SPE 37271
Chemical Dehydration: Correlations between Crude Oil, Associated Water and
Demulsifier Characteristics, in Real Systems
R.L. Márquez-Silva, SPE, S. Key, J. Mariño, C. Guzmán, SPE, and S. Buitrago, INTEVEP, S.A.
Copyright 1997, Society of Petroleum Engineers, Inc.
This paper was prepared for the presentation at the 1997 SPE International Symposium on Oilfield
Chemistry held in Houston, Texas, 18-21 February 1997.
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Abstract
With the aim at finding a method for the selection of suitable
demulsifier for crude oil dehydration, five crude/associated
water/effective demulsifier real systems were evaluated in this
study. Likewise, based on the existing knowledge about the
fundamentals of emulsion stabilization process, the typical
characteristics of each element of the systems, which represent
the variables or factors governing the process, were chosen.
These variables were: in the crude oil, the acidity number, as a
measure of its polarity; in the associated water, the salinity;
and in the demulsifier, the relative solubility number (RSN).
A hypothesis based on the surfactant affinity difference
(SAD) model is proposed. This model was adapted to the
specific case of crude oil chemical demulsification. A simplified
mathematical expression was obtained, which establishes a
relation between the crude oil nature, the associated water
salinity, and the demulsifier hydrophilicity.
The data obtained from the evaluation of the selected
characteristics were introduced into the model. As a result, the
following empirical relationship was obtained:
lnS = -0.77A - 0.28RSN + 8.17
where S is the associated water salinity and A is the crude oil
acidity number, variables which are easy to measure.
RSN values were calculated and compared with those
obtained from experiments. Except in one case, the calculated
RSN value approximates very closely the experimental one. It is
therefore concluded that this correlation serves to select the
appropriate demulsifier to dehydrate a given crude oil, based
on the simple procedure outlined above.
Introduction
The design and selection of demulsifiers for the dehydration of
crude oils have been performed using the classical bottle test.
This consists of a large number of laboratory essays. The
results of these tests should be confirmed, validated and
improved by field tests.
The empirical approach that forces the execution of a large
number of rigorous essays, is a consequence of: the multiple
factors involved in the emulsion stabilization/destabilization
process, the difference between crude oil emulsions, and the
changes that take place in these emulsions during the life of
the production well. Besides, the techniques used to
investigate the main factors related to demulsifier performance
are tedious and complicated. Instead, the use of an empirical
procedure, like the bottle test, gives the most practical
solution.
Because of the increasing knowledge of the factors related
to formation/breaking of the crude oil emulsion, demulsifier
selection could be carried out in the future on a more scientific
base.
Background
Emulsion stability is governed by different factors that
characterize a component or have an effect on the system:
- Water phase salinity and pH,
- Oil organic nature (paraffinic, aromatic or asphaltenic),
- Relative water/oil surfactant affinity,
- Oil/water ratio,
- Oil and water viscosity and density difference,
- Temperature.
At the same time, the affinity or relative solubility of the
surfactant in the oil or the water phase depends on the salinity
of the water phase, the oil nature, and the temperature.
Therefore, in a water/oil/surfactant system, if the surfactant
affinity to the oil phase is greater than to the water phase, the
system forms an water-in-oil emulsion . On the other hand, if
2 MARQUEZ-SILVA, S. KEY, J. MARIÑO, C. GUZMAN, S. BUITRAGO
the surfactant affinity to the water phase is greater than to the
oil phase, a oil-in-water emulsion is formed. In case the
surfactant has the same affinity to both phase, the emulsion
formed is unstable, and the phases tend to separate [2].
A thermodynamic model is available in order to calculate
the surfactant relative affinity to the phases involved [2]. This
model includes most of the mentioned factors and represents a
description of the surfactant affinity difference (SAD). The
SAD model is expressed by the following mathematical
expression:
SAD/RT = lnS - KEACN - f(A) + σ - aT(T-2).........................(1)
SAD/RT = α - EON - KEACN - θ(Ai) + bS + CT(T-28)........(2)
(1) For anionic surfactants
(2) For non ionic surfactants
where:
S: Aqueous phase salinity,
EACN: Equivalent Alkane Carbon Number
characteristic of the oil,
σ: Characteristic parameter of the anionic
surfactant,
α and EON: Characteristic parameters of the polar and
non polar portion of the non-ionic
surfactant,
f(A) y θ(Ai): Factors that consider the effect of the
presence of alcohols in the surfactant
(cosurfactants), and
K, k, aT, CT y b: Positive coefficients that quantify the
relative importance of each variable in the
system.
This model could be adapted to the specific case of oil
chemical dehydration, which consists of breaking of a water-in-
oil emulsion, stabilized for natural surfactants present in the oil,
by addition of a demulsifier agent.
The main purpose of this study is establishing a
methodology for the demulsifier selection, based on the
identification of a particular physicochemical property,
characteristic of each component of the emulsified system.
These characteristics should be closely associated with the
variables or factors involved in the emulsion stabilization
process, in order to develop a methodology that is more
practical and less time-consuming than the classical bottle test.
Experimental approach
Oil/Water/Demuslifier systems selection. Five different
systems were selected in this study (Table 1), considering:
production rate; light, medium and heavy oils; different
geographic areas; and oils difficult to dehydrate. Chemical
demulsifiers are actually in use in the field, and considered in
this study as the most effective, for the dehydration of each
selected crude oil systems.
SPE 37271
Crude oil analysis. The analysis carried out for
characterizing the crude oils were:
q Density and viscosity, related to the water droplet settling
velocity.
q Acidity, as an indication of the presence of carboxylic and
naphthenic acids in the crude oil that function as natural
surfactants.
q Saturate, aromatic, resin and asphaltene composition
(SARA), to establish the crude oil type (polarity).
Associated water analysis. To characterize the aqueous
phase the following analysis were made:
q pH, which affects the emulsion stability.
q Salinity, expressed as anions and cations concentration, in
mmols of NaCl.
q Electrical conductivity.
Demulsifier analysis. A detailed characterization of the
surfactants was carried out, taking in account the following
analysis:
q Relative solubility number (RSN), this is a measure of the
resultant affinity of the polar (hydrophilic part) and non-
polar (lipophilic part) components of the surfactant.
q Solubility in water.
q Average molecular weight.
q Cloud point, a measure of the surfactant hydrophilicity.
Results and Discussion
Correlations between properties. The physicochemical
characterization of each component of the system is presented
in Table 2. The analysis of these data is based on the SAD
model, discussed earlier.
This model was adapted to the crude oil chemical
dehydration making the following assumptions:
1. The maximum efficiency of the surfactant is reached when
the SAD expression is equal to zero. In this case, the surfactant
affinity is equal to both, water and oil phases and it will stay at
the interface.
2. The RSN estimates the surfactant hydrophilicity and it is
included to substitute the terms σ, α y EON in these equations.
3. Based on the fact that the operational temperature in the
dehydration process is constant, the temperature effect on the
surfactant interfacial activity is ignored.
4. The analysis the effect of the alcohol present in the
surfactant is not considered in the analysis.
With these assumptions in mind, the mathematical
expression of the model applied to a crude oil /water/surfactant
system becomes:
SAD/RT = lnS - k EACN + k' RSN = 0............................(3)
SAD/RT = k'' RSN - k EACN + bS = 0............................(4)
(3) For anionic surfactants
(4) For non ionic surfactants
SPE 37271 CHEMICAL DEHYDRATION: CORRELATIONS BETWEEN CRUDE OIL, ASSOCIATED WATER AND
DEMULSIFIER CHARACTERISTIS, IN REAL SYSTEMS
In this study, equation 3 was arbitrarily selected and
arranged as follows:
lnS = k EACN + k' RSN.....................................................(5)
where k y k' are constants.
Relation between associated water salinity, S and RSN. The
salinity, S, is related to the surfactant affinity to both, water
and oil phases by means of the effect known as "salting out",
that establishes the surfactant solubility reduction in presence
of electrolytes in the system [3]. In addition, the relation
between the salinity and the critical adsorption concentration,
CAC (equivalent to the critical micellar concentration, CMC,
but related to an interface), is well known. It is established that
as the salinity increases, the CAC decreases, therefore more
concentration of the surfactant at the interface, which is a
favorable condition to the demulsifier performance [4].
For the five systems evaluated, a clear relation between
water associated and RSN was not found, as it is shown in Fig.
1.
Relation between crude oil nature and RSN. The evaluation of
the acidity number, A and SARA composition of the crudes
under study, showed: lower polarity, lower acidity and an
important content of saturates compounds (non polar) in
Lagotreco, El Furrial and Merey-Zuata crude oils samples. On
the other hand, the crude oils Merey-Hamaca and Tia Juana
Pesado have a relatively high A, due to the presence of
carboxylic and naphthenic acids, which have been identified as
natural surfactants in crude oils [5-6]. In addition, this crude
oils has higher content of aromatics, resins and asphaltenes,
where metals and heteroatoms, like oxygen, nitrogen and
sulfur, are present. This add more polar character to these
fractions.
According to these results, it is possible that more stable
water-in-oil emulsions are formed, with Merey-Hamaca and Tia
Juana Pesado crudes, than with the others.
From the point of view of the demulsifier selection, the
SARA and A results (Table 2) indicate the need of a less polar
demulsifier for polar crude oil, RSN of 8. For a non-polar crude
oil (paraffinic), the demulsifier should be polar, and RSN higher
or equal to 12. Fig. 2 shows the inverted correlation between
acidity number and RSN on a semilog scale. The surfactant
hydrophilicity neutralizes or balances the hydrophilicity of the
natural surfactants present in the crude oil, whose
concentration is estimated by the crude oil acidity number, A.
Based on these analysis, the substitution of EACN term in
equation 5 by the crude oil acidity number, A, is inferred, since
it represents a measure of the crude oil polarity.
Relation between associated water salinity, S, crude oil acidity
number, A and RSN. From the early considerations, the
simplified model (eq. 5) takes the following form:
3
lnS = k A + k' RSN............................................................(6)
where A stands the crude oil acidity number.
The application of this model to the evaluated systems
shows that they match the following correlation:
lnS = a A + b RSN + c.......................................................(7)
Using minimum square fit of the experimental data available,
the values of a, b and c coefficients, were calculated and the
following correlation results:
lnS = -0.77 A - 0.28 RSN + 8.17......................................(8)
In Table 3 the values of RSN, calculated from the data
available from the A and S, are showed and compared with
experimental data. With the only exception of Merey-Hamaca
crude oil, the calculated RSN values fit well with the
experimental ones, considering the inner experimental error
associated to the measure of A, S and RSN parameters.
As a result, this model is proposed as a method for
selection of demulsifier used in dehydration of crude oil/water
systems, when the crude oil acidity number and water salinity
are known, which are parameters easy to measure in the
laboratory.
Conclusions
Based on the surfactant affinity difference (SAD) model, that
relates the crude oil nature, associated water salinity and the
surfactant hydrophilicity, a model was developed using the
crude oil acidity number, the associated water salinity and the
relative solubility number of the surfactant as the relating
parameters. This model allows the appropriate selection of the
demulsifier products for the dehydration of specific crude oils,
and is presented as an alternative to the bottle test.
References
1. Myers, D., Emulsions. Surfactant Science and Technology, VCH
Publishers, Inc., New York, (1988). 209-250.
2. SALAGER, J.L., Rev. Tecn. INTEVEP (1987) 7, No 1, 3-15.
3. Myers, D., Surfactants in Solutions: Micellization and Related
Association Phenomena. Surfactant Science and Technology,
VCH Publishers Inc., New York, (1988), 88-147.
4. AVEYARD, R.; BINK, B.P.; FLETCHER, P.D.; LU, J.R. J.
Colloid Science (1990) 139, No 1, 128-138.
5. JONES, T.; NEUSTADTER, E.; WHITTINGHAM, K. J.
Canadian Petr. Techn (June 1978), 100-108.
6. LAYRISSE, I.; RIVAS, H.; ACEVEDO, S. J. Disp. Sci. and
Techn. (1984) 5, No. 1, 1-18.
4 MARQUEZ-SILVA, S. KEY, J. MARIÑO, C. GUZMAN, S. BUITRAGO SPE 37271

Table 1. Crude oil/associated water/demulsifiers systems selected.

Crude Oil El Furrial Merey- Lagotreco Tía Juana Merey-Zuata

Hamaca Pesado

Production rate 210,000 100,000 185,000 130,000 4,000

(Bl/day)
API Gravity 28 15 31 10.8 16.6
Company LAGOVEN CORPOVEN MARAVEN MARAVEN MARAVEN
Region Oriente Oriente Occidente Occidente Oriente
Demulsifier A B C D E
SPE 37271 CHEMICAL DEHYDRATION: CORRELATIONS BETWEEN CRUDE OIL, ASSOCIATED WATER AND 5
DEMULSIFIER CHARACTERISTIS, IN REAL SYSTEMS

Table 2. Characterization of crude oil/associated water/demulsifier systems.

Crude El Furrial Merey- Lagotreco Tía Juana Merey-

Hamaca Pesado Zuata

Density (o API) 28 15 31 10.8 16.6

Viscosity (cP) 25 646 16 3240 425
Salinity (PTB) 5 140 235 111 19
Acidity (mg KOH/g crude) 0.04 1.86 0.28 4.1 0.97
Saturates (%) 46.1 23.2 44.7 19.2 31.2
Aromatics (%) 41.3 47.1 39.3 57.0 36.2
Resins (%) 10.3 24.2 13.5 15.4 25.8
Asphaltenes (%) 2.3 5.5 2.7 8.4 6.8
Interfacial tension (dyna/cm) 29 15 18 5 4
BS&W (%) trazes 39.5 25.9 23.0 -
Associated Water
pH 8.1 7.5 8.2 9.9 9.6
Conductivity 2.02 35.5 7.4 2.14 9.38
Surface Tension (dyna/cm) 71 44 56 51 49
Salinity (mmols NaCl) 27.3 438.4 94.8 32.1 101.3
Demulsifier A B C D E
RSN (ml water/g sample) 17.4 6.0 11.3 4.4 7.4
Solubility in water (to 1%) muddy muddy muddy muddy muddy
Cloud Point (o C) <25 <25 <25 <25 <25
Interfacial Tension (dyna/cm) 4.5 3.3 0.2 5.1 8.1
Adsorption Velocity:
Product 12.36 2.02*10-2 5.32 - -
Active in toluene 7.21 0.33 0.88 - -
Non volatile actives (%) 55.6 32.0 51.8 43.8 61.1
Non polar actives (%) 0 38.3 13.5 39.3 -
Polar actives (%) 100 61.0 84.5 61.0 -
Average Molecular Weight 4222 19551 8599 12189 3812
Alcohol in solvent (%) 0 10.9 40.7 0 0
Aromatics in solvent (%) 80.3 52.3 59.0 28.2 97.3
6 MARQUEZ-SILVA, S. KEY, J. MARIÑO, C. GUZMAN, S. BUITRAGO SPE 37271

Tabla 3. Values of RSN calculated from experimental data using the proposed model.

System Acidity Salinity RSN RSN

Experimental Experimental Experimental Calculated

El Furrial 0.04 27.3 17.4 17.2

Merey-Hamaca 1.86 438.4 6.0 2.3
Lagotreco 0.28 94.8 11.3 12.2
Tía Juana Pesado 4.10 32.1 4.4 5.5
Merey-Zuata 0.97 101.3 7.4 10.1
SPE 37271 CHEMICAL DEHYDRATION: CORRELATIONS BETWEEN CRUDE OIL, ASSOCIATED WATER AND 7
DEMULSIFIER CHARACTERISTIS, IN REAL SYSTEMS

450

400

350

300

250

200

150

100

50

0 5 10 15 20

RSN (ml)

Fig. 1. Relation between associated water salinity, S, and demulsifier relative solubility number, RSN.

10

0,1

0,01

0 5 10 15 20

RSN (ml)

Fig. 2. Relation between crude oil acidity number, A, and demulsifier relative solubility number, RSN.