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New Developments in the Formulation of Dispersions

UMIST Manchester, UK, September 29 - October 1, 2003
EMULSION PROPERTIES

TYPE O/W, W/O, other… and INVERSION

DROP SIZE (Average & Distribution) %
>>> influences other properties

STABILITY (against some Decay)

diameter
VISCOSITY (Rheological Behavior)

Jean-Louis Salager depend on 3 kinds of

Lab. FIRP, Formulation
University of The Andes, VARIABLES Composition
Mérida Venezuela Emulsification Protocol

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1 Physicochemical FORMULATION 1 Physicochemical FORMULATION

Nature of each components: --> in general more than 3
Electrolytes in aqueous phase (Na, Ca etc...)
Oil Alkane Carbon Number ACN (complex mixture as crude)
Surfactant Characteristics ..... often mixtures
Temperature (Pressure only in extreme cases)
Nature of each components: --> in general more than 3
Electrolytes in aqueous phase (Na, Ca etc...)
Oil Alkane Carbon Number ACN (complex mixture as crude)
Surfactant Characteristics ..... often mixtures
Temperature (Pressure only in extreme cases)

How many 2 COMPOSITION How many

variables ? At least 2 independent variables ?
(Surf. Conc. + WOR) --> often more

5 3
4 2

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1 Physicochemical FORMULATION 3 kinds of VARIABLES

Nature of each components: --> in general more than 3
Electrolytes in aqueous phase (Na, Ca etc...)
Oil Alkane Carbon Number ACN (complex mixture as crude) 1. FORMULATION 5
Surfactant Characteristics ..... often mixtures 2. COMPOSITION 2
Temperature (Pressure only in extreme cases) 3. Emulsification PROTOCOL 3
2 COMPOSITION How many Systematic Study with = 10 variables ?
At least 2 independent variables ?
(Surf. Conc. + WOR) --> often more
if 5 values for each variable
3 Emulsification PROTOCOL >>> 100.000
Phenomenon (shear, turbulence) experiments are required
Emulsor Device (efficiency ?)
Energy Input (rpm) 3 Too many degrees of freedom !!!
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Influence of FORMULATION
Emulsion type related to Formulation Yardsticks
O/W or W/O Curvature
for instance wedge theory (Langmuir)
1949 HLB (Hydrophilic Lipophilic Balance) ....... empirical
W/O
oil emulsion 1954 Winsor R ratio ................................ theoretical
induces type
surf curvature 1964 PIT (Phase Inversion Temperature) ............ empirical
water O/W 1971 CER (Cohesive Energy Ratio) ....................... mixed
Winsor III systems 1977 Correlations for 3 phase behavior .... empirical
Kabalnov A. et al. zero curvature structures
Langmuir, 12, 276 (1996) for instance microemulsion 1988 SAD (Surfactant Affinity Difference) ............. mixed
Acosta E. et al., Langmuir, NO STABLE EMULSION
19, 186 (2003)

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Surfactant Affinity Difference SAD has been generalized to

SAD = *w - *o = RT lnKP many real systems
(for instance for ionic systems)
e. g. Surfactant Parameters
ALCOHOL TEMPERATURE (for “pure” or collective behavior surfactants)
WATER SALINITY TYPE & CONC.

> in SAD/RT expression, the surfactant parameter is :

SAD/RT = lnS - K ACN - f(A) + - aT T=0 (in same ACN units - used for comparison) :
<
l /K for ionic surfactants
OIL ALKANE SURFACTANT
CARBON NUMBER HYDROPHILE & l ( -EON)/K for nonionic surfactants
HYDROPHOBE

/K = o/K + 2.25 SACN

depends on all formulation variables as Winsor’s R ratio
/K = o/K + 2.25 SACN
Characteristic SACN = Surfactant
quantifies the physicochemical formulation at interface of structure and Alkyl Carbon Number
head group (tail length)
considerable reduction in number of degrees of freedom same for all
surfactants
Salager J. L. et al., Langmuir, 16: 5534 (2000)

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Chart for Surfactant intrinsic hydrophilicity SAD has been generalized to

Surfactant Characteristic Parameter
/K (ionic) or [ -EON] / k (nonionic)

40
iso-alkyl-phenol-EON=5 (α-EON)/k
equivalent
many real systems
n-alcohol-EON=5
20 n-alkyl trimethylammonium
nd n-alkyl piridinium
20
Span 20 e. g. Temperature Effect
n-alkyl ammonium Tween 85
(for “pure” or collective behavior surfactants)
0 0
at pH 3

isoalkyl-phenol-EON=10 l aT = 0.01 (°C-1) for anionic surfactants

-20 -20
l aT = 0.02 (°C-1) for cationic surfactants
n-alcohol-EON=10 alkyl benzoate

cT = 0.04 - 0.08 (°C-1) for nonionic surfactants

-40 -40
iso-alkyl benzene sulfonate
l
iso-alcohol-EON=10
n-alkyl carboxylate

-60
n-alkyl sulfate
(sodium salts) -60
Tween 60 actually it varies with EON and Temperature as
alkyl sulfonate
H of transfer from water to oil.
-80
0 2 4 6 8 10 12 14 16 18 20
2210 + 450 EON
Surfactant Alkyl Carbon Number (SACN) cT = ( T in K )
T2 case of ethoxylated nonylphenols

Salager J. L. et al., Techniques de l'Ingénieur J2-157 (2001) Skauge A., Fotland P., SPE Reservoir Eng., 5: 60 (1990)
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SAD has been generalized to all formulation variables are included in a

many real systems Single Formulation Variable SAD

e. g. Na salts electrolytes SURFACTANT

CONCENTRATION
For sodium salts, there is a way to calculate 2 COMPOSITION less important
equivalent salinity because VARIABLES
l same salinity in mol /L for same X anion Z valence WATER-TO-OIL RATIO
l equivalent salinity by using VAF (valence activity factor) more important

Seq (in equivalent wt.% NaCl) =

FORMULATION (SAD)
2 58.5
COMPOSITION (WOR)
MW
S (in g/100 mL of NaX salt)
Value to enter 1+ Z anion
in SAD = lnS ...
VAF Value from experiment
Bidimensional Mapping
Antón R.E., et al., J. Colloid Interface Sci. 140: 75 (1990)

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BIDIMENSIONAL MAPPING GENERAL PHENOMENOLOGY

(emulsion type) on bidimensional mapping
EMULSION STABILITY EMULSION VISCOSITY
FORMULATION as SAD

Lipophilic
+

W
GENERALIZED FOR MULATION

w/O/W stable low

high
O

W/O +

unstable
+

stable

low
A
W2
medium
+ +
W1

W/O
B
O

C W
1
W/O
SAD = 0

inversion line unstable low

0

unstable low
A-
unstable

- C-
Hydrophilic

B O/W
O1

O/W

low
W O1

O/W

high
O2
O
stable medium
o/W/O low
stable
-

W
-

Oil COMPOSITION Water

OIL COMPOSITION WATER

Salager J. L. et al., J. Dispersion Sci. Technology, 4: 313 (1983) Miñana M. et al., J. Dispersion Sci. Technology, 7: 331 (1986)

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GENERAL PHENOMENOLOGY Dynamic inversion takes place ...

on bidimensional mapping when a formulation or composition variable
is continuously or lumpwise changed
EMULSION DROP SIZE (at constant stirring conditions)
Complex
GENERALIZED FOR MULATION

small

large Tradeoffs
+
+

W/O
W/O
Formulation

Viscoelastic
small
SAD = 0

SAD = 0

shearing of
HIPR emulsion
small
O/W
x
small

Best compromise O/W

low tension vs high
large dynamic Initial
coalescence rate
-

inversion Emulsion
-

OIL COMPOSITION WATER oil composition water

Perez M. et al., J. Dispersion Sci. Technology, 23: 55 (2002)
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+ General Trends
W/O
A
in crossing inversion line Inversion line can be shifted by ...
Formulation

- No delay when formulation is changed increase increase in increase in

B (transitional inversion) in oil surfactant stirring
O/W concentration
A
- viscosity energy
Delay when composition is changed in
+
Composition both directions (catastrophic inversion) B+ + + A+ C +
B B +

Formulation
+ C + C
W/O A W/O W/O A

+
W/O + A O/W
A +
- O/W - O/W
C W/O
- - - - - - -
B A C B A C B A C

O/W
increase in oil water
- A
- - -
O/W water viscosity Composition
B B A

Silva F. et al., Colloids Surfaces A 132: 221 (1998)

Salager J. L., In Encyclopedia of Emulsion Technology, vol. 3, Becher P., Ed., M. Dekker (1988) Peña A. et al., Colloids Surfaces A, 181: 319 (2001)

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Dynamic inversion also depends

3D Representation of these effects
on protocol, i.e., on ...
l Rate of change (addition)
Formulation +
W/O l Stirring energy and duration
SAD
concentration

- l Formulation ...
Increasing
Surfactant

Viscosity of phases
Stirring energy or
Increasing

Sajjadi S. et al., Ind. & Eng. Chem. Res., 41: 6033 (2002)
Lee J. M. et al., Langmuir 18: 7334 (2002)
Marquez L. et al. Polymer Int. 52: 590 (2003)
Zambrano N. et al. Ind. & Eng. Chem. Res. 42: 50 (2003)
O/W Mira I. et al. Ind. & Eng. Chem. Res., 42: 57 (2003)
oil Sajjadi S. et al., Colloids Surfaces A , 218: 241 (2003)
Composition water Saw L. et al., J. Colloid Interface Sci., 257: 163 (2003)
Tyrode E. et al., Ind. & Eng. Chem. Res., 42: 4311 (2003)
….
Salager J. L. et al., Ind. & Eng. Chem. Res., 39, 2665 (2000)

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= Translation of previous know-how +

Formulation SAD W/O
surfactant concent.

into equilibrium and transient conditions

phase viscosity
stirring energy

-
to attain emulsion properties or changes
in order to carry out
Process Development and Process Design
O/W
6 Unit Operations oil Composition water
Unit Operation # 25 / 36 Unit Operation # 26 / 36

Formulation-Composition Physico-Chemical Quench

(slow) Programming
Keeping drop size depends on stability, but ...
While moving slowly on the same side of inversion line a “rapid” move (= quench) preserves the drop size
properties are preserved and trends obeyed while changing other properties

W/O emulsion nonionic

W/O

or Formulation
breaking W/O more viscous, surfactant PIT emulsification method

Temperature
(e. g., crude then less stable initial small drop emulsion
Formulation

dehydration and less viscous is unstable

or desalting)
at constant a rapid cooling

O/W more viscous,

O/W results in a stable
W/O fine drop size emulsion
more stable and
smaller drops (cream) Oil Water
Oil Composition Water

Unit Operation # 27 / 36 28 / 36

Using the Delay Feature

oil is added little by little,

anionic surfactant to initial O/W emulsion while heating
until a very high internal phase ratio is +
W/O
attained (because of delayed inversion) SAD
or Formulation
Temperature

-
very efficient low stirring is applied
to produce fine drop size emulsion
O/W Lin T. et al., Cosmet. Toiletries 98: 67 (1983)
Mason T. et al., Phys. Rev. Lett., 77: 16 (1996)
which is then diluted and cooled
O/W
Oil Water
oil Composition water

Unit Operation # 29 / 36 Unit Operation # 30 / 36

Crossing thru Crossing thru

Transitional Inversion Catastrophic Inversion
By changing phase behavior at equilibrium By increasing internal phase content water with
hydrophilic
Formulation or oil phase surfactant
Temperature

W/O
Temperature increase (nonionic) Increase in water content
Temperature

W/O O/W

oil water
O/W

O/W emulsion W/O miniemulsion

MOW W/O emulsion Multiple em. O/W emulsion
Unit Operation # 31 / 36 32 / 36

Crossing thru In spite of current shortcomings

Catastrophic Inversion FORMULATION ENGINEERING
By increasing stirring energy ( ) could help in developing and designing batch
and eventually stirring time and continuous emulsification processes
+ for manufacturing food, paints, cosmetics
W/O
SAD and pharmaceuticals, dehydrating crude oil,
increasing

-
stirring

treating liquid wastes etc...

sometimes in large scale plants

such as the production of
O/W
water
heavy crude oil-in-water emulsified fuel.
oil Composition

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Emulsification Plant
Formulation
operated by BITOR
formulation

Engineering
1 Flow Chart a subsidiary of
2
3
Petroleos de Venezuela
oil composition water
CRUDE OIL Most emulsion manufacturing
90°C DILUTION
Low shear WATER processes could be dealt with a
WATER + dynamic (cold)
SURFACTANT 1
mixer static
mixer 3
Formulation Engineering Approach
CRUDE 2 80/20
OIL 1
static mixers 70/30 40°C
2 65°C O/W 70/30 Probably as well as many other
75°C O/W 80/20 final emulsion Product Engineering Problems

Salager J. L. at al., In Encyclopedic Handbook of Emulsion Technology, J. Sjöblom, Ed. (2001)

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Ask for a copy of this presentation
Formulation Engineering Approach at email : salager@ula.ve
will progress through
> innovative conceptualization
> integration of multidisciplinary teams

Research targets in the near future:

> Systematization of unit operations
> Understanding of complex cross effects
> Standardization of transient protocols

A lot of work for many of us !

Visit our web site at www.firp.ula.ve