Probing W/O Crude Emulsions by Organic Acid Doping: Interactions of Asphaltenes and Acids

Probing W/O Crude Emulsions by Organic Acid Doping:
Interactions of Asphaltenes and Acids

Discoidal Aggregates
Elastic Film
Interface, neutral pH
Interface, elevated pH,

TAN > TBN
Jeronimo Merino*, Vincent J. Verruto, and Peter K. Kilpatrick

NC State University, Chemical & Biomolecular Engineering
*PLAPIQUI, Bahia Blanca, Argentina
8th Int. Conf. on Petroleum Phase Behaviour & Fouling June 11th, 2007
1/22
Lessons Learned This Week

Asphaltenes, Naphthenates (Na and
Ca) can stabilize w/o and o/w
emulsions by forming strong elastic
films
Prediction is not always easy
What happens when asphaltenes,
naphthenates, and resins interact?
2/22
Asphaltenes and Their Solubility in

Mixtures of Heptane and Toluene
100
Decreased
Solubility
% Precipitated (w/w)
80
AH - Arab Heavy
B6 - Santa Barbara
CS - Canadon Seco
HO - Hondo
60
Solubility
Limit
40
20
0
0
20
40
60
% Toluene (v/v)
80
100
3/22
Fractionation of Asphaltenes into Less and More

Soluble Fractions Demonstrates Solubility is an
Aggregation-Related Phenomenon
100
B6
Whole and
Soluble
fractions
readily
dissolve
Precipitate
often
required
heating to
80C to redissolve
80
Whole
Soluble
Precipitate
60
40
20
0
0
20
40
60
% Toluene (v/v)
80
100
Spiecker et al. JCIS, 267, 178-193 (2003)
4/22
Effect of Resins on Solubility of Asphaltenes

100
Soluble
Soluble w Resins
% Precipitated
80
Precipitated
Precipitated w Resins
60
40
20
0
0
20
40
60
80
100
Spiecker et al. ColSurfA 2003

5/22
Shear Interfacial Rheometry Expts on

Asphaltenic Films + Resins
4 hrs
10
12 hrs
12
8 hrs
G'(Pa)
14
Control
4 hr solute removal
8 hr
12 hr
4 hr replace w/ Resins
8
6
4 hrs, NO Resins
Asph solution replaced

with solute-free oil
All further elasticity
increases due to
consolidation
4 hrs, WITH Resins
2
(Spiecker and PKK, Langmuir 2004)
10
15
20
25
30
35
Time (hrs)
40
45
50
6/22
Emulsion Stability by Centrifugation

Oil
Emulsify on
Virtis IQ2 @ 15K
RPM for 5 min
Resuspend
droplets and
transfer to a
2mL tube
Centrifuge
@ 14,500 RPM, 1hr
Water
After aging 24 hrs,
settled emulsion
Creamed Oil (CO)

Compact Emulsion Phase
Pipette off CO
and remove
emulsion phase
Eppendorf MiniSpin
Obtain mass of
resolved water
Resolved Water
Record volume
observed visually
% waterresolved =
mH 2O ,res H 2O
w,emuls (2mL)
7/22
100
Role of Asphaltene Chemistry on W/O

Emulsion Stability
Weakly surface-active,
non-polar, aromatic
asphaltenic aggregates
100
% Water Resolved
80
i. 0.5% (w/w)
asphaltenes in
HepTol
60
ii. Emulsified 50:50

(v/v) with water
40
iii. Centrifuged to
judge emulsion
stability
AH
B6
CS
HO
20
Increasingly Soluble
0
0
20
40
60
80
100
% Toluene
8/22
Hondo (HO) Asphaltenes Mixed with -Cholanic

Acid, Emulsified with NaCl-laden Water
100
Unstable
90
wt% Brine recovered
80
70
60
pH = 13.2
pH = 12.5
pH = 12.0
pH = 11.5
pH = 10.8
pH = 10.0
50
40
30
20
LC-stabilized
Asphaltene-stabilized
10
Emulsion Stability - CA+Asph in Brine at varying pH
0
0
0.2
0.4
0.6
0.8
1.2
1.4
1.6
wt% CA-material in the emulsion
i.
ii.
iii.
0.5 % (w/w) HO asphaltenes in 50:50 (v/v) heptane: toluene

Increasing amounts of -cholanic acid (0.025 1.5 %, w/w)
Varying pH (9-13); 50:50 (v/v) w/o emulsion
9/22
How does pH impact pure asphaltenes?

pH 12
pH 7
Water Resolved, wt%
120
100
HONDO: 1% HOW in
50:50 HepTol Emulsified
with Water 40:60 O/W
(v/v), Water pH Adjusted
and with 1% NaCl
80
60
40
Very
Significant
Increase
20
0
Increased
0
20
Stability
40
60
80
100
% Toluene
10/22
Does CA at pH 12 Destabilize 1% HO Emulsions?

Displacement Mechanism
Water Resolved, wt%
100
80
60
300 ppm
Solvation Mechanism
40
1% HO in 50:50 Heptol pH 12
-CA: 0.005 - 2 %
20
0
0.0
0.5
1.0
1.5
2.0
0.00
- Cholanic Acid, wt%
0.05
0.10
0.15
0.20
11/22
0.25
Is this a general phenomenon or

does it only occur with Hondo
asphaltenes?
12/22
Do we see similar destabilization of

emulsions in crude oils?
100
Water Resolved, wt%
80
60
HONDO Crude Oil

50:50 Crude:Heptol
30:70 Crude:Heptol
40:60 heptol (v/v)
1% (w/w) NaCl in Water at pH 12
40
20
0
0.0
0.5
1.0
1.5
2.0
2.5
3.0
Notes:
1:1 Diluted Crude
7% asph
10% resins
destabilization @
3,000 ppm CA
3.5

13/22
Similar Destabilization seen with South

American
#1
Crude
Oil
100
Water Resolved, wt%
80
60
40
Latin American #1 Crude Oil

diluted in 40:60 heptol (v/v)
30:70 Crude:heptol
1% (w/w) NaCl in Water at pH 12
40:60 Crude:Water (v/v)
20
0
0.0
0.5
1.0
1.5
2.0
2.5
Notes:
3:7 Diluted Crude
1% asph
2% resins
1.2 TAN
destabilization @
10,000 ppm CA
3.0

14/22
What about other possible

carboxylic acids that might be
present in the crude oil (other than
tetra acids)?
15/22
O
H2C
OH
H/C
H3C
Model Carboxylic Acids
OH
H3C
CH3
OH
Asphaltene
like
H
H
H3C
O
CH3
OH
HO
Molecular
structure
O
O
H
OH
16/22
CEF Design and Measurement Principles

+
+
0 kV/cm
droplets form short chains parallel

to electric field
+
V
-
droplet chains lengthen and bridge

entire gap
critical electric field - water bridges

electrodes, conductivity jumps
CEF is a measure of the electric field strength required

to induce the flow of current through an emulsion
Asphaltenes form a barrier to current flow until the
encased electrolyte causes film rupture and water
coalescence
17/22
Role of pH and Acid Molecular Structure

cef for 30/70 % V water/EB emulsions @ 1% salt and 0.5%
carboxylic acid in the oil phase: Effect of pH
1.2
1.65
1.5
1.35
"pH=12"
0.68
0.63
0.8
0.6
0.4
0.2
0
0.7
0.78
0.5
0.14
0.22
0.83
"pH=7"
1
0.77
"pH=12"
1.12
"pH=7"
0.83
1.5
cef (kV/cm)
0.75
0.8
0.64
0.6
0.58
0.54
0.55
0.6
0.4
0.4
0.2
0.34
0.3
0.25
0.27
0.2
0.04
carboxylic acid structure
0.04
2na
9ph
an
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c
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ca
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c
2na
ph
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1,
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en
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lc
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un
de
cy
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4p
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bl
an
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0.04
bl
an
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1.8
1.6
1.4
1.2
1
un
de
en
cy
ty
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lc
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5b
-c
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1,
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lb
ah
en
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2na
ph
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oi
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29n
ap
an
ht
tr
ac
ho
en
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e
ca
rb
ox
yl
ic
cef (kV/cm)
cef for 30/70 % V water/GCB emulsions @ 1% salt and 0.5%

carboxylic acid in the oil phase: Effect of pH
carboxylic acid structure
i. Both crude emulsions are slightly destabilized by high pH

ii. Naphthenic acids destabilize emulsions at high pH
iii.Asphaltenic acids stabilize emulsions at all pHs
18/22
But what role do the acids and

bases that are naturally present
in asphaltenes and resins play in
the stabilization or
destabilization of asphaltene
emulsions? As functions of pH?
19/22
CEF Studies on Whole Crude Emulsions:

pH 7, 60 C, 1% NaCl
water
Critical Electric Field (kV/cm)
HO
y = 0.34582 + 0.27709x R= 0.96401
AH
HO
B4
B6
CS
AB
ANS
TH
SJV
Alba
SM
SCS
Africa
c.e.f.
2.5
2
1.5
AH
1
SA#1
0.5
0
0
10
Asphaltene
x Delta H/C
wt
% A x H/C
20/22
pH Dramatically Affects CEF

4.0
SA#1
ARAB HEAVY
HONDO
CEF (KV/CM)
3.5
3.0
2.5
2.0
1.5
1.0
0.5
0.0
10
12
pH
21/22
Do the kinetics of the emulsion

stability reveal any specific
molecular rearrangements at the
interface?
22/22
The Effects of Resins on CEF Kinetics:

B6
Asphaltenes
B6
Resins
2.0
1.5
1a0r
1a0.75r
1a0.25r
1a1r
1a0.5r
1a2r
1a4r
Cef (KV/cm)
1.0
0.5
0.0
0
Yang et al., Energy and Fuels 2007
500
1000
1500
Time (min)
23/22
The Effects of Resins on CEF Kinetics:

AH Asphaltenes-AH Resins 1% AH
1a0.2 5r AH
1a0.5r AH
1a0.7 5r AH
1a1r AH
1a2r AH
1.4
1.2
1.0
CE F (KV /cm)
0.8
0.6
0.4
0.2
0.0
500
(min)
8th Int. Conf. on Petroleum Phase Behaviour & Fouling JuneTime
11th, 2007
1000
1500
24/22
Mixture Effects:
Crudes + Model Solutions
B 6 + model oil of B6 A spha ltenes in Heptol (R /A = 0.63)
2.5
Cef KV /cm
1.5
0.5
500
1000
Time (min)
1500
25/22
Asphaltene
Resin
(1) (2)
Aggregation
Molecular Rearrangement,
Adsorption of Outermost Resins
Diffusion to the O/W Interface
(3) (4)
8th
Reptation of Resins through

Int. Crosslinked
Conf. on Petroleum
Phase Behaviour
& Fouling
Asphaltene
Network
June 11 ,
th
Interfacial Displacement
2007of Asphaltenes by Resins
26/22
Conclusions
W/O Emulsion Stability in Crude Oils is
dominated by the formation of high modulus
elastic films of asphaltenes
This stability can be judged by CEF, % W Res
In certain conditions (pH, Conc), naphthenic
acids and their soaps can stabilize W/O
emulsions by a liquid crystal mechanism
Certain organic acids, under appropriate
conditions of pH, strongly destabilize
asphaltene emulsions, likely by a displacement
mechanism
27/22
Conclusions (cont)
Only acids with an appropriate tendency to
adsorb at the oil-water interface, and which do
not strongly associate with asphaltenes appear
to destabilize asphaltene emulsions in this
fashion
Asphaltene emulsion stability is a strong
function of water pH
Basic asphaltenes appear to exhibit enhanced
emulsion stability at elevated pH, while acidic
asphaltenes appear to exhibit diminished
emulsion stability at elevated pH
28/22
Acknowledgements
NSF
Foundation Grant TSE0124760
Maria Lupe Marques, Olugbenga Falode
29/22

Probing W/O Crude Emulsions by Organic Acid Doping: Interactions of Asphaltenes and Acids

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Probing W/O Crude Emulsions by Organic Acid Doping:

Interactions of Asphaltenes and Acids

Interface, elevated pH,

Jeronimo Merino*, Vincent J. Verruto, and Peter K. Kilpatrick

Lessons Learned This Week

Asphaltenes and Their Solubility in

Fractionation of Asphaltenes into Less and More

Spiecker et al. JCIS, 267, 178-193 (2003)

Effect of Resins on Solubility of Asphaltenes

Spiecker et al. ColSurfA 2003

Shear Interfacial Rheometry Expts on

Asph solution replaced

4 hrs, WITH Resins

Emulsion Stability by Centrifugation

Creamed Oil (CO)

Role of Asphaltene Chemistry on W/O

ii. Emulsified 50:50

Hondo (HO) Asphaltenes Mixed with -Cholanic

wt% Brine recovered

Emulsion Stability - CA+Asph in Brine at varying pH

wt% CA-material in the emulsion

0.5 % (w/w) HO asphaltenes in 50:50 (v/v) heptane: toluene

How does pH impact pure asphaltenes?

Water Resolved, wt%

Does CA at pH 12 Destabilize 1% HO Emulsions?

Water Resolved, wt%

- Cholanic Acid, wt%

- Cholanic Acid, wt%

Is this a general phenomenon or

Do we see similar destabilization of

Water Resolved, wt%

HONDO Crude Oil

- Cholanic Acid, wt%

Similar Destabilization seen with South

Latin American #1 Crude Oil

- Cholanic Acid, wt%

What about other possible

Model Carboxylic Acids

CEF Design and Measurement Principles

droplets form short chains parallel

droplet chains lengthen and bridge

critical electric field - water bridges

CEF is a measure of the electric field strength required

Role of pH and Acid Molecular Structure

carboxylic acid structure

cef for 30/70 % V water/GCB emulsions @ 1% salt and 0.5%

carboxylic acid structure

i. Both crude emulsions are slightly destabilized by high pH

But what role do the acids and

CEF Studies on Whole Crude Emulsions:

Critical Electric Field (kV/cm)

y = 0.34582 + 0.27709x R= 0.96401

pH Dramatically Affects CEF

Do the kinetics of the emulsion

The Effects of Resins on CEF Kinetics:

The Effects of Resins on CEF Kinetics:

Diffusion to the O/W Interface

Reptation of Resins through

Maria Lupe Marques, Olugbenga Falode

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