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Article
Effect of Steam-Assisted Gravity Drainage (SAGD) Produced
Water Properties on Oil/Water Transient Interfacial Tension
Maryam Razi, Shayandev Sinha, Prashant R. Waghmare, Siddhartha Das, and Thomas Thundat
Energy Fuels, Just Accepted Manuscript • DOI: 10.1021/acs.energyfuels.6b01686 • Publication Date (Web): 19 Oct 2016
Downloaded from http://pubs.acs.org on October 28, 2016

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Page 1 of 9 Energy & Fuels

1
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7 Effect of Steam-Assisted Gravity Drainage (SAGD) Produced
8
9
Water Properties on Oil/Water Transient Interfacial Tension
10
11
Maryam Razi a, Shayandev Sinha b, Prashant R. Waghmare c, Siddhartha Das b* and Thomas
12 Thundat a*
13 a Department of Chemical and Materials Engineering, University of Alberta, Edmonton, AB, T6G 1H9, Canada
14 b Department of Mechanical Engineering, University of Maryland, College Park, MD 20742, USA
15
16 c Department of Mechanical Engineering, University of Alberta, Edmonton, AB, T6G 1H9, Canada
17 KEYWORDS: Steam assisted gravity drainage (SAGD), Oil/Water separation, Interfacial tension, humic acids (HAs), Ward-
18 Tordai, Langmuir isotherm
19
ABSTRACT: Steam assisted gravity drainage (SAGD) produced water (PW) consists of oil, solids, clays, petroleum-derived
20
compounds and other dissolved organic matters (DOMs) which make the SAGD PW highly stable and therefore very hard
21
to treat. Developing a correlation between SAGD PW properties and dynamics of interfacial tension between dispersed
22
and continuous phases is important to understand the coalescence of dispersed phase droplets, which in turn leads to
23
demulsifications of these difficult emulsions produced during SAGD operations. This work sheds light on the interfacial
24
activity of SAGD PW endogenous surfactants, humic acids (HAs), as well as the interaction dynamics of these compounds
25
with naphtha-diluted Alberta oil sand bitumen (AOSB) present in a model SAGD PW. We quantify the dynamics of the
26
interfacial tension of a naphtha-diluted AOSB oil drop in pure water as well SAGD synthetic brine. Our results pinpoint
27
the distinctive influence of the percentage weight composition of the naphtha-diluted AOSB and the surrounding model
28
SAGD PW pH on the dynamics of this oil-water interfacial tension. We anticipate that the results of this study will bring
29
about a better understanding of interfacial film properties leading to a predictable coalescence mechanism in SAGD PW
30
emulsions facilitating the design of next generation SAGD deoiling unit operations.
31
32
33
34 process that has found extensive recent applications owing to
35 INTRODUCTION advantages such as significantly greater per well production
36 rates, greater reservoir recoveries, reduced water treating
Whether it is bitumen films in emulsions occurring in oil 3
37 costs, and dramatic reductions in SOR (steam/oil ratio). A
sands extractions techniques or bitumen droplets present in
38 typical characteristic of the SAGD produced water (PW) is
oil sands process-affected water (OSPW), the interfacial
39 the presence of complex emulsions where the dispersed
properties of oil/water system and the ability to treat emul-
40 phase is heavy oil with high viscosity (100−10000 mPa.s at
sions play vital roles in designing bitumen recovery tech-
41 1 room temperature) present in bulk water. Such oil-in-water
niques which promote environmental sustainability. In an
42 emulsions are generally very difficult to treat due to high
oil production setting, these emulsions are typically very
TDS (Total Dissolved Solids), TSS (Total Suspended Solids)
43 stable due to the stabilizing interactions (e.g., pickering
and high oil content. In order to treat such emulsions specif-
44 emulsion effects or electrostatic stabilization) in the presence
ic to the SAGD process or other oil recovery processes, there
45 of highly surface-active and localized (at the oil-water inter-
have been extensive efforts employing chemical, electrical,
46 face) endogenous chemical moieties such as saturates, as-
thermal, ultrasonic and biological demulsification techniques
47 phaltenes, resins, aromatics and also solids, clays, naphthenic 4
or a combination of them. For example, Razi et al. evaluated
48 acids and waxes. The occurrence of these stable emulsions
the effect of a different formulation of demulsifiers on the
49 induces challenges associated with oil transportation or cata- 5
efficiency of chemical demulsification of heavy crude oil. On
50 lytic poisoning, enforcing a constant need to find more effi-
the other hand, Petrowski et al. examined the stability of an
cient and sustainable methods and techniques to handle and 6
51 2 emulsion using microwave irradiation , while Gao used
break such emulsions.
52 Gibbs adsorption isotherm to monitor the interfacial tension
53 characteristics of the interfacial film of water-in-diluted bi-
Understanding the handling of emulsions is central for the 7
54 tumen emulsion droplets. Further, Poteau et al. investigated
successful operations of most of the Enhanced Oil Recovery
55 the effect of pH on stability and dynamic properties of as-
(EOR) processes. Steam Assisted Gravity Drainage (SAGD),
56 phaltenes and other amphiphilic molecules at the oil/water
utilized to produce bitumen and heavy crude oil, is one such 8
57 interface and Angle et al., monitored the effect of surface
58 1
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16-17
activity of simulated tailing ponds natural surfactants on tively. CHNS elemental analysis of the bitumen sample,
1 dynamic interfacial tension of toluene-diluted bitumen in which has been done using Flash 2000 elemental analyzer
9 5-9
2 simulated tailings water. These studies primarily focus on (Thermo Fisher), is also provided in Table 1.
3 general behaviors of oil-water interfacial tensions in context
of EOR systems. Studies more specific in context of SAGD
Table 1. CHNS analysis of AOSB (Alberta Oil Sands
4
10 11
are those by Nguyen et al. and Thakurta et al. Nguyen et Bitumen)
5
6 al. examined the effect of diluents on interfacial rheology in
Elemental Analysis Results of AOSB sample
7 SAGD emulsions and related that to its emulsion stability,
8 while Thakurta et al. characterized the dissolved organic
Carbon Hydrogen Nitrogen Sulfur
9 matter (DOM) in SAGD boiler blow-down (BBD) water.
10 Average 83.22608795 10.16238556 0.552172315 5.308692646
In addition to these understandings on crude oil-water or
11 bitumen-water interfacial tensions, understanding of interac-
12 Error
tion of humic acids (HAs), which are endogenous surface
13 (SD) 0.586248542 0.467123537 0.015116601 0.13411086
active components naturally present in SAGD PW, with bi-
14 tumen is also vitally important for optimizing the perfor- 15
SARA analysis of AOSB sample
15 mance of the SAGD process. While there has been substan-
16 tial research on quantifying different properties of humic Saturates, wt% 17.30
12-14
17 acids as surfactants , relatively less is known on the humic-
18 acid-bitumen interactions in the functioning of the SAGD Aromatics, wt% 39.70
19 process.
20 Resins, wt% 25.70
21 There is a significant need for understanding the interfacial
22 interactions of diluted bitumen with the endogenous surface Asphaltenes, wt% 17.30
-active components present in the SAGD PW. These interac-
23
tions are the basis for the bitumen film stability which is a Properties of AOSB sample
15
24
predominant factor in SAGD produced water emulsions sta-
25 bility. These natural surfactants which mostly include naph- o
26 Density, g/cc at 15.6 C 1.011
thenic acid (NAs) and humic acid (HA) compounds have the
27 capability to modify the interfacial properties of oil/water API gravity 8.46
28 emulsions encountered in SAGD operations. Adsorption
29 mechanism of these surface active compounds at the o
Viscosity at 40 C, cP 26900
30 oil/water interface in SAGD operations is not well-
9 o
31 understood. There are only a few publications which ad- Viscosity at 60 C, cP 3070
32 dress the interaction effects of endogenous surfactants with
33 diluted bitumen in tailing ponds and aquifers, whereas the
34 effects of SAGD PW characteristics on dynamic interfacial
35 properties of diluted bitumen drops affected by natural sur- Methods. Industrial treated Naphtha (SAN # 7764) provided
36 factants have not yet been reported. Therefore, in the first by Syncrude Canada Ltd., has been used as diluent. Naphtha-
37 section of this study, we present the dynamic interfacial ten- diluted bitumen (or dilbit) solutions with different dilution
38 sion effects, and in the second section of this work, we exam- ratios were prepared using the following method: Bitumen
ine the effects of interaction of natural surfactants present in sample was weighed and added to graduated bottles contain-
39
naphtha-diluted bitumen and endogenous surfactants in a ing pre-weighed naphtha, followed by agitating the prepared
40
model SAGD PW on interfacial properties of oil/water. In solution using a digital vortex mixer (Fisher Scientific) with a
41 this regard, it is anticipated that the results of this study
42 mixing speed of 3000 rpm for the duration of 15 minutes.
bring about a better understanding of interfacial film proper- Different dilution ratios of bitumen ranging from 20 wt% to
43 ties which lead to a predictable coalescence mechanism in 60 wt% were eventually prepared using this method. The
44 SAGD PW emulsion separation studies and facilitate the water used in these experiments was milli-Q water (pH=5.73)
45 design of next generation SAGD de-oiling unit operations. obtained from lab-scale Millipore purification process. The
46 SAGD synthetic brine used and referred to throughout this
47 paper was prepared from Fisher Scientific ACS-grade CaCl2,
48 NaCl, MgCl2, Na2CO3, KCl, FeSO4, NaHCO3 salts in 18 MΩ
49 EXPERIMENTAL SECTION cm milli-Q water from our lab-scale Millipore purification
50 process. The amount of each compound present in SAGD
Materials. Alberta oil sand bitumen (AOSB) provided by
51 synthetic brine is 45, 1021, 24, 100, 50, 10 and 220 (mg/L), re-
Syncrude Canada Ltd. has been used as received. The results
52 spectively. This SAGD synthetic brine exhibits the same pH
of the SARA (Saturates, aromatics, resins and asphaltenes)
53 15 at ambient conditions (pH 9.3), density (0.998 g/mL), ionic
analysis of the sample are provided in Table 1. TAN (total –4
54 strength (4.29 × 10 mol/mol) as the actual SAGD produced
acid number, obtained by ASTM D664 method), sulphur
55 water.
content and ash content of the bitumen sample are known to
56 be 3.5 mg of KOH/g of bitumen, 5.3, and 0.59 wt %, respec-
57
58 2
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18
Surfactant solutions for interfacial studies were made by dis- Fig.1. (a) Steelink model of the humic acid monomer , (b) a
1 solving a given mass of humic acids (HAs) in this buffer solu- portion of proposed "type" structure of humic acid (repro-
19
2 tion. As needed, the pH of different solutions was adjusted duced from , courtesy of Ray von Wandruszka).
3 by adding pre-prepared ACS-grade Fisher Scientific 1.0 M
4 NaOH or 1.0 M HCl. The pH of all aqueous liquids was meas- Dynamic Interfacial Tension: Measurement and Analy-
5 ured using a Mettler Toledo Benchtop pH-meter. A three- sis. Adsorption analysis of endogenous surfactants present in
6 point calibration was carried out using standardized Fisher SAGD PW at O/W interface has been carried out using dif-
7 Scientific solutions for pH 4, 7, and 10. ferent runs of dynamic interfacial tension measurement.
These measurements were performed using a pendant drop
8
SAGD PW samples, WLS (warm lime softening) inlet and tensiometer (KRÜSS GmbH Drop Shape Analyzer, DSA100)
9
BBD (boiler blowdown) water have been obtained from Sun- which employs time-dependent drop shape analysis. A drop
10 cor Energy. Commercial humic acid (HA, Sigma-Aldrich, shape analysis system can be used to determine the dynamic
11 technical grade) was used as model natural surfactants pre- interfacial tension between two liquids which is quantified
12 sent in SAGD produced water. The published chemical struc- from an estimation of the dynamic (or time-varying) shape of
13 tures of these surfactants, the Steelink model of the humic the pendant drop.
14 acid monomer and a proposed typical structure of these sur-
15 factants are depicted in Figure 1.a and Figure 1.b, respectively. The pendant drop shape is primarily determined by the in-
16 Two sets of experiments have been conducted; in the first terplay of surface tension and gravitational forces, with the
17 set, dynamic and equilibrium interfacial tension of dilbit former seeking to minimize the drop surface area by enforc-
18 samples with different dilution ratios has been studied in ing it into a spherical-cap shape while the latter deforming
19 pure water. No surfactant was present in the buffer solution and elongating the drop from its spherical-cap shape. The
20 for this run. Temperature and pH of the aqueous phase re- drop shape analysis is based on the Young-Laplace equation
21 mained constant in all of the experiments. In the second runs that relates the pressure difference (Laplace pressure) across
22 of experiments, dynamic interfacial tension of dilbit in SAGD a curved interface to the principal radii of curvature 𝑅! and
20-32
synthetic brine solutions with different pH values has been the drop-surrounding liquid interfacial tension 𝛾:
23
monitored.
24 ! !
25 𝛾 + = ∆𝑃 ≡ ∆𝑃! − ∆𝜌𝑔𝑧 (1)
(a) !! !!
26
27 where 𝑅! and 𝑅! are the principal radii of curvature,
28 ∆𝑃 ≡ 𝑃!" − 𝑃!"# is the Laplace pressure across the interface,
z is the vertical height from the drop apex, and ∆𝜌 = 𝜌! − 𝜌
29
is the density difference of two medium (see Fig. 2). Drop-
30
phase and continuous phase densities are denoted as 𝜌! and
31 𝜌, respectively. As shown in eq.(1), this pressure gradient ∆𝑃
32 can be written in terms of a reference pressure ∆𝑃! (pressure
33 at 𝑧 = 0) and a hydrostatic pressure of ∆𝜌𝑔𝑧. To obtain prin-
34 cipal radii of curvature for a pendant drop, one can consider
35 drop radius 𝑅! at the apex, i.e., 𝑅! = 𝑅! = 𝑅! . Accordingly,
36 for each point above this apex, 𝑅! = 𝑥/𝑠𝑖𝑛 𝜑 (see Fig. 2).
37 Consequently, eq. (1) reduces to
38 ! !"# ! ! ∆𝜌𝑔𝑧
39 + = ∓ (2)
!! ! ! !
40
(b) Using axisymmetry, eq. (1) can be expressed in terms of the
41
42 cylindrical coordinates 𝑟 , 𝑧 and the tangent angle 𝜑 (see
43 Fig. 2). In this case, the Young–Laplace equation can be ob-
44 tained as a coupled set of three first-order differential equa-
45 tions with three boundary values in terms of the arc length 𝑠
46 measured from the drop apex, which is solvable by numerical
procedures and results in:
47
48 !" !"# ! ! ∆!"#
=− + ∓ (3a)
!" ! ! !
49
50 !"
= cos 𝜑 (3b)
51 !"
52 !"
53 = sin 𝜑 (3c)
!"
54
55 0 = 𝑥 𝑠 = 0 = 𝑧 𝑠 = 0 = 𝜑 𝑠 = 0 (3d)
56
57
58 3
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The dilbit drop volume was kept constant for the total aging
(b)
1 time of the droplet. Each experiment has been repeated five
2 times to ensure the reproducibility of the interfacial tension
3 measurements. Temperature for all the experiments was kept
4 constant at 23 °C.
5
6
7
RESULTS AND DISCUSSION
8
9 In Fig. 4, we show the dynamic interfacial tension (IFT) of
10 dilbit in pure water (pH=5.74), for different dilution ratios
11 ranging from 20 to 60 wt%, plotted as a function of time (see
12 Fig. 4). We observe that increasing the dilution ratio causes
13 an increase in the IFT at t=0. By definition, x wt% of a dilbit
Fig.2. (a) a schematic of pendant drop hanging from a needle.
14 drop implies (100-x) % of bitumen in x% of naphtha solvent.
(b) a dilbit drop image which is captured by CCD camera in
15 Consequently, smaller wt% of dilbit drop implies a larger
the experiments.
16 amount of bitumen in a smaller amount of the naphtha sol-
17 Drop shape is recorded by the camera and the fitting of the vent. Accordingly, such smaller wt% of the dilbit drop will
18 numerically computed theoretical drop shape to this record- also imply larger concentration of asphaltene within the
19 ed image eventually yields the interfacial tension between drop. This can explain smaller value of the IFT at t=0 for
20 the two phases. smaller wt% of the dilbit drop, given that larger asphaltene
concentration in a dilbit drop has been known to cause a
21 33
Different volumes of dilbit droplets (ranging from 15 μL-40 larger reduction in the IFT. The central finding expressed in
22
μL) depending on the dilution ratio, were generated at the Fig. 4 is the temporal variation of the IFT for different wt% of
23
tip of an inverted needle (20-gauge diameter) immersed in a the dilbit drop. In fact, for 20 wt% of dilbit drop in pure wa-
24 ter, we observe that the IFT curve reaches near-equilibrium
25 cuvette filled with water. The needle was connected to a sy- 33
ringe (500 μL, Hamilton Co., USA). The syringe was mounted values, which is consistent with the finding of Zakar et al.
26 We hypothesize that this dynamic lowering of the surface
in a syringe holder positioned above a cuvette containing 25
27 tension of the dilbit drop is caused by the gradual adsorption
mL of the aqueous phase. The needle was immersed in the
28 cuvette aqueous phase by adjusting the syringe position. To of the asphaltene present within the dilbit drop on the oil-
29 obtain a clear visualization on the computer screen, the water interface. We employ a combination of the Ward-
30 alignment adjustments were made in such a way that the Tordai surface adsorption model and the Langmuir isotherm
31 drops were in line with the tensiometer charge-coupled de- to theoretically explain this time-dependent asphaltene ad-
32 vice (CCD) camera.
20-32
A schematic diagram of the method sorption from the bulk phase (within the dilbit drop) to the
33 is depicted in Fig. 3. oil-water interface and the corresponding time-dependent
34
34 lowering of the IFT. Following Mysels , we can express the
35 Ward-Tordai equation as:

{ } { }
36
D D
() c t − ∫ c (τ ) d t − τ + c t − c (τ ) d (t − τ ) ,
t t

r b ∫0
37 Γ t =2 (4)
π b 0
38
39 where D is the average diffusivity of asphaltene migrating
40 from the dilbit drop bulk phase to the oil-water interface, r is
41 the drop radius, Γ(t) is the surface concentration of asphal-
42 tene adsorbed at the oil-water interface, and cb is the bulk
43 concentration of asphaltene within the oil drop and c(τ) is
44 the sub-surface asphaltene concentration. Also “d” in eq. (4)
45 is the differential, i.e., “d” of dx. Therefore, in eq. (4), we have
46 the dx1 (where x1 = t − τ ) and dx2 (where x2 = t − τ ). Lang-
47 muir isotherm provides the equations of state (EOS) relating
48 this sub-surface concentration with the surface concentra-
49 Fig.3. Schematic diagram of the method used for adsorption tion as well as the surface concentration with the surface
50 analysis of endogenous surfactants present in SAGD pro- pressure (i.e., the decrease of the surface tension from the
51 duced water. bulk value). Therefore:
52
53 Dynamic interfacial tension 𝛾!(!) measurements were initiat- 1 Γ
c= , (5)
54 ed immediately as the droplet generated to record images at KL Γ∞ − Γ
55 the rate of 1 frame/s for the whole duration of the experi-
56 ment. The recordings continued until the dilbit drop de-
57 tached from the needle.
58 4
59
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⎛ Γ ⎞
1 Π = γ 0 − γ = −nRT Γ ∞ ln ⎜ 1− ⎟, (6)
⎝ Γ∞ ⎠
2
3
4 where KL is a constant, Γ∞ is the saturation surface excess, R
is the universal gas constant, T is the absolute temperature, n
5
is an integer (takes a value of 1 for non-ionic surfactants or 2
6
for ionic surfactants), Π is the surface pressure, and γ0 and γ
7 are the bulk value (or value at t=0) and the dynamic value of
8 the surface tension of the oil-water interface. In Fig. 5, we
9 compare the result from this theoretical model with the ex-
10 periments for two chosen values of dilbit weight percentage
11 (see the caption of Fig. 5 for the parameters values). We got
12 reasonably acceptable match for the experimental trend us-
13 ing our theoretical predictions. Of course, our theoretical
14 predictions yield similar acceptable match for experimental
15 results corresponding to other dilbit weight percentage; we
16 intentionally do not show them here for the sake of brevity.
17
18
Fig.5. Comparison of the Oil/Water dynamic interfacial ten-
19 sions (IFT) obtained from the theoretical model, i.e., eqs. (4-
20 6) (shown by continuous lines) with the experimental results
21 (shown by markers) for two values (20% and 30%) of dilbit
22 weight percentage. Parameters used in the theoretical model
23 −10 2 −1 −6 −2 3 -1
are D=3.5×10 m s , Γ∞ =4 ×10 mol m , KL=1838 m mol
24 and r=0.001 m at T=298 K. The bulk concentrations are, cb,30%
−4 −4 −3
25 =7×10 and cb,20% =8×10 mol m .
26
27 Fig. 6 depicts IFT versus t for dilbit/SAGD synthetic brine
28 interface at different pH values of the aqueous phase for 40
29 wt% dilbit ratio. As seen in this figure (Fig. 6), in pH values
30 of 7-9, the dynamic interfacial tension of naphtha-diluted
31 bitumen/SAGD synthetic brine is decreasing. However, to-
wards the basic spectrum of the pH values (pH=9), which is
32
relevant for SAGD operations (pH 9 to 11), the instability of
33
the dilbit drop is observed. The fluctuations in dynamic in-
34 terfacial tension in this case can be related to the frequent
35 Fig.4. Variations in Oil/Water dynamic interfacial tension: adsorption and desorption of indigenous surfactants present
36 Effect of different dilution ratios of naphtha-diluted bitumen in the oil phase. Observed increase in interfacial activity of
37 (dilbit) on Oil/Water dynamic interfacial tension (water in surfactants at higher pH values, responsible for such fre-
38 these sets of experiment is milli-Q water and pH of the aque- quent adsorption-desorption dynamics, is consistent with
9
39 ous solution has been measured as 5.74). Please see the Sup- the work reported by Angle et al. The initial IFT (i.e., IFT
40 plementary Material (Figs. S1-S6), where the plots for each value at t=0) is almost the same for all of pH values. The de-
41 weight percentage of dibit/pure-water have been provided tachment time of dilbit drop from the needle is different for
42 with appropriate error bars. different pH values. As seen in this figure as pH goes toward
43 basic pH values, the detachment time of dilbit drop from the
44 needle reduces from 1800 sec to 100 sec. This can be related
45 to the increase in the rate of reaction of surfactants at the
46 neck of droplet at higher pH values.
47

48
49 In Fig. 7, we depict the variation of the IFT of the dilbit-
50 SAGD (synthetic brine) interface for pH values 9.5 and 10 for
51 40 wt% dilbit ratio. Most remarkably, we find that the IFT
52 increases with time. While at pH=9.5, the dynamic IFT does
53 decrease with time for the first 415 sec (see inset of Fig. 5),
54 this temporal enhancement of the IFT is prevalent for the
55 rest of the cases (for larger time for pH=9.5 and for all time
56 for pH=10). It is expected that larger the increase in pH val-
57
58 5
59
60
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ues, greater will be the interfacial activity of the surfactants.

1 The fact that by increasing pH from 7 to 9 there is a reduc-
2 tion in IFT (see Fig.6) is due to the increased saponification
3 of indigenous surfactants present in bitumen (asphaltenes) at
4 basic pH values which causes the enhanced interfacial activi-
5 ty of these surfactants and a lower IFT is expected. It has
35-36
6 been previously shown by earlier publications that indig-
7 enous surfactants present in bitumen reorganized as
8 nanoclusters at these bitumen concentrations. It can be con-
9 cluded that at higher pH values, transport, rearrangement,
and reordering of surfactants occur over larger timescales. It
10
is also concluded that at higher pH values, the complexity of
11
nature of dilbit/SAGD brine interfaces is much higher, pav-
12 ing the way for such highly non-intuitive IFT versus t varia-
13 tion.
14
15 It is due to the fact that as pH of SAGD synthetic brine in-
-
16 creases, the consumption of free OH ions in SAGD brine is
+
17 decreasing and thus there is a decrease in the H ions in solu-
18 tion. This is the same as the response associated with the
19 saponification of carboxylic groups in higher pH values of Fig.7. IFT versus t for 40 wt% naphtha-diluted bitu-
SAGD brine solution. The interaction of indigenous surfac- men/SAGD synthetic brine at increasing basic pH values (9.5
20
tants present in bitumen with HAs present in SAGD synthet- and 10) of SAGD synthetic brine. Please see the Supplemen-
21
ic brine at dilbit/SAGD brine interface is evident from the tary Material (Fig. S8, S9), where the plots for each pH have
22 been provided with appropriate error bars.
23 reductions in IFTs which is an indicator of elevated interfa-
cial activity of surfactants. These results are in accordance
24 9
with the work done by Angle et al. in which they concluded
25
that IFTs of heavy crude oils interfaces are less at high pH
26
values in comparison with lower pH values. CONCLUSIONS
27
28 In this study the effect of bitumen dilution ratios and pH of
29 model SAGD produced water on dynamic interfacial tension
30 of naphtha-diluted bitumen/SAGD synthetic brine interface
31 has been monitored. A theory based on the combination of
32 Ward-Tordai model (for surface concentration) and Lang-
muir isotherm has been applied to explain the experimental
33
trends. Dynamic IFT of naphtha-diluted bitumen in SAGD
34
synthetic brine solutions with different pH values has been
35 monitored and it has been concluded that as pH goes to-
36 wards basic pH which is the case for SAGD operations (pH
37 range 9-11), there is no exponential reduction in interfacial
38 tension between O/W interface. To the best of our
39 knowledge, it is the first time that such a study has been
40 done for SAGD PW. The results of this study can usher in a
41 better quantification of interfacial film properties, thereby
42 paving the way for a controllable de-emulsification mecha-
43 nism for emulsions in SAGD PW, which in turn will be vital
44 for designing next generation SAGD de-oiling unit opera-
tions.
45
46 Fig.6. IFT versus t for 40 wt% naphtha-diluted bitu-
47 men/SAGD synthetic brine at different pH values (7.1, 8.0
48 and 9.0) of SAGD synthetic brine. Please see the Supplemen-
49 tary Material (Fig. S7), where the plots for each pH have been
50 provided with appropriate error bars.
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AUTHOR INFORMATION (3) Nguyen, D.; Balsamo, V.; and Phan, J., Effect of diluents
1 and asphaltenes on interfacial properties and steam-assisted
2 Corresponding Author gravity drainage emulsion stability: interfacial rheology and wet-
3 * Siddhartha Das tability. Energy Fuels. 2014, 28 (3), 1641–1651.
4 E-mail: sidd@umd.edu. Fax: +1 301.314.9477 (4) Bosch, R.; Axcell, E.; Little, V.; Cleary, R.; Wang, S.; Gabel,
Tel: +1 301.405.6633 R.; and Moreland, B. A Novel Approach for Resolving Reverse
5
Emulsions in SAGD Production Systems. Can. J. Chem. Eng.
6 *Thomas Thundat 2004, 82(4), 836-839.
7 E-mail: thundat@ualberta.ca. Fax: +1 780.492.2881. (5) Razi, M.; Rahimpour, M. R.; Jahanmiri, A.; and Azad, F. Ef-
8 Tel: +1 780.492.2068. fect of a different formulation of demulsifiers on the efficiency of
9 chemical demulsification of heavy crude oil. J. Chem. Eng. Data.
10 2011, 56, 2936–2945.
11 (6) Petrowski, G.E.; VanAtta, J.R. J. Am. Oil Chem. Soc.
12 Springer 1973, 50(284), 110-111.
Author Contributions (7) Gao, S. Stability of Water-in-Diluted Bitumen Emulsion
13
M.R. conceived the experiment. M.R. and P.W. designed the Droplets, PhD thesis, department of chemical and materials
14 engineering, University of Alberta, Spring 2010.
experiments. M.R. conducted the experiments and collected
15 (8) Poteau, S.; Franc, J.; Argillier, O. Influence of pH on Stabil-
data. M.R., P.W. and T.T. analyzed the data. S.S. and S. D.
16 ity and Dynamic Properties of Asphaltenes and Other Am-
performed the theoretical modeling. P.W., S.D. and T.T.
17 phiphilic Molecules at the Oil-Water Interface. Energy Fuels.
played an advisory role. All authors contributed to the writ-
18 2005, 19, 1337-1341.
ing of the manuscript. All authors have given approval to the
19 (9) Angle, C. W.; Hua, Y. Tailings Pond Surfactant Analogues:
final version of the manuscript. Effects on Toluene-Diluted Bitumen Drops in NaHCO3/K2CO3
20
Solution. Part 1: Dynamic Interfacial Tension. Energy Fuels. 2013,
21 Notes 27, 3603−3612.
22 The authors declare no competing financial interest. (10) Nguyen, D.; Phan, J.; Balsamo, V. Effect of diluents on in-
23 terfacial properties and SAGD emulsion stability: 1. Interfacial
24 rheology, Proceedings of SPE. heavy oil conference, Calgary,
25 Alberta, Canada, 11-13 June 2013, SPE 165405.
26 ACKNOWLEDGMENTS (11) Thakurta, S. G.; Maiti, A.; Pernitsky, D. J.; Bhattacharjee, S.
27 Dissolved Organic Matter in Steam Assisted Gravity Drainage
This work was supported by Canada Excellence Research Boiler Blow-Down Water, Energy Fuels. 2013, 27, 3883−3890.
28
Chairs (CERC) Program and Natural Sciences and Engineer- (12) Guetzloff, T. F.; Rice, J. A. Does humic acid form a mi-
29
ing Research Council of Canada (NSERC). The authors would celle?, Sci. Total Environ. 1994, 152, 31-35.
30 like to acknowledge IOSI (Institute for Oil Sands Innovation) (13) Terashima, M.; Fukushima, M.; Tanaka, S. Influence of pH
31 at University of Alberta for the elemental analysis of bitumen on the surface activity of humic acid: micelle-like aggregate for-
32 sample. The authors also would like to thank the support mation and interfacial adsorption, Colloids Surf., A. 2004, 247,
33 from Advanced Water Research Lab (AWRL) University of 77–83.
34 Alberta specifically Mohtada Sadrzadeh, for providing SAGD (14) Mamba, B.B.; Krause, R.W.; Malefetse, T.J.; Sithole, S.P.;
35 produced water samples. Finally, Shayandev acknowledges Nkambule, T.I. Humic acid as a model for natural organic matter
36 Laboratory of Physical Sciences (LPS) for partly supporting (NOM) in the removal of odorants from water by cyclodextrin
polyurethanes, Water SA. 2009 (35) 0378-4738.
37 his graduate studies.
(15) Bhattacharjee, S. Oil Sands, book chapter, A bridge be-
38 tween conventional oil and a sustainable energy future, 2010.
39 (16) Bakker, G., Gordon, M.R. and Associates Ltd. The Corro-
40 sive Nature of Diluted Bitumen and Crude Oil Literature Review;
ABBREVIATIONS
41 Technical Report for Enbridge, December 2011.
42 SAGD, steam assisted gravity drainage; PW, produced water; (17) Clark, J. S. Stationary Gas Turbine Alternative Fuels,
43 DOMs, dissolved organic matters; HAs, humic acids; AOSB, American Society for Testing and Materials, ASTM STP. 809,
44 Alberta oil sand bitumen; OSPW, oil sands process-affected 1983.
water; EOR, Enhanced Oil Recovery; SOR, steam/oil ratio; (18) Hagiopol, C.; Atkinson, D. L. Modified polyphenol binder
45
TDS, Total Dissolved Solids; TSS, Total Suspended Solids; compositions and methods for making and using same, Patent
46 Georgia-Pacific Chemicals Llc. WO 2014055463 A1, 2014, also
TLF, thin liquid film; BBD, boiler blow-down; NAs, naph-
47 thenic acids; SARA, Saturates- aromatics- resins and asphal- published as U.S. Patent 20140094562 A1, Apr 3, 2014.
48 tenes; TAN, total acid number; ASTM, American Society for (19) Wandruszka, R. V. Humic acids: Their detergent qualities
49 Testing and Materials; CHNS, Carbon Hydrogen Nitrogen and potential uses in pollution remediation, Geochem. Trans.
50 Sulfur; WLS, warm lime softening. 2000, 1-10.
51 (20) Buckley, J. S.; Fan, T. Crude Oil/Brine Interfacial Ten-
sions, Proceedings of the International Symposium of the Society
52 REFERENCES
of Core Analysts, Toronto, Canada 2005, 1-12.
53 (1) Kokal, S. L. Crude oil emulsions: A state-of-the-art review. (21) Yang, Y.; Dicko, C.; Bain, C. D.; Gong, Z.; Jacobs, R. M. J.;
54 Soc. Pet. Eng. J. 2005, 77497, 5-13. Shao, Z.; Terry, A. E.; Vollrath, F. Behavior of silk protein at the
55 (2) Peng, J.; Liu, Q.; Xu, Z.; and Masliyah, J. Novel Magnetic air–water interface, Soft Matter. 2012, 8, 9705-9712.
56 Demulsifier for Water Removal from Diluted Bitumen Emulsion.
57 Energy Fuels. 2012, 26, 2705−2710.
58 7
59
60
ACS Paragon Plus Environment
 Energy & Fuels Page 8 of 9

(22) Tripp, B. C.; Magda, J. J. and Andrade, J. D. Adsorption of (29) Joos, P., Hunsel, J. V. Adsorption kinetics of micellar Brij
1 Globular Proteins at the Air/Water Interface as Measured via 58 solutions. Colloids Surf. 1988 (33) 99–108.
2 Dynamic Surface Tension: Concentration Dependence, Mass- (30) Jeribi, M.; Almir-Assad, B.; and Langevin, D. Adsorption
3 Transfer Considerations, and Adsorption Kinetics. J. Colloid Kinetics of Asphaltenes at Liquid Interfaces. J. Colloid Interface
4 Interface Sci. 1995, 173, 16–27. Sci. 2002, 256, 268-272.
(23) Lin, S. Y.; Lu, T. L. and Hwang, W. B. Adsorption Kinetics (31) Buckley, J. S.; and Fan, T. Crude Oil/Brine Interfacial Ten-
5
of Decanol at the Air-Water Interface. Langmuir. 1995, 11, 555– sions. Petrophysics. 2007, 48(3), 175-185.
6 562. (32) Kelesoglu, S.; Meakin, P.; and Sjoblom, J. Effect of Aque-
7 (24) Rotenberg, Y.; Boruvka, L. and Neumann, A. W. Deter- ous phase pH on the Dynamic Interfacial Tension of Acidic
8 mination of surface tension and contact angle from the shapes of Crude Oils and Myristic Acid in Dodecane. J. Dispersion Sci.
9 axisymmetric fluid interfaces. J. Colloid Interface Sci. 1983, 93, Technol. 2011, 32, 1682-1691.
10 169–183. (33) Zarkar, S.; Pauchard, V.; Farooq, U.; Couzis, A.; Banerjee,
11 (25) Berry, J. D.; Neeson, M. J.; Dagastine, R. R.; Chan, D. Y. C.; S. Interfacial Properties of Asphaltenes at Toluene−Water Inter-
12 Tabor, R. F. Measurement of surface and interfacial tension us- faces. Langmuir. 2015, 31, 4878−4886.
ing pendant drop tensiometry. J. Colloid Interface Sci. 2015, 454, (34) Mysels, K. J. Diffusion-controlled adsorption kinetics:
13
226–237. General solution and some applications. J. Phys. Chem. B 1982,
14 (26) Lucassen, J.; Drew, M.G.B. The Crystal Structure of Sodi- 86, 4648.
15 um Diheptylsulphosuccinate Dihydrate and Comparison with (35) Angle, C. W.; Hua, Y. Dilational Interfacial Rheology for
16 Phospholipids, J. Chem. Soc., Faraday Trans. 1, 1987, 83(10), 3093. Increasingly Deasphalted Bitumens and n-C5 Asphaltenes in
17 (27) Germansheva, I.; Panaeve, S. Kolloidn. Zh. 1981, 44, 661. Toluene/NaHCO3 Solution. Energy Fuels. 2012, 26, 6228−6239.
18 (28) Serrien, G.; and Joos, P. Dynamic Surface Properties of (36) Mullins, O. C. The Modified Yen Model. Energy Fuels.
19 Aqueous Sodium Dioctyl Sulfosuccinate Solutions. J. Colloid 2010, 24, 2179−2207.
20 Interface Sci. 1990, 139, 149-159.
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