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An integrated radiotracer approach for the laboratory evaluation of scale

inhibitors performance in geological environments

Article  in  Chemical Engineering Science · November 2006

DOI: 10.1016/j.ces.2006.07.034

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 Chemical Engineering Science 61 (2006) 7057 – 7067
www.elsevier.com/locate/ces

An integrated radiotracer approach for the laboratory evaluation of scale

inhibitors performance in geological environments
E. Stamatakis a,b,c,∗ , C. Chatzichristos c , J. Sagen c , A.K. Stubos b , I. Palyvos a ,
J. Muller c , J.-A. Stokkan d
a School of Chemical Engineering, National Technical University of Athens (NTUA), Greece
b National Centre for Scientific Research Demokritos (NCSRD), 15310 Agia Paraskevi, Attica, Greece
c Institute for Energy Technology (IFE), P.O. Box 40, NO-2027 Kjeller, Norway
d M-I Production Chemicals, Spelhaugen 18, Fyllingsdalen, Bergen, Norway

Received 28 December 2005; received in revised form 14 July 2006; accepted 14 July 2006
Available online 25 July 2006

Abstract
The applicability of a newly developed radiotracer technique as a reliable laboratory procedure for the evaluation of scale inhibitors
performance to prevent mineral precipitation is demonstrated. The performance of two new environmentally friendly inhibitors to prevent
calcite and barite scale was evaluated experimentally in connection with a standard phosphonate-type scale inhibitor using the radioactive tracer
technology. The radiotracers 47 Ca and 131 Ba were employed in order to monitor at real-time calcite and barite scale formation, respectively.
The results show that the developed radiotracer technique can be established as a novel method for the determination of the minimum inhibitor
concentration (MIC) under dynamic, reservoir conditions. In addition, the radioactive tritiated water (HTO) was used as a reference water
tracer to identify the inhibitors’ properties, such as adsorption/desorption characteristics, in sandpack-flooding tests. Further issues regarding
the implementation of the radiotracer technology for the laboratory evaluation of scale inhibitors performance are also discussed.
䉷 2006 Elsevier Ltd. All rights reserved.

Keywords: Adsorption; Desorption; Inhibition; Porous media; Precipitation; Radiotracer

1. Introduction chemical inhibition is the preferred method of maintaining well

Scale formation can be defined as the unwanted deposition of
a solid layer of salts on a surface. This surface can be anything
like a heat-transfer surface, the walls of pipelines or vessels,
the pore surfaces in rock formations or membranes. In particu-
lar, the formation of mineral scales from produced water/brines
in oil/gas wells, pipelines and the near wellbore formation is
called oilfield scale. The direct cost of removing oilfield scale
from one well can be as high as $2.5M, and the cost of deferred
production even higher (Wigg and Fletcher, 1995). Just as pre-
vention is better than cure in medical practice, keeping pro-
ducing oil wells healthy is ultimately the most efficient way to
produce hydrocarbons. In most cases, scale prevention through
∗ Corresponding author. National Centre for Scientific Research Demokri-
tos (NCSRD), 15310 Agia Paraskevi, Attica, Greece. Tel.: +302106503408.
E-mail address: manas@ipta.demokritos.gr (E. Stamatakis).
0009-2509/$ - see front matter 䉷 2006 Elsevier Ltd. All rights reserved.
doi:10.1016/j.ces.2006.07.034
productivity. Inhibition techniques can range from basic dilu-
tion methods, to the most advanced and cost-effective methods
of threshold scale inhibitors. There are literally thousands of
scale inhibitors for diverse applications ranging from heating
boilers to oil wells. Most of these chemicals block the growth
of the scale particles by “poisoning” the growth of scale nu-
clei. Threshold scale inhibitors interact chemically with crystal
nucleation sites and substantially reduce crystal growth rates.
Threshold scale inhibitors effectively inhibit formation of min-
eral scales at concentrations on the order of 1000 times less
than a balanced stoichiometric ratio (Rosenstein, 1936). This
considerably reduces the treatment cost. Inhibitors commonly
used in the oil industry include phosphates and polyphosphates,
phosphate esters, organic phosphonates, polyacrylates, and var-
ious other polymers and copolymers of phosphonates, carboxy-
lates, and sulfonates (Ralston, 1972; Matty and Tomson, 1988).
The choice of inhibitors depends on the particular solution
7058 E. Stamatakis et al. / Chemical Engineering Science 61 (2006) 7057 – 7067
composition, compatibility, stability, and temperature. Al-
though the inhibition method was invented in 1936 by
Rosenstein (1936), the detailed mechanism of inhibition is
still not fully understood. In addition, there is no appropriate
theory or model available for the use of inhibitors in the con-
trol of scale deposits (Vetter, 1976). The suitable inhibitor to
use and its effective concentration still remain empirical often
requiring extensive testing for each individual case.
In general, inhibition treatments are carried out by squeezing
(injecting) an aqueous solution of the inhibitor several meters
into the formation where the inhibitor is retained within the
rock. The subsequent release of inhibitor into the produced
water provides protection against scaling; the treatments are
repeated when the concentration of inhibitor in the produced
water falls below the threshold level for effective inhibition.
The two inhibitor squeeze technologies currently used by
the industry are identified by the mechanisms by which the
inhibitor is retained within the formation. In the adsorption
squeeze, the inhibitor is retained by adsorption onto the reser-
voir rock and is released by desorption. In the precipitation
squeeze the inhibitor is retained within the formation as a (solid
or liquid) precipitated phase and is released by re-dissolution
(Rabaioli and Lockhart, 1996a). In both treatments, a dilute
aqueous solution of the inhibitor is pre-flushed in order to cool
the formation in the near wellbore area and then a concentrated
inhibitor slug (10–15%) is positioned several meters from the
wellbore by means of brine post-flush. The well is shut-in for a
period of time (6–48 h) to allow the inhibitor to react with the
rock. Finally, the well is put back on production and the scale
inhibitor returns to the wellbore at a concentration above its
threshold level. The success of a squeeze treatment is judged
by its effective lifetime (Stokkan, 1999).
This paper describes a new approach to the laboratory
evaluation of scale inhibitors performance to prevent mineral
precipitation. A large number of radiotracer experiments have
been carried out to study the kinetics of crystallization of var-
ious compounds in the presence or absence of scale inhibitors
(Choppin and Rydberg, 1980; Reddy and Nancollas, 1971).
However, there is a lack of literature regarding the dynamic
study of scaling mechanisms in porous media using radiotrac-
ers. McElhiney and co-researchers, in their study on the in
situ determination of BaSO4 precipitation, were aware of this
shortage and they pointed out the need of the use of radiotrac-
ers to monitor SO−2 4 (McElhiney et al., 2001). In our previous
work, we presented the advantages of the radioactive tracer
technology for laboratory experimental investigations of the
scaling phenomena involved in geological systems under flow
conditions (Stamatakis et al., 2005a). Here, we suggest that the
developed radiotracer technique could be established as a novel
method for the determination of the minimum inhibitor concen-
tration, MIC, necessary to avoid scale formation. In that respect,
the performance of two new environmental friendly inhibitors
to prevent calcite and barite scale is evaluated experimentally
in connection with the performance of a standard phosphonate-
type scale inhibitor using the radioactive tracer technology. The
nuclides 47 Ca and 131 Ba are used as tracers in order to monitor
calcite and barite scale formation, respectively, in the absence
and presence of scale inhibitors. A semi-empirical model for
scale control, based on our experimental data, is presented. In
addition, HTO (tritiated water molecule; formed when a tritium
atom, 3 H, substitutes a hydrogen atom in the water molecule)
was used as a radioactive tracer to identify the inhibitors’
properties, such as adsorption/desorption characteristics, in
sandpack-flooding tests. Further possible implementations of
the radiotracer technology for the laboratory evaluation of scale
inhibitors performance to prevent scaling are also considered.
2. Experimental procedures and tests
Recently, a need for the so-called “green inhibitors” to
control mineral scale formation has emerged. In that respect,
two newly developed scale inhibitors with good environmen-
tal characteristics were selected for this study; polymaleic
acid (PMA) and sulfonated polyphosphinocarboxylic acid
(S-PPCA) are classified, environmentally acceptable sub-
stances (>20% biodegradable), showing good adsorption and
inhibition properties. S-PPCA is a product especially developed
for high-temperature/high-pressure/high-salinity (HP/HT/HS)
reservoirs and gives longer squeeze life than standard in-
hibitors, while PMA can easily be used up to about 140 ◦ C. In
addition, the commonly used phosphonate-type scale inhibitor
amino (methylene phosphonic acid) disodium salt (Na2 AMP)
is used as reference during the tests, since its properties are
well known. All inhibitor products have been provided by M-I
Production Chemicals. Table 1 summarizes the properties of all
scale inhibitors employed in this work together with their anal-
ysis methods. The influence of the presence of PMA, S-PPCA,
and NA2 AMPon the scale formation of calcium carbonate and
barium sulfate in aqueous supersaturated solutions has been
investigated in the present study at 100 ◦ C. The experimental
system used in this study is illustrated in Fig. 1 and is similar
to the one described in our previous investigation (Stamatakis
et al., 2005a).
The nuclides 47 Ca and 131 Ba were employed as tracers in
order to monitor CaCO3 and BaSO4 precipitation, respectively,
in the absence and presence of scale inhibitors. Both nuclides
emit gamma radiation, which can be measured online when
the tracer is inside the sandpack. These measurements do not
distinguish between aqueous and solid-phase concentrations.
A scintillation
-detector (noted as detector 1 in Fig. 1) mea-
sures the radiotracer (47 Ca or 131 Ba) accumulation at the inlet
due to scale precipitation. A scintillation detector consists of a
scintillator optically coupled to a photomultiplier tube which
produces a pulse of electric current when light is transmitted
to the tube from the scintillator. For
-rays, sodium iodide with
small amount of thallium impurity, NaI(Tl), is the most com-
mon scintillator. A gamma scanner was also used to measure
the scale distribution along the sandpack. The gamma scanner
consists of a collimated NaI(Tl) detector that can move along
the sandpack. The collimator is made of lead and ensures that
the detector can only detect gamma radiation from a small slice
of the sandpack defined by the collimator opening. Thus, by
moving the detector and collimator along the sandpack, the
spatial radiotracer distribution can be measured.
 E. Stamatakis et al. / Chemical Engineering Science 61 (2006) 7057 – 7067 7059

Table 1
Scale inhibitor properties

Inhibitor Type/content Analysis Scale properties

PMA Co-polymer Polymer method (fluorescence or hyamine) Scale squeeze and topside application. Can eas-
ily be used up to about 140 ◦ C. Can be used
as non-aqueous SI. Suitable for sulfate and car-
bonate scale.
S-PPCA Polyacrylate ICP for high level detection (>100 ppm). HP/HT/HS scale inhibitor. Suitable for carbon-
Polymer (fluorescence or hyamine) for lower ate and sulfate scale and as topside/squeeze
concentrations (under testing) product. Can be used in a solvent package as
non-aqueous product
Na2 AMP Amino(methylene phosphonic ICP, molybdenum blue Scale inhibitor, suitable for both
acid) disodium salt carbonate and sulfate scales

data log

pressure gauge
∆p
anionic solution transmitter
(NaHCO3 or Na2SO4) pH electrod

glycol bath
detector 1

sandpack
H2O
back-pressure
valves regulator (BPR)

heating tube filter

balance pump
piston sample collector
cylinders labeled cationic
H 2O solution
(47CaCl2 or 131BaCl2)
- scanner

balance pump

Fig. 1. Experimental setup illustration.

Uncharged silicate sand was used as a packing material in
order to avoid nuclide accumulation due to sorption. Table 2
presents the test matrix with all the laboratory experiments
performed. Three kinds of tests were carried out. Slug tests
(see Section 3.1), where the studied inhibitors were co-injected
in the sandpack along with tritiated water (HTO) in order to
obtain the adsorption/desorption properties of the chemicals on
the porous solid. Continuous injection tests (see Section 3.2),
where supersaturated solutions with the presence of a specific
inhibitor pass through the sandpack and the scaling induction
time is measured for different saturation ratios and inhibitor
concentrations. Finally, squeeze tests (see Section 3.3), where
a “squeeze treatment” is effectively simulated in the sandpack
and the related sorption/diffusion properties of the inhibitors are
evaluated. The inhibitors were provided by the manufacturer
in the form of liquid solution of the substance in water with
given active concentration. To prepare further solutions with
pre-defined active inhibitor concentrations for use in this work
the initially provided water solutions were properly diluted.
Thus, it is important to note here that all inhibitor concentrations
in this study refer to their active concentrations by volume, i.e.,
the volume of the original active inhibitor solutions in the bulk
volume of the final solution.
3. Results and discussion
The concentrations of the inhibitors did not decrease to any
significant extent the solution supersaturation with respect to
calcite or barite. This fact suggests that the inhibition action of
these compounds is caused by preferential adsorption at the ac-
tive growth sites of the new nuclei or/and the seed crystals and
not by any kind of chelating process (Klepetsanis et al., 2000).
7060 E. Stamatakis et al. / Chemical Engineering Science 61 (2006) 7057 – 7067

Table 2
List of the laboratory experiments

RUN Test Concentration (g/l) SRa T (◦ C) P (bar) Q (ml/min) tind (min) Inhibitor
47 CaCl NaHCO3
2

1 Slug 100 10 0.2 – 200 ppm of each product

2 Calcite scale 1.39 1.05 50 100 10 0.2 62 –
3 Calcite scale 1.39 1.05 50 100 10 0.2 210 20 ppm S-PPCA
4 Calcite scale 1.39 1.05 50 100 10 0.2 130 10 ppm S-PPCA
5 Calcite scale 1.39 1.05 50 100 10 0.2 295 25 ppm S-PPCA
6 Calcite scale 1.39 1.05 50 100 10 0.2 – 40 ppm S-PPCA
7 Calcite scale 0.55 0.42 15 100 10 0.2 179 –
8 Calcite scale 0.55 0.42 15 100 10 0.2 323 1 ppm S-PPCA
9 Calcite scale 0.55 0.42 15 100 10 0.2 967 5 ppm S-PPCA
10 Calcite scale 0.55 0.42 15 100 10 0.2 – 10 ppm S-PPCA
11 Calcite scale 0.55 0.42 15 100 10 0.2 705 1 ppm PMA
12 Calcite scale 0.55 0.42 15 100 10 0.2 1993 2 ppm PMA
13 Calcite scale 0.55 0.42 15 100 10 0.2 – 5 ppm PMA
14 Calcite scale 0.55 0.42 15 100 10 0.2 396 1 ppm Na2 AMP
15 Calcite scale 0.55 0.42 15 100 10 0.2 1011 2 ppm Na2 AMP
16 Calcite scale 0.55 0.42 15 100 10 0.2 – 5 ppm Na2 AMP
17 Barite scale 0.22b 2.58c ∼3900 100 10 0.2 150 –
18 Barite scale 0.22b 2.58c ∼3900 100 10 0.2 200 30 ppm PMA
19 Barite scale 0.22b 2.58c ∼3900 100 10 0.2 – 40 ppm PMA
20 Barite scale 0.22b 2.58c ∼3900 100 10 0.2 165 30 ppm S-PPCA
21 Barite scale 0.22b 2.58c ∼3900 100 10 0.2 175 40 ppm S-PPCA
22 Barite scale 0.22b 2.58c ∼3900 100 10 0.2 190 50 ppm S-PPCA
23 Barite scale 0.22b 2.58c ∼3900 100 10 0.2 – 100 ppm S-PPCA
24 Barite scale 0.22b 2.58c ∼3900 100 10 0.2 170 30 ppm Na2 AMP
25 Barite scale 0.22b 2.58c ∼3900 100 10 0.2 – 60 ppm Na2 AMP
26 Squeeze 1.39 1.05 50 100 10 0.2 – 10% S-PPCA
27 Squeeze 1.39 1.05 50 100 10 0.2 – 10% Na2 AMP
28 Squeeze 1.39 1.05 50 100 10 0.05 – 10% Na2 AMP
a SRs were calculated using the computer program multiSCALE (version 5.1), assuming mixing 1:1 of the two solutions at the experimental temperature

and pressure (http://www.petronett.com/multiscale/).

b Concentration (g/l) for 131 BaCl .
2
c Concentration (g/l) for Na SO .
2 4

Chelating inhibitors tie up the reactants ions (e.g., Ba2+ , Ca2+ )
in a soluble form reducing the solution saturation ratio. How-
ever, as chelating agents consume scale ions in stoichiometric
ratios, their efficiency and cost-effectiveness as scale inhibitors
are relatively poor (Crabtree et al., 1999).
An additional comment regarding the possibility of forming
Ca–inhibitor or Ba–inhibitor precipitates should be made here.
In our case, no such precipitates have been observed in the XRD
and SEM images that were taken for runs 4, 19. Moreover, the
studies reported in the literature show that polymeric inhibitor
precipitation as Ca–inhibitor complex is regulated by temper-
ature, Ca2+ and inhibitor concentration and pH. In particular,
it has been found that for low Ca2+ conc. (<500 ppm) the in-
hibitor solution is homogeneous (one single phase) to high pH
values (>10). For higher Ca2+ conc. a phase separation may
occur at lower pH values depending on the temperature and in-
hibitor concentration (Rabaioli and Lockhart, 1996b; Lawless
et al., 1993). Similar results have been found for the inhibi-
tion of barium sulfate precipitation where Ba–inhibitor com-
plexes are no likely for pH
8 (Jones et al., 2003). In our study
the system pH was kept between 6 and 7, while [Ca2+ ] was

500 ppm and [Ba2+ ] was
150 ppm.
3.1. Slug test
A slug test has been performed using the silicate sandpack
with the aim of estimating the inhibitors’ sorption character-
istics. A given amount of the S-PPCA and PMA scale in-
hibitors (200 ppm, 500
l each) was injected in the sandpack
along with tritiated water (HTO) which is a reference ideal wa-
ter tracer. Pure water was used in the experiment at a flowrate
of 0.2 ml/min. The back pressure in the sandpack was approx-
imately 10 bar and the experiment was performed at 100 ◦ C.
Sample fractions were collected every 2.5 min (0.5 ml) and ana-
lyzed for their content of inhibitor and HTO. Note that tritiated
water is an ideal water tracer, since selective absorption and ad-
sorption effects within the reservoir can be excluded, and there
are no precipitation or dissipation problems that other chemi-
cal compounds may exhibit. HTO concentration at the outlet
of the sandpack should in principle always peak after the injec-
tion of one pore volume. Similar behavior of other substances
indicates no sorption on the porous medium. On the contrary,
a delay in the occurrence of the peak in outlet concentration
provides quantitative information on the sorption properties of
the injected chemicals on the porous solid. HTO was analyzed
 E. Stamatakis et al. / Chemical Engineering Science 61 (2006) 7057 – 7067 7061

1.2 the Langmuir isotherm was also used for the simulations of the
HTO simulation slug and squeeze tests with the following coefficients:
HTO experimental data
1.0 S-PPCA simulation
S-PPCA experimental data • for S-PPCA:
0.8 PMA simulation
Relative con

PMA experimental data

 = 0.865 ml/g, b = 2.03;
0.6
• for PMA:
0.4
 = 2.98 ml/g, b = 8.76.
0.2

0.0 3.2. Continuous injection

0 1 2 3 4 5 6 7
Pore volumes
Fig. 2. Production curves of the tested scale inhibitors (PMA, S-PPCA) and
the reference water tracer HTO compared with the simulation curves (run 1).
Table 3
Recoveries of S-PPCA and PMA scale inhibitors in a sug test (run 1)
Inhibitor S-PPCA PMA
% Recovery 98.7 99.1
using a liquid scintillation counter and measured in cpm units
(counts per minute).
As shown in Fig. 2, the two scale inhibitors tested are reach-
ing the outlet of the sandpack with a time lag compared to
HTO. Given the fact that HTO does not interact (adsorb) on
the solid, this time lag virtually means that the inhibitors have
been adsorbed onto the porous medium. Their final recoveries,
however, were measured higher than 98%, indicating no strong
interactions with the porous medium or any kind of degradation
and are summarized in Table 3.
The delay in the occurrence of the peak of the outlet inhibitor
concentration can be fitted by 1-D convection/dispersion sim-
ulator that solves the mass and momentum conservation equa-
tions in the porous domain in order to provide the adsorption
characteristics of the two inhibitors (Sagen et al., 2004). Fig. 2
compares the experimental data with the produced simulation
curves assuming that adsorption on the porous domain takes
place instantaneously so that the concentration in the liquid
and on the rock is in equilibrium at all times. The equilibrium
condition in the simulator is given by the Langmuir type of
isotherm
c
(c) = , (1)
1 + bc
which provides the adsorbed amount of the inhibitor compo-
nent. (c) is defined as adsorbed inhibitor quantity per unit
mass of rock material. A Langmuir type of isotherm was cho-
sen after a series of static (equilibrium) sorption experiments
performed in this study and aiming to identify the characteris-
tic sorption isotherms of the various inhibitor solution samples
on crushed sandstone at elevated temperatures. It was found
that the Langmuir isotherm fits better the data for both PMA
and S-PPCA inhibitors than the Freundlich fit. Consequently,
8
To keep scaling cations and scaling anions separate, compos-
ite brines were prepared, such that mixing them in a 1:1 ratio
would result in the desired brine composition. The combined
supersaturated solution passes through the porous medium and
scale crystals nucleate and grow in the pore space.
The induction time, tind , of scale precipitation was then de-
termined at various saturation ratios (SR column in Table 2)
HTO and inhibitor concentrations, Cinh . The results are summarized
in Table 2. Note that the measured induction times using the ra-
> 99.9
diotracer technique were reproducible within 10% throughout
this study.
The saturation ratio, SR, is defined as
mCa2+ mCO2−
SR = 3
(2)
KSP
where mi is the a molality of ion i and Ksp is the stoichiometric
solubility product. When SR > 1, the solution is oversaturated,
while at SR = 1 the solution is at equilibrium with the solid
phase.
For the radiotracer method, the induction time is defined
as the time which elapses between the first addition of the
anionic solution into the sandpack and the moment when the
counting rate R significantly exceeds the statistical fluctuations
of the initial (or background) counting rate of the implemented
radiotracer (Stamatakis et al., 2005b).
In the present work this is defined as

R R0 + |10|. (2 )
This marks the onset of a significant change in our system, as
explained above. In Eq. (2 )  is the standard deviation of the
initial (or background) counting rate defined by


n
i=1 (R0i − R0 )
2
= , (3)
n−1
where R0i is the count-rate of tracer’s background for the ith
measurement, R0 is the average of all R0i measurements, indi-
cating the initial tracer background, and n is the number of the
measurements.
To obtain the initial tracer background, the sandpacks were
initially saturated with 50% labeled cationic solution and 50%
H2 O. Then, using detector 1, several count-rates R0i were mea-
sured.
7062 E. Stamatakis et al. / Chemical Engineering Science 61 (2006) 7057 – 7067

50 Table 5
no inhibitor The inhibition index (InhI) of S-PPCA at 100 ◦ C for calcite precipitation
10ppm

20ppm RUN SR SI (log SR) t0 (min) tinh Cinh (ppm) InhI log(tinh /t0 )
40 25ppm
40ppm
2 50 1.7 62 0 0
3 50 1.7 210 20 0.53
count-rate (cps)

4 50 1.7 130 10 0.32

30 5 50 1.7 295 25 0.68
7 15 1.18 179 0 0
8 15 1.18 323 1 0.26
130 min
20 9 15 1.18 967 5 0.73
210 min
10 15 1.18 – 10 –
62 min
295 min

10
1.0

0
0 1 2 3 4 5 6 7 8 9 10 11 12 0.8
Time (hour)

InhI [log (tinh /t0)]

Fig. 3. 47 Ca count-rate as a function of time in the absence and in the 0.6
presence of S-PPCA (runs 2–6).

0.4
Table 4
Induction times for calcite precipitation at SR = 15 and 100 ◦ C for the SR = 50
inhibitors tested SR = 15
0.2
y = 0.027x (R2 =0.99)
RUN SR Induction time (min) Scale inhibitor (ppm)
y = 0.15x (R2 =0.97)
PMA S-PPCA Na2 AMP 0.0
0 5 10 15 20 25 30
7 15 179 0 0 0
Cinh (mg/l)
8 15 323 – 1 –
9 15 967 – 5 –
10 15 – – 10 – Fig. 4. Inhibition index of S-PPCA for CaCO3 precipitation as a function of
11 15 705 1 – – inhibitor concentration at 100 ◦ C.
12 15 1993 2 – –
13 15 – 5 – –
14 15 396 – – 1 that observed in the absence of inhibitors (t0 ). A dimensionless
15 15 1011 – – 2 parameter, called inhibition index, InhI, is defined as
16 15 – – – 5
InhI = log(tinh /t0 ). (4)

3.3. CaCO3 scale formation
A series of dynamic scaling experiments in sandpacks were
performed using different concentrations of S-PPCA at SR=50
and T = 100 ◦ C. The results show a definite dependence of
calcite’s induction time, tind , on the inhibitor concentration,
Cinh . For 40 ppm active inhibitor concentration (run 6) no scale
was observed after one day, while for Cinh = 10 ppm (run 4)
the induction time was 130 min, for Cinh = 20 ppm (run 3)
the induction time was 210 min, for Cinh = 25 ppm (run 5) the
induction time was 295 min and finally we measured 62 min
induction time with no inhibitor presence (run 2) (see Fig. 3).
Similar tests were also performed for all three scale inhibitors
at SR = 15 and T = 100 ◦ C. The results are summarized in
Table 4. As indicated there, the MIC, for PMA and NA2 AMP
is between 2 and 5 ppm, while MIC is between 5 and 10 ppm
for S-PPCA under the same conditions.
As expected, the induction time for CaCO3 precipitation in
the presence of scale inhibitors (tinh ) is delayed compared to
It has been determined experimentally for S-PPCA at two dif-
ferent values of saturation ratio. The results are summarized in
Table 5.
InhI has been reported to be directly proportional to the in-
hibitor concentration, Cinh (He et al., 1999):
InhI = log(tinh /t0 ) = binh Cinh , (5)
where binh (in l/mg or l/mmol) is called the inhibitor efficiency
and is a constant for a given set of chemical and physical pa-
rameters, such as saturation ratio, temperature and molar ratio
of [Ca2+ /[HCO− 3 ]. An example of the linear relationship be-
tween InhI and Cinh is illustrated in Fig. 4 for S-PPCA at two
different degrees of supersaturation (SR=50 and 15) at 100 ◦ C.
It is shown that (as expected) for higher degrees of solution
supersaturation, more additive chemical (inhibitor) is needed
to inhibit calcite scale formation.
As mentioned previously, similar tests were also performed
for all three scale inhibitors at SR = 15 and T = 100 ◦ C. Fig. 5
compares the inhibitor efficiencies, which have been obtained
 E. Stamatakis et al. / Chemical Engineering Science 61 (2006) 7057 – 7067 7063

500
1.2 no inhibitor 30 < MIC < 40 ppm
PMA
30 ppm PMA
(binh = 0.538 l/mg)
400 40 ppm PMA
1.0

count-rate (cps)
300
InhI [log (tinh/t0)]

0.8 Na2AMP
(binh = 0.370 l/mg)
200
0.6

S-PPCA
100
0.4 (binh = 0.150 l/mg)

0.2 0
0 50 100 150 200 250 300
Time (min)
0.0
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5 Fig. 6. 131 Ba count-rate as a function of time in the absence and in the
Cinh (mg/l) presence of PMA (runs 18, 19).

Fig. 5. Inhibitor efficiency, binh , for all three products for CaCO3 precipitation
at SR = 15 and 100 ◦ C. 500
no inhibitor 50 < MIC < 100
30 ppm S-PPCA
at these conditions. Thereupon, the additives may be arranged 400 40 ppm S-PPCA
in the following order with respect to their inhibition efficiency, 50 ppm S-PPCA
binh , for calcite precipitation at SR = 15 and 100 ◦ C: 100 ppm S-PPCA
count-rate (cps)

300
PMA > NA2 AMP > S-PPCA.
From Eq. (5) one can predict the MIC as follows:
200
∗ /t )
log(tinh
∗ 0
MIC = Cinh = , (6)
binh
100
∗ must be set equal to the time period during which the
where tinh
system should be protected from scaling. The time t0 (induction
time without presence of inhibitor) can be estimated using the 0
following correlation (Stamatakis et al., 2005b): 0 50 100 150 200 250 300
Time (min)
3.0 959.8 1849.9
log t0 = 3.2 − − + , (7) Fig. 7. 131 Ba count-rate as a function of time in the absence and in the
SI T SI × T
presence of S-PPCA (runs 20–23).
where T is the absolute temperature in K, and SI is the saturation
index (SI = log SR).
Finally, we should note that the parameter binh has been found e.g., nonlinear regression analysis from the available experi-
to be a function of saturation index, SI, temperature, T (◦ K), mental data.
and the molar ratio of [Ca2+ ] to [HCO− 3 ], MR (He et al., 1999):

log binh = 1 + 2 SI + 3 /T + 4 log MR, (8) 3.4. BaSO4 scale formation

where 1 , 2 , 3 , 4 are constants, characteristic for each in-
hibitor product.
Eq. (8) and the experimental data from the work of He
et al. (1999) are consistent with observations that higher in-
hibitor concentrations are needed for higher degrees of super-
saturation or higher temperatures because of faster nucleation
rates. The MR dependence of binh comes from the fact that at
a given SI, T and Cinh , the inhibition efficiency increases as
the ratio of lattice cations in the nucleating crystals (Ca2+ in
CaCO3 ) to the lattice anion (CO2− 3 ) increases. These coeffi-
cients (1 to 4 ) are dimensionless and can be obtained from
Similar to the CaCO3 case, the performance of the new in-
hibitors (PMA and S-PPCA) to prevent barite scale was checked
experimentally in connection with the performance of a com-
monly used phosphonate-type scale inhibitor (Na2 AMP) (see
Figs. 6–8).
The influence of the inhibitor concentration on the induc-
tion time of barite precipitation was found to be stronger for
PMA than for S-PPCA and Na2AMP. It can be deduced from
Figs. 6–8 that S-PPCA presents a higher threshold concen-
tration necessary to avoid barite scale than the other two
scale inhibitors. In particular, the products seem to follow the
7064 E. Stamatakis et al. / Chemical Engineering Science 61 (2006) 7057 – 7067

500 Table 6
no inhibitor 30 < MIC < 60 ppm Typical MICs measured from offshore scale rig tests and from our work

30 ppm Na2AMP Offshore scale rig tests Our work

400 60 ppm Na2AMP
FW A : SW FW B : SW
◦
T ( C)
count-rate (cps)

107 98 100
300 SRcalcite 15–75 5–21 15–50
SRbarite 500–2000 2500–3500 ∼ 3900

Typical MIC Na2 AMP 4–50 ppm 4–50 ppm 2–100 ppm
200 (for both calcite & S-PPCA 5–40 ppm 5–40 ppm 5–50 ppm
barite scale) PMA 4–30 ppm 4–30 ppm 2–40 ppm

FW A: formation water A; FW B: formation water B; SW: seawater.

100

Finally, a note should be made at this point regarding the

0 availability of independent experimental information on the
0 50 100 150 200 250 300
scale inhibitor efficiencies (binh ) and MIC values. There are no
Time (min)
scale inhibitor efficiencies available for the chemicals tested in
Fig. 8. 31 Ba count-rate as a function of time in the absence and in the this work, so no comparison can be made for binh . However,
presence of NA2 AMP (runs 24, 25). the manufacturer of those chemicals has determined the MIC
in an offshore scale rig under real conditions. Table 6 summa-
rizes the properties of the various systems and compares them
210
with our results. The MIC ranges given in the table regarding
PMA
the offshore scale rig tests refer to mixtures of FW (formation
S-PPCA
water) to SW (seawater) in percentage ranging from 90:10 to
Na2AMP
190 60:40. For our study, MIC ranges refer to our measurements
induction time (min)

no inhibitor
over the different SR values used during our experimental pro-
cedures for both calcite and barite scale formation.
170
3.5. Squeeze tests

150 A particular aim of the present testing program is to deter-

130
-10 0 10 20 30 40
Inhibitor concentration (ppm)
Fig. 9. Induction times as a function of concentration for each inhibitor for
the precipitation of barium sulfate.
following order with regard to MIC under the tested conditions:
MICPMA < MICNa2 AMP < MICS-PPCA .
Further investigation has to be carried out to verify the above
order of efficiency under various conditions of SRs and tem-
peratures. In any case though, the radiotracer technique seems
to constitute a very promising and reliable method for the es-
tablishment of a new laboratory blocking test that can be used
for the determination of the MIC, necessary to avoid scale.
It should be stressed that the measured induction times were
reproducible within 10%. Fig. 9 shows all measured induction
times for each inhibitor, where error bars have been added. For
PMA and NA2 AMP, the distinction is obvious. For S-PPCA
there may be an overlap but again the trend—of increased in-
duction times with increasing inhibitor concentration—remains
clear.
mine the physical properties that are crucial for the behavior of
the inhibitor component in a squeeze process, such as diffusion
and adsorption/desorption. Diffusion leads to spreading of the
50 60 concentration profile during the shut-in period of the well, after
the inhibitor has been injected and over-flushed. The adsorp-
tion/desorption properties affect the time period for which the
back-produced concentration stays above the MIC value. These
properties are required for the efficient design of a field squeeze
treatment (inhibitor selection, threshold concentration, etc.).
The operational procedure for the determination of the dy-
namic adsorption/desorption characteristics of the inhibitor
products is presented in detail below and summarized in
Table 7:
1. Squeeze the sand-pack with the inhibitor solution at 60 ◦ C
and shut-in for 20 h allowing some inhibitor to adsorb on
the solid matrix.
2. Start pumping with the scaling solutions through the sand-
pack with no gas phase present.
3. Measure p and pH changes during flooding.
4. Collect samples periodically and analyze for Ca and in-
hibitor concentration.
Following the experimental procedure described above, a series
of squeeze tests were executed for S-PPCA and NA2 AMP scale
inhibitors. As already mentioned, the major aim of these tests
 E. Stamatakis et al. / Chemical Engineering Science 61 (2006) 7057 – 7067 7065

Table 7 3.5E+04
Squeeze procedure
q=0.2 ml/min
3.0E+04
Shut-in conditions q=0.05 ml/min
Temperature 60 ◦ C
2.5E+04

Na2AMP (mg/l)
Pressure 10 bar
Shut-in-time 20 h 2.0E+04
Flood conditions
Temperature 100 ◦ C 1.5E+04
Pressure 10 bar
Sand-pack 60 cm length × 6 mm internal diameter 1.0E+04
Packing-material silica sand 63–125
m
Porosity ∼ 42% 5.0E+03
Permeability ∼12 Darcy
Flow rates (a) 0.2 ml/min combined flow rate 0.0E+00
(50:50 mix, 0.1 ml/min per brine) 0 5 10 15 20 25 30 35 40
(b) 0.05 ml/min combined flow rate
Pore volumes
(50:50 mix, 0.025 ml/min per brine)
Fig. 12. NA2 AMP return curves obtained from two different flow rates (runs
27, 28).

3.5E+04
run 26
3.0E+04 5.0E+04

Inhibitor concentration (mg/l)

4.5E+04 simulation

2.5E+04 4.0E+04 experimental data (run 26)

S-PPCA (mg/l)

3.5E+04
2.0E+04
3.0E+04
2.5E+04
1.5E+04
2.0E+04
1.0E+04 1.5E+04
1.0E+04
5.0E+03 5.0E+03
0.0E+00
0.0E+00 0 3.75 7.50 11.25 15.00 18.75
0 5 10 15 20 25 Pore volumes
Time (hours)
Fig. 13. Calculated outlet concentration for the inhibitor S-PPCA. Open
Fig. 10. S-PPCA return mass after a squeeze test (run 26). circles indicate measured points. The injected flow rate is 0.2 ml/min.

3.5E+04 was identical for both inhibitors (q = 0.2 ml/ min) (see runs
run 27 26, 27). To check for the influence of the flow velocity on the
3.0E+04
adsorption characteristics, a squeeze test for NA2 AMP was also
2.5E+04 carried out at q = 0.05 ml/ min (run 28) as shown in Fig. 12.
Na2AMP (mg/l)

Specific features of such return curves (peak, position of 50%

2.0E+04 recovery point, tail) offer the possibility to deduce sorption
1.5E+04
parameters for the inhibitor (Sorbie et al., 1992).
Based on the results from the static tests (see Section 3.1),
1.0E+04 we consider that the adsorption of the tested inhibitors on
the porous medium can be described by a Langmuir type of
5.0E+03 isotherm (see Eq. (1)) and the same adsorption coefficients for
0.0E+00
S-PPCA, as in Section 3.1, were used in the 1-D simulation
0 5 10 15 20 25 code.
Time (hours) In Fig. 13 the computed outlet active concentrations of the
inhibitor S-PPCA from the simulation are plotted versus in-
Fig. 11. NA2 AMP return mass after a squeeze test (run 27). jected water volume.
Figs. 14 and 15 show the corresponding simulation results
has been the measurement of adsorption/desorption isotherm and measured data for runs 27 and 28, respectively (NA2 AMP
data that are crucial for simulating back production of inhibitors scale inhibitor), using the Langmuir coefficients as they were
in the field. calculated again from the static experiments.
Figs. 10 and 11 present the return curves of S-PPCA and It is important to emphasize once more that the same adsorp-
NA2 AMP scale inhibitors, respectively. The squeeze procedure tion coefficients determined from the static experiments were
7066 E. Stamatakis et al. / Chemical Engineering Science 61 (2006) 7057 – 7067

5.0E+04 0.3
Inhibitor concentration (mg/l)

4.5E+04 simulation

4.0E+04 experimental data (run 27)

0.25
3.5E+04

Concentration (ml/gr)
3.0E+04
0.2
2.5E+04
2.0E+04
1.5E+04 0.15
1.0E+04
5.0E+03 0.1
0.0E+00
0 3.75 7.50 11.25 15.00 18.75
0.05
Pore volumes

Fig. 14. Calculated outlet concentration for the inhibitor Na2 AMP. Open 0
circles indicate measured points. The injected flow rate is 0.2 ml/min. 0 5 10 15 20 25 30 35
Time (hours)

5.0E+04 Fig. 16. Kinetic curve for S-PPCA equilibrium during the static adsorption
Inhibitor concentration (mg/l)

4.5E+04 simulation
test.
4.0E+04 experimental data (run 28)

3.5E+04
3.0E+04 However, there is a question about the desorption process
2.5E+04 which is depicted in the experimental curves of Figs. 13–15.
2.0E+04 Note that the full duration of the squeeze test (desorption) is
1.5E+04 of the order of 20–30 h.
1.0E+04
5.0E+03
• The fact that the adsorption isotherms were used for the
0.0E+00 desorption process as well. The process might not be fully
0 3.75 7.50 11.25 15.00 18.75 reversible.
Pore volumes

Fig. 15. Produced concentration for the inhibitor Na2 AMP. Open circles
indicate measured points. The injected flow rate is 0.05 ml/min.
also used for simulating both the dynamic slug and the squeeze
tests. It has been found that those coefficients give reasonable
fits for the measured produced concentration of the inhibitors
during the back production. There is no doubt that by tuning
the simulator (by changing e.g., the isotherm Langmuir coef-
ficients) better match between simulated and measured curves
could be obtained. However, in Figs. 13–15 we attempt to
demonstrate the performance of the isotherms obtained from
simple independent static (equilibrium) measurements on the
simulation of dynamic (flow) experiments. Therefore, the same
adsorption coefficients as determined from the static tests were
employed in the simulations. In that respect, the observed dis-
crepancy between the experimental-simulated curves is mainly
due to:
• The fact that the isotherms were measured at static conditions
while tests are dynamic.
• The fact that the simulator assumes instantaneous equilib-
rium conditions. It is obvious from the slug experimental
data that instantaneous equilibration may not be fully at-
tained during the dynamic experiments. Fig. 16 shows the
equilibration time (about 10 h) needed for adsorption for
S-PPCA on crushed sandstone during the static experiments.
This equilibration time is satisfied during the dynamic ex-
periments because of the extended shut-in period of 20 h.
4. Conclusions
We successfully evaluate the capability of two new “green”
inhibitors to prevent calcite and barite deposition under dy-
namic reservoir conditions using the radiotracer technology.
The developed radiotracer technique can be established as a
novel method for the determination of the minimum inhibitor
concentration, MIC, necessary to avoid scale under flow condi-
tions. The radiotracer technique is sensitive to scaling, resulting
generally in shorter induction times compared to other methods
as demonstrated in a previous study (Stamatakis et al., 2005a).
The dynamic adsorption/desorption characteristics of the new
inhibitors were studied in experimental slug and squeeze tests.
The delay in the occurrence of the peak of the outlet inhibitor
concentration from the slug test can be fitted by 1-D convec-
tion /dispersion simulator to provide the adsorption character-
istics of the inhibitors, assuming that adsorption on the porous
domain takes place instantaneously so that the concentrations
in the liquid and on the rock are in equilibrium all the time.
The equilibrium condition in the simulator can be described by
the Langmuir type of isotherm and its coefficients , b can be
determined from simple static experiments. It has been found
that those coefficients give also reasonable fit for the measured
produced concentration of the inhibitors during the back pro-
duction of both slug and squeeze tests.
Further experimental work related to inhibitors evaluation
can be carried out using radiotracer technology in order to es-
tablish correlations for the effect of the inhibitor concentration
on the reaction rates.
 E. Stamatakis et al. / Chemical Engineering Science 61 (2006) 7057 – 7067
Acknowledgments
Partial funding of the work by the European Commission
FP5 contract No ENK6-2000-00052—ARISSTON is gratefully
acknowledged by the authors.
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