Asphaltenes at OilGas Interfaces Foamability Even
Asphaltenes at OilGas Interfaces Foamability Even
Asphaltenes at OilGas Interfaces Foamability Even
and interfaces
Article
Asphaltenes at Oil/Gas Interfaces: Foamability Even
with No Significant Surface Activity
Mélanie Arangalage 1,2,3,4 , Jean-Philippe Gingras 2,3,4 , Nicolas Passade-Boupat 2,3,4 ,
François Lequeux 1,2,3 and Laurence Talini 1,2,3, *
1 CNRS, Sciences et Ingénierie de la Matière Molle, ESPCI Paris, PSL Research University, Sorbonne
Université, 75005 Paris, France; [email protected] (M.A.); [email protected] (F.L.)
2 Laboratoire Physico-Chimie des Interfaces Complexes, ESPCI, 10 rue Vauquelin, 75005 Paris, France;
[email protected] (J.-P.G.); [email protected] (N.P.-B.)
3 Bâtiment CHEMSTARTUP, Route Départementale 817, 64170 Lacq, France
4 Total S.A., 64170 Lacq, France
* Correspondence: [email protected]; Tel.: +33-140794679
Received: 4 December 2018; Accepted: 19 December 2018; Published: 21 December 2018
Abstract: In the oil industry, oil foams can be found at different steps from the crude oil treatment
to the gas stations. Their lifetime can sometimes reach several hours and be much longer than
the residence times available for gas/liquid separation. However, the conditions of formation and
stability of such foams have been poorly studied in the literature, in contrast to the foamability of
aqueous systems. On the fields, it is currently observed that crude oils enriched with asphaltenes
form particularly stable foams. In this work, we have studied the influence of asphaltenes on
the foamability of oil mixtures. All the experiments were performed on model systems of crude
oils, that-is-to-say decane/toluene mixtures containing asphaltenes at concentrations ranging from
0.01 to 5 wt%. We in particular demonstrate that, within the investigated concentration range,
asphaltenes from two different wells do not have any significant surface active properties despite
their contribution to the foamability of oil mixtures. We show that the formation of an asphaltene
layer at the interface with air that has been evidenced in the past results from solvent evaporation.
Using a recently developed experiment based on the Marangoni effect with our model oils, we
demonstrate that asphaltenes are not surface active in those oils. We further characterize the oil
foamability by measuring the lifetime of the foam formed by blowing nitrogen through the liquid in
a column. At concentrations larger than 1 wt%, asphaltenes significantly enhance the foamability
of the oil mixtures. Moreover, the closer the asphaltenes are to their limit of precipitation the larger
the foamability. However, we evidence that the oil mixtures themselves foam and we show the
importance to consider that effect on the foamability. In addition, we observe that the foamability
of the asphaltenes solutions unexpectedly varies with the initial height of the liquid in the column.
We suggest that, although not significantly modifying the surface tension, the asphaltenes could be
trapped at the oil/gas interface and thus prevent bubble coalescence.
Keywords: asphaltenes; foamability; layer formation; evaporation; oil foam; bubble lifetime
1. Introduction
Crude oils are complex mixtures of hydrocarbons and various organic compounds [1–3] including
asphaltenes, which are polyaromatic molecules with side alkane chains. Asphaltenes molecules can
self-assemble into clusters of colloidal size (a few tens of nanometers) [4–6]. Usually, asphaltenes
are rather defined by their class of solubility than by their chemical formula, which makes them
very diverse in chemical nature [6]. By definition, they are species that are insoluble in alkanes
and soluble in aromatic solvents such as benzene or toluene. They therefore can be dispersed in
toluene/alkane mixtures, up to a given proportion of alkane, above which they precipitate. Although
their physical properties may be as diverse as their chemical nature, asphaltenes are generally known
to exhibit remarkable interfacial properties [4]. For example, their behavior at water/oil interfaces
has been extensively studied in the literature [7–11], leading to the now commonly accepted idea that
asphaltenes are responsible for the stability of water/oil emulsions. Indeed, their high polarity due
to the presence of polar groups (carboxylic acids, alcohol, etc.) allows them to adsorb at oil/water
interfaces. J. D. McLean et al. [9] demonstrated that this stabilization is increased when approaching
the precipitation limit which corresponds to the observation of precipitated asphaltenes with the naked
eye when adding some alkane to a mixture of toluene and asphaltenes. Sometimes, it has also been
observed that a rigid layer can form [12,13] at the water/oil interface limiting coalescence of oil or
water droplets.
Asphaltenes can also adsorb at solid/oil interfaces [4,14–17], especially at the surface of clay, silica
or metal oxides particles present in oil wells. For example, the acidic groups of asphaltenes interact with
the cations contained in clays. The particles, which wettability is thus modified, can have surface-active
properties and increase the stability of crude oil emulsions through a “Pickering” process.
Determining the origin of foamability of oil mixtures is a major stake for the oil industry. On one
hand, oil foams may be used as fracturing fluids and their stability is then required and obtained by
addition of surfactants [18]; on the other hand unwanted foaming of oil is currently observed and
can be a hindrance to extraction and recovery processes. For instance, during the oil/gas separation
steps, crude oils initially maintained at high pressure in oil reservoirs, are brought back to atmospheric
pressure and vaporization of light elements such as methane or ethane may generate extremely stable
foams. The lifetime of these foams can range from several minutes to hours, drastically reducing the
yield of the separators, which are not designed for such residence times. Furthermore, oil transport
in pipelines can also be affected by foaming phenomena. Actually, under certain flow geometries,
foam plugs can form and slow down the transport of crude oil. In the field, it was observed that crude
oils from wells containing large amounts of asphaltenes form particularly stable foams. It therefore
seems that there is a link between the presence of asphaltenes, foamability and stability of oil/gas
interfaces. However, the behavior of asphaltenes at oil/gas interfaces and their influence on the
foamability of crude oil remains poorly studied in the literature in contrast to their effects on water/oil
or solid/oil interfaces.
F. Bauget et al. [19] studied the effect of asphaltenes on the dynamic and static properties of
oil/gas interfaces. They measured the foamability of solutions of asphaltenes in toluene by blowing
gas into a glass column containing these solutions. They observed that at high concentrations of
asphaltenes (>5 wt%) the foamability increases significantly similarly to the increase in viscosity.
Moreover, single film lifetime measurements were performed. They observed that the lifetime of these
films increases with the concentration of asphaltenes from 15 wt%. This increase could not be fully
explained by the increase of the viscosity. They concluded that, at high concentrations, asphaltenes
show surface-active properties at oil/gas interfaces. Surface tension measurements allowed them to
support this hypothesis, in particular the significant decrease in surface tension they observed over
very long times, of the order of 105 s. In the same pending drop experiments, the formation of a
solid shell at the air/drop interface was observed, together with an increase in the surface elasticity.
According to the literature [12,19,20], the adsorption kinetics of asphaltenes at liquid/gas interfaces
are slow because asphaltenes clusters behave like proteins. After a diffusion and adsorption step, the
asphaltenes molecules reorganize into a network structure. It therefore takes a long time to reach a
state of equilibrium compared to a purely diffusive process.
Nevertheless, the mechanism of foam stabilization by asphaltenes remains obscure. In particular,
in [19], at short times (t < 100 s) no significant decrease in surface tension was reported for asphaltenes
concentrations smaller than 5 wt%. That result is in apparent contradiction with the observed foaming
Colloids Interfaces 2019, 3, 2 3 of 17
of the same low concentration asphaltene solutions [19] and the fact that the time scales of a foaming
process are expected to be within the same range.
In the present work, we focus on relatively dilute (wt% < 5) asphaltenes solutions in pure toluene
and a toluene/decane mixture, for which negligible viscosity increases are expected. We report
measurements of the surface tension of these solutions using two different techniques. We emphasize
how pending drop measurements over long times may be affected by solvent evaporation. We further
report foamability measurements of asphaltenes solutions in toluene and decane mixtures, and we
evidence that a large part of the foamability results from the foaming of the solvent mixture itself. In
addition, we study the influence of the solubility of the asphaltenes on the foamability. Finally, we
investigate the effect of the content of asphaltenes on the foamability and we suggest a mechanism
explaining why, although not decreasing surface tension, asphaltenes contribute to the stabilization of
oil foams.
2.1. Materials
We focus on the behavior of asphaltenes extracted from two fields TR and MO. Toluene (≥99.8%),
decane (≥99.0%) n-heptane (≥99.0%) and pentane (≥99.0%) were supplied from Sigma Aldrich
(Saint-Louis, MO, US). All the concentrations are given by weight percentage (wt%). For the extraction
of asphaltenes, PTFE filters with a porosity of 5 µm were purchased from Merck (Darmstadt, Germany)
For the Marangoni flow experiments hollow glass spheres (HGS) purchased from Dantec Dynamics
(Nozay, France), with an average diameter of 10 µm and a density of 1.1, were chosen as tracers and
mixed with the liquid bath.
2.2. Methods
experiments were performed at room temperature and atmospheric pressure. Two solutions were
used: pure toluene containing 5 wt% of asphaltenes TR and a decane/toluene (45/55 wt%) mixture
containing 5 wt% of asphaltenes TR.
Colloids Interfaces
Colloids Interfaces 2018, 2, x2018, 2, x 4 of 17 4 of 17
2.2.4. Marangoni Flow Method
2.2.4. Marangoni
2.2.4. Marangoni Flow Method
Flow Method
The highly sensitive method described in reference [22] was used in order to detect the surface
The highly
Theofhighly sensitive sensitive method
methodinterfaces.
described described in reference
in reference [22] was [22] wasinused
used in toorder to detect the surface
activity asphaltenes at oil/air The original experimental setuporder
consists detect
in thethe surface
generation
activity activity of asphaltenes
of asphaltenes at interfaces.
oil/air interfaces. The original experimental setup consists in the generation
of a Marangoni flow atataoil/air
liquid/air interfaceThe byoriginal experimental
suspending a droplet setup of consists
solute over in the generation
a liquid bath.
of a of a
Marangoni Marangoni
flow atflow
a at a
liquid/airliquid/air
interface interface
by by suspending
suspending a dropleta droplet
of soluteof solute
over a over
liquid a bath.
liquidAbath. A
A concentration gradient is generated by condensation of the evaporated solute and, with the
concentration
concentration gradient gradient is generated
is generated by condensation
by condensation of the evaporated
of the evaporated solute
solute forms
and, with and,the with the surface
surface
surface tension of the two liquids being different, a surface tension gradient at the interface.
tension tension
of the of
two theliquids
two liquids
being being different,
different, a surface a surface
tension tension
gradient gradient
forms forms
at the at the interface.
interface. The The
The generated flow is modified in the presence of surface active agents. The addition of a very
generatedgenerated flow is
flowofissurfactants modified
modified in in the presence of surface active agents. The addition of asmall small
very
small amount canthe turnpresence
the flowofinto surface active agents.
an oscillatory The addition
flow allowing of a very
a sensitive detection
amount amount of surfactants canthe turn theintoflowaninto an oscillatory flow allowing a sensitive detection of
of tracesofofsurfactants
surfactants. canFirst
turn flow
we reproduced oscillatory
the experiment flowdescribed
allowing ainsensitive detection
[22] on solutions of
of
traces traces
of of surfactants.
surfactants. First Firstreproduced
we we reproduced the the experiment
experiment described described
in [22] inon[22] on solutions
solutions of of
tetradecyltrimethylammonium bromide (TTAB—Sigma Aldrich) in deonized water (cmc of TTAB
tetradecyltrimethylammonium
tetradecyltrimethylammonium bromide bromide
(TTAB—Sigma(TTAB—Sigma Aldrich) Aldrich)
in deonizedin deonized
water water (cmc
(cmc of TTAB of TTAB
is is
is 5.0 × 10−3 mol/L). The setup consisted of a liquid bath of cylindrical shape containing tracers
5.0 × 105.0
above which
× 10 mol/L).
−3 mol/L).−3
The setup
a droplet
The consisted
of ethanol
setup consisted of a liquid
was formed
of a liquid
withbath ofbath
a neMESYS
of cylindrical
cylindrical shape containing
shape containing
high precision syringe pump
tracers
above above
tracers(Cetoni,
which which
a droplet a droplet
of ethanolof ethanol was
was formedmeasured formed with
with a neMESYS a neMESYShigh high precision syringe pump (Cetoni,
Korbussen, Germany). We quantitatively the flow rate α inprecision
the region syringe
close topump (Cetoni,
the symmetric
Korbussen,
Korbussen, Germany). Germany). We quantitatively
We quantitatively measured measured
the flow the flowα rate α in the region close
the to the
axis according to the method described in [22] using a high speedrate camerain(Mini the region
AX, Photron,close to Tokyo,
symmetricsymmetric
axis axis according
according to the to the method
method described described
in [22] inusing
[22] ausing
high aspeed
high speed
camera camera
(Mini (Mini AX,
AX,
Japan) and the plug-in ParticleTracker for ImageJ [23]. For the oil mixtures containing asphaltenes
Photron, Photron, Tokyo, Japan)the and the plug-in ParticleTracker for ImageJ [23].theForoilthe oil mixtures
studied inTokyo,this work, Japan)weand adapted plug-inthe setup ParticleTracker
by using a droplet for ImageJ
of pentane.[23]. For Indeed, mixtures
pentane is a
containing
containing asphaltenesasphaltenes studied in this wework, we adapted the bysetup by ausing a droplet of pentane.
volatile solvent which isstudied
soluble in in this
toluene work, adapted
or decane/toluene the mixtures.
setup using
In the case droplet
of highlyof pentane.
opaque
Indeed, Indeed,
pentane pentane is a volatile solvent
is a volatile which is soluble in toluene or decane/toluene mixtures. In the In the
solutions, a 2D-version of the solvent
setup was whichused. is The
soluble in toluene
cylindrical liquidor decane/toluene
bath is replaced mixtures.by a rectangular
case case of highly opaque solutions, a 2D-version of the setup was used. The cylindrical liquid isbath is
tank of highly6.9
(section opaque
× 2.2 solutions,
cm and thickness a 2D-version 2 mm)ofconsisting
the setup of was two used.
glassThe cylindrical
slides clipped liquid
on both bath
sides
replaced replaced
by frame. by a rectangular
a rectangular tank (section
tank (section × 2.26.9 × 2.2
andcm and thickness 2consisting
mm) consistingof two of twoslides
glass slides
of a Teflon The motion of the 6.9 tracers cm
are thickness
visualized using2 mm)a laser sheet (StingRay glass640 nm,
clipped clipped
on both onsides
bothofsides
a of a Teflon
Teflon frame. frame.
The The motion
motion of the of the tracers
tracers are are visualized
visualized using ausing
laser asheet
laser sheet
Coherent Inc., Santa Clara, Ca, US) placed vertically as described in Figure 1. The experiments were
(StingRay(StingRay 640 nm, Coherent Inc.,Clara,
Santa Ca, Clara,
US)Ca, US) placed vertically as described in Figure 1. The
performed640 onnm, Coherent
mixtures Inc., Santa
of decane/toluene containing placed
differentvertically
weight as percentage
described inofFigure
decane 1. The
and
experiments
experiments were were performed
performed on on mixtures
mixtures of of decane/toluene
decane/toluene containingcontaining
different different
weight weight
percentagepercentage
different concentration of either asphaltenes TR or MO at their limit of precipitation:
of decaneof decane and different
and different concentration
concentration of either of asphaltenes
either asphaltenes
TR or MO TR or at MO
theiratlimit
theiroflimit of precipitation:
precipitation:
- - A decane/toluene
- A decane/toluene
A decane/toluene (45/55
(45/55 (45/55
wt%)
wt%) wt%)containing
mixture
mixture mixture
containingcontaining
0.0025,
0.0025, 0.0025,
0.05, 0.05,
0.1,0.1,
0.05, 1.5 or 0.1,
1.5 51.5
5orwt% wt% orasphaltenes
of 5 wt%
of of asphaltenes
asphaltenes TR
- toluene TR
TR containing 2 or 5 wt% of asphaltenes TR
- - toluene
- A decane/toluene
toluene containingcontaining
2 or wt%)
(35/65 2 ormixture
5 wt% 5ofwt% of
asphaltenesasphaltenes
containing TR 0.02, TR 0.3, 0.1 or 1.5 wt% of asphaltenes MO
- A decane/toluene
- A decane/toluene (35/65 wt%)(35/65mixture
wt%) mixturecontainingcontaining
0.02, 0.3, 0.02,
0.10.3,
or 1.50.1wt%or 1.5ofwt% of asphaltenes
asphaltenes MO MO
Figure Figure
Figure 1.1. Scheme1. Scheme
Scheme ofofthe ofMarangoni
the Marangoni
theMarangoni setup.
setup.Asetup. A droplet
droplet of pentane
of pentane
A droplet is formed
of pentane is formed
above
is formed aabove
above liquid abath.
liquid
a liquid bath. The
The
bath.
liquid liquid
is seeded
The liquid is seeded
withwith
is seeded with
tracers tracers (not
(not (not
tracers to scale)to scale)
which
to scale) which are illuminated
are illuminated
which by aby
are illuminated by a
vertical vertical
laserlaser
a vertical laser
sheet. sheet.
sheet.
2.2.5. Foamability
Foamability
2.2.5. Foamability Tests Tests
Tests
Classical
Classical
Classical foaming
foamingfoaming
tests tests performed
tests were
were were performed
performed in order
in orderin to
order to measure
measure
measure the foamability
foamability
the foamability of the of
of the different
different
solutions.
solutions.
solutions. The The experimental
Theexperimental
experimental setup
setup setup consisted
consisted
consisted of aof aofglass
glass acolumn
glass column
column (Glasscolumn:
(Glass
(Glass column: column:
85 mL,8585 mL, ᴓ diameter:
ᴓ mL, 2.1 cm,2.1 cm,
diameter:
diameter:
Robu, Robu,
Hattert,Hattert, Germany),
Germany), which which loweris part
lower part is formed
formed of a fritted
of a fritted glass(porosity:
glass filter filter (porosity: 10–16 μm).
10–16 μm).
Once
Once the the studied
studied mixture mixture was placed
was placed inside inside the column,
the column, nitrogennitrogen was injected
was injected through through the fritted
the fritted
glass.
glass. The Therate
flow flow
wasrate was controlled
controlled using ausing a flowmeter
flowmeter (Fisher(Fisher Scientific,
Scientific, Hampton,Hampton,
NH, US).NH, AUS).
glassA glass
reservoir
reservoir was placed
was placed between between the column
the column and theand the flowmeter
flowmeter to prevent
to prevent backflows
backflows of liquid.
of liquid. As the As the
experiments
experiments were performed
were performed under under
a hood,a evaporation
hood, evaporation was prevented
was prevented by placing
by placing a glassaslide
glassonslide on
Colloids Interfaces 2019, 3, 2 5 of 17
2.1 cm, Robu, Hattert, Germany), which lower part is formed of a fritted glass filter (porosity: 10–16 µm).
Once the studied mixture was placed inside the column, nitrogen was injected through the fritted
glass. The flow rate was controlled using a flowmeter (Fisher Scientific, Hampton, NH, US). A glass
reservoir was placed between the column and the flowmeter to prevent backflows of liquid. As the
experiments were performed under a hood, evaporation was prevented by placing a glass slide on the
top of Interfaces
Colloids the open2018,
column.
2, x Images of the experiment are captured using a XCD-U100 camera (Sony,5 Toky, of 17
Japan) at 30 fps. We have checked that similar foamability results were obtained by injecting nitrogen
saturated
Toky, by the
Japan) solvent.
at 30 fps. WeThe initial
have checked H0 similar
heightthat of liquidfoamability
and the final height
results H f of
were foam are
obtained bylisted, the
injecting
final height
nitrogen being reached
saturated a dozenThe
by the solvent. of seconds
initial height 𝐻 beginning
after the of the
of liquid and final height 𝐻 of foam are
theexperiment.
listed,During theheight
the final injection of reached
being nitrogen,a dozen
a stationary state after
of seconds was reached withinofathe
the beginning fewexperiment.
seconds and the
column was then
During divided of
the injection into two parts
nitrogen, (Figure 2): state was reached within a few seconds and the
a stationary
column
- The lower part consisted of a bubbly(Figure
was then divided into two parts liquid 2):
of height Hl .
- The lower part consisted of a bubbly liquid of height 𝐻 .
- The upper part consisted of a foam of height Hm .
- The upper part consisted of a foam of height 𝐻 .
Figure 2. Description
Figure 2. Description of ofthe
thefoamability
foamabilitytest.
test.(a)(a)Scheme
Scheme of of
thethe liquid
liquid column
column during
during a foamability
a foamability test.
test. The upper part of the column consists of a foam of height 𝐻 and the lower part
The upper part of the column consists of a foam of height Hm and the lower part of the column consists of the column
consists of a liquid
of a bubbly bubblyofliquid
heightofHheight 𝐻are
l . (b,c) . (b)photographs
and (c) are photographs
taken beforetaken before
(b) and during(b) (c)
anda during (c) a
foamability
foamability test of
test of a mixture ofadecane/toluene
mixture of decane/toluene
(45/55 wt%)(45/55 wt%) 5containing
containing 5 wt% of asphaltenes.
wt% of asphaltenes. The
The foamability
foamability
is measured isat measured
a nitrogen at a nitrogen
flow × 10−rate
rate of 5 flow 6 m3of /s5and
× 10 minitial
at−6an 3/s and at an initial height of liquid
height of liquid introduced H0
equal to 2.8𝐻cm.
introduced equal to 2.8 cm.
Since it
Since it was
was difficult
difficult to
to observe
observe the
the boundary
boundary between
between the
the bubbly
bubbly liquid
liquid and
and the
the foam,
foam, wewe rather
rather
measured the final height H and extrapolated the foam height H from the final height H
measured the final height 𝐻 f and extrapolated the foam height 𝐻 m from the final height 𝐻f, using aa , using
treatment described
treatment described in
in the
the Appendix
Appendix A.A.
In addition, rather than a foam height
In addition, rather than a foam height 𝐻 Hm,, the
the foamability
foamability can
can be
be evaluated
evaluated as
as aa lifetime
lifetime 𝜏τv: :
𝐻 H f(1
𝜋𝑅2 𝐻 (1 − A)−−𝐻H0
−𝐴)
𝜏 =Hm = πR (1)
τv = = 𝑄 (1)
U𝑈 Q 11−−𝐴A−−𝜑ϕl
With
With U 𝑈 the
the speed
speed ofof the
the flow
flow in
in the
the column,
column, R R the
the radius
radius of
of the
the glass
glass column,
column, Q Q the
the flow
flow rate
rate of
of
nitrogen injection, A the volume fraction of gas in the bubbly liquid and ϕl the volume fraction of
nitrogen injection, A the volume fraction of gas in the bubbly liquid and 𝜑 the volume fraction of
liquid
liquid inin the
the foam.
foam. The
The calculation
calculation ofof the lifetime 𝜏τv (resp.
the lifetime (resp. the
the volume
volume fraction
fraction of
of liquid
liquid in
in the
the foam
foam
𝜑 described in the Appendix B (resp. Appendix C). The lifetime 𝜏
ϕl ) is described in the Appendix B (resp. Appendix C). The lifetime τv is an intrinsic quantity which
) is is an intrinsic quantity which
should
should notnot depend
depend on on the
the foaming
foaming conditions,
conditions, i.e.,
i.e., neither
neither on
on the
the initial
initialliquid height 𝐻
liquidheight H0 nor
nor on
on the
the
flow rate
flow rate Q.Q.
Table
Colloids Interfaces 2019, 1.
3, 2Summary of the different investigated systems and experimental conditions. 6 of 17
Concentration of
Experiment Physical Value Measured Decane/Toluene Ratio
2.3. Summary of the Investigated Systems and Used Techniques Asphaltenes
Tensiometer
Surface tension and evaporation Toluene
For thedrop
(pendant sake of clarity, we summarize in Table 1. the sytems that were investigated5together wt% TR
with
measurements Decane/Toluene (45/55 wt%) 5 wt% TR
the different
method)measurements that were performed.
Marangoni Surface activity at liquid/gas 0.0025, 0.05, 0.1, 1
Decane/Toluene (45/55 wt%)
experimentTable 1. Summary ofinterface
the different investigated systems and experimental conditions. and 5 wt% TR
Between 0.001 and 5
Experiment Physical Value Measured Decane/Toluene Ratio Concentration of Asphaltenes
Impact of asphaltenes Decane/Toluene (45/55 wt%) wt% TR
Foamability test
Tensiometer Surface tension and evaporation Toluene 5 wt% TR
(pendant drop method)
concentration on
measurements
foamability Decane/Toluene (35/65
Decane/Toluene(45/55 wt%)
wt%) Between
5 wt% TR
0.01 and 5
Surface activity at wt% MO
Marangoni experiment Decane/Toluene (45/55 wt%) 0.0025, 0.05, 0.1, 1 and 5 wt% TR
Impact of liquid/gas
asphaltenesinterface
solubility Decane/Toluene varies from 0 5 wt% TR
Foamability test Impact of asphaltenes concentration Decane/Toluene (45/55 wt%) Between 0.001 and 5 wt% TR
Foamability test ononfoamability to 100 wt.(35/65
% inwt%)
decane Between 0.013and wt% MO
foamability Decane/Toluene 5 wt% MO
Foamability test
Impact
Impact of
of the initial
asphaltenes liquid
solubility Decane/Toluene varies from 0 5 wt% TR
on foamability to 100 wt% in decane 3 wt% MO
Foamability test height introduced on Decane/Toluene (45/55 wt%) 5 wt% TR
Impact of the initial liquid height
Foamability test foamability Decane/Toluene (45/55 wt%) 5 wt% TR
introduced on foamability
3.3.Results
Results
3.1.Surface
3.1. SurfaceTension
Tensionfor
forOil
OilMixtures
MixturesContaining
ContainingAsphaltenes:
Asphaltenes:Layer
LayerFormation
Formationand
andEvaporation
Evaporation
Wehave
We haveperformed
performedsurface
surfacetension
tension measurements
measurements with
with aa pending
pending drop
drop apparatus
apparatus that
that are
are
reportedin
reported inFigure
Figure3.3.No
Nosignificant
significantvariation
variationof
ofsurface
surfacetension
tensionwas
wasmeasured
measuredover
overshort
shorttimes
times(<100
(<100s)s)
whateverthe
whatever thesolvent
solventcomposition
compositionandandasphaltenes
asphaltenesconcentration.
concentration. That
That result
result isisin
inagreement
agreementwithwith
reportsof
reports ofsurface
surfacetension
tensionmeasurements
measurements[19] [19]made
madewith
withasphaltenes
asphaltenesofofan
anorigin
origindiffering
differingfrom
fromthethe
onesof
ones ofthe
thepresent
presentwork.
work.
Figure 3. Top curve: Surface tension measurements obtained with the pending drop tensiometer
Figure 3. Top curve: Surface tension measurements obtained with the pending drop tensiometer of a
of a solution of toluene without asphaltenes (green/light symbols) and with 5 wt% of asphaltenes
solution of toluene without asphaltenes (green/light symbols) and with 5 wt% of asphaltenes TR
TR (blue/dark symbols). Bottom curve: same for a mixture of decane/toluene without asphaltenes
(blue/dark symbols). Bottom curve: same for a mixture of decane/toluene without asphaltenes
(yellow/light symbols) and with 5 wt% of aphaltenes TR (red/dark symbols).
(yellow/light symbols) and with 5 wt% of aphaltenes TR (red/dark symbols).
Over longer time scales, the surface tension was observed to vary. That effect was systematically
Over with
associated longerthe
time scales, the
formation of surface tension
a solid layer at was observedoftothe
the surface vary. That effect
droplet, whichwas systematically
prevents proper
associated with the formation of a solid layer at the surface of the droplet, which prevents
surface tension measurements. The layer becomes solid like with elapsed time and it can be observed proper surface
tension measurements. The layer becomes solid like with elapsed time and it can be observed
by gradually deflating the droplet formed by the tensiometer as shown in Figure 4. A photograph of by gradually
deflating
the the droplet
remaining formed
layer after by the tensiometer
deposition of the drop on as shown in Figure
an absorbing 4. Aisphotograph
paper of the5.remaining
shown in Figure
layer after deposition of the drop on an absorbing paper is shown in Figure 5.
Colloids Interfaces 2019, 3, 2 7 of 17
Colloids
ColloidsInterfaces
Colloids Interfaces2018,
Interfaces 2018,2,
2018, 2,2,xxx 777 of
of 17
of 17
17
Figure
Figure 4.
Figure
Figure 4. Photographs
4.
4. Photographsof
Photographs
Photographs ofaaaadroplet
of
of droplet of
droplet
droplet of decane/toluene
of
of decane/toluene (45/55
decane/toluene
decane/toluene (45/55
(45/55
(45/55 wt.
wt.
wt. %)
%) mixture
%)
wt%) mixture containing
mixture
mixture containing 5555 wt%
containing
containing wt% of
wt%
wt% of
of
of
asphaltenes
asphaltenes
asphaltenesTR
asphaltenes TR
TR at
TRat
at t = 2500
atttt===2500
2500 s.
2500s.s. (a)
s.(a)
(a)before
(a)before
beforeand
beforeand (b)
and(b)
and after
(b)after
(b) deflation
afterdeflation
after of
deflation of
deflation the
ofthe
of drop:
thedrop:
the observation
drop:observation
drop: of
observation of
observation an
ofan
of asphaltene
anasphaltene
an asphaltene
asphaltene
layer
layerat
layer
layer atthe
at
at thesurface
the
the surfaceof
surface
surface ofthe
of
of thedrop.
the
the drop.
drop.
drop.
Figure
Figure5.
Figure
Figure 5.Photograph
5. Photographof
Photograph
Photograph ofan
of
of anasphaltenes
an
an asphalteneslayer
asphaltenes
asphaltenes layerformed
layer formedat
formed atthe
at thesurface
the surfaceof
surface of the
the
ofthe drop
drop
thedrop of
of
dropof decane/toluene
decane/toluene
ofdecane/toluene
decane/toluene
(45/55
(45/55 wt%)
wt%)
(45/55 wt%)
(45/55 containing
containing
wt%) containing 5
5 wt%
wt% of
of asphaltenes
asphaltenes at
at tt =
= 2500
2500
containing 5 wt% of asphaltenes at t == 2500 s.
s.
2500 s.
s.
We
Weattribute
We
We attributethe
attribute thelayer
the
the layerformation
layer
layer formationto
formation
formation to an
toto
an effect
anan
effect
effect of
effectofevaporation.
of of
evaporation.
evaporation. Actually,
evaporation.Actually,
Actually, toluene
Actually,
toluene
toluene and
anddecane
toluene
and and
decane kept
decane
decane kept
kept
evaporating
kept
evaporating
evaporating during
evaporating
during
during the
the experiment,
during
the the
experiment,
experiment, and
experiment,andand
and to
to maintain
to to
maintain
maintain the
maintain
thethe
the drop
dropvolume
drop
drop volumeconstant,
volume
volume constant,solvent
constant,
constant, solvent was
solvent was
was
continuously
continuously
continuously injected,
injected, as
as schematically
schematically described
described in
in
continuously injected, as schematically described in Figure6. Figure
Figure 6.
6.
Figure
Figure
Figure 6.
Figure6.
6. Scheme
6.Scheme
Scheme explaining
Schemeexplaining
explaining the
explainingthe
the evaporation
theevaporation
evaporation of
evaporationof
of solvents
ofsolvents
solventson
solvents on the
onthe
on surface
thesurface
the of
surfaceof
surface the
ofthe
of droplet,
thedroplet,
the the
droplet,the
droplet, injection
theinjection
the of
injectionof
injection of
of
the
the
the mixture
mixture
mixture by
by
by the
the
the tensiometer
tensiometer
tensiometer to
to
to compensate
compensate
compensate this
this
this effect
effect
effect and
and
and the
the
the formation
formation
formation of
of
of a
a
a layer
layer
layer of
of
of asphaltenes.
asphaltenes.
asphaltenes.
the mixture by the tensiometer to compensate this effect and the formation of a layer of asphaltenes.
Over time,
Over time, the
the convective
convective flow due to solvent evaporation tends totoaccumulate the asphaltenes at
Over
Over time,
time, the convectiveflow
the convective flowdue
flow dueto
due tosolvent
to solventevaporation
solvent evaporationtends
evaporation tendsto
tends toaccumulate
accumulatethe
accumulate theasphaltenes
the asphaltenes
asphaltenes
the
at surface of the droplet, while diffusion disperses them. The competition between these two effects
at the
at the surface
the surface of
surface of the
of the droplet,
the droplet, while
droplet, while diffusion
while diffusion disperses
diffusion disperses them.
disperses them. The
them. The competition
The competition between
competition between these
between these two
these two
two
is described
effects is by
describedthe Peclet
by thenumber,
Peclet which,
number, over a
which, length
over ascale given
length by
scale the
givendrop
by radius
the drop R, is given
radius R,by:
effects
effects isis described
described by by the
the Peclet
Peclet number,
number, which,
which, over
over aa length
length scale
scale given
given by
by the
the drop
drop radius
radius R,R,is
isis
given
givenby:
given by:
by:
Colloids Interfaces 2019, 3, 2 8 of 17
2
( RD )
Pe =
4/3πR3
≈ 150 >> 1 (2)
Qev
with D = kT/(6πηr) the diffusion coefficient of a spherical particle of radius r in the liquid of viscosity
η, k the Boltzmann constant, T the temperature and Qev the evaporation rate measured using
the tensiometer (Qev = 30 nL/s for a mixture of decane/toluene (45/55 wt%) containing 5 wt% of
asphaltenes TR).
The large value of the Peclet number compared to unity shows that evaporation dominates
diffusion. Thus, diffusion is not efficient enough to rehomogenize the concentration of asphaltenes
inside the drop. As a result, solvent evaporation accumulates the asphaltenes at the interface and a
layer is further formed.
To confirm that picture, we have performed the same experiment within limited evaporation
conditions: the drop was placed in a toluene-saturated atmosphere to limit the evaporation of the
solvent. That experiment was carried out with a mixture of decane/toluene (45/55 wt%) containing
5 wt% asphaltenes. No layer formation was observed over times longer by 1.5 times than the time
at which the layer appeared in experiments with significant evaporation. Owing to condensation
droplets appearing on the visualization window of the tensiometer, no information on the behavior
over longer timescales or quantitative data could be obtained from that experiment. However, it shows
that layer formation results from the evaporation of toluene from the droplet.
In conclusion, in agreement with previously reported data [19], no significant surface tension
variation could be measured with classical tensiometry at short times, i.e., at time scales similar to
lifetimes of the foams studied herein (<100 s) [19]. In addition, we demonstrate that layer formation at
the surface of the droplet does not result from a slow adsorption process of asphaltenes but can be
fully accounted for by evaporation of the solvent that induces an accumulation of the asphaltenes at
that surface. In the following, we investigate the surface properties of solutions of asphaltenes, using
a method which can detect surface tension variations as small as a few 10−3 mN/m, i.e., 100 times
smaller than the limit of classical tensiometry.
3.2. Evaluation of the Surface Activity with the Marangoni Flow Method
We now present the results obtained with a Marangoni-flow-based technique in order to determine
if the asphaltenes present surface active properties at oil/air interfaces. As detailed above, the quantity
that is measured in that experiment is a flow rate α which value depends on the concentration of
surface active components since enough surface active components can stop the continuous Marangoni
flow and make the value of α zero.
We first show the results obtained with aqueous solutions of soluble surfactants, namely TTAB.
Figure 7 is a comparison between the value of the flow rate α in the Marangoni flow method and
the foamability of aqueous solutions of TTAB as a function of the concentration of added surfactant.
The foamability will be defined later in the paper, here it is considered to be a simple indicator of foam
formation. We notice that from 5 × 10−4 cmc the Marangoni flow induced by the setup slows down
until reaching the oscillating area from 5 × 10−3 cmc where by convention the flow rate α is equal to
zero. The foamability of aqueous solutions of TTAB is observed for concentrations above 5 × 10−3 cmc
showing that it is correlated with the threshold concentration of detection of the surface activity of
TTAB. We show in what follows that no such correlation can be observed with asphaltene solutions.
Colloids Interfaces 2019, 3, 2 9 of 17
Colloids Interfaces 2018, 2, x 9 of 17
Figure 7. Velocity
Figure rate
7. Velocity αα
rate obtained
obtainedwith theMarangoni
with the Marangoni flow
flow setup
setup and and foamability
foamability v as a function
𝜏 as aτfunction of
of thethe
concentration of the added surfactant for solutions of TTAB in water.
concentration of the added surfactant for solutions of TTAB in water. The velocity rate was The velocity rate was
Figure 7. Velocity rate α obtained with the Marangoni flow setup and foamability 𝜏 as a function of
measured at the
measured surface
at the surfaceof of
a bath containing
a bath containing the
the studied solutions
studied solutions above
above which
which a droplet
a droplet of ethanol
of ethanol
the concentration of the added surfactant for solutions of TTAB in water. The velocity rate was
is suspended.
is suspended. TheThezerozero valuesofofααcorrespond
values correspond to to the
the suppression
suppression of of
steady
steadyflow. TheThe
flow. value of theof the
value
measured at the surface of a bath containing −1 1 the studied solutions above which a droplet of ethanol
foamability
foamability obtained
obtained forforthe
thesolution at1010−cmc
solution at is only
cmc indicative
is only since the
indicative foamthe
since generated is very stable
foam generated is very
is suspended. The zero values of α correspond to the suppression of steady flow. The value of the
and overfills
stablefoamability
and overfillsthe glass column: the arbitrary value of the foamability is indicated by a black star.
obtained for the solution at 10 cmc is only indicative since the foam generated is very stable star.
the glass column: the arbitrary
−1 value of the foamability is indicated by a black
and overfills the glass column: the arbitrary value of the foamability is indicated by a black star.
The comparison between theflow
flowrate
rateαα inin the
the Marangoni
The comparison between the Marangoniflow flow method
method andandthe the
foamability of of
foamability
decane/toluene (45/55 wt%) mixtures as a function of the concentration of asphaltenes dispersed is
decane/toluene (45/55 wt%)
The comparison between mixtures
the flowasrate
a function of the concentration
α in the Marangoni flow method ofand
asphaltenes dispersed
the foamability of is
represented in Figure 8. The solutions containing asphaltenes being opaque quantitative
represented in Figure
decane/toluene 8. The
(45/55 wt%)solutions
mixtures containing
as a function asphaltenes being opaque
of the concentration quantitative
of asphaltenes measurements
dispersed is
measurements cannot be performed. We arbitrarily assign the qualitative value 1 to the rate α if a
cannotrepresented
be in Figure
performed. We 8. The solutions
arbitrarily assign containing
the qualitativeasphaltenes
value 1being
to theopaque
rate α quantitative
if a continuous
continuous Marangoni flow is induced and the value 0 if the flow is oscillatory or stopped. As shown
measurements
Marangoni flow is cannot
induced beandperformed.
the value We0 arbitrarily
the flowassign
if continuous the qualitative
is whatever
oscillatory value 1As to shown
the ratein α Figure
if a
in Figure 8, the Marangoni flow is always theorconcentration
stopped. of asphaltenes, 8,
continuous
the Marangoni Marangoni flow is induced and the value 0 if the flow is oscillatory or stopped. As shown
their state offlow is always
aggregation continuous
or their origin (MOwhatever the concentration
or TR). This confirms that theofasphaltenes
asphaltenes, their state of
investigated
in Figure 8, the Marangoni flow is always continuous whatever the concentration of asphaltenes,
aggregation
herein do ornot
their origin
have any (MO
surfaceoractive
TR). This confirms
property at thethat theinterface
oil/air asphaltenes investigated
in contrast herein do not
to the commonly
their state of aggregation or their origin (MO or TR). This confirms that the asphaltenes investigated
accepted idea in the oil industry. However, as shown in Figure
have any surface active property at the oil/air interface contrast to the commonly accepted 8, asphaltenes solutions do foamidea in
herein do not have any surface active property at the oil/air interface in contrast to the commonly
significantly.
the oil We show in the following that the contribution to foaming of the asphaltenes is
accepted idea in the oil industry. However, as shown in Figure 8, asphaltenes solutions do foamshow
industry. However, as shown in Figure 8, asphaltenes solutions do foam significantly. We
significant only
in thesignificantly.
following that for solutions of concentrations larger than 1 wt%.
We the
showcontribution
in the followingto foaming
that the of the asphaltenes
contribution is significant
to foaming of theonly for solutions
asphaltenes is of
concentrations larger
significant only forthan 1 wt%.
solutions of concentrations larger than 1 wt%.
Figure 8. Velocity rate α obtained with the Marangoni flow setup and foamability 𝜏 as a function of the
concentration of asphaltenes TR for solution of asphaltenes in decane/toluene mixtures (45/55 wt%). The
Figure 8. Velocity
8. Velocity rate α obtainedwith
withthe
theMarangoni
Marangoni flow flowsetup and foamability 𝜏 as τvaabove
function of the
Figurevelocity rate israte α obtained
measured at the surface of a bath containing setup theand foamability
studied solutions as a function
which aof the
concentration
concentration of asphaltenesTR TRfor
for solution
solution ofofasphaltenes in decane/toluene mixtures (45/55 wt%). The
droplet of pentane is suspended. The values of the flow rate is only qualitative. We assign the value 1wt%).
of asphaltenes asphaltenes in decane/toluene mixtures (45/55
velocity
The velocity rate is measured
rate is measured at the surface
at the surface of a bath containing the studied solutions above which a
if the Marangoni flow is continous and the of a bath
value 0 if containing the studied
the flow is stopped. solutions above
The foamability which
tests were a
droplet
droplet of pentane
of pentane is suspended.
is suspended. The values
Theequal
values of the
of the flow rate is only qualitative. We assign the value 1
performed at a flow rate of nitrogen to 1.04 × 10flow
−5 m /srate
3 and is anonly
initialqualitative. Weofassign
height of liquid 1.8 cm.the value 1
if the Marangoni flow is continous and the value 0 if the flow is stopped. The foamability tests were
if the Marangoni flow is continous and the value 0−5if the flow is stopped. The foamability tests were
performed at a flow rate of nitrogen equal to 1.04 × 10 m−3/s 5 and3 an initial height of liquid of 1.8 cm.
performed at a flow rate of nitrogen equal to 1.04 × 10 m /s and an initial height of liquid of 1.8 cm.
Colloids Interfaces 2019, 3, 2 10 of 17
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3.3.Foamability
3.3. Foamability
3.3.1.Impact
3.3.1. Impactof
ofthe
theConcentration
Concentrationof
ofAsphaltenes
Asphalteneson
onthe
theFoamability
Foamability
Tostudy
To studythetheinfluence
influenceofofasphaltene
asphalteneconcentration
concentrationon onthe
thefoaming
foamingof ofasphaltene
asphaltenesolution,
solution,we we
havemeasured
have measuredthe thefoamability
foamabilityof ofdifferent
differentsolutions
solutionsand
andexpressed
expressedititas lifetimeτ𝜏v . .As
asaalifetime Aspreviously
previously
mentioned,that
mentioned, thatquantity
quantityisisexpected
expectedto tobe
beintrinsic
intrinsicand
andto tobe
beindependent
independentof ofthe
thefoaming
foamingexperiment
experiment
conditions,namely
conditions, namelythe theinitial
initialliquid
liquidheight
heightand
andthe
thegas
gasflow
flowrate.
rate.As
Asshown
shownin inFigure
Figure9,9,thethefoaming
foaming
behaviorisissimilar
behavior similarforforboth
bothnatures
naturesof ofasphaltenes:
asphaltenes: wewe observe
observe that
that the
thefoamability
foamability has has aanon
nonzero
zero
constant value at small asphaltenes concentrations and significantly increases
constant value at small asphaltenes concentrations and significantly increases for concentrations for concentrations
larger than
larger than 11 wt%. In In the
theinvestigated
investigatedconcentration
concentrationrange,
range,nonosignificant
significant change
change of of
thetheviscosity
viscosityby
thethe
by asphaltenes
asphaltenes is is
expected
expected [19].
[19].Both
Bothasphaltenes
asphaltenesare areplaced
placedininaasolvent
solvent such
such as
as to be be at
at their
their
precipitationlimit,
precipitation limit, which corresponds
corresponds to todifferent
differentproportions
proportionsofofthe thedecane/toluene
decane/toluene mixtures forfor
mixtures the
different
the asphaltenes.
different asphaltenes.Therefore,
Therefore,we plot the ratio
we plot between
the ratio betweenthe foamability
the foamabilityof theofmixture
the mixture 𝜏 τv and
mix
the the
and foamability
foamability of of
thethe
mixture
mixturecontaining asphaltenes𝜏 τre f.. Using
containingnonoasphaltenes Using that representation,
representation, the the
foamabilitynot
foamability notonly
onlydisplays
displaysthethesame
samebehavior
behaviorbut butalso
alsosimilar
similarvalues
valuesregardless
regardlessof ofthe
theorigin
originofofthe
the
consideredasphaltenes.
considered asphaltenes.
Figure9. Ratio
Figure of foamability
9. Ratio between the
of foamability foamability
between theof the mixture containing
foamability of the asphaltenes τv mix and
mixture containing
the foamability
asphaltenes 𝜏 of the
andmixture containing
the foamability ofno
theasphaltenes τre f as a function
mixture containing 𝜏
of the weight
no asphaltenes aspercentage
a functionofof
asphaltenes
the weight dispersed
percentageinof mixture Pasph
theasphaltenes : asphaltenes
dispersed in theTR 𝑃 in: decane/toluene
dispersed
mixture asphaltenes TR (45/55 wt%)
dispersed in
(blue circles) and
decane/toluene asphaltenes
(45/55 MOcircles)
wt%) (blue dispersed
and in decane/toluene
asphaltenes (35/65 wt%)
MO dispersed (red squares).
in decane/toluene The flow
(35/65 wt%)
rate
(redofsquares).
nitrogen The
is equal
flowtorate 10−nitrogen
5 × of 6 m3 /s and the initial height
is equal to 5 × 10−6 of mliquid
3/s and the initialHheight
introduced 0 is 1.8ofcm.
liquid
introduced 𝐻 is 1.8 cm.
In the following section, we study the influence of the composition of the decane/toluene mixture
on theInfoamability of asphaltene
the following section, wesolutions.
study theWe in particular
influence of theshow that the of
composition mixtures without asphaltenes
the decane/toluene mixture
also have a non zero foamability, which corresponds to the times τ used above.
on the foamability of asphaltene solutions. We in particular show that the mixtures without
re f
asphaltenes also have a non zero foamability, which corresponds to the times 𝜏 used above.
3.3.2. Impact of the Solubility of Asphaltenes on the Foamability
3.3.2.We
Impact of the Solubility
investigate of the
the effect of Asphaltenes
solubilityonof the Foamability
asphaltenes on the foamability of decane/toluene
mixtures by varying the weight percentage of decane at fixed concentration
We investigate the effect of the solubility of asphaltenes on the foamability of asphaltenes TR or MO
of decane/toluene
(Figures
mixtures10byand 11). For
varying theboth asphaltenes,
weight percentage a maximum
of decane atoffixed
foamability is observed
concentration when approaching
of asphaltenes TR or MO
the precipitation limit. This confirms the results of N. N. Zaki et al. [24] who observed
(Figure 10 and 11). For both asphaltenes, a maximum of foamability is observed when approaching in similar
experiments an increase
the precipitation of foamability
limit. This confirms as thethe asphaltenes
results of N. N. precipitation
Zaki et al. limit was closer.
[24] who observed in similar
In addition, we report in both figures the foamability data obtained with
experiments an increase of foamability as the asphaltenes precipitation limit was closer. the asphaltene-free
oil mixtures (red circles). The foamability of the oil mixtures is smaller than the one
In addition, we report in both figures the foamability data obtained with the asphaltene-free of asphaltene
oil
solutions
mixtures (red circles). The foamability of the oil mixtures is smaller than the one mixtures
but not zero as would be expected for a pure liquid. The foaming of liquid has
of asphaltene
solutions but not zero as would be expected for a pure liquid. The foaming of liquid mixtures has
been evidenced decades ago [25] although it was not fully understood then; it will be the object of a
Colloids Interfaces 2019, 3, 2 11 of 17
Colloids Interfaces 2018, 2, x 11 of 17
Colloids Interfaces 2018, 2, x 11 of 17
been evidenced
forthcoming decades
paper. To ourago knowledge,
[25] although it was
that nothad
effect fully understood
never then; it will
been evidenced in thebe the object of
literature on
aforthcoming
forthcoming paper.
paper.ToTo our
our knowledge,
knowledge, that
that effect
effect had
had never been evidenced in
asphaltenes, and we emphasize that, since it is of the same order of magnitude as the foamabilityon
in the
the literature
literature on
of
asphaltenes,
asphaltenes, and
and we
we emphasize
emphasize that,
that, since
since it
it is
is of
of the
the same
same order
order of
of magnitude
magnitude as
as the
the
asphaltene solutions, it should be taken into account in order to properly quantify the contribution foamability
foamability of
of
asphaltene
asphaltene solutions,
solutions, itit should
should
to foamability of asphaltenes. bebe taken
taken into
into account
account in in order
order to to properly
properly quantify
quantify the the contribution
contribution to
to foamability
foamability of asphaltenes.
of asphaltenes.
Figure12.
Figure Foamability τ𝜏v as a function of the initial height H𝐻0 of
12. Foamability ofliquid
liquidintroduced
introducedininthetheglass
glass
column:decane/toluene
column: decane/toluene (45/55
(45/55 wt%) (blue
(blue circles)
circles) and
anddecane/toluene
decane/toluene (45/55
(45/55 wt%) withwith 55 wt%
wt%ofof
asphaltenesTR
asphaltenes TR(red(reddiamonds).
diamonds). Solid lines are guide
guide for
for the
theeye.
eye.The
Theflow
flowrate
rateofofnitrogen
nitrogenisisequal
equalto
1.04 × 10 −
−5 m 5
3/s. 3
The full line corresponds to the value of the foamability of a decane/toluene
to 1.04 × 10 m /s. The full line corresponds to the value of the foamability of a decane/toluene solution
obtainedobtained
solution by averaging all the measured
by averaging values. values.
all the measured
AApossible
possibleexplanation
explanationisisthat thataasmall
smallquantity
quantityof ofasphaltenes
asphaltenesisiscaptured
capturedatatthe theinterface
interfaceofofthe
the
bubbles
bubblesthatthatrise
risethrough
throughthe theliquid
liquid and
andincreases
increases thethe
lifetime
lifetime of of
thethe
bubble.
bubble.In In
that picture,
that thethe
picture, larger is
larger
is the initial height0 𝐻 , the more asphaltenes can be captured at the surface of bubbles, thus increasing
the initial height H , the more asphaltenes can be captured at the surface of bubbles, thus increasing the
stability of theoffoam,
the stability similarly
the foam, to frothtoflotation
similarly of minerals
froth flotation [26]. The [26]
of minerals contribution of these molecules
. The contribution of these
to the interfacial
molecules to thetension should
interfacial nevertheless
tension be very small.
should nevertheless be The
verydecrease
small. The of interfacial
decrease oftension for
interfacial
dilute
tensionobjects being objects
for dilute RTΓ, wherebeingRTRTΓ, is the thermal
where RT energy and Γ the
is the thermal surfaceand
energy coverage in molecoverage
Γ the surface per square in
meter.
mole perA coverage of oneAaggregate
square meter. coverageper of one nm2 would
1000aggregate perlead
1000 tonm
a decrease
2 would of thetosurface
lead tension
a decrease of
of the
× 10−3tension
4surface mN/m,ofso4 clearly not significant
× 10−3 mN/m, so clearly innot
terms of surface
significant in tension
terms ofand closetension
surface to the lower detection
and close to the
limit
lower ofdetection
the Marangoni
limit of method.
the Marangoni method.
Therefore,
Therefore,we wesuggest
suggestthat
thataasmall
smallquantity
quantityof ofasphaltenes
asphaltenesare aretrapped
trappedatatthetheinterface,
interface,that
thatthey
they
do
do not contribute to the interfacial energy, but that during the drainage of the liquid films withinthe
not contribute to the interfacial energy, but that during the drainage of the liquid films within the
foam,
foam,they
theyare
aretrapped
trappedininthe theliquid
liquidfilms
filmsand
andthen
thenbehave
behaveas asaabarrier
barrieragainst
againstcoalescence
coalescenceofofbubbles
bubbles
(Figure
(Figure13).
13).
Figure 13. Schematical reprensentation of the foam stabilitsation mechanism induced by the presence
surface tension of 4 × 10−3 mN/m, so clearly not significant in terms of surface tension and close to the
lower detection limit of the Marangoni method.
Therefore, we suggest that a small quantity of asphaltenes are trapped at the interface, that they
do not contribute to the interfacial energy, but that during the drainage of the liquid films within the
foam, they
Colloids are2019,
Interfaces trapped
3, 2 in the liquid films and then behave as a barrier against coalescence of bubbles
13 of 17
(Figure 13).
Figure 13. Schematical reprensentation of the foam stabilitsation mechanism induced by the presence
of asphaltenes.
4. Conclusions
In this paper, we have shown that the investigated asphaltenes do not induce significant
modification of the surface tension of decane/toluene mixtures at short time scales (<100 s) for
asphaltenes concentrations up to 5 wt%. Both pending drop tensiometry and a Marangoni flow method
were used, the latter technique allowing the detection of very small relative surface tension variations,
down to a few 10−2 %. That result is in agreement with previous reports in the literature. At longer
times, we observe in the pending drop experiment the formation of a solid layer, which is attributed
in the literature to a slow adsorption process of the asphaltenes at oil/air interfaces. However, we
demonstrate that it rather results from the evaporation of the solvent and can be inhibited by saturating
the atmosphere. In summary, we conclude that the investigated asphaltenes have no significant surface
active properties, either at short or long times.
Nevertheless, the asphaltenes do increase the foamability of decane/toluene mixtures, that effect
being significant for concentrations above 1 wt%. The increase is maximum at the precipitation limit
of the asphaltenes and the same behavior was observed for two asphaltenes of different natures.
In addition, we show that the non-zero foamability of the oil mixture has to be accounted for in order
to properly quantify the effect of asphaltenes on foamability. That point had never been addressed in
the literature, and could explain part of the observed foamability increases that have been attributed
to the presence of asphaltenes only. In the case of oil mixtures containing asphaltenes, we show that
the foamability surprisingly depends on the initial height of the liquid. A mechanism of stabilization
of interfaces by asphaltenes is suggested, in which the bubbles rising in the liquid capture at their
interface the asphaltenes present in solution. During the drainage of the liquid films within the foams,
the asphaltenes trapped in the liquid films could then behave as a barrier against coalescence of
bubbles, even if the contribution to surface energy is negligible. The hypothesis that asphaltenes
may adsorb at air interface but do not lower the surface tension, is consistent with the large size of
the aggregates they can form, leading to smaller surface pressures than the ones resulting from the
adsorption of large quantities of smaller species such as surfactants.
Author Contributions: Investigation, M.A.; Supervision, J.-P.G., N.P.-B., F.L. and L.T.
Funding: This research was funded by Total S.A.
Conflicts of Interest: We declare no conflicts of interest.
Appendix A
In the following appendix we evaluate the foam height Hm and the lifetime τv of a bubble arriving
at the top of the glass column during a foamability test.
The foam height Hm is equal to the following expression, H f being the final height and Hl the
height of the bubbly liquid:
Hm = H f − Hl (A1)
Colloids Interfaces 2019, 3, 2 14 of 17
If we consider a column of foam of radius R, a liquid volume fraction of foam in the upper part equal
to ϕl and a volume fraction of gas in the bubbly liquid A, the volume of liquid introduced initially
H0 πR2 is distributed between:
as Hl = H f − Hm
H0 − H f (1 − A)
then : Hm = (A3)
( ϕ l + A − 1)
Appendix B
The lifetime τv of a bubble arriving at the top of the glass columns during a foamability test is
defined by the following equation
πR2 H f (1 − A) − H0
Hm
τv = = (A4)
U Q 1 − A − ϕl
With U the speed of the flow in the column, R the radius of the glass column, Q the flow rate of
nitrogen injection, A the volume fraction of gas in the bubbly liquid and ϕl the volume fraction of
liquid in the foam.
The calculation of the lifetime τv requires to know the value of the foam height Hm that-is-to-say
the expression of the gas volume fraction A in the bubbly liquid. This magnitude can be estimated
using foamability measurements on a non-foaming liquid. Indeed, in the case of a non-foaming liquid,
the foam height Hm is equal to zero and the injection of nitrogen induces only an increase of the
liquid height.
τv = 0 ↔ Hm = 0
H0
Hf = (A5)
1−A
Figure 15.Evolution
FigureA2. Evolutionofofthe
thegas
gasvolume
volumefraction
fractionAAininthe
thebubbly
bubblyliquid
liquidasasa afunction
functionofofthe
thethe
theinitial
initial
× −5 m3 /s
height 𝐻
height H0 of liquid introduced in the glass column. Q = 1.04 × 10 𝑚 /𝑠
of liquid introduced in the glass column. Q = 1.04 10
Experimentally,
Experimentally, we we obtain
obtain thethe following
following empirical
empirical laws:
laws:
𝐴 ( Q(𝑄)
A| H ) ==6.5
6.5××1010
4 𝑄 − 1.4 × 10
Q − 1.4 × 109 Q𝑄
2 (B4)
(A7)
0
with 𝐻 = 1.18 𝑐𝑚
with H0 = 1.18 cm
A|Q𝐴(H(𝐻 ) =3.23.2××1010
0) =
−1 + 2.7 × 10 exp(−
+ 2.7 × 10−1 exp (−2.4
2.4 ×× 10
101 H𝐻0 )) (B5)
(A8)
withQ 𝑄==1.04
with −5 m
1.04××1010 m3 /s/s
WeWeshould
shouldkeep
keepininmind
mindthat
thatininthe
thecase
case
ofof another
another systemthat
system that does
does not
not foam,
foam, the
the value
value ofofA(𝐴(𝑄,
Q, H𝐻0)
)
evaluatedpreviously
evaluated previouslycan cansometimes
sometimesinduce lifetimesτv𝜏 slightly
inducelifetimes slightly negative.We
negative. Weare,
are,indeed,
indeed,ininananarea
area
where the noise of the measurements prevails. By convention, we will consider
where the noise of the measurements prevails. By convention, we will consider these “negative” these “negative”
lifetimesasasequal
lifetimes equaltotozero.
zero.
AppendixCC
Appendix
Theexpression
The expression of the
of the liquid
liquid volume
volume fraction
fraction 𝜑 is obtained
ϕl is obtained from thefrom theequation
general general ofequation
drainage,of
drainage,
which which expression,
expression, by neglectingbythe
neglecting
capillarythe capillary
suction, is: suction, is:
𝐷𝜑 𝛼𝜌
+ ∇⃗ 𝑔⃗ = 0 (C1)
𝐷𝑡 𝜂
with 𝛼 the permeability coefficient of the foam.
By projecting the previous equation along the vertical axis z oriented upwards, we obtain the
following expression in steady state regime:
𝑑𝜑 𝜕 𝛼𝜌 𝑔
Colloids Interfaces 2019, 3, 2 16 of 17
→
Dϕl αρl →
+ ∇ g =0 (A9)
Dt η
that-is-to-say:
∂ αρl g
U ϕl − =0 (A11)
∂z η
The term in parenthesis corresponds to the flux, which is equal to zero at the interface. Thus, we obtain
the following relation:
αρl g
U ϕl = (A12)
η
That-is-to-say:
αρl g
ϕl = (A13)
ηU
Please note that there are several models in the literature to describe the coefficient of permeability
α. We choose the model of Carman and Kozeny which is an empirical equation for the permeability
of an assembly of spheres providing an expression of the coefficient of permeability α in reasonable
adequacy with the experiments (ϕl > 0.1):
ϕ l 3 d2
α= (A14)
180(1 − ϕl )2
We recall that d is the diameter of a bubble: typically d = 3.2 mm in toluene at a nitrogen injection rate
of 1.04 × 10−5 m3 /s.
Thus,
αρl g ϕ l 3 d2 ρg
ϕl = = 2
· l (A15)
η 180(1 − ϕl ) η
By replacing the expression of α in the previous equation, we obtain the expression of the liquid
volume fraction ϕl :
1
180U 2
ϕl = ( 2 ρl g ) (A16)
d η + 180U
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