Journal of Macromolecular Science, Part B

Physics

ISSN: 0022-2348 (Print) 1525-609X (Online) Journal homepage: http://www.tandfonline.com/loi/lmsb20

A Rheological Study of Xanthan Polymer for

Enhanced Oil Recovery

Ghoumrassi-Barr Sofia & Aliouche Djamel

To cite this article: Ghoumrassi-Barr Sofia & Aliouche Djamel (2016): A Rheological Study of
Xanthan Polymer for Enhanced Oil Recovery, Journal of Macromolecular Science, Part B, DOI:
10.1080/00222348.2016.1207544

To link to this article: http://dx.doi.org/10.1080/00222348.2016.1207544

Accepted author version posted online: 30

Jun 2016.
Published online: 30 Jun 2016.

Submit your article to this journal

View related articles

View Crossmark data

Full Terms & Conditions of access and use can be found at

http://www.tandfonline.com/action/journalInformation?journalCode=lmsb20

Download by: [Library Services City University London] Date: 01 July 2016, At: 05:31
 ACCEPTED MANUSCRIPT

A Rheological Study of Xanthan Polymer for Enhanced Oil Recovery

Ghoumrassi-Barr Sofiaa, Aliouche Djamelb *

a
Division Technologies et Développement, Sonatrach, Boumerdes, 35000, Algérie.
b
Laboratoire de Traitement et Mise en forme des Polymères, F.S.I, Université M’Hamed

Bougara, Boumerdes, 35000, Algérie.

a
sofia.ghomrassi@ep.sonatrach.dz
Downloaded by [Library Services City University London] at 05:31 01 July 2016

b
*Corresponding author: aliouche_dj@umbb.dz ; aliouche.djamel@univ-boumerdes.dz

Xanthan Rheology for EOR in Devonian Oil Field

Abstract:

This study explored the potential application of xanthan gum as a polymer-flooding agent for oil

recovery applications in a specific Devonian oil field. Rheological measurements using

oscillatory and steady shear were carried out to examine the change in shear viscosity when the

polymer was applied under reservoir conditions. The xanthan rheological properties were

described by the Herschel-Bulkley and Ostwald models to characterize its non-Newtonian

behavior. As expected, the results showed that higher xanthan concentrations raised the polymer

viscosity and increased the degree of shear thinning. Addition of alkalis caused the viscosity of

the xanthan solutions to decrease, but they maintained their shear-thinning properties. Polymer

solutions in typical oil field brine increased in viscosity by ca. 400 % for 720 hours storage time.

On the other hand, as expected, the solutions lost their viscosity gradually with increasing

temperature. However, at reservoir temperature (68 °C), the polymer solutions kept more than

60% of their initial viscosity. In oscillatory deformation tests it was observed that all the

measured viscoelastic properties were influenced by temperature and confirmed that xanthan

1
ACCEPTED MANUSCRIPT
 ACCEPTED MANUSCRIPT

solution behaved as a weak-gel. An order-disorder transition exists within the xanthan-brine

solutions which responds to changes in solution concentration, temperature and alkalis.

Keywords:

Enhanced Oil Recovery, Xanthan, Brine water, Viscosity, shear-thinning, oscillatory rheology.
Downloaded by [Library Services City University London] at 05:31 01 July 2016

2
ACCEPTED MANUSCRIPT
 ACCEPTED MANUSCRIPT

1. Introduction

In the last decade techniques to enhance oil recovery (EOR) have received great attention from

the oil industry. In Algeria, for example, a feasibility of chemical flooding study on the oldest oil

field (Tin Fouyé TFY) was done jointly by Sonatrach (national oil group) and Veba-Oil Group

(Germany) in 1993-1994. This study concluded that the polymer flood process could technically

be applied in the TFY field. The TFY oil field, within the Silurian-Devonian F6 reservoir, is
Downloaded by [Library Services City University London] at 05:31 01 July 2016

located 2000 km South East of Algiers, on the flank of the Illizi Basin.

In oilfield operations, water flooding is generally used as an effective method in secondary

recovery. However, when water flooding a reservoir becomes inefficient, in the sense that a large

amount of oil is left behind within the rock, polymer flooding may be considered as a possible

remedy. The poor water flooding efficiency is due to the unfavorable mobility ratio between the

displacing water and the displaced oil [1]. The mobility ratio of oil to water, and the relative

permeability of water and oil are the most sensitive parameters in recovery of residual oil [2-4].

Polymers can control mobility and reduce the formation permeability in the reservoir by

increasing the viscosity of the injected water. The reason for using polymers to reduce mobility

ratio is that they could significantly increase the viscosity of the injected brine water at very low

concentrations (a few hundred ppm). Many researchers have discussed the various aspects of

polymer structure, stability, solution behavior, in-situ rheology, and transport in porous media

that are relevant to the ultimate task of Enhanced Oil Recovery (EOR) [5-7]. So, an important

feature for a potential polymer to be used for polymer flooding in EOR is that the water solution

of the polymer has the desired rheological behavior. In this context, water-soluble polymers have

been extensively used for polymer flooding [8-11]. Currently, both partially hydrolyzed

3
ACCEPTED MANUSCRIPT
 ACCEPTED MANUSCRIPT

polyacrylamide (HPAM) and various biopolymers are applied in oil fields to enhance oil

recovery; they are effective in improving the mobility ratio and reducing the relative

permeability in the porous media. Some biopolymers have important characteristics, such as

excellent viscosifying power even in high salinity waters, resistance to shear degradation,

pseudo-plasticity and stability over large ranges of temperature or pH. Among these, xanthan

gum, which is a biologically produced polysaccharide, has been considered as a viable

Downloaded by [Library Services City University London] at 05:31 01 July 2016

alternative to polyacrylamides for EOR applications [12]. Contrary to polyacrylamides, xanthan

gum is less sensitive to mechanical shear, to elevated salinity and/or to divalent ion

concentration, because of its rigid polysaccharide chains [13]. Many oil reservoirs contain

groundwater with high concentrations of sodium chloride and divalent ions, thus requiring the

use of xanthan biopolymer rather than HPAM. Xanthan gum is an extracellular polysaccharide

produced by the bacterium, Xanthomonas campestris, to give a pentasaccharide repeating unit

[14]. Because the proper viscosity of the displacing fluid is vital in EOR projects, it is important

to control the viscosity of xanthan gum solutions under given salinity and temperature

conditions.

In this study, the polymer flooding characteristics of xanthan gum were examined to explore its

potential for improving oil recovery in a particular oil field, using the Tin-Fouyé Devonian

(TFY) oil field in south east Algeria as a typical example. For this purpose, rheological analysis

of xanthan gum-Devonian brine solutions was carried out to assess its relation to the polymer

flooding. The rheological measurements, for flow and dynamic behavior, were carried out in a

range of polymer concentration, alkali concentrations, temperature and aging time. In order to

4
ACCEPTED MANUSCRIPT
 ACCEPTED MANUSCRIPT

assure its stability, the thermal behavior of xanthan polymer was in this studied by

thermogravimetric analysis (TGA).

2. Experimental

2.1. Materials

- Commercial xanthan gum (Mw=2-5×106 g/mol.) was purchased from AVA Drilling Fluids and

Services Co. (Italy).

Downloaded by [Library Services City University London] at 05:31 01 July 2016

- Alkalis, sodium hydroxide (NaOH) and sodium carbonate (Na2CO3), were reagent grade,

purchased from VWR Prolabo BDH (USA) and used as received.

- The measured salinity of the reservoir water varied between 0.5 and 5.0 g/l, depending on

depth; in a particular TFY oil well, TFY6, the internal pressure Pint.=131.1 bars; internal

temperature Tint.=68 °C, the density of water is 0.97 g/cm3 and viscosity 0.5 Cp. The chemical

composition of the brine reservoir water is summarized in Table 1.

2.2. Methods

2.2.1. Polymer solutions preparation

The polymer solutions were prepared by dissolving the xanthan powders in brine water at

various concentrations (250, 500, 1000, and 2000 ppm). Here, special attention was required to

avoid mechanical degradation of the long chains. All polymer solutions used in this study were

fresh samples. The polymer solutions were prepared by mixing, under stirring, the correct

amount of xanthan gum in TFY brine water. The polymer powder was added slowly at the edge

of a vortex generated by stirring. After a few minutes, the stirring speed was decreased and a

gentle mixing was maintained overnight to ensure full hydration and complete dissolution of the

xanthan. The final solution was obtained by dilution in TFY brine water. Finally, all polymer

5
ACCEPTED MANUSCRIPT
 ACCEPTED MANUSCRIPT

solutions were stored in closed polyethylene containers to minimize oxygen uptake. The various

alkalis solutions were prepared from reagent grade chemicals.

2.2.2. Thermal behavior of the xanthan

Thermogravimetric analysis (TGA) was carried out on a T.A. Instruments-TGA Q50 V6 Build

203 instrument (USA) from room temperature to 600 °C, with a heating rate of 10 °C/min under

a dynamic atmosphere of nitrogen with a flow rate of approximately 40 mL/min. The mass of the
Downloaded by [Library Services City University London] at 05:31 01 July 2016

samples was about 10 mg.

2.2.3. Rheological measurements

The apparent viscosity of various polymer solutions as a function of the shear rate (  ) was

measured using a Low Shear Contraves LS 40 rotational viscometer (Contraves AG,

Switzerland) with Couette vessel. The shear rate range was 0.1-100 s-1; this range encompasses

the shear rates of the injected fluid encountered in the TFY reservoir away from the wellbore

(0.1-10 s-1).

Dynamic viscoelastic and steady flow properties of the freshly prepared xanthan solutions were

carried out under controlled shear rate mode with a Bohlin Gemini II Rheometer from Malvern

Instruments Co. (UK), using a DIN C25 coaxial cylinder. The polymer solutions were placed in

the Couette cell with the rotating inner cylinder of 25 mm in diameter and the outer cylinder

separated by a 2.5 mm gap. For dynamic viscoelastic determinations, two steps of rheological

measurements were performed:

- Deformation sweeps at a constant frequency (1Hz) to determine the maximum deformation of

the sample in the linear viscoelastic range.

6
ACCEPTED MANUSCRIPT
 ACCEPTED MANUSCRIPT

- Frequency sweeps over a range of 0.1-10 Hz at oscillating stress amplitude of 1 Pa This value

was within the linear viscoelastic region of the xanthan solutions, as determined by recording

stress amplitude sweeps at 1 Hz.

3. Results and discussion

3.1. Thermal analysis (TGA) of xanthan polymer

Thermogravimetric analysis is a simple and accurate method for studying the decomposition
Downloaded by [Library Services City University London] at 05:31 01 July 2016

pattern and thermal stability of polymers. Figure 1 gives the details of thermal behavior

according to the primary thermogram and derivative thermogram (DTGA) for the xanthan

polymer. The polymer exhibited a two stage decomposition pattern; its main decomposition

started above 200 °C. The first stage occurred in the temperature range of 30-110 °C with a

maximum DTGA at 68 °C, with 10-13 % of mass loss. This initial slight weight loss in the

sample is related to the loss of adsorbed and free water within the saccharide structure. Water

absorption by xanthan is due to the presence of polar groups in its structure, especially the -OH

groups. The second stage of degradation (240-335 °C) showed a maximum DTGA at 290 °C

with 48-51 % mass loss. Depolymerization and pyrolitic decomposition involved in these high

temperature stages resulted in the formation of H2O, CO2 and CH4 starting from the thermal

scission of the carboxylate groups in the polymer backbone. The additional mass loss up to 550

°C is related to polysaccharide residue and ash [15].

3.2. Rheological behavior of xanthan solutions

The extensive research activity connected with the enhanced oil recovery has laid stress on the

interfacial rheological behavior of oil/water systems. Therefore, the main objectives of the

research program here was to demonstrate that the interfacial rheological properties (viscosity,

7
ACCEPTED MANUSCRIPT
 ACCEPTED MANUSCRIPT

non-Newtonian flow behavior, constants of the Ostwald’s formula and the power law, salts and

temperature dependence of viscosity, and dynamic rheology) are sensitive parameters for

characterization and identification of oil/water systems.

3.2.1. Steady shear of xanthan solutions

The flow of the xanthan gum-Devonian water solutions under shear was characterized at 20 °C

and for the reservoir temperature of 68 °C. Figure 2 shows the experimental results of shear
Downloaded by [Library Services City University London] at 05:31 01 July 2016

stress (Pa) versus shear rate (s-1) for 250 to 2000 ppm solutions to cover low, medium and high

polymer concentrations, at the two temperatures. Typical shear stress-shear rate data for the

polymer solutions of the different compositions are presented in the curves. The xanthan gum

solutions exhibited non-Newtonian flow and shear-thinning behavior, as expected. However,

they exhibit an initial yield stress that must be overcome for the solution to flow. The data were

analyzed by using conventional flow equations which are known as models describing the flow

behavior of gel polymers very well. The Ostwald de Waele (Eq.1) [16] and, especially, the

Herschel-Bulkley (Eq.2) [17] models were more satisfactory than other models, such as

Bingham, Casson or Carreau, to describe the flow behavior of xanthan solutions:

  K n (1)

   0  K n (2)

where  is the shear stress (Pa),  is the shear rate (s-1), 0 is the yield stress (Pa). For both

equations, K is the consistency coefficient (Pa.sn) related to a high shear limiting viscosity and n

is the flow behavior index (dimensionless), a material parameter that determines their shear

thinning nature.

8
ACCEPTED MANUSCRIPT
 ACCEPTED MANUSCRIPT

The rheological parameters for the xanthan gum solutions are shown in Tables 2 and 3 for the

Herschel-Bulkley and Ostwald models reversed relative to equations 1 and 2, respectively. All

samples exhibited a good fit to the Herschel-Bulkley (pseudoplastic with yield stress) and

Ostwald (pseudoplastic without yield stress) equations. The value of K was directly proportional

to the concentration, while the relationship of n and concentration was the opposite. All values of

n were less than 1, indicating that all samples belonged to the class of pseudoplastic fluids.
Downloaded by [Library Services City University London] at 05:31 01 July 2016

However, the tendency for shear-thinning was less pronounced for polymer solutions with low

concentrations, which lost some of their pseudo-plasticity between 20 and 68 °C (n increased).

As can be seen from Tables 2 and 3, the flow behavior index, n, gradually decreased with

polymer concentration indicating more significant shear-thinning behavior for xanthan solutions.

The magnitudes of the yield stress (0) and consistency index (K) obtained from the power law

models increased with an increase in xanthan concentration.

Table 2 shows that the yield stress value, 0, increased gradually with polymer concentration

from 0.025 Pa to 0.096 Pa at 20 °C and from 0.011 Pa to 0.047 Pa at 68 °C for the concentration

range of 250-2000 ppm. The presence of a yield stress indicates that a three-dimensional network

was formed at zero shear conditions. Under shear stress, the three-dimensional network was

broken down.

3.2.2. Viscosity behavior of xanthan solutions

Figure 3 displays the flow behavior of the examined solutions in terms of viscosity, mPa.s,

versus shear rate, s-1, on a semi-logarithmic scale. The curves show that the viscosity was a

strong function of polymer concentration and shear rate. As expected, the higher the polymer

concentration, the higher was the viscosity of the solution, for all shear rates. This behavior was

9
ACCEPTED MANUSCRIPT
 ACCEPTED MANUSCRIPT

attributed to the intermolecular interactions or entanglements that increase the effective

macromolecule dimensions and molecular weight [18]. This high shear thinning of xanthan

solutions is a consequence of the uncoiling and aligning of polymer chains when exposed to

shear flow. In polymer flooding, the increased shear viscosity of xanthan can correct the poor

mobility ratio of the water/oil system and improve the sweep efficiency [19]. The significant

shear-thinning behavior observed is attributed to the disentanglement and alignment of the

Downloaded by [Library Services City University London] at 05:31 01 July 2016

polymer chains along the flow direction. In addition, polysaccharide polymers and, particularly,

xanthan have a tendency to form ordered structures in aqueous environments [20]. In aqueous

solutions xanthan macromolecules form aggregates and entangle, leading to high viscosity at low

shear rates; thus the disordered conformation predominates at low shear rates. Increasing the

shear rate decreases the steady shear viscosity due to the uncoiling and partial alignment of the

polymer chains in the high shear rate region. At high shear rates both conformations, ordered and

disordered, display similar rheological behaviors [21].

Xanthan gum solutions are highly pseudoplastic; although they show a shear-thinning behavior

under an applied shear rate; the initial viscosity is recovered almost instantaneously when the

shear rate is removed [22].

3.2.3. Temperature dependence of the viscosity of xanthan solutions

The xanthan molecule can undergo an order-disorder transition by varying either the temperature

or salinity of the solution. This transition may be characterized by the viscosity: as the transition

temperature is reached; a rapid decrease in viscosity occurs [23, 24].

As shown in Fig. 3, xanthan viscosity mainly decreased at 68 °C (reservoir temperature) for all

polymer concentrations. To clarify the effect of temperature, flow of 2000 ppm xanthan-brine

10
ACCEPTED MANUSCRIPT
 ACCEPTED MANUSCRIPT

solution was studied at 20, 40, 68, 80, 100 and 120 °C. Figure 4 shows the shear rate dependence

of the viscosity for 2000 ppm xanthan solution at various temperatures; this concentration was

used for all further figures.

The xanthan solution viscosity decreased with increased temperature, especially in the low shear

rate range (<20 s−1) where it reduced dramatically. When the shear rate was higher, the change of

apparent viscosity at different temperatures was consistent. This behavior is associated with
Downloaded by [Library Services City University London] at 05:31 01 July 2016

conformational changes of the xanthan macromolecule, the conformation shifts from an ordered

(low temperature) to a disordered (high temperature) state [25, 26].

For the flow conditions of TFY reservoir, the average shear rate away from the injection well has

been estimated to be around 8-10 s-1, therefore evolution of the xanthan-brine viscosity at low

shear rate (10.80 s-1) was evaluated at the considered temperatures. For this purpose we

determined the viscosity retention rate T expressed by the following equation:

T
 T (%)  x100 (3)
 20

where T is the viscosity at a given temperature and 20 the initial viscosity at 20 °C. This

parameter gives an estimation of the viscosity loss as a function of temperature. Figure 5 shows

the evolution of T  with temperature at a shear rate of 10.80 s−1, the T value of the

polysaccharide decreased with increased temperature and was merely 50% when the temperature

reached 77 °C; this is in agreement with the result reported by Xu et al. for the rheological study

of aqueous welan and xanthan gum solutions [19]. The viscosity loss of xanthan increased with

temperature and at the reservoir temperature (68 °C) the polymer solution maintained more than

60% of T whereas at 120 °C it even retained 20 % of its initial viscosity. Temperature

11
ACCEPTED MANUSCRIPT
 ACCEPTED MANUSCRIPT

dependences of the rheological parameters of xanthan are shown in Tables 4 and 5 for the

Herschel-Bulkley and Ostwald models, respectively. For both models the flow behavior index, n,

gradually increased with temperature, indicating a slight loss in pseudo-plasticity for the xanthan

solutions. The magnitude of the consistency index (K) mostly decreased with an increase in

temperature for both models while the value of the yield stress (0), calculated from the

Herschel-Bulkley model, changed randomly but mainly decreased at high temperature. This
Downloaded by [Library Services City University London] at 05:31 01 July 2016

phenomenon shows that the microstructure of the xanthan solution had a poor temperature

resistance; however, part of the shear thinning behavior was preserved even at high temperature.

3.2.4. Polymer long-term stability in TFY specific field conditions:

In polymer flood projects chemical solutions have to be designed in a way that they keep their

mobility control properties over a long period of time under the conditions prevailing in the

reservoir, especially the temperature and salinity level. Long-term stability tests are run for

various parameters, including temperature, salinity and pH. Stability is most often defined in

terms of viscosity retention of the polymer solution at a specified shear rate. Therefore, the long-

term stability of the viscosity of xanthan polymer solutions was investigated. Polymer solutions

were prepared in TFY brine, oxygen was removed and the solutions were sealed in glass

ampoules and kept for aging at 68°C. After selected storage time steps, one ampoule of each

series was opened and checked for apparent viscosity. Figure 6 depicts the influence of the

storage time on the apparent viscosity of polymer-brine solution containing 2000 ppm of

xanthan. In all plots presented in the figure the viscosity increased with storage time, by a factor

of ca. 4 at 720 hrs (30 days), Ash et al. reported substantial increase in viscosity after 500 days

even when solutions were not previously degassed [27]. The viscosity of the xanthan-brine

12
ACCEPTED MANUSCRIPT
 ACCEPTED MANUSCRIPT

solutions increased gradually with time, but the pseudoplastic behavior of xanthan was

maintained for all storage times. Seright and Henrici [28] reported that xanthan solution could

maintain at least half of its original viscosity for a period of 5 years if the temperature did not

exceed 75-80 °C. On the other hand, they found that the stability at high temperatures was much

greater in saline solutions than in deionized water. This occurs due to the ordered helical

conformations present in saline where the molecule is more protected from chain scission
Downloaded by [Library Services City University London] at 05:31 01 July 2016

reactions.

As in temperature dependence, the viscosity retention rate time of the xanthan solutions

stored was evaluated, at low shear rate (10.60 s-1), as follows:

t
 time (%)  x100 (4)
0
where t is the viscosity at a given storage time and0 the initial viscosity of the fresh samples

(day 1). Evolution of the parameter time is shown in Fig. 7. Thus, up to 48 hours of time storage,

no significant change in viscosity was noticed; after this limit, for a week to a month, the

viscosity increased sharply. The magnitude of the apparent viscosity increased up to three times

with increase in storage time (for one month).

3.2.5. Effect of alkali addition in TFY water brine

Injection of alkali and polymer together in a single slug has been found to increase oil recovery;

the alkalis can reduce the viscosity of xanthan solutions [29, 30]. The viscosity of xanthan

solutions is reduced in the presence of alkalis through the charge shielding mechanism by cations

provided by the alkalis and through hydrolysis of the xanthan backbone. The effect of sodium

hydroxide concentration on the viscosity of xanthan-brine solutions, at 68 °C, is shown in Fig. 8.

13
ACCEPTED MANUSCRIPT
 ACCEPTED MANUSCRIPT

From the figure the viscosity of the xanthan solutions decreased as the NaOH concentration was

increased.

It is of interest to examine the rate of change in the viscosity with respect to NaOH concentration

at low shear rate. Therefore the viscosity retention rate was determined from the following

equation:

 ci
Downloaded by [Library Services City University London] at 05:31 01 July 2016

 r (%)  x100 (5)

 c0

where  ci is the viscosity of xanthan solution at a given NaOH concentration (Ci) and c0 the

viscosity of xanthan solution without NaOH. Figure 9 shows the effect of alkali concentration on

the viscosity retention of polymer solutions containing 2000 ppm xanthan. The low-shear

viscosity dropped from 100 % (by definition) in the absence of alkali to about 60 % in 1.0 wt%

NaOH, and then it remained nearly constant. It should also be noted that the polymer solution

kept 50% of its initial viscosity in 10% NaOH.

Due to their buffering action and low reactivity with the rock matrix, buffered alkalis have been

suggested for use in alkali/polymer slugs [31]. Figure 10 shows the effect of alkali type on the

shear viscosity of xanthan solutions having 2000 ppm polymer with an alkali concentration of 1

%. With the addition of a strong alkali (sodium hydroxide) the xanthan viscosity decreased

significantly at all shear rates; however addition of sodium carbonate (buffered alkali) produced

a small initial drop of the viscosity which then decreased at a much slower rate than for NaOH.

At shear rates >20 s-1, the polymer solution viscosities were nearly the same for all the samples.

The effect of alkali type on the flow index was also remarkable, as shown in Table 6. Strong

alkali caused a significant increase of the flow index whereas buffered alkali caused only a slight

14
ACCEPTED MANUSCRIPT
 ACCEPTED MANUSCRIPT

increase of the n index. Thus, the viscosity loss of the xanthan solutions was less in the presence

of sodium carbonate. Therefore, in alkali/xanthan processes it would be valuable to use a

buffered alkali rather than strong alkali.

3.2.6. Dynamic shear properties of xanthan-TFY brine solutions

In the last part of this work, the dynamic response of the polymer-TFY brine solutions are

reported. The viscoelastic properties of the xanthan solutions were described in terms of two
Downloaded by [Library Services City University London] at 05:31 01 July 2016

dynamic mechanical properties: the elastic modulus, G’, (also known as dynamic rigidity),

reflecting the reversibly stored energy of the system, and the viscous modulus, G’’, reflecting the

irreversible energy loss. Another measure of the viscoelastic properties of the xanthan solutions

is the loss tangent, tan , which is defined as tan  = G”/G’, where  is the phase angle between

the viscous and the elastic moduli during one deformation cycle (for elastic structures >0°,

whereas for plastic structures >90°). Figure 11 presents frequency sweeps for xanthan-TFY

brine solutions in the temperature range of 20-68 °C (polymer concentration=2000 ppm). As

seen from the plots, G’ was much greater than G’’ at all values of showing a predominant

elastic behavior. G’ increased with the increase in  whereas, G’’ was less dependent on

frequency.

Moreover, a crossover between these two moduli at any temperature was not observed

throughout the measured frequency range. Such elastic properties may be related to the rigid

conformation of xanthan in solution which implies a much more limited mobility of the chains

than in the random coil conformation, and hence much longer relaxation time, resulting in higher

elastic properties and a weak three-dimensional network, as described by Doublier and Cuvelier

[32]. On the other hand, one can notice that G’ and G’’ decreased with increasing temperature;

15
ACCEPTED MANUSCRIPT
 ACCEPTED MANUSCRIPT

this reduction is related with the conformational changes of the polymer, so the loss in

viscoelastic properties is due to the helix-coil transition which strongly affects the rheology of

the polymer solution.

The fact that the dynamic mechanical loss tangent values for all the gels tested were much

smaller than unity indicates predominantly elastic behavior (Fig. 12). For all samples the tan 

values were in the range of 0.035-0.40, indicating that the elastic nature prevailed over the
Downloaded by [Library Services City University London] at 05:31 01 July 2016

viscous nature; the lost tangent increased with increasing temperature, showing that the xanthan-

brine solutions became less elastic. This behavior may be classified as being due to the sample

being a typical weak gel [33].

4. Conclusion

A suitable chemical system for polymer use in the TFY oil field was successfully studied; this

study examined the applicability of xanthan gum to oilfield operations. For such an application

for use in the TFY Devonian oil field areas xanthan polymer solutions must withstand a

temperature of 68°C and above, and salt concentrations in the reservoir. In the brine reservoir,

the polymer solutions displayed non-Newtonian behavior and strong shear-thinning at 20 and 68

°C. Various degrees of shear-thinning were described for the various polymer concentrations.

The smaller the value of flow behavior index (n), the greater is the degree of shear-thinning.

Modeling analysis showed that the yield stress and consistency index values increased gradually

with polymer concentration. From the flow behavior comparison of all tested solutions, two

profiles can be found: for shear rates higher than 10 s-1, all polymer solutions showed similar

flow behavior independent of the polymer solution concentration; and for shear rates less than 10

s-1, viscosity behavior was dictated by the polymer concentration.

16
ACCEPTED MANUSCRIPT
 ACCEPTED MANUSCRIPT

The viscosity loss of xanthan solutions increased gradually with increasing temperature; at the

reservoir temperature (68 °C) the viscosity of the polymer solution lost 40% of its initial value.

Long-term stability tests were run for polymer-brine viscosity retention at low shear rate. In all

cases presented, the polymer solutions viscosity increased, even at 720 hours; the pseudoplastic

behavior of xanthan was maintained for all storage times. The viscosity of xanthan solutions was

reduced in the presence of alkalis through the charge shielding mechanism; however, buffered
Downloaded by [Library Services City University London] at 05:31 01 July 2016

alkali was less detrimental (compared to strong alkali) to the flow of xanthan-brine solutions.

Viscoelastic properties were investigated using oscillatory deformation tests. It was observed that

all measured viscoelastic properties, including G’, G” and tan , were influenced by temperature

and confirmed that xanthan polymer behaves as a weak-gel.

An order-disorder transition existed which responded to changes in concentration, temperature

and alkalis within the xanthan-brine solutions. High concentration and time aging are in favor of

the ordered structure, and high temperature and addition of alkalis favor the disordered structure.

The study proves the technical feasibility of chemical flooding in the TFY field with the xanthan

solutions; it is possible to use the low saline formation water as mixing water for the xanthan

polymer.

17
ACCEPTED MANUSCRIPT
 ACCEPTED MANUSCRIPT

References:

1. Sorbie, K.S. Polymer-improved oil recovery, CRC Press; Boca Raton 1991. pp. 247-259.

2. Larson, R.G.; Davis, H.T.; Scriven, L.E. Displacement of residual non-wetting fluid for

porous media, Chem. Eng. Sci., 1981, 36, 75-85.

3. Homsy, G. Viscous fingering in porous media, Ann. Rev. Fluid Mech., 1987, 19, 271-311.

4. Sorbie, K.S.; Clifford, P.J. The simulation of polymer flow in heterogeneous porous media. In
Downloaded by [Library Services City University London] at 05:31 01 July 2016

Water soluble polymers for petroleum recovery. Ed Stahl, G.A.; Schulz, D.N., Plenum

Publishing Corp., New York, 1988.

5. Szabo, M.T. An evaluation of water-soluble polymers for secondary oil recovery. Part 1 and 2.

J. Pet. Tech. 1979, 31, 553-570.

6. Wever, D.A.Z.; Picchioni, F.; Broekhuis, A.A. Polymers for enhanced oil recovery: A

paradigm for structure-property relationship in aqueous solution, Prog. Polym. Sci. 2011, 36,

1558-1628.

7. Abidin, A.Z.; Puspasari, T.; Nugroho, W.A. Polymers for Enhanced Oil Recovery

Technology, Proc. Chem. 2012, 4, 11-16.

8. Chatterji, J.; Borchardt, J.K. Applications of Water-Soluble Polymers in the Oil Field. J. Pet.

Tech. 1981, 33, 2042-2056.

9. Kjøniksen, A.L.; Beheshti, N.; Kotlar, H.K.; Zhu, K.; Nyström, B. Modified polysaccharides

for use in enhanced oil recovery applications. Eur. Polym. J. 2008, 44, 959-967.

10. Long, J.; Li, H.; Xu, Z.; Masliyah, J. H. Improving oil sands processability using a

temperature-sensitive polymer. Energy and Fuels, 2011, 25, 701-707.

18
ACCEPTED MANUSCRIPT
 ACCEPTED MANUSCRIPT

11. Taylor, K.C.; Nasr-El-Din, H.A. Water-soluble hydrophobically associating polymers for

improved oil recovery: A literature review. J. Pet. Sci. Tech. 1998, 19, 265-280.

12. Palaniraj, A.; Jayaraman, V. Production, recovery and applications of xanthan gum by

Xanthomonas campestris, J. Food Eng. 2011, 106, 1-12.

13. Alquraishi, A.A.; Alsewailem, F.D. Xanthan and guar polymer solutions for water shut off in

high salinity reservoirs. Carbohydr. Polym. 2012, 88, 859-863.

Downloaded by [Library Services City University London] at 05:31 01 July 2016

14. Leela, J.K.; Sharma, G. Studies on xanthan production from Xanthomonas campestris.

Bioprocess. Eng. 2000, 23, 687-689.

15. Zohuriaan, M.J.; Shokrolahi, F. Thermal studies on natural and modified gums. Polym. Test.

2004, 23, 575-579.

16. Chhabra, R.P.; Richardson, J.F. Non-Newtonian flow in the process industries: Fundamentals

and engineering applications. Non-Newtonian fluid behavior and rheometry. Butterworth

Heinemann, Great Britain, 1999, pp. 38-71.

17. Barnes, H.A.; Hutton, J.F.; Walters, K. An Introduction to Rheology, Elsevier Applied

Science, New York, 1989, p. 78.

18. F.R. Dintzis, G.E. Babcock, R. Tobin, Studies on dilute solutions and dispersion of the

polysaccharide from Xanthomonas campestris NRRL B-1459, Carbohydr. Res. 13 (1970) 257–

267.

19. Xu, L.; Xu, G.; Liu, T.; Chen, Y.; Gong, H. The comparison of rheological properties of

aqueous welan gum and xanthan gum solutions, Carbohydr. Polym. 2013, 92, 516-522.

20. Rinaudo, M.; Milas, M., Xanthan properties in aqueous solutions, Carbohydr. Polym. 1982,

2, 264-269.

19
ACCEPTED MANUSCRIPT
 ACCEPTED MANUSCRIPT

21. Chen, C.S.H.; Sheppard, E.W. Conformation and shear stability of xanthan gum in solution.

Polym. Eng. Sci. 1980, 20, 512-516.

22. Richardson, R.K.; Ross-Murphy, S.B. Nonlinear viscoelasticity of polysaccharide solutions.

2. Xanthan polysaccharide solutions. Int. J. Biol. Macromol. 1987, 9, 257-264.

23. Paoletti, S.; Cesaro, A.; Delben, F. Thermally induced conformational transition of xanthan

polyelectrolyte. Carbohydr. Res. 1983, 123, 173-178.

Downloaded by [Library Services City University London] at 05:31 01 July 2016

24. Milas, M.; Rinaudo, M., Conformational Investigation on the bacterial polysaccharide

Xanthan. Carbohydr. Res. 1979, 76, 189-196.

25. Garcia-Ochoa, F.; Santos, V.E.; Casas, J.A.; Gomez, E. Xanthan gum: production, recovery,

and properties, Biotech. Adv. 2000, 18, 549-579.

26. Garcia-Ochoa F.; Casas J.A. Apparent yield stress in xanthan gum solution at low

concentration. Chem. Eng. J. 1994, 53, 41-46.

27. Ash, S.G.; Clark-Sturman, A.J.; Calvert, R.; Nisbet, T.M. Chemical stability of biopolymer

solutions. SPE 12085, 1983, San Francisco.

28. Seright, R.S.; Henrici, B.J. Xanthan stability at elevated temperatures, SPE/DOE 14946,

1986, Tulsa.

29. Alam M.W.; Tiab D. Mobility control of caustic flood. Energy Res., 1988, 10, 1-19.

30. Nasr-El-Din, H.A.; Green, K.A.; Schramm, L.L. The Alkali/Surfactant/ Polymer Process:

Effects of Slug Size, Core Length and a Chase Polymer, Oil Gas Sci. Tech. 1994, 49, 359-377.

31. Nasr-El-Din, H.A.; Hawkins, B. F. Recovery of residual oil using alkali, surfactant and

polymer slugs in radial cores, Oil Gas Sci. Tech. 1991, 46, 199-219.

20
ACCEPTED MANUSCRIPT
 ACCEPTED MANUSCRIPT

32. Doublier, J.L.; Cuvelier, G. Gums and hydrocolloids: Functional aspect. Carbohydrates in

food. In Eliasson A.C. Ed., Marcel Dekker, New York, 1996, pp. 283-318.

33. Clark, A.H.; Ross-Murphy, S. B. Structural and mechanical properties of biopolymer gels.

Adv. Polym. Sci., 1987, 83, 57-192.

Downloaded by [Library Services City University London] at 05:31 01 July 2016

21
ACCEPTED MANUSCRIPT
 ACCEPTED MANUSCRIPT

Table 1. Devonian brine chemical composition

Cations (g/l) Anions (g/l)

Ca2+ 0.0358 Cl- 1.435

Mg2+ 0.0153 (SO4)2- 1.765

Downloaded by [Library Services City University London] at 05:31 01 July 2016

K+ 0.0250

Na+ 1.4200 HCO3- 0.542

Li+ 0.0009

Total: 1.497 Total: 3.742

22
ACCEPTED MANUSCRIPT
 ACCEPTED MANUSCRIPT

Table 2. Herschel-Bulkley model data analysis for xanthan-brine solutions

Polymer concentration (ppm) 0 (Pa) K (Pa.sn) n R2
20 °C 250 0.025 (0.002)* 0.023 (0.0008) 0.668 (0.007) 0.9988
500 0.058 (0.007) 0.042 (0.002) 0.648 (0.013) 0.9958
1000 0.082 (0.006) 0.068 (0.002) 0.572 (0.008) 0.9983

2000 0.096 (0.029) 0.290 (0.007) 0.357 (0.004) 0.9993

68 °C 250 0.011 (0.001) 0.006 (0.0003) 0.826 (0.011) 0.9979
Downloaded by [Library Services City University London] at 05:31 01 July 2016

500 0.014 (0.001) 0.012 (0.0004) 0.748 (0.007) 0.9989

1000 0.039 (0.004) 0.033 (0.002) 0.592 (0.010) 0.9973

2000 0.047 (0.010) 0.338 (0.027) 0.413 (0.012) 0.9952

* Standard deviation

23
ACCEPTED MANUSCRIPT
 ACCEPTED MANUSCRIPT

Table 3. Ostwald model data analysis for xanthan-brine solutions

Polymer concentration (ppm) K (Pa.sn) n R2
20 °C 0.0322
250 0.602 (0.004) 0.9976
(0.0005)*
500 0.0657 (0.001) 0.561 (0.006) 0.9938
1000 0.109 (0.001) 0.485 (0.004) 0.9959
2000 0.544 (0.007) 0.334 (0.003) 0.9937
68 °C 250 0.008 (0.0002) 0.751 (0.006) 0.9967
Downloaded by [Library Services City University London] at 05:31 01 July 2016

500 0.016 (0.0002) 0.692 (0.004) 0.9982

1000 0.051 (0.001) 0.510 (0.004) 0.9953
2000 0.323 (0.001) 0.349 (0.001) 0.9992
*Standard deviation

24
ACCEPTED MANUSCRIPT
 ACCEPTED MANUSCRIPT

Table 4. Temperature dependence of the Herschel-Bulkley model parameters for xanthan-brine

solutions
Temperature (°C) 0 (Pa) K (Pa.sn) n R2
20 0.096 (0.029)* 0.290 (0.007) 0.357 (0.004) 0.9993
40 0.285 (0.024) 0.207 (0.015) 0.447 (0.011) 0.9966
68 0.047 (0.010) 0.338 (0.027) 0.413 (0.012) 0.9952

80 0.146 (0.016) 0.164 (0.010) 0.462 (0.014) 0.9979

Downloaded by [Library Services City University London] at 05:31 01 July 2016

100 0.057 (0.018) 0.118 (0.008) 0.559 (0.014) 0.9973

120 0.033 (0.017) 0.115 (0.008) 0.565 (0.014) 0.9974

*standard deviation

25
ACCEPTED MANUSCRIPT
 ACCEPTED MANUSCRIPT

Table 5. Temperature dependence of the Ostwald model parameters for xanthan-brine solutions

Temperature (°C) K (Pa.sn) n R2

20 0.544 (0.007)* 0.334 (0.003) 0.9937
40 0.408 (0.010) 0.343 (0.006) 0.9913
68 0.323 (0.001) 0.349 (0.001) 0.9992
80 0.262 (0.004) 0.365 (0.004) 0.9955

100 0.147 (0.003) 0.518 (0.006) 0.9969

Downloaded by [Library Services City University London] at 05:31 01 July 2016

120 0.131 (0.003) 0.541 (0.006) 0.9972

*standard deviation

26
ACCEPTED MANUSCRIPT
 ACCEPTED MANUSCRIPT

Table 6. Alkali addition effect on flow index (n) of the 2000 ppm xanthan-brine solution
Model data analysis Alkali n R2
0% alkali 0.334 (0.003) 0.9937
1% Na2CO3 0.339 (0.002) 0.9955
Ostwald
1% NaOH 0.423 (0.003) 0.9971

0% alkali 0.357 (0.004) 0.9993

Herschel-Bulkley 1% Na2CO3 0.389 (0.012) 0.9962

Downloaded by [Library Services City University London] at 05:31 01 July 2016

1% NaOH 0.424 (0.011) 0.9970

27
ACCEPTED MANUSCRIPT
 ACCEPTED MANUSCRIPT

100 1.2
Downloaded by [Library Services City University London] at 05:31 01 July 2016

90
1.0

Deriv, Weight (%/°C)

80
Weight Loss (%)

0.8
70
0.6
60

50 0.4

40 0.2

30
0.0
20
100 200 300 400 500 600
Temperature (°C)
Fig.1. TGA and DTGA curves of xanthan polymer

28
ACCEPTED MANUSCRIPT
 ACCEPTED MANUSCRIPT

10
(a)
Shear stress (Pa)

1
Downloaded by [Library Services City University London] at 05:31 01 July 2016

0.1 2000 ppm

1000 ppm
500 ppm
250 ppm
0.01
0.1 1 10 100 1000
Shear rate (s-1)

10
(b)

1
Shear stress (Pa)

0.1

2000 ppm
1000 ppm
0.01
500 ppm
250 ppm

0.1 1 10 100 1000

Shear rate (s-1)

Fig. 2. Shear stress as a function of the shear rate for the xanthan-Devonian water solutions at 20

°C (a) and 68 °C (b).

29
ACCEPTED MANUSCRIPT
 ACCEPTED MANUSCRIPT

500
2000 ppm
1000 ppm
400
500 ppm
Viscosity (mPa.s)

250 ppm
300
Downloaded by [Library Services City University London] at 05:31 01 July 2016

200

100

(a)
0
0.1 1 10 100 1000
Shear rate (s-1)

300
2000 ppm
250 1000 ppm
500 ppm
200 250 ppm
Viscosity (mPa.s)

150

100

50

(b)
0

0.1 1 10 100 1000

Shear rate (s-1)

Fig. 3 Viscosity as a function of the shear rate for the xanthan-Devonian water solutions at 20 °C (a)

and 68 °C (b).

30
ACCEPTED MANUSCRIPT
 ACCEPTED MANUSCRIPT

500
20 °C
40
400 68
80
Viscosity (mPa.s)

100
300
120
Downloaded by [Library Services City University London] at 05:31 01 July 2016

200

100

0
0.1 1 10 100 1000
Shear rate (s-1)

Fig. 4. Influence of temperature on xanthan-brine solution viscosity (Polymer concentration =

2000 ppm).

31
ACCEPTED MANUSCRIPT
 ACCEPTED MANUSCRIPT

100

80
Downloaded by [Library Services City University London] at 05:31 01 July 2016

60
T (%)

40

20

0
20 40 60 80 100 120
Temperature (°C)
Fig. 5. Influence of temperature on viscosity retention rate of xanthan-brine solution (Polymer

concentration = 2000 ppm).

32
ACCEPTED MANUSCRIPT
 ACCEPTED MANUSCRIPT

1000
720 Hours
160
800
48
24
Viscosity (mPa.s)

0
600
Downloaded by [Library Services City University London] at 05:31 01 July 2016

400

200

0
0.1 1 10 100 1000
Shear rate (s-1)
Fig. 6. Influence of time aging on xanthan-brine solution viscosity (Polymer concentration =

2000 ppm).

33
ACCEPTED MANUSCRIPT
 ACCEPTED MANUSCRIPT

350

300

250
Downloaded by [Library Services City University London] at 05:31 01 July 2016

time (%)

200

150

100

50

0
0 100 200 300 400 500 600 700 800
Storage Time (Hours)
Fig. 7. Storage time effect on low shear viscosity of xanthan-brine solution (T=68 °C; Polymer

concentration = 2000 ppm).

34
ACCEPTED MANUSCRIPT
 ACCEPTED MANUSCRIPT

500
NaOH conc.
0
400 0.5
1.0
5.0
10.0
Downloaded by [Library Services City University London] at 05:31 01 July 2016

Viscosity (mPa.s)

300

200

100

0
0.1 1 10 100 1000
Shear rate (s-1)

Fig. 8. Influence of alkali concentration on viscosity of xanthan-brine solution (T=68 °C;

Polymer concentration = 2000 ppm).

35
ACCEPTED MANUSCRIPT
 ACCEPTED MANUSCRIPT

100

80
visc. Ret. (%)
Downloaded by [Library Services City University London] at 05:31 01 July 2016

60

40

0 2 4 6 8 10
NaOH concentration (%)

Fig. 9. Influence of alkali concentration on initial viscosity of xanthan-brine solution (T=68 °C;

Polymer concentration = 2000 ppm).

36
ACCEPTED MANUSCRIPT
 ACCEPTED MANUSCRIPT

500
No alkali
Downloaded by [Library Services City University London] at 05:31 01 July 2016

Na2CO3
400
NaOH
Viscosity (mPa.s)

300

200

100

0
0.1 1 10 100 1000
Shear rate (s-1)

Fig. 10. Influence of alkali-type on xanthan-brine solution viscosity (T=68 °C; Polymer

concentration = 2000 ppm).

37
ACCEPTED MANUSCRIPT
 ACCEPTED MANUSCRIPT

10

1
G', G'' (Pa)

0.1
Downloaded by [Library Services City University London] at 05:31 01 July 2016

0.01 G’ G’’
20 °C
40 °C
68 °C
0.001
0.1 1 10
 (Hz)

Fig. 11. Frequency dependence of G’ (filled symbols) and G’’ (open symbols) at different

temperatures for 2000 ppm xanthan-brine solutions

38
ACCEPTED MANUSCRIPT
 ACCEPTED MANUSCRIPT

0.8

20 °C
40
68
0.6
Tan 

0.4
Downloaded by [Library Services City University London] at 05:31 01 July 2016

0.2

0.0
0.1 1 10
 (Hz)
Fig. 12. Dynamic mechanical loss tangent (tan  at different temperatures for 2000 ppm

xanthan-brine solutions

39
ACCEPTED MANUSCRIPT