Journal of Petroleum Science and Engineering 191 (2020) 107151

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Journal of Petroleum Science and Engineering

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

Determination of the concentrations of polyacrylamide-type polymers by a

modified nitrogen digestion method
Jian Hou a, Ming Han a, b, *, Alhasan Fuseni b
a
Beijing Research Center, Aramco Asia, Beijing, 100102, PR China
b
EXPEC Advanced Research Center, Saudi Aramco, Dhahran, 31311, Saudi Arabia

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

Keywords: This paper presents a laboratory study on the effectiveness of the nitrogen digestion method to determine the
Polymer flooding polymer concentrations for 3 different kinds of polyacrylamide–type polymers including partially hydrolyzed
Polymer concentration polyacrylamides, sulfonated polyacrylamides, and cationic polyacrylamides. Different from the classic nitrogen-
Polyacrylamide-type polymer
bromination method for determination of polymer concentrations, the nitrogen digestion method is based on the
Nitrogen digestion
Infrared spectroscopy
digestion of amide groups in the polymers as free nitrate ions. The experimental results show good correlations
Hydrolysis degree between the nitrogen content and polymer concentration for individual polymers in aqueous solution with pH
range from 5 to 8. It turns out the error of the correlations ranging from �2.0% to �8.6%. Sodium and calcium
ions do not impact the nitrogen content measurement, providing the reliability of the measurement in high
salinity environment. The influence of anionic surfactant is negligible, however, quaternary ammonium cationic
surfactant and betaine-type surfactants have strong impact on the polymer concentration measurement because
of the presence of nitrogen in the surfactant molecular structures. In order to improve correct the accuracy of
polymer concentration results caused by the hydrolysis reaction of acrylamide groups that happen in the long
time polymer flooding process especially at high temperature, infrared (IR) spectroscopy analysis was introduced
to identify the hydrolysis degree based on the absorption peaks at 1568 cm 1 and 1671 cm 1, representing
acrylamide group and acrylic acid group, respectively. The absorbance ratio (Ra) of the peak intensities was
correlated with the hydrolysis degree (HD) as Ra ¼ 1.35–0.590*HD. Consequently, a normalized correlation was
set up based on the polymer concentration, nitrogen content and hydrolysis degree to improve the accuracy of
polymer concentration measurement.

1. Introduction flooding processes. In some circumstances, the polymer concentrations

Water-soluble polymers have been widely used to increase the vis­
cosity of injection water for water/oil mobility ratio control to improve
oil production (Needham and Doe, 1987; Taylor and Naser-El-Din, 1998;
Green and Willhite, 1998; Jang et al., 2015; Liu et al., 2017).
Polyacrylamide-type polymers are the most commonly used
water-soluble polymers in field applications (Morgan and McCormick,
1990; Alsofi et al., 2013; Sheng et al., 2015; Zhang et al., 2019). Once
the polymer solutions are injected into the subterranean oil-bearing
formations, the concentrations can be changed owing to retentions in
the porous media, and mechanic or chemical degradation (Knight, 1973;
Chang, 1978; Kamal et al., 2015; Sun et al., 2019; Liang et al., 2019).
These changes in polymer concentration result in viscosity loss of the
polymer solutions that make uncertainties of the overall polymer
in different corresponding wells were analyzed, showing the polymer
breakthrough and polymer flow directions. Therefore, it is important to
monitor the process by measuring the polymer concentrations in pro­
duced fluids to evaluate polymer flooding performance.
The determination of polymer concentration could be a difficult task
because complex scenarios were encountered in the sample collections
and analyses. The polymer solutions are usually prepared in brines
containing a variety of salts and alkaline materials (Fakhru’l-Razi et al.,
2009). The produced aqueous solutions are normally turbid or colored
due to the presence of crude oil or solid materials. Some surfactant
compositions are present, especially in surfactant-polymer and
alkaline-surfactant-polymer flooding processes (Deng et al., 2005). In
addition, under high pH or high temperature conditions, polymer hy­
drolysis that converts amide groups to carboxyl groups can cause errors

* Corresponding author. Beijing Research Center, Aramco Asia, Beijing, 100102, PR China.
E-mail address: ming.han@aramco.com (M. Han).

https://doi.org/10.1016/j.petrol.2020.107151
Received 17 November 2019; Received in revised form 28 February 2020; Accepted 2 March 2020
Available online 3 March 2020
0920-4105/© 2020 Elsevier B.V. All rights reserved.
J. Hou et al.
in the analysis results (Ryles, 1988; Jung et al., 2012). All these factors
could contribute to the uncertainties in determining the polymer con­
centrations in produced fluids.
Many methods have been developed for polymer concentration
analysis, including nitrogen-bromination method (Scoggins and Miller,
1975, 1979; S� aez-Plaza et al., 2013a,b), turbidimetric method (Allison
et al., 1987), gel permeation chromatography (GPC) method (Taylor and
Naser-El-Din, 1994). The nitrogen-bromination method and its auto­
mated method flow injection analysis (FIA) were useful for the deter­
mination of acrylamide copolymers in process streams and surface
waters (Taylor et al., 1998). The improvements of the method are
needed to prevent the interferences from other organic substances on the
reaction of acrylamide groups, bromine water and CdI2-starch agents.
The turbidimetric method has advantages in fast operation and high
sensitivity in analysis of partially hydrolyzed polyacrylamides (Allison
et al., 1987). However, it was not applicable with sulfonated and
cationic polyacrylamides analysis (Tyssee and Vetter, 1981; Lu and Wu,
2003). GPC method was used regardless of the interferences in produced
water, but the tedious operation procedure and high-cost equipment
requirements narrow down its application in oil fields (He et al., 1990;
Barth et al., 1994; Woo et al., 2016).
Nitrogen digestion method was set up to determine polyacrylamide
concentrations based on the measurement of nitrogen content in the
polymer solution that is in proportion to the polymer concentration
(Chen et al., 2016). To measure the total nitrogen content, oxidation
substances like potassium persulfate convert the nitrogen in the amine
groups on the side chain of polymers into free nitrate ions (Fig. 1). This
eliminates the interference in the solutions by destroying the molecular
structures of the polymers in solution. After the digestion of polymers, a
color reagent is applied to combine with the nitrate ions and the
maximum absorption wavelength of the resultant solution is moved to
the visible light range to get high sensitivity. The nitrogen content is
calculated from the read-out of absorbance values by a spectropho­
tometer. A calibration curve of nitrogen content or absorbance value
versus polymer concentration is used to identify the concentration of an
unknown polymer solution.
This work presents a study of the feasibility of nitrogen digestion
method for kinds of polyacrylamide-type polymers such as partially
hydrolyzed polyacrylamides, sulfonated polyacrylamides, and cationic
polyacrylamides. A modified nitrogen digestion method is set up by
coupling the nitrogen digestion value with the hydrolysis degree (HD)
value measured by infrared spectroscopy to determine the polymer
concentrations regardless of the hydrolysis reaction of polymers in
application process.
2. Experimental
2.1. Materials
A series of commercial polymer samples were used in this study,
including partially hydrolyzed polyacrylamides HPAM-S5H (30% HD),
HPAM-S4H (40% HD), and HPAM-S6H (20% HD); sulfonated poly­
acrylamides SPAM-S1H, SPAM-S2L and SPAM-A1M, and cationic poly­
acrylamide polymers CPAM-A2L and CPAM-A3L.
Three surfactants used in this work were anionic surfactant SASC-1,
quaternary ammonium cationic surfactant SCSC-2, and betaine type
zwitterionic surfactant SBSC-3, which were purchased from Sinopharm
Fig. 1. Mechanism of the nitrogen digestion to determine polymer concentrations, including the oxidation of amide group to nitrate ions, color development reaction
of the nitrate solutions and measurement using a visible light spectrophotometer.
2
Journal of Petroleum Science and Engineering 191 (2020) 107151
Chemical Reagent Beijing. They were chosen to investigate the effects of
different types of surfactants on the applicability of nitrogen digestion
method in the mixture of surfactants and polymers.
The salts and alkali used in this work were NaCl, CaCl2, MgCl2,
Na2SO4, Na2CO3 and NaOH in analytical grade from Sinopharm
Chemical Reagent Beijing.
The total nitrogen analysis reagents used in the nitrogen digestion
method were from Merck Company. It contained 4 reagents in the
package, including N-1K and N-2K for the oxidation of acrylamide
groups in the polymers, and N-3K and N-4K as colorimetric reagents to
move the strongest absorption of nitrate ions to 580 nm. Digestion tubes
are included in the package for the oxidation of polymer solutions.
Measuring tubes are pre-packed with N-4K to be inserted in the spec­
trophotometer directly. Both digestion and measuring tubes are 10 mL
in volume and 16 mm in diameter.
2.2. Equipment
The digestion device (CR320) made by Merck Company was used to
provide high temperature for the oxidation of the amide groups in the
polymer. It was able to heat 12 tubes at the same time.
Visible light spectrophotometer (Pro 100) made by Merck Company
was used to measure the absorbance with wavelengths from 320 nm to
1100 nm.
FTIR Spectrometer (Nicolet iS10) made by Thermo Scientific was
used to determine the hydrolysis degree of polyacrylamide-type
polymers.
2.3. Nitrogen contents of polymers
250 μL polymer solution was diluted in 10 mL de-ionized (DI) water
in a clean digestion tube. The oxidation reagent N-1K reagent and N-2K
reagent were added and dissolved into the solution. The digestion tube
was placed in the digestion device (CR320) and kept at 120 � C for 1 h.
After the tube was cooled down to room temperature, 1 mL of the
digested sample was taken and mixed with the N-4K in the measuring
tubes. Then 1 mL of the N-3K was added in the measuring tubes. Shake
the tube to ensure the solution homogeneity. After 10 min for the color
development reaction, the measuring tube was inserted into the
analyzing slot of Pro 100 spectrophotometer. The nitrogen content and
absorbance values were automatically read out in a few seconds. As the
absorbance values could change with time, the measurements should be
taken within 20 min upon the addition of colorimetric reagent.
2.4. Total organic carbon (TOC) method to determine polymer
concentration
TOC analysis of polymer concentration was performed on Shimadzu
TOC-L instrument. Solutions for TOC analysis should be diluted to an
appropriate concentration that make the organic carbon fraction below
250 mgC/L. The TOC calibration line of partially hydrolyzed poly­
acrylamide HPAM-S4H were depicted from 20 ppm to 500 ppm.
2.5. Coreflooding test
A carbonate outcrop was used in the core flooding test. Core plug
length was 7.16 cm and diameter was 3.81 cm. The air permeability was
J. Hou et al. Journal of Petroleum Science and Engineering 191 (2020) 107151

103.65 md and the porosity was 13%. The weight was 186.6 g. The brine
permeability of the core plug was 63 md and 1 pore volume (PV) was
10.6 mL.
The core plug was saturated with connate water (compositions can
be found in Han et al., 2013) under vacuum. The saturated core plug was
then submerged in the connate water to establish the ionic equilibrium
between rock and brine. In the coreflooding process, 1 PV polymer so­
lution in synthetic seawater (composition can be found in Han et al.,
2013) was injected, followed by 4 PVs seawater flooding. The injection
flow rate is 0.5 mL/min. The effluent was collected at a constant time
interval (12 min) for polymer concentration analysis.

2.6. Hydrolysis of polyacrylamides

Partially hydrolyzed polyacrylamides and sulfonated poly­

acrylamides were used to develop the polymers with given hydrolysis
degree by alkaline post-hydrolysis method (Kudryavtsev et al., 1988).
0.5% of polymer such as HPAM-S4H or SPAM-A1M solution was pre­
Fig. 2. Nitrogen contents of 2000 ppm partially hydrolyzed polyacrylamide
pared in DI water. Pre-calculated amounts of 1% NaOH were added to
HPAM-S4H in different NaCl concentrations.
the solutions. The solutions were stirred slowly for 10 min and then put
in an oven at 90 � C for 2 h to undergo the hydrolysis reaction. The initial
pH value of the solutions was around 12 and it dropped to 9 when the deviation of 2.6%, demonstrating the nitrogen digestion analysis was
hydrolysis reaction finished. The gel-like products were freeze-dried for feasible with calcium concentration up to 5000 ppm. The linear rela­
48 h to have dried powder products, which were further dried in an oven tionship between nitrogen content and polymer concentration of HPAM-
at 95 � C for 24 h. Using this alkaline post hydrolysis method, we ob­ S4H in produced water with a salinity of 67,819 ppm (the composition
tained partially hydrolyzed polyacrylamides with hydrolysis degree of can be found in Han et al., 2013) further proves the applicability of the
45%, and 56% and hydrolyzed sulfonated polyacrylamides with hy­ method in high salinity environment (Fig. 4).
drolysis degree of 9%, 10%, 13% and 17%.
3.2. Interferences of surfactants on polymer concentration measurements
2.7. Infrared (IR) spectra of polymers
Surfactants have been commonly used in conjunction with polymers
The drop preparation method was used in the IR analysis. KBr disks
for improving oil productions (Liu et al., 2008; Olajire, 2014; Kamal
were prepared and coated with polymer solution. Then the KBr disks
et al., 2017; Sheng, 2014). In a surfactant-polymer (SP) flooding process,
with polymer were heated at 90 � C for 30 min. The dried sample disks
the surfactant in the mixed solution can interfere the accuracy of poly­
were detected with Nicolet iS10 FTIR Spectrophotometer. Sixteen co-
mer concentration analysis. In this work, different types of surfactants
added spectra were recorded for each specimen at a resolution of 4
(anionic, cationic, and zwitterionic surfactants) were selected to inves­
cm 1, in a wavenumber range of 650–4000 cm 1. As water has ab­
tigate the feasibility of the nitrogen digestion method in the presence of
sorption at 1640 cm 1, a spectrum of a KBr disk coated with water was
surfactants. The aforementioned SASC-1 was an anionic surfactant that
collected as background. The spectra of polymer samples were all pro­
has no nitrogen atoms in the molecules. SCSC-2 was a quaternary
cessed by subtracting the water background spectrum in the OMNIC 7.3
ammonium cationic surfactant and SBSC-3 was a betaine type zwitter­
software to eliminate the water interference.
ionic surfactant. It should be aware that both SCSC-2 and SBSC-3 pro­
vided nitrogen in the molecules. Fig. 5 depicts the measured nitrogen
3. Results and discussion contents of 2,000 ppm HPAM-S4H in the presence of 2,000 ppm of the 3
surfactants, respectively. It shows that the presence of SASC-1 leads to a
3.1. Applicability of nitrogen digestion method in different salinity brines

In polymer flooding applications, the injected polymers are usually

prepared in brines. As the salinity of polymer solutions changes during
the propagation in subterranean formations, it is necessary to probe into
the influences of different brines on the nitrogen digestion analysis to
ensure the accuracy of the polymer concentration measurement.
Therefore, we looked into the effects of sodium ions on the nitrogen
content in 2000 ppm partially hydrolyzed polyacrylamide HPAM-S4H in
aqueous salty solution. The NaCl concentrations were prepared at 0.1
mol/L (5850 ppm), 0.5 mol/L (29,250 ppm), 1 mol/L (58,500 ppm), and
2 mol/L (117,000 ppm). As the pH could affect the hydrolysis of poly­
acrylamide, the nitrogen contents were evaluated in the pH range from 5
to 8. The experimental results of partially hydrolyzed polyacrylamide
HPAM-S4H in different NaCl solutions are depicted as histograms in
Fig. 2. It shows that the measured nitrogen content presented a deviation
of 6.6% in this salinity range.
To study the effects of divalent ions on the nitrogen digestion anal­
ysis, the nitrogen contents of 2000 ppm partially hydrolyzed poly­
acrylamide HPAM-S4H with different calcium concentrations (500 ppm, Fig. 3. Nitrogen contents of 2000 ppm partially hydrolyzed polyacrylamide
1000 ppm, 2000 ppm, and 5000 ppm) in addition to 1 mol/L NaCl were (HPAM-S4H) in different calcium concentrations in the presence of 1 mol/
determined. Fig. 3 shows that the measured nitrogen contents with a L NaCl.

3
J. Hou et al.
Fig. 4. Correlation between nitrogen content and polymer concentration for
partially hydrolyzed polyacrylamide HPAM-S4H in produced water.
deviation of 3.8% from the reference nitrogen content. It demonstrates
the polymer concentration obtained was not affected by the presence of
anionic surfactant. However, the nitrogen content results of HPAM-S4H
in the presence of SCSC-2 and SBSC-3 turned out to be about 10% and
about 30% respectively higher than the reference value. It testifies
obviously the surfactants containing nitrogen atoms contribute to the
overall nitrogen content. Obviously, the nitrogen digestion analysis
cannot be applied to surfactant-polymer formulations that are composed
of quaternary ammonium cationic surfactant or betaine type surfactant.
The obtained polymer concentration should be adjusted by the known
surfactant concentration by other means.
3.3. Applicability of nitrogen digestion method for different kinds of
polyacrylamides
Fig. 6 presents a histogram of the nitrogen contents of 7 polymers at
250 ppm in 1 mol/L NaCl solution. The nitrogen contents vary with the
polymer types. Even for the same type of partially hydrolyzed poly­
acrylamide, the polymers with different hydrolysis degrees presented
Fig. 5. Nitrogen contents of 2000 ppm partially hydrolyzed polyacrylamide
HPAM-S4H in the presence of 2000 ppm SASC-1, SCSC-2 and SBSC-3,
respectively.
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Journal of Petroleum Science and Engineering 191 (2020) 107151
different nitrogen contents at the same polymer concentration. It is
worth to recall that the cationic polymers (CPAM-A2L and CPAM-A3L)
possessed quandary ammonium groups that contribute the nitrogen
content but the variation were not significant in the measurement. Also,
Fig. 6 shows the calculated polymer concentrations obtained based on
measured nitrogen contents. It appears the calculated polymer concen­
trations were not the same as the known polymer concentrations, which
demonstrated a variation of less than 10%. As the response signals of the
nitrogen digestion analysis vary with the polymers, it is crucial to set up
a correlation curve for each polymer.
Fig. 7 presents the nitrogen contents as a function of polymer con­
centration for 7 different polymers. It shows that the polymer concen­
trations fit very well linearly with nitrogen contents for all polymers
studied including partially hydrolyzed polyacrylamides, sulfonated
polyacrylamides and cationic polyacrylamides. The polymer concen­
tration ranged from 100 ppm to 1000 ppm. The correlation between
nitrogen content (CN) and polymer concentration (Cp) can be described
by the following expression:
CN ¼ a � Cp þ b (1)
where a and b are constant. Table 1 summarizes the correlations for each
polymer. It is interesting to note that the difference of the correlation for
a polymer from its analogue is attributed to the distinctive chemical
structure with the amide group or sometimes quaternary ammonium
group. To ensure the measurement accuracy, the nitrogen content of DI
water and pure brines was measured as control test. The absorbance
value was 0.01 and the nitrogen content was less than 1 mgN/L. The
detection limit of polymer concentration was about 50 ppm. The mea­
surement errors were in the range of �2.0% to �8.6% as shown in
Table 1.
Here is an example to verify the accuracy of the nitrogen digestion
analysis, a polymer flooding experiment was conducted to measure the
dynamic polymer adsorption onto a carbonate core plug by injecting
2000 ppm partially hydrolyzed polyacrylamide HPAM-S4H. The
collected effluents were measured by nitrogen digestion analysis in
comparison with total organic carbon (TOC) analysis. Fig. 8 shows the
variation of the polymer concentrations in collected effluents as a
function of injection volume. It indicates the consistency of the polymer
concentrations obtained by the two methods. The dynamic adsorption
was 0.053 mg/g-rock by nitrogen digestion analysis and 0.051 mg/g-
rock by TOC analysis. The experimental results further demonstrate
the accuracy of the nitrogen digestion method.
Fig. 6. Nitrogen contents and calculated concentration of various kinds of
polyacrylamides at 250 ppm in 1 mol/L NaCl.
J. Hou et al. Journal of Petroleum Science and Engineering 191 (2020) 107151

Fig. 7. Correlation between nitrogen content and polymer concentration for 7 polymers.

Table 1
Summary of the correlations between CN and Cp for different polymers.
Polymer type Polymer Correlation Error
name

Partially hydrolyzed HPAM-S5H CN ¼ 0.126*Cp þ �5.2%

polyacrylamide 18.2
HPAM-S4H CN ¼ 0.111*Cp þ �8.6%
2.86
Sulfonated polyacrylamide SPAM-S1M CN ¼ 0.0902*Cp þ �2.0%
10.0
SPAM-S2L CN ¼ 0.0987*Cp þ �4.0%
12.3
SPAM-A1M CN ¼ 0.125*Cp þ �2.0%
4.25
Cationic polyacrylamide CPAM-A2L CN ¼ 0.104*Cp þ �5.2%
11.4
CPAM-A3L CN ¼ 0.103*Cp þ �8.4%
16.4

3.4. Effect of hydrolysis degree on the nitrogen content

In polymer flooding application, polymers can undergo hydrolysis of
amide groups to acrylic acid groups during the propagation in the sub­
terranean formations, especially with the exposure to a high tempera­
ture aqueous environment (Moradi-Araghi and Doe, 1987; Levitt et al.,
2011). The loss of amide groups can make errors in the concentration
measurement that is based on nitrogen content.
To elucidate the effects of hydrolysis degree on the determination of
polymer concentration, some partially hydrolyzed polyacrylamides
were measured using the nitrogen digestion analysis. Fig. 9 shows the
Fig. 8. Effluent polymer concentration in a core plug polymer flooding ob­
tained by nitrogen digestion method and TOC method.
variation of nitrogen content as a function of polymer concentration
from 100 ppm to 1000 ppm of partially hydrolyzed polyacrylamides
with the hydrolysis degrees of 30%, 45%, and 57%, respectively. Also,
the experimental results show that the nitrogen contents of high HD
polyacrylamides are lower than that of low HD ones. This is consistent
with the fact that the hydrolysis of polyacrylamides led to the loss of

5
J. Hou et al.
Fig. 9. Correlation between nitrogen content and polymer concentration of
partially hydrolyzed polyacrylamides with different hydrolysis degrees in 1
mol/L NaCl.
amide groups and the decrease of nitrogen content.
3.5. Determination of hydrolysis degree of polyacrylamides by IR
spectroscopy
The determination of the components of acrylamide (AM) and
acrylic acid (AA) using IR spectroscopy was well documented (Guerrero
et al., 1985; Yuan et al., 1987). It was found that the peak at 1568 cm 1
represents the asymmetric stretching vibration of C– – O in –COO- of AA
1
groups, while the peak at 1671 cm represents the asymmetric
stretching vibration of C– – O in –CONH of AM groups.
Fig. 10 shows the IR spectra of partially hydrolyzed polyacrylamides
with different HDs, namely 30%, 40%, 45% and 57%. It demonstrates
obviously that the increase of HDs was associated with the increase in
the intensity of the peak at 1568 cm 1 and decrease in the intensity of
the peak at 1671 cm 1. Herein, we define Ra as the absorbance ratio of
Fig. 10. Infrared spectra of partially hydrolyzed polyacrylamides with different
hydrolysis degrees. The arrows indicate the two peaks of AM (1671 cm 1) and
AA (1568 cm 1) and the red dash lines indicate the top of the peaks. (For
interpretation of the references to color in this figure legend, the reader is
referred to the Web version of this article.)
6
Journal of Petroleum Science and Engineering 191 (2020) 107151
the intensity of peak at 1671 cm 1 versus the intensity of peak at 1568
cm 1 to correlate with the hydrolysis degree.
Fig. 11 shows the IR spectra of sulfonated polyacrylamides with
different hydrolysis degrees of 0%, 9%, and 13%. As expected, with the
sulfonated monomers in the polymer structure, the IR spectra could be
distinct from those of partially hydrolyzed polyacrylamides. The peaks
of the antisymmetric stretching vibration of C– – O in –COO- and in
–CONH shifted to 1544 cm 1 and 1668 cm 1, respectively. Similarly, we
use the parameter Ra to represent the absorbance ratio of the intensity of
the peak at 1668 cm 1 versus the intensity of the peak at 1544 cm 1.
Fig. 12 presents the correlation of Ra with the hydrolysis degrees for
partially hydrolyzed polyacrylamides and sulfonated polyacrylamides.
The correlation can be expressed as following:
Ra ¼ 1:35 0:590∗HD (2)
It fitted both partially hydrolyzed polyacrylamides and sulfonated
polyacrylamides with an error less than � 8%. Whereas, the detection
limit in hydrolysis degree is about 10%.
3.6. Correlation of nitrogen content, hydrolysis degree and polymer
concentration
In order to get more accurate polymer concentration when hydro­
lysis occurs, the hydrolysis degree should be taken into account for the
adjustment of the value obtained from nitrogen content. In principle, the
nitrogen content in partially hydrolyzed polyacrylamide can be
expressed as following
CN ¼ Cp ∗ ð1 HDÞ∗MN = ðMAA ∗ HD þ ð1 HDÞ ∗ MAM Þ (3)
where MN, MAA and MAM are the molecular weight of nitrogen atom, the
molecular weight of acrylamide acid and the molecular weight of
acrylamide respectively. When MN ¼ 14, MAA ¼ 94 (in the form of so­
dium acrylate) and MAM ¼ 71, Eq (3) can be written as
CN ¼ Cp �ð1 HDÞ�14 = ð94�HD þ ð1 HDÞ�71Þ
which is
�
CN Cp ¼ 0:61 þ 2:49 = ðHD þ 3:09Þ (4)
It means that the nitrogen content obtained by the nitrogen digestion
analysis and the hydrolysis degree of the polymers obtained by infrared
Fig. 11. Infrared spectra of sulfonated polyacrylamides with different hydro­
lysis degrees. The arrows indicate the two peaks of AM (1668 cm 1) and AA
(1544 cm 1) groups and the red dash lines indicate the bottom of the peaks.
(For interpretation of the references to color in this figure legend, the reader is
referred to the Web version of this article.)
J. Hou et al.
Fig. 12. Correlation of Ra with hydrolysis degrees of partially hydrolyzed
polyacrylamides and sulfonated polyacrylamides.
spectroscopy analysis can be correlated in a normalized curve in the
form of Eq (4). It is set as a material balance-based model for the cor­
relation. Fig. 13 shows the line of CN/Cp versus 1/(HDþ3.09) along with
the experimental data from Figs. 7b and 9. The slope of the fitted
experimental line was 2.03 and the intercept was 0.475. Comparing to
the model described in Eq (4), the experimental data present the similar
trend with relatively small variation. The difference of the experimental
data from the model can be attributed to the salt environment, such as
ion type, ion composition, ion concentration, which is dissimilar from
ideal electrolyte pairs in the model. In this case, by knowing the CN and
HD, polymer concentration should be obtained from the fitted experi­
mental line when the polymer solutions are in the particular salt envi­
ronment. This helps the accurate determination of polymer
concentrations regardless of the changes in the hydrolysis degree.
4. Conclusions
1) The nitrogen digestion method is an effective way for determining
the concentration of polyacrylamide-type polymers, including
partially hydrolyzed polyacrylamide, sulfonated polyacrylamides,
and cationic polyacrylamides.
2) The polymer concentration results obtained by nitrogen digestion
method are accurate and reliable in high salinity brine conditions,
since sodium and calcium ions do not influence the nitrogen content
measurement.
3) The influence of anionic surfactants is negligible in the nitrogen
content measurement. However, the method is not directly appli­
cable in the presence of quaternary ammonium cationic surfactants
and betaine-type surfactants because of the presence of nitrogen in
the molecule structures.
4) Coupled with the hydrolysis degree determined by using infrared
spectroscopy, the nitrogen digestion method is modified to provide
more accurate polymer concentrations regardless of the changes in
hydrolysis degree.
Declaration of competing interest
The authors declare no competing interests on this paper.
CRediT authorship contribution statement
Jian Hou: Conceptualization, Methodology, Data curation, Writing -
original draft. Ming Han: Investigation, Supervision, Writing - review &
7
Journal of Petroleum Science and Engineering 191 (2020) 107151
Fig. 13. Variation of CN/Cp versus 1/(HDþ3.09) for partially hydrolyzed
polyacrylamides with different hydrolysis degrees.
editing. Alhasan Fuseni: Validation, Resources.
Acknowledgement
The authors are grateful to Mr. Dongqing Cao for his support in
conducting coreflooding experiment and helpful discussion.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.petrol.2020.107151.
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