Journal of Petroleum Science and Engineering 58 (2007) 111 118

www.elsevier.com/locate/petrol

Influence of polymer bases on the synergistic effects obtained

from mixtures of additives in the petroleum industry:
Performance and residue formation
a,

Luciana S. Spinelli , Aline S. Aquino , Renata V. Pires , Elaine M. Barboza ,

b
a
Ana Maria T. Louvisse , Elizabete F. Lucas
a

Institute of Macromolecules/Federal University of Rio de Janeiro, IMA/UFRJ, Cidade Universitria,

Centro de Tecnologia, Bloco J, Ilha do Fundo 21945-970, Rio de Janeiro, Brazil
b
Petrobras Research Center/CENPES Q. 7 Cidade Universitria, Ilha do Fundo 21949-900, Rio de Janeiro, Brazil
Received 29 June 2006; received in revised form 17 October 2006; accepted 20 November 2006

Abstract
Undesirable residue formation and lower performance can be observed during the use of polymer-based chemical additives in the
petroleum industry when such compounds are mixed during a number of operations, such as oil production. In this work a demulsifier, a
flocculant and a scale inhibitor and their respective polymeric bases were tested. These were evaluated through specific performance
tests for each additive and a solubility test to assess residue formation. By correlating the performance of commercial additives and the
respective polymeric bases, we can conclude that the polymeric base is responsible for the positive synergistic effects on demulsifier
performance in the presence of other additives and for the negative synergistic effects on scale-inhibiting performance, also in the
presence of other additives. Moreover, we found that the polymeric base can be responsible for the residue formation from the scale
inhibitor and flocculant mixture, although it is not be responsible for the residue formation of the flocculant alone.

2007 Elsevier B.V. All rights reserved.

Keywords: Synergy; Performance tests; Polymer additives; Demulsifier; Flocculant; Scale inhibitor
anatravalloni@petrobras.co

1. Introduction
Chemical additives, especially polymeric additives,
are widely used in the oil industry in a large number of
operations, such as drilling, production, transportation
and treatment. Such additives are used to correct opera-

Corresponding author. Tel.: +55 21 2562 7033; fax: +55 21

2270 1317. E-mail addresses: spinelli@ima.ufrj.br (L.S.
Spinelli),
lilica_line@yahoo.com.br (A.S. Aquino),
renatavpires@ig.com.br (R.V. Pires),
embarboza@yahoo.com.br (E.M. Barboza),

m.br (A.M.T. Louvisse),

elucas@ima.ufrj.br (E.F.
Lucas).
0920-4105/$ - see front matter
2007 Elsevier B.V. All rights
reserved. doi:
10.1016/j.petrol.2006.11.009

tional problems as well as

in the operation itself.
Problems
such
as
inorganic
deposition,
emulsion build-up and
corrosion
are
very
common during such
opera-tions and are solved
through the addition of
varied chemical additives
at different concentrations
( Hudgins, 1994; Davies
et al., 1996, 1997).
Commercial
additive
formulations can contain
more than one kind of active

component, also known as base. Normally, each base has a alcohols, working as coparticular effect on each kind of oil to be treated, and solvents additives and/or to render the
are added to the formulation, such as aromatic compounds and formulation less viscous and

pumpable, so as to allow
injection in line ( Grace,
1992).

112

L.S. Spinelli et al. / Journal of Petroleum Science and Engineering 58 (2007) 111118

of such additives,
aiming at minimizing
Since usually petroleum is produced
any undesirable effect.
together with water and gas, so-called
The aim of this
demulsifiers are added to destabilize the
work is to evaluate the
water-in-oil (W/O) emulsions. Such
influence
of
the
emulsions can form depending on the
polymeric-bases
on
petroleum composition and on the
the synergistic effects
turbulent flow regimen associated with
that occur when some
the production technique. Such products
additives
aim at promoting the separation and
(demulsifiers,
removal of water from the oil, and at the
flocculating
agents
same time preventing the separatedand scale inhibitors)
water from containing a high residual oil are used in admixtures
content, which could cause the formationin
the
petroleum
of oil-in-water (O/W) emulsion ( Paulisindustry.
et al., 1993).
During oil production, it is usual to co-2. Experimental
produce a portion of the water employed section
for injection. As a consequence, huge
volumes of water are generated, which in2.1. Materials
offshore operations have to be discarded in
the sea. Such water, called produced water, Commercial
is an oil-in-water (O/W) emulsiondemulsifier,
normally treated using floccu-lating agents flocculating agent and
that can be adsorbed on the interface of thescale
inhibitor
oil drops so as to promote theadditives, supplied by
neutralization of charges and/or thePETROBRAS, as well
formation of inter-particle bridges ( Feder
et al., 2004; Fernandes et al., 2005).
The presence of water in petroleum
production leads to corrosion and formation
of salt deposits (scales). When this occurs,
corrosion and scale inhibitors are used in
order to prevent corrosion of pipes as well as
scale formation, either through deposits on
surfaces or through formation of scaling
crystals, such as calcium carbonates and
barium, strontium and calcium sulfates (
Hasson et al., 1997; Drela et al., 1998; He et
al., 1999; Dyer and Graham, 2002).

Synergistic effects can occur when

chemical additives are used in admixtures
in the petroleum industry. Such effects can
enhance or diminish the performance of
each additive and/or can cause undesirable
residue. The knowledge of these kinds of
effects permits (1) optimizing the amount
of each additive added, (2) preventing
dam-ages and (3) reducing residue
disposal.

The identification of the constituents

of the formula-tions responsible for the
synergistic effects leads to reformulation

as their respective
polymer bases, block
copolymer
of
poly(ethylene oxideb-propylene oxide)
COP1 (Dow Qumica,
Brazil),
cationic
polyacrylamide
PAMC (CYTEC) and
poly(sodium
acrylate)PAS
(Oxiteno, Brazil) were
used. Another block
copolymer of poly
(ethylene
oxide-bpropylene oxide)
COP2 (Dow Qumica,
Brazil) was used in
order to compare its
efficiency
to
the
COP1; these two
polyoxides differ in
terms of arrangement
of
their
blocks.
Petroleum of medium
API grade and oily
water
from
the
Campos Basin were
also used in the study.
2.2. Methods
We characterized the
commercial additives by
Fourier
Transform
Infrared
spectrometry
(FTIR) and the polymeric
bases
by
size
exclusion
chromatography (SEC),
hydrogen
nuclear
magnetic resonance (1HRMN), besides FTIR.
For each additive, we ran
specific
performance
tests,
that
is,
demulsification,
flocculation and scale
inhibition tests. We
conducted these tests
with the commercial
additives
individually
and in binary and ternary
mixtures, and also with
the polymeric bases

individually and in binary and ternaryis a solid sample, we

mixtures. Besides this, we performed residue mixed it with KBr
powder.
formation tests for these same systems.

2.2.1. Characterization

2.2.1.2.
Size
exclusion
2.2.1.1. Fourier transform infrared chromatography
spectroscopy (FTIR). We performed (SEC). We used SEC
to
determine
the
FTIR on a Perkin Elmer
1720x
spectrometer,
taking average molar mass of
1
measurements from 4000 to 400 cm , the polymeric bases,
COP1 and COP2. The
1
with 2 cm
resolution. Each measureexperiments
ment was an average of 20 scans. For
commercial
additives
(demulsifier, were performed on
flocculant and scale inhibitor) and styrenedivinylbenzene
polymeric bases (COP1, COP2 and
copolymer columns
PAS), which are liquid samples, we 4
3
performed qualitative analyses on AgBr (10 10 500100
using
cell. For polymeric base PAMC, which ),
tetrahydrofuran as a

solvent
and
polystyrene
as
standards, in a Waters
600E. The detection
system was refraction
index.
PAS
and
PAMC are watersoluble samples and
we did not have
water-soluble columns
available. Thus, we
con-sidered the molar
mass provided by the
suppliers.

2.2.1.3.
Hyd
rogen
nuclear
magnetic resonance
1
(H
NMR).
We
1
carried out H NMR
spectroscopy in a

L.S. Spinelli et al. / Journal of Petroleum Science and Engineering 58 (2007) 111118

emulsions,
adding
0.03%v/v oil in brine
Varian UNITY 300 instrument working
with the aid of the Ultra
at 300 MHz, at 30 0.1 C, using
Turrax blender at 13
deuterated chloroform as a solvent. We
000 and 15 000 rpm,
performed quantitative analyses for
during approximately
copolymers COP1 and COP2 to
25 min. After that, we
determine the ethylene oxide/ propylene
conducted the jar test,
oxide ratio.
which
consists
in
agitating the O/W
2.2.2. Performance tests
emulsion for 10 min.
O/W
emulsion
2.2.2.1. Demulsification test. We evaluated
containing
the
the per-formances of the commercial
flocculating product at
demulsifier and of the demulsifying
concentration of 50
polymer bases in the laboratory by
mg/L
was
also
preparing a synthetic water-in-oil (W/O)
analyzed.
For
the
emulsion using petroleum and brine at a
evaluation
of
the
concentration of 55 000 mg/L sodium
influence
of
the
chloride
and
calcium
chloride
remaining additives on
(NaCl:CaCl22H2O

10:1).
Thisthe
flocculant
emulsion was prepared at 50/50% v/vperformance, we ran
oil/water with the aid of an Ultra Turrax tests by adding the
blender, at a rotation of 6000 rpm for 3 flocculant with the
min. In this experiment, brine is dispersed
demulsifier and/or the
in oily continuous phase, producing the
scale inhibitor at the
water-in-oil emulsion. We per-formed
respective
water-oil gravity separation tests (bottle
concentrations of 100
test) for the freshly prepared W/O
and 10 mg/L. We used
emulsion to assess the efficiency of the
the same procedure
products, at concentrations of 10, 50 and
with
the
PAMC
100 mg/L. This test involves observing the
polymer base and to
amount of water separated over time from
evaluate the influence
the emulsions placed in 100-mL graduated
of the
cylindrical test tubes immersed in a
temperature-controlled bath at 60 C. The
demulsifier was dissolved in a xylene and
ethyl alcohol solution (1:1 by volume) and
added to the emulsion. We also evaluated
the influence of the other additives at a
constant concentration of 10 mg/L in water,
adding to emulsion so after the demulsifier.
We used the same methodology for the
polymer base COP1, to evaluate the
influence of the addition of PAMC and
PAS. We calculated the performance
percentage of the product as a demulsifier
by the ratio between volume of separated
water and total volume of water.
2.2.2.2. Flocculation test. We evaluated the
perfor-mance of the commercial flocculant
and its polymer base based on the
preparation
of
oil-in-water
(O/W)

113

addition of COP1
and/or PAS. Twenty
minutes after ending
the jar test, we
determined the total
oil and grease content
(TOG) of the samples
using ultraviolet spectrometry (UV). TOG
values can be obtained
by several techniques,
including UV, which
permits, by using the
calibration curve of oil
solutions,
obtaining
absorptions relative to
the compounds that
constitute
the
petroleum. And by
correlating solutions
of
known
concentrations
and
unknown
concentration samples
in the same solvent, it
is possible to obtain
TOG values. Just as
the TOG obtained by
other techniques, such
values
are
not
absolute, but they are
comparable with the
results
of
other
methods.
To assess TOG
with the aid of UV, we
plotted a calibration
curve
for
the
absorbance versus the
concen-tration
of
petroleum
in
chloroform solution at
400 nm wavelength.
Based
on
the
calibration curve, the
values of the oil
contained
in
the
flocculated
systems
were obtained through
oil
extraction
in
chloroform, and the
absorbance
was
measured at a fixed
wavelength of 400

nm. Although the maximum absorptionsresulting from brine

are at about 250 nm, we chose 400 nm inwith large amounts of
order to minimize the interference of thecalcium salts.
solvent, as shown in
Fig. 1. We This test consists of
calculated the flocculation efficiencythe preparation of two
percentage of the samples analyzed insynthetic brines, one of
containing
the jar test by the difference of the TOG them
calcium
ions
and the
value of blank oily water and TOG value
other
containing
of oily water containing additives,
divided by the TOG value of blank oilybicarbonate ions. The
concentrations of
water.
2.2.2.3. Scale inhibition test. We employed
this test to evaluate the ability of the scale
inhibitor to prevent the precipitation of
solids adhering to the surface, mainly

Fig.
1.
Graphic
of
absorptions of oil in
chloroform
at
a
concentration (mg/L) of: (a)
0.0; (b) 10.0; (c) 20.0; (d)
30.0; (e) 75.0; (f ) 125.0;
(g) 150.0; (h) CHCl3.

114

L.S. Spinelli et al. / Journal of Petroleum Science and Engineering 58 (2007) 111118

weight.

To evaluate the
influence of the other
cations and anions present in these brines
additives
on
the
are presented in Table 1. Both brines were
behavior
of
the
Table 1
flocculant in brine, we
saturated by bubbling with CO2 at anConcentration of cations
performed other tests,
approximate flow rate of 300 mL/min. and anions present in the
in the same way
These brines were then admixed atbrines
described,
50/50%v/v in an appropriate flask, whichIons
Concentration in brine already
except
for
the
addition
containing
calcium
ion
contained a sufficient volume of
(g/L)
of the second additive.
concentrated solution so that the final
concentration of the products having aCa+2
We added 100
12.15
3.68
mg/L
demulsifier
scale inhibition character was 10 and 50Mg+2+
33.00
and/or 100 mg/L scale
mg/L. We placed these flasks in a Na
Cl
48.83
inhibitor
to
the
temperature-controlled bath at 70 C for 24

HCO 3

flocculant-containing
h and then carried out complexometric
brines, and ran the
titrations using a 0.01 M EDTA solution as
same tests in produced
a titrating solution and eriochrome black T
oily water.
as indicator. The value of the products
inhibition percentage was assessed based
The mass of actual
on the obtained data using Eq. (1)
residue formed as a
consequence of the
addition of
these
% Inhibition
compounds
was
VaVc=VbVc& 100
1
calculated
by
subtracting
the
mass
In order to evaluate the influence of
of residue obtained in
the other additives on the performance of
the
additivethe scale inhibitor, we added a flocculant
containing tests from
and/or demulsifier solution together with
the mass of residue
the scale inhibitor, sufficient to reach 10
obtained in the blank
mg/L. We ran these tests for commercial
tests.
additives as well as for the polymer
We performed the
bases.
same tests for the
polymer bases in
2.2.2.4. Residue formation test. Since
brine.
solubility is a relevant property for
evaluating the compatibility among
3. Results and
polymer additives, we evaluated the
discussion
formation of a deposit resulting from the
admixture of commercial additives and
3.1. Characterization
the admixture of polymer bases in brine
and in oily water.
FTIR was used to
We placed flocculant solutions at 100, 200
obtain
qualitative
and 500 mg/L in the oven at a temperature of
spectra
of
the
60 C, as well as the demulsifier and scale
commercial
products.
inhibitor solutions alone, at a concentration of
As
expected,
the
100 mg/L, and then the mixture of both
spectra
are
(demulsifier and scale inhibitor), each at a
characteristic
of
concentration of 100 mg/L. Besides this, we
formulation
due
to
ran a blank test, placing 500 mL brine alone
their
complexity.
in the oven under the same conditions.
Although it was not
The solutions were kept in the oven
possible to identify all
during 24 h and then vacuum-filtered to
the compo-nents of
collect the residues formed. These
the formulations, the
residues were oven dried under vacuum
absorption
bands
(80 to 90 C) until reaching constant

related to the each polymeric base were

observed.
The main absorptions observed for the
demulsifier formulation are relative to: (i)
1
OH axial stretching (at 3494 cm ); (ii)
COC symmetric and asymmetric axial
1
stretching (at 1111 and 1015 cm ); (iii)
CH2 and CH axial stretching (at 2873
1
cm ); and (iv) CH2 angular stretching
1
(at 866 cm ). The same absorptions were
observed at the spectra of COP1 and
COP2.

We observed the following main

absorption bands at the spectrum of the
commercial flocculant: C_O axial
stretching related to amide group
overlapped with NH2 stretching (at
1
1674 cm
); and CH2 angular
stretching and CH axial stretching (at
1
1464 and 2354 cm , respectively). The
same absorptions were observed at the
spectra of PAMC.
The commercial scale inhibitor
exhibited a spectrum containing the
following absorption bands: carboxylate
1
1
anions (at 1575 cm and 1404 cm ) and
1
COC (at 1089 cm ). The spectrum
of poly(sodium acrylate) presented the
same absorption bands, as expected.
SEC allowed the assessment of the
average molecular mass number, average
molecular mass weight and polydispersion
of such measurements for COP1 and COP2
1
copolymers. H-RMN mainly assessed the
com-position (number of EO and PO
groups shown as EO/PO rate) of the
copolymers. The main characteristics of
these bases are listed in Table 2, and Fig.
2 shows the COP1 and COP 2 structures
1
that were determined by H-NMR.

L.S. Spinelli et al. / Journal of Petroleum Science and Engineering 58 (2007) 111118

Table 2
Main characteristics of polymeric bases
Polymeric
bases

Properties
Mn

Mw

Mn/Mw

COP1
COP2
PAMC
PAS

6900
7800
a
High
a
High

7100
8000
a
High
a
High

1.03
1.02

Molecular weight in a range of 1.10 and 1.10

g/mol.

115

effect for all the

binary and ternary
mixtures based on the
performance of COP1
alone. This means that
the

3.2. Demulsification
The best performance among the
three demulsifier concentrations was
shown by 100 mg/L. Positive synergistic
effects were observed by adding the
scale inhibitor and the mixture of this
concentration with the flocculant to the
demulsifier, in binary and ternary
mixtures, as shown in Fig. 3.
We first observed which one of these
bases performs better as a demulsifier.
Fig. 4 shows that COP1 promotes water
oil separation while COP2 does not show
the same efficiency as a demulsifier. COP1
is the base of commercial demulsifier and
COP2 is another block copolymer of PEOPPO. Thus, this difference in performance
is due to the fact that COP1 and COP2
have different structures ( Fig. 2), in spite
of the fact that both are PEO-PPO block
copolymers, having similar molecular
weight, and the EO-PO ratio of COP2
leads to an HLB value that favors the
destabilization of W/O emulsions better
than COP1 HLB. The COP1 structure
involves hydrophilic adjacent groups (OH
group beside the ethylene oxide segment)
while COP2 has an alternate structure (
Mansur et al., 1998, 2004). The adjacent
structure promotes the destabilization of
W/O emulsions, so as to facilitate the
positioning at the interface of the oil and
water drops, displacing their natural
stabilizer agents and promoting phase
separation.

Thus, we carried out the study of the

synergistic effects among the mixtures of
polymeric bases using COP1. Fig. 4
shows a positive, significant synergistic

Fig. 3. Destabilization of
W/O emulsions by
commercial additives.

positive
synergistic
effects observed for
the
commercial
additives stem, at least
in part, from the
behavior
of their
polymeric bases.
3.3. Flocculation
The
optimum
concentration for the
commercial flocculant
was 50 mg/L, the
efficiency of which
was
74%.
The
addition
of
commercial
demulsifier did not
cause any synergistic
effect,
while
the
addition of
commercial scale inhibitor
promoted a negative
synergistic
effect.
Table 3 shows the
performance data for
the flocculation of
commercial additives,
polymeric bases and
their mixtures.
On checking the
effect of the joint use
of the poly-meric
bases on the PAMC
efficiency, a negative
synergistic effect can

be observed for both the binary and On the other hand,

ternary
mixtures
containing
thethe PAS polymeric base
polymeric demulsi-fier base. Thestrongly aids in the
addition of COP1, which destabilizesflocculation
of
W/O emulsion and tends to stabilizesynthetic oily water
O/W emulsion, causes competition withwhen added to PAMC,
the flocculant action of the PAMC, so thethat is, the joint use of
total effect becomes nil.

Fig. 2. Copolymers structures.

PAMC and PAS yields

a positive synergistic
effect. The interaction
between PAMC, which
is cationic, and PAS,
which is

116

L.S. Spinelli et al. / Journal of Petroleum Science and Engineering 58 (2007) 111118
Table 4
Scale inhibition efficiency for the commercial additives, polymeric
bases and their mixtures
Commercial additives

Polymeric Bases

Systems

Systems Efficiency (%)

Efficiency (%)
10 mg/L 50 mg/L

Fig. 4. Destabilization of W/O emulsions by polymeric bases. ()

COP1 (100 mg/L); ( ) COP1 (100 mg/L) + PAMC (10 mg/L); ()

COP1 (100 mg/L) + PAS (10 mg/L); () COP1 (100 mg/L) + PAMC

Scale inhibitor
Scale inhibitor
Flocculant
Scale inhibitor
Demulsifier
Scale inhibitor
Flocculant
Demulsifier

58
52

33
31

52

35

35

31

10 mg/L 50 mg/L
PAS
PAS
PAMC
PAS
COP1
PAS
PAMC
COP1

Error: 1.5%. (10 mg/L) + PAS

(10 Mg/L); ( ) COP2 (100 mg/L).

Flocculant
Demulsifier
theScale inhibitor

anionic, reduces the interfacial tension of

system, improving the flocculation process.

These results suggest that the synergistic effects

observed for the commercial additives are not
caused by the kind of polymeric base used in the
respective for-mulations. Other constituents of the
additives are probably responsible for the variation
in the flocculation efficiency.

Error: 1.5%.

3.4. Scale inhibition

Calcium carbonate precipitation tests led to
the assessment of the scale-inhibiting
efficiency as well as to knowledge of some
positive or negative interference of the other
additives on performance. For the sake of
comparison, Table 4 shows the values for
scale inhibition efficiency for the commercial
additives as well as for the polymeric bases.
At a 10 mg/L PAS concentration, the addition
of PAMC (flocculating base) did not cause any
change in PAS efficiency. Since the scaleinhibition process seems to be related to the
growth of crystals by linking PAS molecules and
calcium ions, the PAS molecules are not
Table 3
Flocculation efficiency for commercial
polymeric bases and their mixtures

additives,

Commercial additives

Polymeric Bases

Systems

Efficiency (%)

Systems

Flocculant
Flocculant
Demulsifier
Flocculant
Scale inhibitor

74
77

PAMC
PAMC
COP1
PAMC
PAS

61

Efficiency (%)
12
0
43

75

available to interact
with
PAMC
molecules,
as
observed in the
flocculation
tests.
So, the addition of
PAMC does not have
any influence on the
scale-inhibition
process.
However,
the
addition
of
demulsifier polymer
base (COP1) caused
a large reduction in
the performance of
that base as a scale
inhibitor. It is most
likely that there is an
interaction between
the COP1 and PAS
molecules.
In
commercial
additives,
we
observed a negative
influence of the
flocculant as well as
of the demulsifier. In
this
case,
the
negative action of
the
flocculant
additive cannot be
assigned
to
the
action
of
its
polymeric
base.
When
simultaneously using

73
73

44
38

43

38

11

38

the three polymeric bases, the negative

synergistic effects were potentialized, as had
been observed for commercial additives.

The PAS concentration of 50 mg/mL is

above the optimum concentration since that
the efficiency has decreased. This means that
it is not useful to have too many inhibitor
molecules in the system. Besides this, the
effect caused by the addition of the other
bases is

Fig. 5. Residue formation in brine for commercial

additives and their mixtures.

L.S. Spinelli et al. / Journal of Petroleum Science and Engineering 58 (2007) 111118

milder. Concerning the effect of the other

additives, the lower the efficiency of the
scale inhibitor, the lower the negative
effect caused by these other additives. A
possible suggestion is that if there is any
interaction among the various additives,
these occur only for a reduced number of
scale inhibitor molecules, due to the
relatively low concentration of the other
additives, so that the system still contains
free scale inhibitor mole-cules above the
optimum concentration.

3.5. Residue formation

This test aims at evaluating the
solubility of additives, usually using
produced oily water.
However, in order to highlight the
effect of the normally present salts in
oily waters on the solubility of the
commercial additives, at first we used
brine alone. The resulting data are
summarized in Fig. 5.
When independently tested, the three
additives formed residues, with the larger
amount being originated by the
demulsifier. The amount of residue formed
by the flocculant increased with the rise in
its concentration in salt solution. Broadly
speaking, the joint use of these additives
causes a residue amount that corresponds
to the sum of the residue formed by each
additive individually. However, the
addition of a scale inhibitor to the
flocculant causes a positive synergistic
effect, promoting the reduction in the
amount of deposit generated by the
flocculant alone. Such positive synergism
still occurs as a result of the mixture of the
three additives.
We then performed the same test as
with brine with produced oily water
instead, and observed that the residue
contents were clearly higher than those
obtained for brine whose salinity was
similar to that of the oily water. This
behavior is related to the lower solubility
of the additives caused by the presence of
oil in the produced water.

Fig. 6. Residue formation in

brine for polymeric bases
and their mixtures.

117

Assessment of the
solubility
of
the
polymeric bases in
brine ( Fig. 6) showed
that the amounts of
residue formed is
clearly lower than
those generated by
commercial
formulations.
A residue is formed
whenever
the
polymeric
bases
COP1
and
PAS
(respectively of the
demulsifier and of the
scale inhibitor) are
added to brine, while
the
flocculant
polymeric
base,
PAMC, does not form
any residue. This
means
that
the
polymeric base does
not cause the deposit
generated
by
the
commercial
flocculant. The combined
use of the bases does
not cause a summation
of the amount of
residues
formed.
Addi-tionally,
a
positive
synergistic
effect is observed
when the PAMC is
added
to
PAS,
meaning that
the
polymeric base is
responsible for the
synergistic
effect
observed
with
commercial additives.
4. Conclusions
Regarding residue
formation as well as
the
specific
performance of each
additive,
polymeric
bases are at least in
part responsible for
the
positive
and

negative synergistic effects shown byCENPES/PETROBRAS,

FAPERJ,
commercial additives.
CAPES,
CNPq/PIBIC
The polymeric base is responsible for
ANP/
the positive synergistic effect occurringand
FINEP/CTPETRO
for
in the presence of the flocculant and/or
support;
the scale inhibitor on the demulsifier financial
performance, as well as by the negativePETROBRAS for the
synergistic effect occurring by thecommercial additives;
presence of demulsifier and the mixture Dow Qumica, Oxiteno
of demulsifier and flocculant on theand CYTEC for the
perfor-mance
of
scale
inhibitor.polymer samples; and
Furthermore, it is also respon-sible forTRIBEL and KOLETA
the lower residue formation observed in AMBIENTAL
for
the flocculating mixture and scalerecycling the chemical
inhibitor, which is a positive synergistic waste produced by the
effect.
experiments.
Acknowledgments
The authors would like to thank

Appendix A.
Nomenclature

Va
Volume of
EDTA utilized in the
sample
containing
the product
after
precipitation
Vb
Half of the
EDTAvolume utilized in
the calcium-

containing
brine before
precipitation
(total
volume is related to
the titrated volume by
the
mixture
calcium and
bicarbonate in
a 1:1 ratio.

118

L.S. Spinelli et al. / Journal of Petroleum Science and Engineering 58 (2007) 111118
Grace, R., 1992. Commercial
2468.
emulsion
breaking.
In:
Mansur, C.R.E., Barboza,
S.P.,
Gonzalez,
G.,
Vc
Volume of EDTA utilized in theSchramm, L.L. (Ed.),
Lucas,
E.F.,
2004.
blank (without product) afterEmulsions: Fundamentals
and Applications in the
Pluronic

tetronic
precipitation.
Petroleum
Industry.
polyols: study of the
American Chemical Society,
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