Sorption Study of c-ALO(OH)
Nanoparticle-Crosslinked Polymeric Scale
Inhibitors and Their Improved Squeeze
Performance in Porous Media
C. Yan, A.T. Kan, W. Wang, F. Yan, L. Wang and M.B. Tomson, Rice University
Summary
Polymeric scale inhibitors are widely used in the oil and gas field
because of their enhanced thermal stability and better environ-
mental compatibility. However, the squeeze efficiency of such
threshold inhibitors, not only polymeric scale inhibitors but also
phosphonates, is typically poor in conventional squeeze treatment.
In this research, nanoparticle (NP)-crosslinked polymeric scale
inhibitors were developed for scale control. Nearly monodis-
persed boehmite [c-AlO(OH)] NPs with average size of 2.8 nm
were synthesized and used to crosslink sulfonated polycarboxylic
acid (SPCA). Crosslinked AlO(OH)-SPCA nanoinhibitors were
produced and developed to increase the retention of SPCA in for-
mations by converting liquid-phase polymeric scale inhibitors
into a viscous gel. Study of sorption of SPCA onto AlO(OH) NPs
under different pHs with and without assistance of Ca2 was dis-
cussed. In addition, study of sorption of various types of scale
inhibitors [SPCA; phosphino-polycarboxylic acid (PPCA); and
diethylenetriaminepentatakis(methylene phosphonic acid) (DTPMP)]
onto AlO(OH) NPs was performed. Squeeze simulation of neat 3%
SPCA, AlO(OH) (3%)-SPCA (3%) NPs, and AlO(OH) (3%)-SPCA
(3%)-Ca NPs was investigated. The results showed that the addition
of Ca2 ions improves the squeeze performance of SPCA, and the
normalized squeeze life (NSL) of such material (8,952 bbl/kg) was
improved by a factor greater than 60 compared with that of SPCA
alone (152 bbl/kg).
Introduction
Threshold scale inhibitors, including phosphonates and polymeric
scale inhibitors, are commonly used in the oil and gas industry to
prevent scale formation, which reduces and even ceases produc-
tion and increases operation cost (Rosenstein 1936; Kan et al.
2005; Kelland 2006; Kan and Tomson 2012). Squeeze treatment
of such scale inhibitors is the most widely applied and most effi-
cient approach to prevent scale formation. But with increased con-
cerns toward the environment, phosphonates are prohibited in the
North Sea. Moreover, they are perceived to be unstable under
high-temperature conditions compared with polymeric scale
inhibitors, which typically have better thermal stability (Graham
et al. 1998; Wang and Wylde 2009; Fan et al. 2011; Wang et al.
2012). Sulfonated polymers such as sulfonated polycarboxylic
acids have been developed to meet the increasingly strict bioaccu-
mulation, biodegradation, and ecotoxicity regulations (Dickinson
et al. 2011). Sulfonated polymers with molecular weight of 2,000
have better thermal stability and brine compatibility, and a higher
biodegradation rate (Dickinson et al. 2011; Wang et al. 2012).
However, sulfonated polymeric scale inhibitors are well-known to
have poor squeeze performance because of their inertness toward
formation rock. Squeeze performance of sulfonated polymer is
even poorer than that of polyacrylates and polyacrylate-based
Copyright V
C 2014 Society of Petroleum Engineers
This paper (SPE 164086) was accepted for presentation at the SPE International
Symposium on Oilfield Chemistry, The Woodlands, Texas, USA, 810 April 2013, and
revised for publication. Original manuscript received for review 26 February 2013. Revised
manuscript received for review 1 August 2013. Paper peer approved 18 September 2013.
August 2014 SPE Journal
terpolymers (Collins et al. 1999). Thus, the use of such inhibitors
in squeeze treatment is very expensive. Therefore, it is very im-
portant and challenging to improve the squeeze performance of
sulfonated polymers so they can be used efficiently.
Generally, enhancing the efficiency of squeeze treatments is one
of the main topics for scale inhibitors, which depends upon the treat-
ment lifetime of specific inhibitors. The squeeze lifetime of phospho-
nates can be extended by performing precipitation squeeze, in which
long-term inhibitor flowback with produced brine is controlled by
their low solubility (Kan et al. 1994; Jordan et al. 1995; Friedfeld
et al. 1998; Frostman et al. 1998; Xiao et al. 2001; Kan et al. 2004;
Tomson et al. 2006). The other way to improve efficiency is to mix
metal ions such as Mg2 and Zn2 with scale-inhibitor solutions. By
introducing Zn2 ions to BHPMP (bis-hexamethylenetriaminepenta(-
methylenephosphonic acid)) and PPCA pill solutions, squeeze per-
formance of both inhibitors was improved (Kan et al. 2009). In
addition, nanoinhibitors were also developed to carry and deliver
scale inhibitors. Ca-DTPMP, Zn-DTPMP, and SiO2-Zn-phosphonate
NPs were synthesized to lengthen the squeeze lifetime (Shen et al.
2008; Zhang et al. 2010; Zhang et al. 2011a, b). Al-SPCA inhibitor
NPs were also developed to increase the retention of sulfonated poly-
carboxylic acid (Yan et al. 2012a, b). NSL (the number of barrels of
produced water protected per kilogram of inhibitor injected) is used to
evaluate and compare the squeeze performance of different scale
inhibitors (Kan et al. 2009).
Alternatively, viscous solutions or gels may be an effective
approach to improve both placement and retention of polymeric
scale inhibitors in heterogeneous reservoir formations. Viscous
fluids with both Newtonian and non-Newtonian properties were
investigated experimentally and theoretically in the past decade to
better control their placement (Sorbie et al. 2006; Heath et al.
2008; Selle et al. 2009). Simulation of applying a shear-thinning-
inhibitor slug showed dramatic effects on inhibitor placement in a
linear heterogeneous system (Sorbie et al. 2006). Field tests of
squeezing viscosified scale inhibitors have shown successful pre-
vention of scaling (Selle et al. 2009). The viscosity of squeezed
species and their retention could be increased by mixing various
types of polymers. Viscous fluids based on xanthan have been
used in the central North Sea for horizontal wells. More than 25%
of injected fluid can go through the toe section of the wells by
manipulating injection rate, indicating the enhanced placement of
scale inhibitors. The squeeze performance of such fluids is either
the same or improved compared with that of the conventional
squeeze treatments. There is no formation damage from squeezing
viscous fluid in both laboratory and field tests (James et al. 2005).
Compared with the solid-state scale inhibitors, which are com-
monly introduced during the stimulation process, viscous scale
inhibitors could also be delivered by means of the fracturing pro-
cess. However, tests of compatibility of viscous solutions or gels
with fracturing fluid should be performed. In addition, the conduc-
tivity of the proppant pack should not be affected by the use of
such materials (Powell et al. 1995; Gupta et al. 2008). Because
most solid-state inhibitors contain phophonates, how to make
polymeric scale inhibitors solid is still challenging. NP-enhanced
squeeze performance for polymeric scale inhibitors could provide
an effective approach to produce polymeric-scale-inhibitor solids.
687
 (a) (b) (c) (d) (e) (f)

Fig. 1Physical appearances of AlO(OH)-SPCA solutions at

different preparation stages. Bottles from left to right represent
the synthesis steps mentioned in text. (a) Initially formed
AlO(OH) particles; (b) Peptized AlO(OH) NPs; (c) Mixture of
AlO(OH) NPs and SPCA; (d) AlO(OH)-SPCA NPs after sonica-
tion; (e) AlO(OH)-SPCA NPs in 1% KCl; and (f) AlO(OH)-SPCA
NPs in 3% KCl.
20 nm

120
Fig. 2TEM image of AlO(OH) NPs with average size of 2.8 nm.
100

80
Counts

60

40

20

0
1.24
1.46
1.71
2.01
2.37
2.79
3.28
3.86
4.54
5.34
6.28
7.39
8.69
10.22

Size (nm)

Fig. 3DLS result of particle size and size distribution of

AlO(OH) NPs.

Review of Previous Studies

Synthesis and Characterization of AlO(OH) NPs and
ALO(OH)-SPCA NPs. In previous studies, aluminum-tri-sec-
butoxide was used as precursor to synthesize AlO(OH) NPs, which
is similar to a previous study by Yoldas (1975). The physical
appearance of the solution sample during specific synthesis stages 20 nm
is shown in Figs. 1a through 1f. First, aluminum-tri-sec-butoxide
was added to boiling water, during which it was hydrolyzed and Fig. 4TEM image of AlO(OH) (3%)-SPCA (3%) NPs prepared
formed a white precipitate with micrometer-sized particles (Fig. 1a). after 30-minute sonication with average size of 36.5 nm.

After being peptized with nitric acid to a final pH of 4, the mixture

120.0
becomes transparent, indicating the decrease of particle size
(Fig. 1b). As shown in Fig. 2, AlO(OH) nanoparticles with an aver-
100.0
age size of 2.8 nm formed. The dynamic light-scattering (DLS)
result in Fig. 3 is consistent with the transmission-electron-micros-
80.0
copy (TEM) observation and shows a narrow size distribution. In
Counts

Stage 3, various amounts of SPCA were mixed with the AlO(OH)

60.0
NP suspension, during which the initial particle size increased to
700 nm (Fig. 1c). After 30-minute sonication in Stage 4, particles
40.0
were broken up and the size decreased to 36.5 nm, as shown in
Fig. 1d. The TEM image (Fig. 4) and DLS result (Fig. 5) also con-
20.0
firm the size decrease and show the monodispersity. Also included
in Fig. 1 are the appearances of the suspension in Step 4 with the
0.0
addition of 1 and 3% KCl (Figs. 1e and 1f, respectively).
38.5
40.7
43.0
45.4
48.0
50.7
53.6
56.6
59.8
63.2
66.8
70.6
74.6
78.8
83.3
88.0
93.0
98.3

Size (nm)
Investigation of Particle Stability and Viscosity. Stability of
Fig. 5DLS result of hydrodynamic radius of AlO(OH) (3%)- AlO(OH)-SPCA NPs was studied under different temperatures,
SPCA (3%) NPs with average size of 54 nm with narrow size salinities, and pH measurements because these are three important
distribution. parameters to be considered in inhibitor squeeze processes. To

688 August 2014 SPE Journal

summarize, in 1% KCl, NP size increases slightly from 56 to 96
nm. However, particle size increases to hundreds of nanometers
in 2% KCl and above. The critical coagulation concentration of
AlO(OH)-SPCA NPs is approximately 1% KCl. The average par-
ticle size remains in a narrow range of 38 to 75 nm at pH of 5 to
11. At a pH measurement greater than 5, both carboxylic and sul-
fonic groups of SPCA were deprotonated and remained highly
negatively charged. The particle size increases dramatically at pH
lower than 5 or greater than 11. At pH of 5, there is limited
change of particle sizes (56 to 64 nm) with increase of tempera-
ture from 25 to 110 C.
In addition, the AlO(OH)-SPCA NP solution can be modified
to yield different viscous fluids in a wide range of viscosity (1 to
50,000 cp) by changing reaction conditions, including concentra-
tion of AlO(OH) and SPCA, temperature, shear rate, and salinity.
When SPCA concentration was fixed at 3% (30 g/L) and
AlO(OH) concentration increased from 0.5 to 6%, viscosity
increased from 1.8 to 50,000 cp. When AlO(OH) concentration
was kept unchanged at 3% (30 g/L) and SPCA concentration
increased from 0.5 to 3%, viscosity reached the maximum at 1%
SPCA and then decreased with increase of SPCA concentration.
When shear rate increased from 10 rev/min to 100 rev/min, vis-
cosity decreased from 2,419 to 153 cp, indicating the shear-thin-
ning property of this material. In addition, viscosity slightly
increased from 153 to 186 cp when KCl (1 to 5%) was added.
When temperature increased from room temperature to 90 C, vis-
cosity decreased to 48 cp. Moreover, viscosity recovered only
approximately half of the original value (78 cp) when the sample
was naturally cooled to room temperature. All experimental
details and data have been reported by Yan et al. (2012).
In this paper, the study of SPCA sorption onto AlO(OH) NPs
under different pHs with and without assistance of Ca2 ions and
the study of sorption of various types of scale inhibitors (SPCA,
PPCA, and DTPMP) onto AlO(OH) NPs were discussed. Squeeze
simulation of neat 3% SPCA, AlO(OH) (3%)-SPCA (3%) NPs, and
AlO(OH) (3%)-SPCA (3%)-Ca NPs in an Iceland spar calcite col-
umn was investigated. The squeeze simulation of AlO(OH)-SPCA
NPs shows that up to 77% of scale inhibitor is retained in the Iceland
spar calcite column and the returned concentration can inhibit barite
at SI 1.7 (SR 50). (SI is the saturation index, and SR is the satu-
ration ratio.) The NSL is up to 8,972 bbl of produced water per kilo-
gram of inhibitor injected, which is nearly 60 times higher than that
of squeezing a solution of neat SPCA by itself (152 bbl/kg).
Experimental Specifications
Chemicals. NaCl [American Chemical Society (ACS) reagent,
99.9%, Fisher Scientific], KCl (ACS reagent, 99.3%, Fisher Sci-
entific), CaCl22H2O (ACS reagent, 99%, EMD), and 8 N NaOH
(8.00 6 0.04 N, 13 cm3, HACH company) were used in synthesis
without further purification. SPCA used in this study was obtained
from Kemira Incorporated. PPCA, H-{[CH2CH(COOH)]x-
PO(OH)-[CH2CH(COOH)]y}z-H (Bellasol S-29, molecular
weight 3,800, BWA), is a polyacrylic acid tagged with a phos-
phino group in the molecules to facilitate measurement. DTPMP
used in this study was obtained from Solutia Incorporated, as a
50% (wt/wt) solution under the trade name Dequest 2060S.
Characterization Methods. Average particle size and size distri-
bution were measured by Brookhaven Instruments 90Plus DLS.
Samples for DLS were diluted 30 times to avoid the saturation of
instruments. TEM images were obtained with a JEOL 2010 trans-
mission electron microscope at an acceleration voltage of 100 kV.
All samples were prepared by dispersing the desired amount of
NPs in deionized water. Drops of the sample suspension were de-
posited onto a copper grid with carbon film followed by slow
evaporation of solvents. Both aluminum and sulfur concentrations
were determined by inductively coupled plasma optical emission
spectrometry (ICP-OES) (Optima 4300Dv, Perkin Elmer 2011).
Concentration of polymer was calculated from the sulfur concen-
tration. The background sulfur concentration from synthetic brine
is approximately 0.5 mg/L, which was subtracted from the total
August 2014 SPE Journal
sulfur concentration. An assay method developed by the Brine
Chemistry Consortium was used to measure and confirm the
active concentration of returned polymer.
Study of Sorption of SPCA Onto ALO(OH) NPs With and
Without Ca21 Ions. Reactions were performed in a 70 C jack-
eted-beaker water bath. With vigorous stirring by a magnetic stir-
rer, SPCA (25.7%) was continuously added into 20 cm3 of 3%
AlO(OH) NPs solution, preloaded in a 50-cm3 glass bottle, by
means of a syringe pump (New Era N100) at a rate of 1 cm3/h. The
pH of inhibitor solutions was adjusted from 1 to 5 by adding
NaOH or HCl. To study the Ca2 effect on SPCA sorption, another
syringe pump was used to add the CaCl2 solution. Both the SPCA
and CaCl2 solution were added at the same rate. Samples were ana-
lyzed for solution phase inhibitor concentrations after 0.5-, 1-, 1.5-,
and 3-hour reaction time. The solid-phase concentrations were cal-
culated by subtracting the final concentration of scale inhibitor from
the initial concentration of scale inhibitor in solution. pH was moni-
tored by pH probe (Fisher, AccuBasic 15).
Study of Sorption of PPCA and DTPMP Onto ALO(OH)
NPs. Reactions were carried out in a 70 C jacketed-beaker water
bath. PPCA solution (50%) and DTPMP solution (50%) were
both diluted to 25.7% with deionized water to compare with
SPCA solution (25.7%). The pH of the previously discussed scale
inhibitors was adjusted to 3 by adding NaOH. To 20 cm3 of 3%
AlO(OH) NPs solution in a 50-cm3 glass bottle with vigorous stir-
ring with a magnetic stirrer, PPCA solution (25.7%) or DTPMP
(25.7%) was continuously added into the solution by means of a
syringe pump (New Era N100) at a rate of 1 cm3/h. Samples were
analyzed for solution phase scale-inhibitor concentrations after
0.5-, 1-, 1.5-, and 3-hour reaction time. The solid-phase concen-
trations were calculated by subtracting the final concentration of
scale inhibitor from the initial concentration of scale inhibitor in
solution. pH was monitored by pH probe (Fisher, AccuBasic 15).
Squeeze Simulation of 3% SPCA Solution. The squeeze per-
formance of 3% SPCA in a calcite column was studied. A glass
column (10-cm length, 0.6-cm inner diameter) with two 10-lm
stainless-steel filters at both ends was packed with grounded calcite
(Iceland spar, 106 to 180 lm). The pore volume (PV) of the col-
umn is approximately 1.1 cm3 and porosity is 0.45. Approximately
1/2 PV (0.5 cm3) of 30 g/L SPCA (pH 5.5) solution premixed
with 1% KCl was injected into the previously discussed column at
70 C. SPCA was then pushed to the other end by injecting 0.5 cm3
of 1% KCl. The injection rate is 8 cm3/h, which corresponds to a
linear flow velocity of 50 ft/D. Then, the column was shut in over-
night (approximately 16 hours) at 70 C. Then, the column was
eluted with a synthetic brine (1 M NaCl, 0.1 M CaCl2, 7 mM N-(2-
Acetamido)iminodiacetic acid (ADA), at pH 6.6) at 70 C and at
8-cm3/h flow rate. The effluent solution was collected and analyzed
for sulfur concentration, which was converted to the SPCA concen-
tration to obtain the polymer-flowback curve. The details of testing
procedures and conditions are listed in Table 1.
Squeeze Simulation of AlO(OH)-SPCA NPs. Approximately 1/
2 PV (0.5 cm3) of AlO(OH)-SPCA NP suspension (pH5.5) with
and without 0.6% CaCl2 premixed with 1% KCl (wt/wt) was
injected into the calcite (Iceland spar, 106 to 180 lm) column
(10-cm length, 0.6-cm inner diameter) at a rate of 8 cm3/h. Then,
SPCA was pushed to the other end by injecting 0.5 cm3 1% KCl
at the same rate. The system was shut in overnight (16 hours).
The column was then continuously eluted from the opposite direc-
tion with a large volume of synthetic brine (1 M NaCl, 0.1 M
CaCl2, 7 mM ADA buffer, at pH 6.6) at 70 C to study the flow-
back characteristics of AlO(OH)-SPCA NPs. The details of test-
ing procedures and conditions are listed in Table 1.
Inhibition-Efficiency Test. To test the efficiency of the returned
scale inhibitor, a barite-nucleation-inhibition test was used.
689
 TABLE 1EXPERIMENTAL PARAMETERS USED FOR SQUEEZE SIMULATION OF NEAT 3%
SPCA, AlO(OH) (3%)-SPCA (3%) NP SOLUTIONS, AND AlO(OH) (3%)-SPCA (3%)-Ca NP
SOLUTIONS

Average NP radius 54 nm
Column dimension 1-cm length; 0.6-cm inner diameter
Calcite-particle/glass-bead radius 106 to 180 lm
Porosity 0.45
Initial SPCA concentration 3%
pH of SPCA 5.5
AlO(OH)-SPCA NPs concentration AlO(OH) 3%, SPCA 3%
Electrolyte composition 1% KCl
Flow rate 50 ft/D
Temperature 70 C
Pressure 1 atm
Shut-in time 16 hours
Brine composition 1 M NaCl, 0.1 M CaCl2, 7 mM ADA buffer, pH 6.6

Synthetic brine with the same composition as that used in squeeze
simulation was used to make a cationic solution containing
1.56 mM BaCl2 (Solution A), an anionic solution containing
1.56 mM Na2SO4 (Solution B), and an inhibitor in sulfate solution
containing 0.6 mg/L SPCA and 1.56 mM Na2SO4 (Solution C).
The blank experiment was performed by adding 7 cm3 each of
Solutions A and B with magnetic stirring in a 30-cm3 glass vial at
room temperature to determine the barite-nucleation rate in the
absence of inhibitor by use of the turbidity method (He et al.
1994). Then, 7 cm3 each of Solutions A and C were mixed to
determine the nucleation-inhibition efficiency of the neat SPCA at
0.3 mg/L. Finally, an effluent sample collected from squeeze sim-
ulation experiment of AlO(OH)-SPCA NPs after 2,000 PVs was
adjusted to 0.3-mg/L concentration by dilution with synthetic
brine and Na2SO4 was added to a final sulfate concentration of
1.56 mM (Solution D). Then, 7 cm3 of Solution A was mixed
with 7 cm3 of Solution D to determine the inhibition efficiency of
SPCA in the effluent solution of the squeeze-simulation
experiment.
Results and Discussion
Sorption Study and Reaction Mechanism. To better understand
the reaction and sorption mechanism and to extend research to
SPCA pH = 1 SPCA pH = 3
450
Solid Phase Conc. (g/KgAlOOH)
other types of scale inhibitors, experiments have been designed
and carried out. In Fig. 6, adsorption isotherms of SPCA onto
AlO(OH) NPs under different pH values, with and without assist-
ant of Ca2 ions, have been shown. Without adding Ca2 ions,
concentration of solid-phase SPCA reached the peak value when
SPCA was added for approximately 1 hour. Then, it dropped with
more addition of SPCA for up to 3 hours. Note that the rate of
SPCA addition is equal to adding 1% SPCA to the solution per
hour. The maximum adsorption of SPCA onto AlO(OH) NPs
increases from 219 to 323 g/kg when pH of the SPCA decreases
from 5 to 1. However, with presence of Ca2 ions, the concentra-
tion of solid-phase SPCA increased continuously with an increase
of calcium concentration. After the 3-hour addition, 387 mg/g of
SPCA was adsorbed onto the AlO(OH) NPs (orange line), and it
is five times higher than the adsorption without Ca (green line). In
addition, pH change of the reaction systems with time is displayed
in Fig. 7. pH values decreased with time when SPCA at pH was
added, and increased in other experiments. All pH values reached
a plateau for the approximately 1-hour addition of SPCA and
stayed relatively stable for up to 3 hours. The stabilized pH values
are all higher than the expected values when mixing AlO(OH)
NPs with specific SPCA solution. For example, when SPCA at pH
5 was added to AlO(OH) NPs (pH 3.3), the equilibrium pH after
1 hour is approximately 5.5, indicating the production of hydroxyl
group. Thus, the proposed reaction mechanism is ion exchange
SPCA pH = 5 SPCA pH = 5 with Ca
between SPCA molecules and OH groups in AlO(OH) NPs,
which is accompanied by increase of pH. It is consistent with the
previously reported study of adsorption of phosphate onto

400

350 SPCA pH = 1 SPCA pH = 3 SPCA pH = 5 SPCA pH = 5 with Ca

300 6

250 5.5

200 5

150 4.5
pH

100 4

50 3.5

0 3
0 5 10 15 20 25 30
2.5
Solution Phase Conc. (g/L)
2
0 50 100 150 200
Fig. 6Study of SPCA sorption onto AlO(OH) NPs where the
AlO(OH) NPs are at 3.3 pH at 70 C and the SPCA solution was Time (min)
adjusted to pH measurements of 1, 3, and 5 and slowly added
into the AlO(OH) solution. Under pH 5, Ca21 was added to Fig. 7The pHs change with time when SPCA with various pH
assist the SPCA adsorption. BluepH of SPCA 5 1; redpH of values was added to AlO(OH) NPs at pH 3.3 (70 C). Blueinitial
SPCA 5 3; greenpH of SPCA 5 5; yellowpH of SPCA 5 5 pH of SPCA 5 1; redinitial pH of SPCA 5 3; greeninitial pH
with Ca21. of SPCA 5 5; yellowinitial pH of SPCA 5 5 with Ca21.

690 August 2014 SPE Journal

 SPCA
300
Solid Phase Conc. (g/Kg AlOOH)
250
200
150
100
50
0
0 5
Solution Phase Conc. (g/L)
Fig. 8Study of SPCA, PPCA, and DTPMP sorption onto
AlO(OH) NPs where the AlO(OH) NPs are at 3.3 pH at 70 C. All
inhibitor solutions were adjusted to pH 3 and 25.7% active con-
centration. Blue 5 SPCA; red 5 PPCA; green 5 DTPMP.
AlO(OH) NPs (Watanabe et al. 2011). The peak pH value
appeared in the 1-hour addition, which is consistent with the time
at which maximum value of solid-phase concentration of SPCA
appears. It demonstrated that the adsorption process ceased when
exchange of all hydroxyl groups finished. Therefore, at lower pH
values, when more carboxylate and sulfonate groups were proto-
nated, reactions were driven forward compared with that under
pH 5, when the exchanged OH are neutralized. The adsorption
of SPCA onto the AlO(OH) NPs is limited to the surface area
of NPs.
At pH 5.5 without addition of calcium, the maximum adsorp-
tion of SPCA onto AlO(OH) is 219 mg/g. The calculated surface
area of 3% AlO(OH) NPs is approximately 660 m2/g. If the nomi-
nal surface-area coverage for SPCA is assumed to be 1 m2/mg,
then the adsorption is equivalent to approximately 30% of mono-
molecular surface coverage on AlO(OH) particles. However, with
assistance of calcium, the maximum adsorption is 387 mg/g
AlO(OH). Thus, the monomolecular surface coverage on
AlO(OH) particles by SPCA is increased to approximately 53%,
which is approximately 2 times higher than that of experiment
without calcium. Maximum adsorption can be controlled not only
by pH but also by the addition of metal ions. More SPCA de-
sorbed from the AlO(OH) NPs when total concentration of SPCA
increased to 3% (3-hour addition) without addition of calcium.
Concentration of Al3 ions increased slightly when SPCA was
SPCA-ICP
100000
10000
Polymer conc. (mg/L)
1000
100
10
1 this condition, and it is not a good candidate for squeeze
0.1
0.01
0.001
0 2
Fig. 10Plot of the SPCA and aluminum concentrations of the
effluent vs. number of PV for the squeeze simulation of AlO(OH)
(3%)-SPCA (3%) NPs experiment. Blue: returned SPCA concentra-
tion measured by ICP-OES. Red: returned SPCA concentration
measured by assay method. Green: returned Al31 concentration
measured by ICP-OES.
August 2014 SPE Journal
PPCA DTPMP SPCA-ICP SPCA-assay
100000
10000
Polymer conc. (mg/L)
1000
100
10
1
0.1
0.01
0 20 40 60 80 100
PV
10 15 20 25
Fig. 9Plot of the SPCA concentration in the effluent vs. the
PV of effluent for the squeeze simulation of neat-3%-SPCA
experiment. Blue: returned SPCA concentration measured by
ICP-OES. Red: returned SPCA concentration measured by
assay method.
added. The amount of released Al3 ions from AlO(OH) NPs is
independent of polymer sorption.
In Fig. 8, adsorption isotherms of other scale inhibitors such as
PPCA and DTPMP were demonstrated. Compared with SPCA,
concentration of solid-phase PPCA and DTPMP reached maxi-
mum value also in the approximately 1-hour addition. It is con-
sistent with the proposed mechanism and confirms that the
maximum adsorption of all three scale inhibitors is constrained by
the ALO(OH) NP surface area. The peak values of adsorbed scale
inhibitors are similar and range from 232 to 255 g/Kg ALO(OH),
indicating the maximum adsorption is not affected or is only
slightly affected by the type of scale inhibitor. When total concen-
tration of scale inhibitors increased to 3%, both polymeric scale
inhibitors (SPCA and PPCA) were desorbed from ALO(OH) NPs.
The concentration of solid-phase SPCA and PPCA dropped from
243 and 255 to 174 and 121 g/kg, respectively. However, there is
no DTPMP released from ALO(OH) NPs when more phospho-
nates were added, which is consistent with the previous study
(Watanabe et al. 2011). The concentration of solid-phase DTPMP
keeps stable at 232 g/kg.
Squeeze Simulations of Neat-3%-SPCA Solution. Fig. 9 is a
plot of the 3%-SPCA return curve. It is constructed by plotting
the returned polymer concentration in solution vs. the total vol-
ume of return flow, normalized by the column PV. The polymer
concentration peaked at 31 102 mg/L and decreases to approxi-
mately 1 mg/L in approximately 12 PV. There is only 0.7% of
total squeezed SPCA retained in the column after the first 3 PV.
SPCA-assay Al
Then, it decreased to less than 0.1 mg/L within 80 PV. No poly-
mer is detected after 80 PV. The active concentration of SPCA is
measured by assay (red square). This result is consistent with the
squeeze simulation of 1% SPCA under the same conditions (Yan
et al. 2012 a, b). The squeeze performance of SPCA is independ-
ent of the initial concentration of SPCA in laboratory tests. It also
confirms that SPCA does not adsorb well onto calcite. The NSL is
152 bbl/kg. As a result, squeeze efficiency of SPCA is poor under
treatment.
Squeeze Simulation of ALO(OH) (3%)-SPCA (3%)
4 6 8 10 Nanoinhibitor. The squeeze performance of AlO(OH) (3%)-
SPCA (3%) nanoinhibitor in a ground-core (Iceland spar calcite)
PV
column was shown in Fig. 10 for first 10 PV (blue line). The ini-
tial concentration of returned polymer is up to 18,506 mg/L. It is
consistent with the results of the adsorption study showing that
more than 2% SPCA was in solution when total 3% SPCA was
added. There is only 20% of total squeezed SPCA retained in the
column after the first 3 PV. SPCA concentration dropped from
18,506 to 10 mg/L during 3 PV, then decreased to 3 mg/L in
691
 SPCA-ICP Al SPCA-assay
10000
1000
Polymer conc. (mg/L)
100
10
1
0.1
0.01
0.001
0 200 400 600 800
PV
Fig. 11Plot of the SPCA and aluminum concentrations of the
effluent vs. number of PV for the squeeze simulation of AlO(OH)
(3%)-SPCA (3%)-Ca NPs experiment. Blue: returned SPCA con-
centration measured by ICP-OES. Red: returned SPCA concen-
tration measured by assay method. Green: returned Al31
concentration measured by ICP-OES.
approximately 10 PV. The experiment was stopped at 10 PV
because the retention of SPCA did not improve significantly. The
efficiency of squeezing ALO(OH) (3%)-SPCA (3%) nanoinhibitor
is still not ideal even though 20% of SPCA is retained in the col-
umn. However, the results showed that the addition of ALO(OH)
NPs to the SPCA solution improves the retention percentage of
SPCA in the calcite column. The active concentration of SPCA
was also tested by an assay method (shown as red line) when it
dropped to 39.6, 11.7, 4.1, and 2.8 mg/L. The actual measured
value from an assay method is 29.6, 5.6, 3.2, and 2.1 mg/L. The
large difference for the first two points may be because the residue
of free sulfate in SPCA was also measured by ICP-OES and
counted as sulfur from SPCA. Another reason is that even though
the calculated concentration of SPCA is 39.6 and 11.7 mg/L, the
active concentration at these points is only 29.6 and 11.7 mg/L,
respectively. The last two data points showed that the returned
polymer concentration is close to the active concentration. If it is
assumed that return profile after 10 PV is similar to that of squeez-
ing AlO(OH) (3%)-SPCA (1.5%) NPs reported previously (Yan
et al. 2012 a, b), there should be only 6% of SPCA retained in the
column and the concentration of returned polymer should drop to
and be stable at 0.3 ppm after 1,000 PV. The estimated NSL is
2,310 bbl/kg. The returned concentration of Al3 ions is also
monitored (green line). Al3 concentration is up to 7330 mg/L,
indicating that the returned polymer is accompanied with the loss
of AlO(OH) NPs. Aluminum concentration dropped from 7330
mg/L to below 1 ppm after 2 PV and remained at approximately
0.3 mg/L for 10 PV. There is approximately 40% AlO(OH) NPs
retained in the column after the first 3 PV. The flow-out
AlO(OH)-SPCA NPs indicated that the NPs may transport
through the porous media.
Squeeze Simulation of AlO(OH) (3%)-SPCA (3%)-Ca21
Nanoinhibitor. Results of squeeze simulation of AlO(OH) (3%)-
SPCA (3%) nanoinhibitor with presence of 0.6% CaCl2 in a
ground-Iceland-spar calcite column are shown in Fig. 11 (blue
line). The initial concentration of returned polymer is only 6393
mg/L, which is approximately one-third of the maximum value of
squeezing AlO(OH) (3%)-SPCA (3%) nanoinhibitor without
Ca2. There is approximately 62.7% of total squeezed SPCA
retained in the column after the first 3 PV, which is more than three
times higher than that of squeezing AlO(OH) (3%)-SPCA (3%)
nanoinhibitor alone. SPCA concentration dropped from 6393 mg/
L to 10 mg/L during 60 PV, then decreased to 1 mg/L in approxi-
mately 290 PV. It keeps fluctuating from 0.5 to 0.9 ppm during
1,000 PV. Approximately 57% of the total injected inhibitors was
flushed out of the column in 1,000 PV. The results showed that
retention of AlO(OH) (3%)-SPCA (3%) is significantly enhanced
692
35
30
Turbidity (NTU)
25
20
15
10
5
0
0 20 40 60 80 100 120 140
Time (min)
Blank 0.3 ppm SPCA 0.32 ppm SPCA from effluent
1000 1200
Fig. 12Inhibition-efficiency test of column effluent from
squeeze simulation of AlO(OH) (3%)-SPCA (3%)-Ca NPs experi-
ment. 50 cm3 of effluent is collected from the AlO(OH)-SPCA NP
squeeze-simulation experiment after 1,000 PV. The final con-
centrations of Ba21 and SO2 4 ions after mixing are 106.86 and
74.88 mg/L, respectively. Red line 5 blank with no inhibitor;
blue line 5 effluent diluted to 0.32 ppm; green line 5 control
experiment where the barium and sulfate mixed solution also
contained 0.3 ppm of neat SPCA inhibitor for comparison.
by adding Ca2. Ca2 ions may be crosslinked among the free
SPCA molecules and improve the adsorption of SPCA onto
AlO(OH) NPs. Another possibility is that Ca2 crosslinked among
SPCA molecules and AlO(OH)-SPCA NPs. The results are con-
sistent with the adsorption study in this research, showing that the
adsorption of SPCA was improved by adding Ca2, and the results
reported in previous publications, showing that the squeeze per-
formance of PPCA was improved by adding Zn2 (Kan et al.
2009). The NSL is 8,972 bbl/kg for this AlO(OH) (3%)-SPCA
(3%) nanoinhibitor squeeze simulation with 0.6% CaCl2, which is
approximately 60 times higher than squeezing the neat 3% SPCA
solution by itself and four times higher than squeezing AlO(OH)
(3%)-SPCA (3%) nanoinhibitor solution. The returned polymer
concentration was also confirmed by an assay method, shown as a
red line. The results are consistent with those measured by ICP-
OES, indicating that the returned polymer concentration converted
from sulfur concentration is equal to the active polymer concentra-
tion. The returned concentration of Al3 ions is also monitored
(green line). Al3 concentration is only 23.6 mg/L, indicating that
there is only a small amount of AlO(OH)-SPCA NPs flowing out
with polymer in solution phase. Thus, AlO(OH)-SPCA NPs were
crosslinked by Ca2 ions. The Al3 concentration dropped quickly
from 23.6 to 0.2 ppm in approximately 1.5 PV and remained stable
for 200 PV. Then, it steadily increased to 1.1 ppm in 380 PV and
decreased gradually to 0.7 ppm in 1,000 PV. The increased Al3
and SPCA concentration may be caused by the addition of Ca2
ions. After 1,000 PV, only 2% of AlO(OH) NPs flowed out.
As shown in Fig. 12, the inhibition efficiency of the returned
SPCA from the squeeze simulation of AlO(OH)-SPCA-Ca NPs
experiment was similar to that of the original SPCA for barite in-
hibition. Barite at SI 1.7 (SR 50) can be effectively inhibited
for more than 2 hours at room temperature. These results showed
that the sulfonated polymer released from the AlO(OH) NPs is
still effective after desorption. Therefore, the result showed that
there is no chemical bonding between SPCA and AlO(OH) NPs.
SPCA released into brine solution still can retain its scale-inhibi-
tory efficiency.
Conclusions
This paper reviewed the synthesis and characterization of
AlO(OH)-SPCA NPs. Particle size can be decreased to 20 to
60 nm, with narrow size distribution. They are stable in 1% KCl,
pH measurements of 5 to 9, and temperature from 25 to 110 C.
The previously discussed results demonstrate that AlO(OH)-
SPCA nanoinhibitors could be applied at realistic oilfield condi-
tions. Sorption study of SPCA showed that concentration of
SPCA in solid phase increased when pH of SPCA decreased. The
August 2014 SPE Journal
addition of Ca2 ions can increase the sorption of SPCA under
the same condition. Sorption of PPCA onto AlO(OH) NPs showed
behavior similar to that of SPCA. More addition of polymeric
scale inhibitors after maximum adsorption will desorb polymers
from AlO(OH) NPs. However, for DTPMP, the adsorption kept
stable with continuous addition of phosphonate after peak value.
Squeeze performance of neat 3% SPCA showed results similar to
those of 1% SPCA. The NSL is only 152 bbl/kg. Squeeze per-
formance of AlO(OH) (3%)-SPCA (3%) nanoinhibitors suspen-
sion shows a limited improvement, which has estimated NSL of
2,310 bbl/kg. Squeeze performance of ALO(OH) (3%)-SPCA
(3%)-Ca nanoinhibitors suspension shows a return performance
for 1,000 PV at or above 0.5 ppm. There is 77% SPCA retained in
the column in the first 3 PV. After 1,000 PV of flowing synthetic
brine, 47% of total injected SPCA still retained in the column.
The NSL has been improved nearly 60 times and four times com-
pared with that of the neat 3% SPCA alone and ALO(OH) (3%)-
SPCA (3%) NPs. SPCA from the column effluent retains its scale-
inhibition efficiency. It can inhibit barite at SI 1.7 (SR 50) for
more than 2 hours, indicating that polymers are physically
attached to ALO(OH) NPs. Therefore, there is no chemical bond-
ing between ALO(OH) NPs and SPCA, and chemical properties
of SPCA remain the same. These results showed a new scale-
treatment nanotechnology for efficiently squeezing polymeric
scale inhibitors with sulfonate groups. Transport of ALO(OH)-
SPCA NPs in intact oilfield core is currently being studied.
Acknowledgments
This work was financially supported by the Brine Chemistry Con-
sortium companies of Rice University, including Baker Hughes,
BP, Champion Technologies, Chevron, Clariant, ConocoPhillips,
Dow, Halliburton, Hess, Kemira, Kinder Morgan, Marathon Oil,
Multi-Chem, Nalco, Occidental, Petrobras, Saudia Aramco,
Schlumberger, Shell, Shengli Engineering & Consulting, Statoil,
Southwestern Energy, and Total, and by the China-US Center for
Environmental Remediation and Sustainable Development and
Department of Energy/NETL, No. DE-FE0001910.
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694
Chao Yan is a research scientist at the Department of Civil
and Environmental Engineering, Rice University, Houston. He
holds a PhD degree in chemistry from George Washington Uni-
versity, Washington, D.C.
Amy Kan is a codirector of the Brine Chemistry Consortium,
Rice University. She holds a PhD degree from Cornell University.
Kan serves as an associate editor for SPE Journal and as a
member of the executive committees for the SPE International
Oilfield Scale Conference and the SPE International Nano-
technology Conference.
Wei Wang is a research scientist at the Department of Civil
and Environmental Engineering, Rice University. She holds a
PhD degree in chemistry from Columbia University.
Fei Yan is a research scientist at the Department of Civil and
Environmental Engineering, Rice University. He holds a PhD
degree in civil engineering from the University of Texas at Austin.
Lu Wang earned her bachelors degree in environmental sci-
ence from Nankai University, Tianjin, China. She holds a mas-
ters degree in civil and environmental engineering from Rice
University and is pursuing a PhD degree in environmental engi-
neering at Rice University. Wangs doctoral research focused
on application of carbon-based nanomaterials for oil detec-
tion and study of polymer transport in carbonate and sand-
stone porous media.
Mason B. Tomson has been a professor of civil and environ-
mental engineering at Rice University since 1987. He holds a
PhD degree in physical chemistry from Oklahoma State Univer-
sity, Stillwater, Oklahoma.
August 2014 SPE Journal