
normally which
exist indicates
as aggregates
Polymers 2023, 15, x FOR PEER REVIEW 13 of 19
pseudoplastic
at low shear rates, fluidbutbehavior
when the remains,
shear andrate the consistency
increases, exponent gradually
the aggregates k of the diutan gum
dissociate
Polymers 2023, 15, x FOR PEER REVIEW
and scleroglucan
under shear and the solutions wasmolecules
individual larger than that of the
rearrange xanthan gum
themselves alongsolution,
the directionas13shown
of 19
in
of flow.
Polymers 2023, 15, x FOR PEER REVIEW Figure 12. The apparent viscosity of diutan gum and hard scleroglucan solution 13 of 19was
The result is a decrease in apparent viscosity, and the molecular weights of diutan gum
themselves
higher
and along the with
compared
scleroglucan direction
that of
are larger of flow.
relative The
the xanthan result
to thosegum is solution,
of a decrease
xanthan andin apparent
gum, the viscosity,
strengths
which can and
of thickening
exhibit higher
the molecular
themselves
performances
viscosities weights
along the
at low of diutan
direction
of the
shearthree
rates gum
of[3,44].
were flow. and scleroglucan
The result
as follows: diutanis a gum are
decrease larger relative to
in apparent> viscosity,
> scleroglucan those
xanthan gum. andof
xanthan
themselves gum,
the molecular which
along the can
weights ofexhibit
diutan
direction ofhigher
gum The
flow. viscosities
andresult isatalow
scleroglucan shear rates
are larger
decrease in [3,44].
relative
apparent to thoseand
viscosity, of
Table
xanthan
the molecular 2 shows
gum, which
weightsthe
canofparameters
exhibit
diutanhigher
gumof the
andpower-law
viscosities at low
scleroglucan model
shear for the[3,44].
rates
are larger apparent
relative to viscosity
those of
versus
xanthan the
Table 2shear
gum, shows ratethe
which of parameters
can diutan
exhibitgum,
higherofxanthan
the gum,
power-law
viscosities at and scleroglucan
model
low shearfor solutions viscosity
the[3,44].
rates apparent at 90 °C.
The power-law
versus the shear model
rate fits
of well
diutan (R 2 > 0.99) for the pseudoplastic behavior of xanthan gum,
gum, xanthan gum, and scleroglucan
Table 2 shows the parameters of the power-law model for the apparent viscosity solutions at 90 °C.
diutan
versus gum,
The power-law and
the shearmodel scleroglucan
rate offits solutions
well (R
diutan 2
gum,> 0.99) in the
for the
xanthan range
gum, of shear
pseudoplastic rates
and scleroglucan from
behavior 0.01 to
of xanthan
solutions 1000
at 90 s−1,
gum,
°C.
and
The has
diutan been and
gum,
power-law used numerous
scleroglucan
model fits welltimes
(R >by
solutions
2 other
0.99) in researchers
forthe
therange of to fit the
shear
pseudoplastic relationship
rates fromof0.01
behavior between
to 1000
xanthan the
s−1,
gum,
apparent
and hasgum,
diutan viscosity
been and and shear times
usedscleroglucan
numerous rate ofby
solutionsbiopolymer
other solutions
researchers
in the range of to [2,28,39,41,45,46].
fit
shear the relationship
rates from 0.01 As toshown
between1000 thesin
−1,

Tablehas2,been
apparent
and the power
viscosity
used andrate
shear
numerous exponent
rate ofby
times nother
of all
biopolymer three was
solutions
researchers less
thethan 1, which
[2,28,39,41,45,46].
to fit relationship As indicates
shown
between in
the
pseudoplastic
Table
apparent2, the fluidand
power
viscosity behavior
rate
shear remains,
exponent nandof the
rate of biopolymer all consistency
three exponent
than k1,ofwhich
was [2,28,39,41,45,46].
solutions less theAsdiutan gum
indicates
shown in
and scleroglucan
pseudoplastic
Table solutions
fluid behavior
2, the power was larger
remains,nand
rate exponent than that
of the of the
all consistency xanthan
three was less gum
exponent solution,
than k1,ofwhich as
the diutanshown gum
indicates in
Figure
and 12. Thefluid
scleroglucan
pseudoplastic apparent
solutions
behavior viscosity
was larger
remains, of than
diutan
and thatgum
the of the and
consistency hard
xanthan scleroglucan
k of thesolution
gum solution,
exponent as shown
diutan was
gum in
higher
Figure compared
and scleroglucan with thatviscosity
12. The apparent
solutions of the
was xanthan
larger of than
diutangum
thatgum solution,
of theand and the
hard
xanthan strengths
solution,of
scleroglucan
gum asthickening
solution
shown wasin
performances
higher 12. Theofapparent
Figure compared the three
with were as xanthan
thatviscosity
of the follows:
of diutan diutan
gum gum gumand> hard
solution, scleroglucan
and the > xanthan
strengths
scleroglucan of gum.was
thickening
solution
performances
higher compared of the three
with thatwere as xanthan
of the follows: gumdiutan gum > scleroglucan
solution, and the strengths > xanthan gum.
of thickening
performances of the three were as follows: diutan gum > scleroglucan > xanthan gum.

Figure 12. Variation in apparent viscosity of biopolymer solutions with

with shear
shear rate
rate at 90 ◦°C.
at 90 C.

TableTable 2 shows
2. Power-law the parameters
model parameters ofof the power-law
biopolymer model
solutions for the apparent viscosity
at 90 °C.
versus then shear rate of diutan gum, xanthan gum, and scleroglucan solutions at 90 ◦−1C.
Biopolymer Type K (mPa·s ) n 2 R2 Shear Rate Range (s )
The power-law model fits well (R > 0.99) for the pseudoplastic behavior of xanthan gum,
Diutan gum 444.06
diutan gum, and scleroglucan0.250
solutions in the range0.9908 0.01002
of shear rates from 0.01 < 1000
< to 1000 s−1 ,
Scleroglucan and334.93
has been used numerous times by other researchers
0.248 0.9985to fit the relationship
0.01001 < between
< 1000the
apparent viscosity and shear rate of biopolymer solutions [2,28,39,41,45,46]. As shown in
Xanthan gum 186.10
Table 0.305n of all three was less
2, the power rate exponent 0.9956 0.01003 pseudoplastic
than 1, which indicates < < 1000
fluid behavior remains, and the consistency exponent k of the diutan gum and scleroglucan
3.2.2. Linear
solutions was Viscoelastic
larger thanZone
that LVR Test
of the xanthan gum solution, as shown in Figure 12. The
apparent viscosity of diutan gum and hard scleroglucan
A dynamic rheological test of the biopolymer solutionssolution
is used was higher
to better compared
evaluate their
with that of the xanthan gum solution, and the strengths of thickening
structure. The methods commonly used to examine the structure of the solutions performances of are
the
three
Figure were
oscillatory as
12. Variationfollows:
amplitude diutan
scans
in apparent gum > scleroglucan
andofoscillatory
viscosity > xanthan
frequency
biopolymer solutions with gum.
scans. Oscillation
shear rate at 90 °C. amplitude
scanning
Figure is first
12. Variation used to viscosity
in apparent determine the linearsolutions
of biopolymer viscoelastic region
with shear rateLVR
at 90of °C.biopolymer
Table
Table 2. 2. Power-law
Power-law modelmodel parameters
parameters of of biopolymer
biopolymer solutions
solutions at 90 90 ◦ C.
at°C.
Figure 12. Variation in apparent viscosity of biopolymer solutions with shear rate at 90 °C. frequency
solutions because, in general, the appropriate strain applied by oscillation
Table 2. Power-law
scanning model
n) mustType
parameters
be within of biopolymer solutions at[39,47].
90 °C.
Biopolymer Type Biopolymer
K (mPa·s K the
(mPalinear
n ·sn )
viscoelastic
n region
R2 R2 Shear Rate
Shear Rate Range
Range(s(s−1−1)
)
An high plateau
Table 2. Power-law model of elastic modulus
parameters G’ independent
of biopolymer solutions at of
90 shear
°C. stress τ or shear strain is
Biopolymer Type
Diutan gum K 444.06
(mPa·s )
Diutan gum n
0.250
444.06 0.250 R 2
0.9908
0.9908 Shear
0.01002 Rate
0.01002 Range
<< <<1000 (s
1000 −1)
considered to be the linear viscoelastic region. The linear viscoelastic regions of the three
Biopolymer Type K 444.06
(mPa·s n) n R0.9985
2 Shear
0.01002 Rate Range (s−1)
Diutan gum
Scleroglucan 334.93 Scleroglucan
biopolymer solutions are 0.250
334.93 in Figure
shown
0.248 0.248 0.9908
13, which shows that a0.01001
0.9985 0.01001
linear <<< <<<1000
1000
viscoelastic
1000region
Diutan gum 444.06 Xanthan
existed for diutan 0.250
gum gum, scleroglucan,
186.10 0.305
and xanthan0.9908
0.9956 0.01002
0.01003
gum, and that 0.01001
the modulus<< <<<of 1000
1000
elasticity,
Scleroglucan
Xanthan gum 334.93
186.10 0.248
0.305 0.9985
0.9956 0.01003 << < 1000
1000
G’, remained virtually constant 0.248 with increasing0.9956 shear stress, τ, until it reached
0.01001 the critical
Scleroglucan
Xanthan gum 334.93
186.10 0.305 0.9985 0.01003 << << 1000
1000
3.2.2. Linear Viscoelastic Zone LVR Test
Xanthan gum 186.10
3.2.2. Linear Viscoelastic Zone 0.305
LVR Test 0.9956 0.01003 < < 1000
A dynamic rheological test of the biopolymer solutions is used to better evaluate
3.2.2.ALinear
dynamic Viscoelastic
rheological Zone LVR
test of Test
the biopolymer
their structure. The methods commonly used tosolutions
examineistheused to better
structure ofevaluate their are
the solutions
3.2.2.ALinear
structure. The
dynamic Viscoelastic
methods
rheological Zone LVR
commonly
test of Test
theused to examine
biopolymer the
solutions structure
is used toof the
better solutions
evaluate are
their
oscillatory amplitude scans and oscillatory frequency scans. Oscillation amplitude scanning
oscillatory
structure.
isAfirst
dynamicamplitude
The to
used methods scans
rheological
determine and
commonly
test
the linearoscillatory
of theused
biopolymer
viscoelasticfrequency
to examine the
solutions
region LVRscans.
structure
isof
used Oscillation
toof
better
biopolymer amplitude
the solutions
solutionstheir
evaluate are
because,
scanning
oscillatory
structure. is first used
amplitude to determine
scans and the
used linear
oscillatory
to viscoelastic
frequency
examine the region
scans.
structure LVR
Oscillation
in general, the appropriate strain applied by oscillation frequency scanning must be are
The methods commonly of the of biopolymer
amplitude
solutions within
solutions
scanning
oscillatory because,
is
the linear first
amplitude in general,
used
viscoelastic to the
determine
scans
regionand appropriate strain
the linearfrequency
oscillatory
[39,47]. applied
viscoelastic byOscillation
region
scans. oscillation frequency
LVR of biopolymer
amplitude
scanning
solutions must
is be used
because,
first within tothe
in general, linear
the viscoelastic
determine the linearregion
appropriate strain [39,47].
applied
viscoelastic by oscillation
region frequency
LVR of biopolymer
A
scanning high
mustplateau
be of
withinelastic
the modulus
linear G’ independent
viscoelastic region of shear
[39,47]. stress
solutions because, in general, the appropriate strain applied by oscillation frequency τ or shear strain is
considered
A high
scanning to
must be
plateauthe linear viscoelastic
of elastic
be within modulus
the linear region. The
G’ independent
viscoelastic linear viscoelastic regions of the
of shear stress τ or shear strain
region [39,47]. three
is
biopolymer
considered
A highto solutions
be the of
plateau are
linearshown in Figure
viscoelastic
elastic modulus G’13,
region. which shows
The linear
independent that a stress
linearregions
ofviscoelastic
shear τviscoelastic
or shearof the region
three
strain is
existed for diutan gum, scleroglucan, and xanthan gum, and that the modulus of elasticity,
Polymers 2023, 15, 4338 13 of 18

A high plateau of elastic modulus G’ independent of shear stress τ or shear strain is

considered to be the linear viscoelastic region. The linear viscoelastic regions of the three
Polymers 2023, 15, x FOR PEER REVIEW 14 of 19
biopolymer solutions are shown in Figure 13, which shows that a linear viscoelastic region
existed for diutan gum, scleroglucan, and xanthan gum, and that the modulus of elasticity,
G’, remained virtually constant with increasing shear stress, τ, until it reached the critical
stress value,
stress value, ττcc (τcc,, the
the stress
stress at the inflection point). The critical stress
stress value
value ττcc reflects the
shear resistance
resistance of the molecular agglomerates, and the initial molecular agglomerates are
destroyed when τ >τ >τcc.. If
If the
the critical
critical stress value τcc of
of the solution is large, the molecular
chains overlap and entangle with each other and can withstand greater shear stress, so
they will have excellent viscoelastic properties properties [39].
[39]. The plateau values of the diutan gum
and scleroglucan solutions were higher than that of xanthan gum, and their critical stress
values τ c were also higher than that of xanthan gum. This indicates that the viscoelasticity
of the diutan gum and scleroglucan solutions is more prominent compared with xanthan
gum, and they can withstandwithstand larger
larger stresses.
stresses.

Figure 13.
Figure 13.Oscillation
Oscillationamplitude
amplitude scanning
scanning curves
curves of biopolymer
of biopolymer at 90 ◦ Catand
solutions
solutions 901 °C and 1 Hz
Hz frequency.
frequency.
3.2.3. Oscillation Frequency Sweep Test
3.2.3.Figure
Oscillation Frequency
14 exhibits Sweepmodulus
the dynamic Test (i.e., storage modulus G0 and loss modulus G00 )
of diutan
Figuregum,
14 xanthan
exhibits gum, and scleroglucan
the dynamic modulussolutions versus
(i.e., storage the oscillation
modulus G’ and frequency
loss modulusat a
temperature of 90 ◦ C and 0.1 Pa shear
G”) of diutan gum, xanthan gum, stress. The three biopolymer
and scleroglucan solutionssolutions
versus show a gradual
the oscillation
increase
frequency in at
oscillation frequency.
a temperature of 90At °Caand
concentration
0.1 Pa shear ofstress.
1500 mg/L, the storage
The three modulus
biopolymer G0 of
solutions
all three 00 0
show a biopolymers
gradual increasewas greater than thefrequency.
in oscillation loss modulus At G , and the storage
a concentration of modulus
1500 mg/L,G and
the
loss modulus G 00 of diutan gum were greater than those of xanthan gum and scleroglucan,
storage modulus G’ of all three biopolymers was greater than the loss modulus G”, and
indicating
the storagethat the viscoelasticity
modulus G’ and lossofmodulusthe solutions
G” ofwas dominated
diutan gum were by the elastic
greater component,
than those of
and the viscoelasticity of diutan gum was greater than that of xanthan
xanthan gum and scleroglucan, indicating that the viscoelasticity of the solutions was gum and scleroglucan.
It can also bebyseen
dominated thefrom Figure
elastic 14 that the
component, andoverlap frequency (the
the viscoelasticity of frequency
diutan gum corresponding
was greater
to the intersection of G 0 and G 00 ) of xanthan gum and scleroglucan was considerably larger
than that of xanthan gum and scleroglucan. It can also be seen from Figure 14 that the
than that of diutan gum, which shows a typical naturally ordered
overlap frequency (the frequency corresponding to the intersection of G’ and G”) of structure. Another feature
of this structure
xanthan gum and is the strong frequency
scleroglucan dependencelarger
was considerably of the than
dynamic
that modulus
of diutan[2]. Figure
gum, 15
which
shows the relationship between the complex viscosity and the oscillation
shows a typical naturally ordered structure. Another feature of this structure is the strong frequency of the
three
frequencyunderdependence
the same conditions, and it canmodulus
of the dynamic be seen that[2].the complex
Figure viscosity
15 shows theofrelationship
diutan gum
was also higher than that of xanthan gum and scleroglucan.
between the complex viscosity and the oscillation frequency of the three under the same
conditions, and it can be seen that the complex viscosity of diutan gum was also higher
than that of xanthan gum and scleroglucan.
Polymers 2023, 15, 4338 14 of 18
Polymers 2023, 15, x FOR PEER REVIEW 15 of 19

14.The
Figure 14. Therelationship
relationshipbetween
betweenthe the
elastic modulus
elastic G0 and
modulus G′viscous modulus
and viscous G00 of the
modulus G”biopoly-
of the
biopolymer
mer solutions
solutions and the and the oscillation
oscillation frequency ◦
frequency
at 90 C at
and90 0.1
°C Pa
andshear
0.1 Pa shear stress.
stress.

Figure 15.
Figure 15.Relationship
Relationship curves
curves between
between complex
complex viscosity
viscosity and oscillation
and oscillation frequencyfrequency of the
of the biopolymer
biopolymer solutions
◦ at 90 °C, under a shear stress
solutions at 90 C, under a shear stress of 0.1 Pa. of 0.1 Pa.

concentration of
At a concentration of 1500
1500 mg/L,
mg/L, diutan gum showed greater viscoelasticity
viscoelasticity than
xanthan gum and scleroglucan, which is due to the formation of a stronger stronger network
structure in the
the diutan
diutan gum
gum solution.
solution. The molecules of diutan gum possess a distinct distinct
double-helix structure, and its side chains are all distributed in the center of the double-
large number
helix main chain so that a large number ofof water
water molecules can enter into the inner part
double-helix structure and attach themselves to the side chains through hydrogen
of the double-helix
bonding. In contrast, the molecules of xanthan gum and scleroglucan solutions are only
enhanced
enhanced by byintermolecular
intermolecular and intramolecular
and intramolecularforces without
forces a network
without structure,
a network which
structure,
is also similar to the findings of Ke Liang et al. [2,29]. Therefore, diutan gum has
which is also similar to the findings of Ke Liang et al. [2,29]. Therefore, diutan gum has strong
water
strongretention and viscoelastic
water retention properties.
and viscoelastic properties.

3.3.
3.3. Long-Term
Long‐Term Stability
Stability of
of Diutan
Diutan Gum
Gum and
and Scleroglucan
Scleroglucan
The
The biopolymers exist in an anaerobic, high-temperature
biopolymers exist in an anaerobic, high-temperature environment
environment during
during the
the
months-long oil flood in the formation. To test whether biopolymer
months-long oil flood in the formation. To test whether biopolymer solutionssolutions can maintain
can
sufficient
maintain apparent
sufficientviscosity,
apparentaging needsaging
viscosity, to beneeds
simulated
to beinsimulated
an anaerobic,
in anhigh-temperature
anaerobic, high-
ambient system. A 1500 mg/L solution of diutan gum and scleroglucan
temperature ambient system. A 1500 mg/L solution of diutan gum and scleroglucan with a mineraliza-
with
a mineralization of 220 g/L was prepared. The samples were loaded in a glove box after
Polymers 2023,
Polymers 2023, 15,
15, 4338
x FOR PEER REVIEW 16
15 of 19
of 18

designation
tion of 220 g/Landwasthenprepared.
placed inThe an oven
samplesat 100
were°C loaded
to carryinout the evaluation
a glove of the long-
box after designation
term thermal stability performance, ◦ and to determine the change
and then placed in an oven at 100 C to carry out the evaluation of the long-term in apparent viscosity
thermalof
the biopolymer solution with aging time.
stability performance, and to determine the change in apparent viscosity of the biopolymer
As can
solution withbe seentime.
aging in Figure 16, the apparent viscosity of the diutan gum solution
remained
As canrelatively
be seen in stable in 16,
Figure thethefirstapparent
10 daysviscosity
of aging,ofalways around
the diutan gum 90solution
mPa·s, but in the
remained
period from
relatively 10 toin21
stable days,
the firstthe
10 apparent viscosity
days of aging, decreased
always aroundsubstantially,
90 mPa·s, but andin on
thethe 21st
period
day, only 13.3 mPa·s remained, corresponding to an 85.01% loss of apparent
from 10 to 21 days, the apparent viscosity decreased substantially, and on the 21st day, only viscosity. In
the period from 21 to 32 days, the apparent viscosity was maintained at
13.3 mPa·s remained, corresponding to an 85.01% loss of apparent viscosity. In the period around 12 mPa·s.
After21
from 32todays, the the
32 days, apparent
apparentviscosity
viscosity dropped to a single
was maintained at digit
aroundand12 gave
mPa·off a “caramel”
s. After 32 days,
odor.
the The apparent
apparent viscosity viscosity
droppedoftothe scleroglucan
a single digit and solution
gave offdid not change
a “caramel” much
odor. Theinapparent
the first
20 days ofofaging,
viscosity remaining atsolution
the scleroglucan about 70did mPa·s. It then rose
not change muchslightly
in thefrom
first 20
20 to 39 days,
days and
of aging,
on the 39thatday,
remaining about the mPa·s. It viscosity
70apparent then rose was stillfrom
slightly 63.7620mPa·s, corresponding
to 39 days, and on the to a loss
39th day,rate
the
apparent viscosity was still 63.76 mPa·s, corresponding to a loss rate of only 10.46%.
of only 10.46%.

Figure 16.
Figure 16. Variation
Variation in
in apparent
apparent viscosity
viscosity of
of diutan
diutan gum
gum and
and scleroglucan
scleroglucan solutions with aging
solutions with aging time.
time.

From the above results, it can be determined that the diutan gum has a certain
certain long-
long-
term stability in terms of temperature and salt resistance. It can be kept stable for about
10 days
days at 100 ◦°C
at 100 C and
and with
with aa 220
220 g/L
g/L mineralization degree, after which, the structure
begins to change, the intermolecular hydrogen bonding weakens, and the molecular chain
begins to break; thus, the apparent viscosity decreased considerably. On the other hand,
the long-term stability of scleroglucan was better than that of diutan gum; it could be
maintained at 100 ◦°C C and 220 g/L mineralization for
g/L mineralization for about
about 40 days, which can mainly be
attributed to its rigid triple-helix structure.
structure.

4. Conclusions
4. Conclusions
In
In this
thisstudy, the the
study, viscosity changes,
viscosity and rheological
changes, and long-term
and rheological stability properties
and long-term stability
of diutan gum, xanthan gum and scleroglucan were investigated under
properties of diutan gum, xanthan gum and scleroglucan were investigated simulated extreme
under
reservoir environments. The results were as follows:
simulated extreme reservoir environments. The results were as follows:
(1) At the same temperature and mineralization degree, the thickening and viscosity-
(1) At the same temperature and mineralization degree, the thickening and viscosity-
increasing performance of diutan gum were better than those of xanthan gum and
increasing performance of diutan gum were better than those of xanthan gum and
scleroglucan, and the amount of diutan gum required to achieve the same apparent
scleroglucan, and the amount of diutan gum required to achieve the same apparent
viscosity was lower than that of xanthan gum and scleroglucan.
viscosity was lower than that of xanthan gum and scleroglucan.
(2) Diutan gum and scleroglucan showed better temperature resistance than xanthan gum.
(2) Diutan gum and scleroglucan showed better temperature resistance than xanthan
Diutan gum could withstand a maximum temperature of 100 ◦ C, with an apparent
gum. Diutan gum could withstand a maximum temperature of 100 °C, with an
viscosity retention rate of 89%; scleroglucan’s viscosity was stable up to 150 ◦ C, with an
apparent viscosity retention rate of 89 %; scleroglucan’s viscosity was stable up to 150
apparent viscosity retention rate of 118.27%.
°C, with an apparent viscosity retention rate of 118.27 %.
Polymers 2023, 15, 4338 16 of 18

(3) Diutan gum and scleroglucan showed better salt resistance than xanthan gum, and both
could tolerate up to 220 g/L of mineralized simulated brine, with a 90.12% apparent
viscosity retention of diutan gum and 70.04 % of scleroglucan, with minor apparent
viscosity loss. The acid and alkali resistance of the three biopolymer solutions was rela-
tively high, with a slight decrease in apparent viscosity under heavily acidic conditions
and an approximately constant apparent viscosity under alkaline conditions.
(4) In the rheological test, the solutions of diutan gum, xanthan gum, and scleroglucan
all distinctly showed pseudoplastic fluid behavior, and the diutan gum had strong
water retention and viscoelastic properties due to its peculiar double-helix structure.
(5) Both diutan gum and scleroglucan have certain long-term stability in terms of tem-
perature and salt resistance. Diutan gum can remain stable for about 10 days at
100 ◦ C and 220 g/L mineralization, and the apparent viscosity can be maintained
at 90 mPa·s. Scleroglucan can remain stable for approximately 40 days in the same
reservoir environment, with an apparent viscosity retention rate of 89.54%.
After comprehensively analyzing the temperature, salt, acid and alkali resistance,
and long-term stability of the three biopolymers, it is concluded that scleroglucan is more
tolerant to the extreme conditions of the reservoir and has the best potential for drive
modulation applications.

Author Contributions: Conceptualization, L.H. and J.X.; writing—original draft preparation, X.G.;
writing—review and editing, X.G., L.Y. and Y.Z.; All authors have read and agreed to the published
version of the manuscript.
Funding: This work was supported by the China National Petroleum Corporation Scientific Research
and Technology Development Project (No. 2021DJ1605).
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Data Availability Statement: The raw/processed data required to reproduce these findings cannot
be shared at this time, as the data also forms part of an ongoing study.
Acknowledgments: We would like to thank all the participants.
Conflicts of Interest: The authors declare no conflict of interest.

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