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HLD Optimum Formulation as the Emulsion persistance (stability)

Main Principle for Breaking Emulsions has been studied for more than 100 years
vs surfactants, polymers and particles
Recent Advances in
Demulsifier Performance in Crude Dewatering It was only ~ 40 years ago that a
J.L. Salager, A.M. Forgiarini & J.G. Delgado general rule was found
Lab FIRP, University of the Andes, Venezuela
From the surfactant effect in relation
to EOR Optimum formulation

What is physicochemical formulation ?

A concept based on interactions at O/W interface

3 / 72 E853AC 4 / 72 E853AC

Winsor’s Ratio (1954) Winsor research

between molecular interaction energies showed a relation between R
oil surfactant and the phase behavior
(O) (C)
Aco Aco
R= S1 micelle S S S2 micelle
Acw
water W OW O
(W) Acw very pedagogical
but qualitative!
R<1 _ R>1
R < 1, R = 1 or R > 1
related to phase behavior
WI _
2 2 W II
Phase behavior (in two-phase zone at )
Winsor P., Solvent Properties of Amphiphilic Compounds, Butterworth London (1954)

5 / 72 E853AC 6 / 72 E853AC

Winsor research Formulation Scan

showed a relation between R changes the phase behavior Aco
R=
and the phase behavior Acw
liquid crystal microemulsion Example: Formulation variable
R=1 = Salinity of aqueous phase
W III S2
If salinity increases
S
Acw decreases R increases
S
1 transition R < 1 R=1 R>1
W O
complex phase behavior
7 / 72 E853AC 8 / 72 E853AC

Formulation Scan Formulation Scan

phase behavior

WI W III W II W III

2
Salinity
1.0 1.4 2.0 2.8 4.0 5,6 % NaCl
WI W II
2

R>1 Optimum Formulation

R<1 R=1
Shah D., Schechter R., Eds,. Improved Oil Recovery by Surfactant and
Polymer Flooding, Academic Press New (1977)

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Same transition (R < 1 R >1) Optimum Formulation

with all formulation variables able
to alter Axx interactions
systematic studies
two-dimensional scan = series
Aco - 1 / 2 Aoo - 1 / 2 ALL of one-dimensional scans
oil surfactant R=
(C) Acw - 1 / 2 Aww - 1 / 2 AHH formulation
(O) 2 φ (W II)
Aco variable #1 W III
 Salinity (type and conc.) (Salinity)
 ACN and structure 3φ
 Surfactant (Hydroφ part) Optimum
 Surfactant (Lipoφ part) Formulation
water S - ACN
 Temperature 2 φ (W I)
(W)
Acw  Alcohol (type and conc.)
formulation variable # 2 (ACN)

11 / 72 E853AC 12 / 72 E853AC

Optimum Formulation OPTIMUM FORMULATION

empirical correlations
systematic studies (thousands of experiments)

For all systems ionic lnS - K ACN - f(A) + σ - aT ∆T = 0

Ln S containing ionic
Surfactant
3φ surfactants
Salinity Oil Alcohol Temperature
2
Relation: nonionic
LnS = K ACN + ... α - EON + b S - k ACN - φ(A) + cT ∆T = 0
2 or dLnS = K dACN Surfactant
ACN

Salager J. L. et al., Soc. Petroleum Eng. J., 19: 107 (1979) ANIONIC SYSTEMS
Which may be written as : Σ ci X i = 0
Bourrel M. et al., J. Colloid Interface Science, 75: 451 (1980) NONIONIC SYSTEMS
Antón R. E. et al., J. Dispersion Science Technology, 18: 539 (1997) CATIONIC SYSTEMS
13 / 72 E853AC 14 / 72 E853AC

Surfactant Affinity Difference Conceptual Support

(Affinity = - µ*)
Surfactant Affinity Difference SAD
µ = µ*w + RT ln Cw = µ*o + RT ln Co ionic Surfactant
>
HLD = SAD/RT = lnS - K ACN - f(A) + σ - aT ∆T = 0
SAD = µ*w - µ*o = RT ln Co /Cw <
nonionic Salinity Oil Temperature
Surfactant Partition Coefficient Alcohol
Surfactant
>
HLD = SAD/RT = β + b S - k ACN - φ(A) + cT ∆T = 0
At optimum formulation <
CO complex but quantitative
Cw = Co (anionic systems)
thus SAD = 0 CW HLD = Hydrophilic-Lipophilic Deviation
Salager J.L., in Pharmaceutical Emulsions and Suspensions,
Salager et al., Langmuir, 16: 5534 (2000) Nielloud F., Marti-Mestres G., Eds., Chap. 2, Dekker (2000)

15 / 72 E853AC 16 / 72 E853AC
It is a general phenomenon Another general phenomenon
low interfacial tension in WIII system (HLD = 0) in a
narrow zone of any formulation scan
Emulsion stability vs formulation
Experimental Results
at optimum: 3 phases, emulsion inversion and instability
STABILITY (sec)

γ*min O/W W/ O

Surfactant Behavior
Hydrophilic Lipophilic
Salager et al., JDST (1982)

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Stability - Formulation
video Experimental Results

 sequence of test tubes (formulation scan) ...

vs time, i.e.emulsion breaking vs formulation
 showing fastest coalescence at optimum

Bourrel et al. JCIS (1979) Salager et al. JCIS (1980)

19 / 72 E853AC 20 / 72 E853AC

Stability - Formulation Stability - Formulation

Experimental Results Experimental Results

Vinatieri SPEJ (1980)

Milos & Wasan COLS (1982) Anton & Salager JCIS (1986)

21 / 72 E853AC 22 / 72 E853AC
Same instability whatever the Stability - Formulation
surfactant concentration : At HLD = 0 Experimental Results
surfactant does not seem to be at O-W interface
to stabilize emulsion

Anton & Salager JCIS (1986) Kabalnov & Weers, Langmuir (1996)

23 / 72 E853AC 24 / 72 E853AC

Stability - Formulation Stability - Formulation

Experimental Results (change of salt) Experimental Results (different surfactants)

HLD = 0

LnS (wt % salt) Generalized Formulation HLD

HLD = 0
Generalized Formulation HLD

Same plot in HLD scale >>> allows comparisons Same plot in HLD scale >>> allows comparisons
25 / 72 E853AC 26 / 72 E853AC
Why are emulsions very unstable at HLD=0?
Various explanations Emulsion stability vs formulation
 Surfactant is trapped in a microemulsion
General Phenomenology
 Surfactant form liquid crystal bridges
 Holes in interdrop films are unstable

Emulsion
 Tension gradient ~ 0 (no Gibbs-Marangoni effect)

Stability
 Fast transfer to interface and quick apparent equilibration WI WIII WII
 Zero curvature is inconsistent with spherical drops
 etc... MOW
O/W W/ O
Bourrel M. et al., J. Colloid Interface Sci., 72: 161 (1979) Stability deep minimum
Salager J.L. et al., J. Colloid Interface Sci., 77: 288 (1980)
Anton R., Salager J.L., J. Colloid Interface Sci., 111: 54 (1986) at optimum formulation,
Hazlett R. D., Schechter R. S. Colloids Surfaces, 29: 53 (1988)
Kabalnov A. et al., Langmuir, 12: 8 & 12: 276 (1996) i.e., at HLD = 0
Ivanov I. et al., Colloids Surfaces A, 128: 155 (1997)
Fillous L. et al. J, Surfactants & Detergents 2: 303 (1999) - 0 + HLD
Salager JL et al. Langmuir, 18: 607 (2002)

27 / 72 E853AC 28 / 72 E853AC

Desestabilization is based on a
It requires an Accurate Formulation
mixture to attain HLD = 0
 natural surfactant is lipophilic  Mixture formulation must be
 demulsifier surfactant should be hydrophilic so exactly at HLD = 0 ± 0.02
that the mixture of both is balanced (HLD = 0).

Stability (sec)
 Mixing rule should be accurate
unstable with precise numbers
emulsion

proper natural surfactant  Very small range to insure

demulsifier mixture
(asphaltenes …) quick coalescence Formulation HLD
surfactant
Salager J. L., Int. Chem. Eng., 30: 103 (1990)
Krawczyk M., Wasan D. T., Ind. Eng. Chem. Res., 30: 367 (1991)
- HLD = 0 + Kim Y., Wasan D. T., Ind. Eng. Chem. Res., 35: 1141 (1996)
Goldszal A., Bourrel M., Ind. Eng. Chem. Res., 39: 2746 (2000)
Salager J. L., Int. Chem. Eng., 30: 103 (1990)

29 / 72 E853AC 30 / 72 E853AC

Precise Asphaltene (A) – Demulsifier (D) Mix Linear mixing rule for HLD=0 at interface
Optimum at HLD = 0 lnS - K ACN + σ - aT ∆T = 0 Interfacial concentration
and SCPA of asphaltenes

 for a given reservoir ... S, EACN and T are fixed,

SCPSYS = (1-xD) SCPA + xD SCPD = SCPSYS
thus the surfactant characteristic parameter unknown demulsifier
SCP (σ or β) for the mixture must satisfy: but fixed

SCPSYS = σ (or β) = K ACN – lnS + aT ∆T = Constant

Simple A-S surfactants mixture condition (Linear rule) adjust

SCPMix = xD SCPD + xA SCPA = SCPSYS not only SCPD but also
concentration CD (XD )
SCPMix = xD SCPD + (1-xD) SCPA = SCPSYS 2 degrees of freedom
Salager J. L., SPE J., 19: 271 (1979)
31 / 72 E853AC 32 / 72 E853AC

Add CD (hence xD ) unstable

ppm of demulsifier Pour in
emulsion
bottle
Wait some time Proper natural
demulsifier mixture surfactant
surfactant (asphaltenes)
original Homogenize
W/ O - HLD = 0 +
emulsion
Measure water separation

"Bottle test" crude

in practice water

Aspect of test bottles

(changing formulation, i.e. type or concentration of demulsifier)

33 / 72 E853AC 34 / 72 E853AC

Stability measurement as coalesced 2 degrees of freedom = 2 types of scan:

desmulsifier concentration at constant type
volume Vc after some fixed time or time demulsifier hydrophilicity at constant concentration
VC to coalesce a fixed Vc proportion
SCPM = (1-xD ) SCPA + xD SCPD = SCPSYS
Vc / V∞ = 2/3 coalescence proper XD
1100
Stability (s) for 2/3 coalescence

1
1000
Nonylphenol 15EO SCPD = ???
Vc / V∞

Demulsifier Conc. CD = 100ppm

Demulsifier Concentration CD
100
100 CD Scan
Coalesced 900
W/O O/W
Vc
oil W/O O/W
Stability (min)
Stability (min)

800 10 10

Emulsion HLB* D SCPD Scan

700 HLB*d

0
Stability CD 1 1

10 100 1000 10000 Time 600

minimum 1 10 100 1000 8 10 12 14 16 18
Demulsifier EON (SCPD/HLB D )
Demulsifier Concentration C D SCPD as HLB D (Nonylphenol EON series)
0 100 200 300 400 500 600 700 800 900 1000
Interfacial concentration XD is Hence 2 D plot !
Demulsifier related to bulk concentration
Concentration ppm and overall concentration CD
thru adsorption isotherm
Rondon et al., Energy & Fuels 20: 1600-1604 (2006)

35 / 72 E853AC 36 / 72 E853AC
2 D Stability map
More hydrophilic the demulsifier, lower the required amount What happens now if asphaltenes
But there is a best “intermediate” change in type or concentration ?
CD 5000
Stability (as time
This term is now changing
CD scans at cst SCPD 2000 for 50% of water
Demulsifier Concentration CD (ppm)

1000
separation)
1000
< 1 min
1-20 min
100
500 O/W
20-50 min SCPM = x A SCPA + x D SCPD = SCPSYS
Stability (min)

50-100 min
200
100-200 min
10 100 >200 min
20
50
1
15
4.75
10 5.5 20
Two different effects need to be studied:
10
Demulsifier EON
100 1000
10
W/O üAsphaltene concentration (change in XA ) = dilution by solvent
5
Demulsifier Concentration CD HLB 7.5 10 12.5 15.0 17.5
allows to include “all” existing natural surfactants
üAsphaltene type (SCPA ) = change of crude oil
Nonylphenol
EON 4,75 5,5 10 15 20 30
SCPD
Rondon et al., Energy & Fuels 20: 1600-1604 (2006)
37 / 72 E853AC 38 / 72 E853AC

For a given crude oil (SCPA =cst) and Locus of minimum stability C*D vs. CA
exhibits 2 branches and Threshold T
a given demulsifier (SCPD = cst)
What is the C*D at different CA ?

CD (NP5.5EO Concentration, ppm)

1,000 <10 min
CD
10-20 min
500 20-50 min
HLD = 0 when SCPMix = xD SCPD + xA SCPA = SCPSYS
200 C DT
T Saturation 50-100 min
>100 min
CD (NP5.5EO Concentration, ppm)
1,000
CA (Asphaltene Concentration ppm) 1,000 <10 min
10,000
C*D 10-20 min
O/W W/O
Stabilityy (V/Vo=0.5, min)

3,500 20-50 min

100 500
Stability

e l
1,000
100

m a
50-100 min
350
C*D

gi tion
100
T >100 min
200 CDT
10
O/W W/O

Re or
100
50

op
1
50
C*D

Pr
0.1 20
C AT
CAT
10 20 50 100 200 500 1,000 100 350 1,000 3,500 10,000 35,000
20
C D (NP5.5EO Concentration, ppm)

CD
C A (Asphaltene Concentration, ppm)

CA
100 350 1,000 3,500 10,000 35,000 CA
CA (Asphaltene Concentration, ppm)
Rondon et al., Energy & Fuels 22: 702-707 (2008)

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Locus of minimum stability C*D vs. CA Locus of minimum stability C*D vs. CA
exhibits 2 branches and Threshold T
CD 200
CD Best
<5
se
(Tween 80 concentration, ppm)

5-10 min
T
or

10-20 min
ppm
For various 100 a
w

ac
20-50 min
l

m
ia

demulsifiers of 50-100 min

rr

Ha

50
Fu

>100 min
sy ihl

the same For various

ea -B
st

20
family
Vi
Be

O/W crudes (SCPA)

10 W/O with a demulsifier
5 10% (Tween 80)
100 200 500 1,000 2,000 5,000
CD

CA ppm
CA. (Asphaltene concentration, ppm) CA
JG Delgado, PhD dissertation (2011)

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Locus of minimum stability C*D vs. CA Proportional Regime (CD<CDT; CA<CAT )

Unit slope in
A very general plot log-log plot logCD
logCDT T
CA Asphaltene conc. Hamaca, overall C A O/W W/O
PE

NP11EO
O
SL
IT
Stability (min)

crude logCAT
logCA
N
U

XA
CD/CA= kC and XD/XA= k
interface
in log-log it means that X*D SCPA + k SCPD
CD */CA = kC and XD * /XA = k
water
SCPmix =
1+ k
overall C*D Allows to estimate SCPA
Rondon et al., Energy & Fuels 22: 702 (2008)
43 / 72 E853AC 44 / 72 E853AC

Allows to classify …
What is the best Pluronic PEO-PPO-PEO
… demulsifiers and crudes copolymer for Hamaca heavy crude?
 What is the best demulsifier for a crude?
The one that works at the lowest C*D at a
given CA condition in proportional regime CD
ppm

Stability (min)
 What is the worst crude for a demulsifier?
The one that requires the highest C*D at a
given CA condition in proportional regime
CA = 100 ppm

CD ppm CA ppm

45 / 72 E853AC 46 / 72 E853AC
We recently found that extended
surfactants could be very performant But low C*D dose is not enough !
when properly designed
 If it is important to use less demulsifier
C*D (or to spend less money in demulsifier), it is also
important to have a FAST demulsifier...
i. e., a very low minimum stability.

 In other words the emulsion breaking

should be quick… and thus the
instability* is another criterion.
CA
Critical in offshore !
Pereira et al., Energy & Fuels 25: 1045-1050 (2011)

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Double criteria: stability* and C*D dose Double criteria: stability* and C*D dose
Comparing two demulsifiers Comparing two demulsifiers
C*D C*D

CA CD CA CD

The red one requires a lower dose, but a much longer

separation time at optimum… Probably too long ! The blue one requires a lower dose, and a shorter
JG Delgado, PhD Dissertation (2011)
separation time at optimum… It is the best … TWICE!
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Electrostatic dehydrator for laboratory

electrodes
CONDITIONS
voltage, intensity
AC, DC …

Electrodes collect
water as a falling film

water
separation
bottle

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Dynamic Interfacial tension variation

Stability - Formulation $# ' 1.0
general variation ... OK but ... "'= &&
(t) )
)
Pendent drop Tensiometer
Oil phase: crude with 500 ppm R2
% # o ( 0.8 Water phase: NaCl brine
Interfacial tension

g/L NaCl:
0.6
 Second order 0
WI WIII WII 0.01 quickest
(overall) effect
stability

0.4 0.05
can introduce qu 0.1
sh ickes
Dynamic

ort 1
an asymmetry O/W 0.2 de
t
5 quickest
lay
MOW quick
For instance an increase est
W/ O 0.0
in temperature or alcohol 1 10 100 1000 10000
content tends to reduce
surfactant adsorption and time in sec
- 0 + HLD
thus emulsion stability Salinity alters the system formulation and
Temperature
Alcohol content thus the emulsion stability!

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Clever data processing (time scale delay)
Dynamic Interfacial tension variation
Tension

0,75
Scaled

Iso-Propanol (φʼ - 0.25) Pendent drop tensiometer

! n-Decanol Oil phase : crude
Sec-butanol = “speedy González”
1.0 No alcohol (froming drop)
$# ' 0,5 Water phase: 0.01 g/L NaCl
(t) ) n-Octanol
"'= && ) + 100 ppm R2
sec-Pentanol
% # o (0.8 n-Butanol
+ 2% volume of alcohol
0,25
Scaled Time
n-propanol

ter-Pentanol
Interfacial tension

n-Propanol Log (t/τ)

Sec-butanol

0.6 sec-Butanol
0
-3 -2 -1 0 1 2 3
0.4 Time Scale
τ (seg) -0,25
Dynamic

Pendent drop tensiometer

0.2 Oil phase: crude (drop) 1.520 1.875
Water phase: 0.01g NaCl/L brine
23 83 -0,5
+ alcohol 2% v/v + 100 ppm de R2
0.0 174 175
0.01 0.1 1 10 100 1000 10000 25.500 14.000 -0,75
time in sec
Mafisi S., PhD thesis ULA (2005)
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Interfacial Rheology seems to follow Interfacial Rhelogy Effects

HLD formulation variation
 With Spinning Drop Interfacial Rheometer
Interfacial Tension

optimum CD*
CA = 10 ppm
diluted heavy crude required for pulsating drops at the low interfacial
1 wt % NaCl - 30 °C
demulsifier R9F6.5 tension at optimum
mN/m

CD ppm

Interfacial Viscosity mN/m* s

Interfacial Elasticity mN/m

Phase Angle (°)

Marquez R.,
PhD thesis ULA
(2016)
CD ppm CD ppm CD ppm

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electrostatic
Effect of WOR as a dehydratation in
formulation variable 10 minutes

Lab electrostatic dehydrator

Made in FIRP-ULA

Separated water

Borges et al., Energy & Fuels 23: 1568 (2009)

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Benefit with an electrical field body force  Dehydrant/demulsifier must be hydrophilic …

but it must be “soluble” in crude ...
No field No field
200 V/cm
to be able to attain by convection and diffusion
(min for 75% separation)

(min for 75% separation)

200 V/cm
the water drop interface.
Emulsion Stability

Emulsion Stability

Deshydrant
Demulsifier

diffusion
adsorption
drop
Oil which is able to
solubilize a
SM-1310-15, C A = 500 ppm M2C, CA = 1000 ppm hydrophilic
surfactant
Accelerate the measurement ~ 100 times CRUDE convection
Very useful in formulation lab (aromatic gasoil)
61 / 72 E853AC 62 / 72 E853AC

Diluent = cyclohexane Effect of diluent  In order to compete for adsorption with

1,000
4.75 EO natural surfactants
5.5 EO
CD ( concentration, ppm)

Diluent = toluene  demulsifier must be a “big” molecule !!!

100
10 EO
C*D much lower
10,000
natural
10
Asphaltene
concentration in
surfactants

CD concentration, ppm)
crude oil 1,000

1
10 100 1,000 10,000 100,000 100
CA (Asphaltene concentration, ppm) EO
5
5.

EO
10

15
EO
10 CRUDE OIL
CA=10%
1
10 100 1,000 1,0000 100,000
C A (Asphaltene Concentration, ppm)
natural surfactants
CDT ± the same but CRUDE
CAT much higher and demulsifiers

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New family tested by Syncrude Canada

Dehydrant/Demulsifiers
 almost anything has been tried !
 recently Poly-EO-Poly-PO-Poly-EO
 current trends: ethoxylated resins,
extended surfactants and 2-3 D polymeric
DETA
amphiphiles Looks like aphaltenes !

R R Aliphatic bridge
R
Aromatic island
CH2 CH2 ethoxylated resins

O-EOn O-EOn O-EOn O--O-CH2 -CH2--OH

n Polar group
Diethylamine Triamine Poly-oxyalkene (PO y EO)
Venter J. et al. 4th Petrophase Symposium, Trondheim Norway, June 2003

65 / 72 E853AC 66 / 72 E853AC
Historical use of demulsifiers
How about optimizing dendritic structure
demulsifier looking like an asphaltene ? Period
1920
Dose (ppm)
1.000
Chemicla type
Soaps, naphtenic acids, aromatics
and akylaromatics, sulfonates,
sulfated castor oil
1930 1.000 Petroleum Sulfonates, sulfocsuccinic
acids esters, di-epoxides
from 1935 100 – 500 Ethoxylated fatty acids, fatty
alcohols and alkylphenols
from 1950 100 Block Copolymers EO/PO, p-alkyl
phenol formaldehyde resins +
EO/PO and modified products
from 1965 30 – 50 Oxy-alkyl amines, polyamines
from 1976 10 – 30 Oxyalkylates, cyclic p-alkyl phenol
formaldehyde resins and complex
modified products

from1986 5 - 20 Polyesteramines mixtures

Staiss F. et al. Improved Demulsifier Chemistry.

HYBRANE SPE Production Engineering, 6: 334 (1991)
67 / 72 E853AC 68 / 72 E853AC

Component characteristics
 Optimum formulation relationship is a “tip”
HLD = SAD/RT = lnS - K EACN - f(A) + σ - aT ∆T = 0

 Combining the surfactant parameters for the  Demulsifier must be injected as soon
demulsifier and for asphaltenes (as surfactant) as possible (to mix well and get close to
is feasible but not very accurate… the drop interface by convection)
 Combining the oil parameter of asphaltenes
that segregate close to interface with the rest  ... Sometimes “down hole” injection
of oil EACN, would be a significant advance … E
W AR
It would allow to consider asphaltenes with a dual
BE
formulation effect, i.e., as surfactant (SCP) and
polar oil (EACN) and better use the HLD equation ! Overdose O/W emulsification!

69 / 72 E853AC 70 / 72 E853AC

Remark : dehydrant agent (demulsifier) is a

Heating is sometimes necessary
good emulsifier of the O/W type or very welcome !
In order to .....
Emulsion
Stability

O/W unstable
stable emulsion

efficient  Reduce natural surfactant adsorption

too much Mixture natural
hydrophilic surfactant  Reduce crude viscosity
dehydrant
or ASP at high pH
 Increase density difference ∆ρ
- HLD = 0 +
ARE
B EW It will change formulation !

71 / 72 E853AC 72 / 72 E853AC

CONCLUSIONS
 Generalized formulation (HLD) numerical concepts
apply to Asphaltenes / Demulsifier mixtures
 Asphaltenes characteristics parameters may be
estimated from proportional regime zone.
 Optimum Demulsifier dose (and cost) depends on
Ø its hydrophilicity and its nature and structure
Ø the asphaltenes content (only below threshold)
Ø the diluent or crude asphaltenes type (polarity)
 The value of the low stability at optimum depends
on the crude asphaltenes and on demulsifiers
 These advances might lead to predict, design and
optimize demulsifier formulations in a near future.