Colloids and Surfaces A 558 (2018) 200–210

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Colloids and Surfaces A

journal homepage: www.elsevier.com/locate/colsurfa

Evaluation of the efficiency of polyethylenimine as flocculants in the T

removal of oil present in produced water
Allan S. Santosa, Luis Fernando S. Oliveiraa, Anny M.T. Marquesa, Douglas C.A. Silvaa,
⁎
Claudia R.E. Mansura,b,
a
Universidade Federal do Rio de Janeiro/Instituto de Macromoléculas Professora Eloisa Mano/Laboratório de Macromoléculas e Coloides na Indústria de Petróleo (UFRJ/
IMA/LMCP), Centro de Tecnologia, Bl. J, Avenida Horácio Macedo, 2030, Cidade Universitária, Ilha do Fundão, CEP: 21941-598, Rio de Janeiro, Brazil
b
Universidade Federal do Rio de Janeiro – Programa de Engenharia Metalúrgica e de Materiais (PEMM) /COPPE. Centro de Tecnologia, Bl. F, Avenida Horácio Macedo,
2030, Cidade Universitária, Ilha do Fundão, CEP: 21941-598, Rio de Janeiro, Brazil

G R A P H I C A L A B S T R A C T

A R T I C LE I N FO A B S T R A C T

Keywords: Branched polyethylenimines (PEIs) present primary, secondary and tertiary amines along their backbone,
Polyethylenimine making this polymer very pH-influenced: in an acid medium, the amines will be protonated to a certain extent
Flocculant and can be called polyelectrolytes. The objective of this work was to study and evaluate the performance of PEI
Dissolved air flotation as a flocculant polymer in the treatment of oily water from the petroleum industry. An anionic surfactant,
Produced water
sodium dodecyl benzene sulfonate, was used in conjunction with PEI for this purpose. Removal efficiency tests
Oil removal
were performed on a Jartest and on a bench scale Dissolved Air Flotation system (DAF). Two PEIs of different
molar masses (PEI HW Mn ∼ 60,000 and PEI LW Mn ∼ 10,000) were used as cationic flocculants under acidic
conditions for the removal of oil present in the synthetic produced water. Polyethylenimine showed good oil
removal efficiencies. It is important to note that no references were found in literature on the use of poly-
ethylenimines in the treatment of oily water from the petroleum industry, and the search for more efficient
flocculants in oil removal was one of the motivators of this work.

1. Introduction with oil production [1]. The oil can be present in four different forms in
the produced water (also called oily water): free oil, dispersed oil,
Secondary and enhanced oil recovery generate large amounts of emulsified oil and dissolved oil [2]. The emulsified oil constitutes the
produced water, which is one of the largest waste streams associated fraction of interest of this work and, like the other fractions, must be

⁎
Corresponding author.
E-mail address: celias@ima.ufrj.br (C.R.E. Mansur).

https://doi.org/10.1016/j.colsurfa.2018.08.085
Received 3 July 2018; Received in revised form 31 August 2018; Accepted 31 August 2018
Available online 01 September 2018
0927-7757/ © 2018 Elsevier B.V. All rights reserved.
A.S. Santos et al.
treated for final disposal purposes, guided by the current local en-
vironmental legislation.
One of the steps of treating the emulsified fraction of oily water is
the flocculation process, in which colloidal particles are aggregated
together by contact between them [3]. This process usually occurs with
the aid of chemical additives known as flocculants. Usually, the floc-
culants used for the treatment of produced water are water-soluble
polymers, which can be classified in terms of their charge: cationic,
anionic or non-ionic. The main characteristic of flocculant polymers is
their molar mass and, in the case of the polymer being cationic or an-
ionic (also called polyelectrolytes), their charge density can also be
considered as an important property [4].
Polyethylenimine (PEI) is a polymer used in various industry seg-
ments, for example in the preparation of polymer complexes in phar-
maceutical formulations, controlled drug release, in the introduction
and transfer of genes from one cell to another, bacterial cell aggrega-
tion, in the manufacture of paper, amongst other uses [5–8]. Although
PEI has been modificated with ethylene oxide and propylene oxide and
tested to act as a demulsifier for oily water treatment by means of phase
separation [9], no reports have been found in literature on its use as a
flocculant polymer for oily waters from oil recovery processes. Winnik
et al. [10] reported that at pH = 10, PEI is practically an uncharged
polymer. However, at pH = 6.6, PEI is a strong polyelectrolyte, pre-
senting about 20 to 40% of its amino groups protonated. It is also re-
ported by Sharma et al. [6] that charged polymers associate with op-
positely charged surfactants through electrostatic interactions.
Protonated amine groups confer to the polymer charge neutralization
properties [11].
Wang et al. [12] studied the interaction between linear and bran-
ched PEI with the surfactant sodium dodecyl sulfate (SDS), which is an
anionic surfactant with high affinity for PEI. Among their findings, they
realized that when the SDS concentration is equal to the critical micelle
concentration (CMC), visible precipitates start to form, and when the
SDS concentration is higher than the CMC, the interactions are even
stronger, leading to complete precipitation and difficulty in solubilizing
the polymer again in the solution.
Given this scenario, this work aims to study and evaluate the action
of PEI as a flocculating polymer, increasing its interaction with oil
droplets using sodium dodecylbenzene sulfonate (SDBS), an anionic
surfactant that tends to be allocated at the interface Oil / water, due to
the amphiphilic nature of this class of molecules. For this, tests of re-
moval efficiency were carried out in a Jartest and in a Dissolved Air
Flotation system (DAF), built to carry out this work.
In DAF, the air is dissolved in water by pressurizing water in a
pressure vessel and then depressurized into a flotation chamber. The
sudden drop of pressure through the inlet valve in the tank leads to the
formation of small bubbles of air (between 20 and 100 μm), that are
released from the saturated water, which attaches on the oil droplets
and aid in the separation process [13].
2. Materials and methods
2.1. Materials
For the preparation of the synthetic oily water, saline water con-
taining 33,000 ppm salts, 441 ppm of potassium chloride (KCl),
708 ppm of calcium chloride dihydrate (CaCl2.H2O), 2626 ppm of
magnesium chloride hexahydrate (MgCl2.6H2O), 29,250 ppm sodium
chloride (NaCl) and distilled and deionized water. The salts are from
Vetec Quimica (São Paulo, Brazil), with 99% purity. Petroleum used to
prepare synthetic oily water was donated by the Petrobras Research
Center (CENPES) and presented API 16 and water content of 0.34% w/
w.
As a flocculant, two samples of Polyethylenimine (PEI), which is a
cationic polymer, with average number molar masses (Mn) around
10,000 (PEI LW) and 60,000 (PEI HW), and a reference polycondensed
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Colloids and Surfaces A 558 (2018) 200–210
cationic polymer, were used. For the pH adjustment of the poly-
ethylenimine, hydrochloric acid (HCl) from Vetec Quimica (São Paulo,
Brazil), with 37% purity, and sodium hydroxide (NaOH) from B Herzog
(Rio de Janeiro, Brazil), with 99% purity.
An anionic surfactant, sodium dodecylbenzene sulfonate (SDBS)
technical grade, from Sigma Aldrich (São Paulo, Brazil), was used in
conjunction with the flocculant.
The extraction of the residual oil from the treated oily water was
done with toluene ACS, from Vetec Quimica (São Paulo, Brazil), which
was distilled and dried with silica in the laboratory before its use.
Ethanol from ISOFAR (Rio de Janeiro, Brazil), at 95% purity, was used
during extraction in systems where significant amounts of foam were
observed in the organic phase.
2.2. Experimental Procedures
2.2.1. 1H-NMR of polyethylenimines (PEI LW and PEI HW)
Both Polyethylenimines from Sigma Aldrich (in this work labeled as
PEI LW and PEI HW) were characterized by 1H-NMR, with the purpose
to identify their functional groups. The samples were prepared solubi-
lizing 15 mg of the respective PEI in 0,8 mL of D2O. After that, the 1H-
NMR analysis were performed on a VARIAN MERCURY VX 300, and the
spectra recorded in a frequency of 300 MHz.
2.2.2. Polyethylenimine solutions preparation
Solutions of 0.3% w/v of the polyethylenimines were prepared in
distilled and deionized water. The pH of these solutions was adjusted to
pH = 6.6, because initially both polyetelinoimines had a pH value of
10.2. This adjustment was carried out with aqueous solutions of 1 M
hydrochloric acid and 1 M sodium hydroxide, previously prepared from
the received reagents.
The concentration and pH of the polyethylenimines were chosen
based on [10], because according to the authors the polyethylenimine
in these parameters presents 43% of its protonated structure.
2.2.3. Determination of the zeta potential
To determine the zeta potential of the polyethylenimines and the
SDBS surfactant, the Zetasizer particle size analyzer (Malvern, NanoZS)
was used. Samples of the polymer aqueous solutions (0.3% w/v) and
SDBS aqueous solution (10% w/v) were placed in a folded capillary
electrophoresis cell (model DTS 1060C, Malvern) using a syringe, to
prevent the formation of air bubbles. The zeta potential was measured 5
times and the average values were obtained as well as their respective
standard deviations. The absorbance values at the wavelength of
633 nm were obtained by means of a visible ultraviolet spectro-
photometer (Cary 50, Varian), equipped with a 10 mm optical path
quartz cuvette; and the refractive index of the samples, obtained in the
Refractometer (ABBE 32400). Both parameters are requested by the
software that comes with the Zetasizer Nano ZS.
2.2.4. Determination of the micellar concentration of SDBS
The SDBS surfactant had its critical micellar concentration (CMC)
calculated with the aid of a TD 3 Lauda digital tensiometer equipped
with Du Noüy ring. Analysis of the saline water containing the SDBS
surfactant was performed at the concentrations: 1, 2, 4, 6, 8, 10, 20, 40,
60 and 100 ppm. All tensiometer analyzes were performed in duplicate
at room temperature (25 °C).
2.2.5. Synthetic oily water preparation
Oil in water emulsions (O/W) - in this work called synthetic oily
water - were prepared in the laboratory to simulate the produced water
in Oil Fields. This synthetic oily water was prepared in a 5 liters beaker,
initially containing 2 liters of salt water composed of 33,000 ppm salts.
To ensure dispersion of the oil into the water, a homogenizer (Ultra-
Turrax T-50 basic, IKA WERKE) had its shaft inserted into the beaker at
a stirring speed of 6000 rpm. A syringe containing 1 mL of the oil was
A.S. Santos et al.
inserted into the water near the base of the homogenizer shaft, and the
transfer of the oil to water was performed during one minute.
Thereafter, some oily water from within the Beaker was sucked into the
syringe and reinjected several times to minimize oil loss on the walls of
the syringe and the needle.
After adding all of the oil, the stirring speed of the equipment was
raised to 10,000 rpm and the remaining three liters of saline water were
added over a minute, always keeping the Ultra-Turrax rotor just below
the surface, otherwise oily sludges are formed on the surface that di-
rectly affect the homogenization and emulsification of oily water. After
the addition of the remaining saline water, the oily water was sheared
for another two minutes at the speed of 10,000 rpm.
2.2.6. Determination of the droplet size distribution of the synthetic oily
water
The droplet size distribution of recently prepared oil-in-water
(synthetic oily water) emulsions was obtained by light microscopy
using the Zeiss Axio Vert Optical Microscope, with 10x objective and
dark field use.
2.2.7. Construction of the dissolved air flotation system
The dissolved air flotation system (DAF) (Fig. 1) was developed
based on [14]. This is constituted by the Jartest equipment (to be used
as a flotation chamber) and by a pressure vessel, developed in this
work.
The pressure vessel is the location where the water is pressurized
with air, until it the water is ready to be released into the flotation
chamber. This pressurizing, at a given fixed pressure, causes the water
to be saturated with air and its depressurizing in the flotation chamber
at ambient pressure releases small microbubbles that aid in the process
of removing the oil droplets.
The pressure vessel consists of a cylindrical vessel (Fig. 1, item 2),
with a useful volume of 4 liters, made of AISI 316 stainless steel,
equipped with a pressure gauge (Fig. 1, item 5), a 1/8 (Fig. 1, item 3), a
safety valve (Fig. 1, item 6), a ball pressurizing valve of 1/8 (Fig. 1, item
4) and a 1/8 depressurizing needle valve (Fig. 1, Item 7). The Fargon
Air Compressor Model OS SCS 5.5 / 270 (Fig. 1, item 1) completes the
DAF system, responsible for pressurizing the water present in the
pressure vessel. Finally, the jars of Jartest equipment, model ECE
compact laboratory mixer, CLM6 were used as flotation chambers, to-
taling six chambers and being represented in item 8 of Fig. 1.
The pressure vessel was used without packing (which can be used to
increase the saturation efficiency). However, the pressure vessel was
constructed with a screw-threaded cylindrical cap, which allows the use
of packing in future tests.
2.2.8. Determination of the saturation efficiency of the DAF system
The Saturation Efficiency of the DAF system was calculated with the
aid of a depressurized air volume measuring apparatus constructed in
this work (Fig. 2).
The water is pressurized at a certain pressure inside the saturator
vessel (Fig. 2, item 2) and subsequently depressurized to atmospheric
Fig. 1. Representation of Dissolved Air Flotation System.
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Colloids and Surfaces A 558 (2018) 200–210
pressure inside the depressurized air volume meter (Fig. 2, item 10) at a
certain flow controlled by the fixed opening of a needle valve (Fig. 2,
item 9). In this apparatus there is a determined water level and cali-
brated with a marking at the cylindrical section of acrylic. There is a
ball valve on the top of the apparatus that is closed during the test
(Fig. 2, item 8). The other items are similar to those in Fig. 1.
As the water is depressurized into the apparatus, the pressurized air
begins to nucleate in the form of small bubbles. This air tends to ac-
cumulate on top of the apparatus by displacing the liquid present in the
cylindrical section of acrylic, decreasing the height of the liquid
column. Displaced liquid is collected in a graduated beaker. At the end
of the test, the height of the liquid column displaced can be seen from
the initial position of the liquid in the cylinder and the final position.
The diameter of the cross-section of the cylindrical acrylic Section (3
cm) is known. The volume of the pressurized air can then be calculated
using Eq. (1), which calculates the volume of a cylinder:
πd 2h
V=
4 (1)
Where V represents the cylinder volume, π is 3.114159, d is the dia-
meter of the cylindrical cross section, h is the height of the liquid
column displaced at the end of the experiment. Similar equipment was
developed in [15]. The pressures 60, 80, 100 and 120 PSI and two
global average flows were evaluated: 3.0 and 4.0 L / min. Four tests
were performed for each pressure, in each of the flows, totalizing 32
tests. These tests enabled the calculation of the average air volume
collected at each pressure and in each flow, as well as the calculation of
the standard deviation and consequently the calculation of the 95%
confidence limit.
The 95% confidence limit establishes the limits between which the
volume of air released at a certain pressure and flow rate will be, 95%
of the time the test is performed. It can be calculated by Eq. (2):
+ σ
Confidence interval = x − (t )
n (2)
Where x is the sample mean, t the student parameter, σ the sample
standard deviation and n the numbers of samples.
The Student parameter used was for a sample space of 4 and relative
to 95%, corresponding to a value of 3.18 [16].
The maximum values of air saturation in water at 20 °C were ob-
tained in the literature [17], and adapted to the convenient units.
2.2.9. Determination of flocculation efficiency by Jartest
The experiments were performed on Jartest equipment (ECE com-
pact laboratory mixer, CLM6). The procedure consisted in the in-
troduction of 800 mL of oily water into the six jars of the equipment,
divided into three addition stages: 300, 300 and 200 mL. This stepwise
addition was intended to minimize the difference between oil con-
centrations in the Jartest tanks. Then, the anionic surfactant was added
at the concentrations of 25, 100 and 150 ppm under agitation of
200 rpm for 2 min. After this time, the flocculant was added at the
concentrations of 25, 50, 75, 100 and 150 ppm and again the system
A.S. Santos et al.
Fig. 2. Representation of depressurized air volume measuring apparatus.
Fig. 3. 1H-NMR Spectra of polyethylenimines: (a) PEI LW and (b) PEI HW.
was allowed to stir at 200 rpm for 2 min (rapid shaking phase).
Thereafter, the spin speed was reduced to 10 rpm for 10 min (slow
stirring phase). Finally, the oily water present in the equipment vats
was kept at rest for 10 min so that the particles could flocculate.
2.2.10. Determination of flocculation efficiency by dissolved air flotation
Initially, the pressure vessel, shown in item 2 of Fig. 1, is filled with
distilled and deionized water up to 3/4 of its volume (3 liters). Next,
with the aid of the air compressor, the water is pressurized with air at a
certain pressure (the flotation tests were conducted at 120 PSI). After
vigorous, manual and horizontal shaking of the pressure vessel for one
minute, the pressurized water is ready for use in the flotation test.
The procedure for determination of the flocculation efficiency by
dissolved air flotation is analogous to that of the determination of the
flocculation efficiency by Jartest, since the flocculation step of the
Flotation test also follows the same steps performed in the Jartest until
the slow agitation phase. After the slow stirring stage, the pressurized
water is depressurized beforehand in the pressure vessel inside the
Jartest. The water is depressurized by means of small polyurethane
tubes inside the jug of Jartest equipment, in a valve port compatible
with the flow rate 2.5 liters per minute. When the volume inside the
equipment jug reaches the one-liter mark, the valve of the pressure
vessel is closed and the depressurizing is stopped. The process is re-
peated in the other five jars. Then, the flotation chambers are allowed
to stand for 10 min.
2.2.11. Extraction of residual oil from oily water
The extraction process of the residual oil after the flocculation step
was performed by removing 20 mL of aliquots from the jartest vats.
These samples were placed in test tubes and 4 mL of extractive solvent
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Colloids and Surfaces A 558 (2018) 200–210
(toluene) was added to each. These systems were then shaken manually
and allowed to stand for two hours, so that the phases could separate
from each other completely. If emulsion formation was observed during
the extraction process, between toluene and the chemical additives
present, 4 mL of ethanol was added, in order to break this emulsion. At
the end of the extraction process, 6 samples were obtained representing
the polymer concentrations employed in the flocculation and flotation
process: 0 (blank), 25, 50, 75, 100 and 150 ppm.
The concentration of the residual oil from oily water after floccu-
lation tests was assessed on an ultraviolet-visible spectrophotometer
(Varian Cary 50), using quartz cuvette of 10 mm pathlength. For con-
version of the absorbance obtained in the ultraviolet-visible spectro-
photometer concentration in ppm, a previously prepared calibration
curve was used.
3. Results and discussion
3.1. Determination of 1H-NMR Spectra of polyethylenimines (PEI LW and
Pei HW)
The 1H-NMR Spectra of both polyethylenimines are shown in Fig. 3.
PEI LW Spectra (Fig. 3a) has shown two chemical shifts, one located
at δ = 284 and another at δ = 289. These chemical shifts are related to
the alpha hydrogens of CH2 groups bonded to primary, secondary and
tertiary amines. According to Chamberlain [18], the chemical shifts of
alpha hydrogens bonded to primary amines are usually in the range of
2,7 < δ < 3,0 ppm, while the alpha hydrogens bonded to secondary
and tertiary show chemical shifts in the range of 2,2 < δ < 2,8 ppm.
As both ranges overlap each other, the sign peaks from these two kind
of alpha hydrogen also overlap slightly, as can be seen in Fig. 3. Even
A.S. Santos et al.
Table 1
Average zeta potential values of the materials used.
Materials Average Standard Deviation
PEI LW 1,33 0,13
(pH = 1020)
PEI LW 13,86 1,80
(pH = 6,6)
PEI HW 7,914 0,31
(pH = 1020)
PEI HW 14,26 2,04
(pH = 6,6)
SDBS −21,88 2,32
so, it can confirm the expected PEI LW structure.
In an analogous way, the PEI HW spectra (Fig. 3b) has shown two
chemical shifts located at δ = 286 and δ = 2,91, similar to PEI LW. This
is consistent, because both have the same structure, differing from each
other only by molar mass values. These results prove that PEI LW and
PEI HW are indeed branched polymers. If they were not, only the peak
relative to alpha hydrogen bonded to the secondary amine would ap-
pear on the spectra.
On the work of Wang et al. [19], they have done a 1H-NMR PEI
analysis, and they also had spectra with 2 peaks for a branched PEI.
They described these two chemical shifts as being from the hydrogens
of methylene groups bonded to amine groups. The work of Souza et al.
[20] also shows peaks from hydrogens of methylene groups in the range
of 2,2 < δ < 3,0 ppm.
3.2. Determination of the ZETA potential of Pei and SDBS SOLUTIONS
The average zeta potential results for the polyethylenimines and for
the SDBS surfactant can be seen in Table 1.
The zeta potential values confirmed that the protonation of the
structures of the PEI LW and the PEI HW (at pH 6.6) occurred sa-
tisfactorily as they acquired surface positive charges along their struc-
tures, increasing the electrical potential of the molecule in un-
protonated PEIs (with pH = 1020). The PEI's are influenced by the pH
of the medium: its surface charge density depends directly on the pH.
The zeta potential of the SDBS molecule is negative, a result already
expected to be an anionic surfactant. This indicates that, during the oil
flocculation process, the surfactant molecules will migrate to the oil /
water interface, with the hydrophobic part facing the oil and the hy-
drophilic part facing the water. Since the negative charges of the an-
ionic surfactant are located in the hydrophilic part, the oil droplets will
acquire a negative surface charge. The electrostatic attraction between
PEI molecules and negatively charged oil droplets is required for floc-
culation to occur efficiently, and the mechanism is the same Bratskaya
et al. [21] presented in their work between chitosan (flocculant) and
sodium dodecyl sulfate (surfactant).
Fig. 4. Micrographs of Oily Water 1 and 2.
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Colloids and Surfaces A 558 (2018) 200–210
3.3. CMC determination of SDBS surfactant
The determination of the critical micellar concentration (CMC) of
the saline aqueous solution of the SDBS surfactant was performed by
means of the surface tension measurements of the solutions prepared
from SDBS, in different concentrations.
The CMC is the lowest concentration at which the free surfactant
molecules are in equilibrium with the micelles present in the system.
Micelles represent a type of structural arrangement of the molecules of
the surfactant, which are thermodynamically more stable than if the
molecules of the surfactants were free in solution. This means that,
below the CMC, increasing the concentration of the surfactant causes an
increase in the concentration of its free molecules. Above the CMC,
these molecules are organized as micelles, and an increase in con-
centration represents an increase in the concentration of micelles in the
system, whereas the concentration of free surfactants remains constant
[22].
It is shown in [23] that the CMC value of the SDBS surfactant mo-
lecule in water is 3.72 +/- 0.02 × 10-4 mol.L−1. Converting the unit to
ppm, the value reaches 129.63 ppm. However, the result in this work
(Fig. 1) shows a CMC value of 14.5 ppm.
A possible explanation for why the CMC of the SDBS has a value of
14.5 ppm in this salt water (approximately 10 times smaller than that
predicted in pure water), is that the addition of salt reduces the CMC,
being able to arrive in an order of magnitude 100 times lower if the
surfactant is ionic, and the effect is more sensitive in surfactants having
a long hydrophobic chain. The surfactants become even less soluble
with the addition of salt, because the molecules of surfactant have to
compete for the solvation of the water with the salt ions present [22].
3.4. Determination of size of oil droplets of synthetic oily water
The synthetic oily waters were prepared in duplicate and the mi-
crographs obtained under an optical microscope are shown in Fig. 4.
The oil droplet diameter diameters of synthetic oily water 1 and
synthetic oily water 2 can be seen in the graph shown in Fig. 4.
The graph of Fig. 5 shows that both water 1 and water 2 exhibit
similar oil droplet diameter diameters with a higher diameter frequency
between sizes 5 and 8 μm, having a size range from 3 to 20 μm. These
values of droplet diameters are consistent with the values reported in
the work of Moosai and Dawe [13], being within the diameter range of
the oil droplets required to perform this work. In addition, the result
shows that the synthetic oily water prepared as explained in the section
of experimental procedures is reproducible and stable for carrying out
the tests of that work.
3.5. Determination of DAF system saturation efficiency
Tables 2 and 3 show the average values of collected air volume,
standard deviation and 95% confidence limits, calculated by Eq. (2), for
A.S. Santos et al. Colloids and Surfaces A 558 (2018) 200–210

Fig. 5. Graph of Frequency diameters of Oil Droplets.

Table 2
Statistical values of a flow rate of 3 liters per minute.
Pressure (PSI) Average volume of Standard Deviation Upper Confidence Limit Lower Confidence Limit
collected air (mL) (95%) (95%)

120 124,41 3,51 129,99 118,83

100 105,32 3,32 110,59 100,05
80 84,47 4,41 91,49 77,45
60 66,80 1,87 69,77 63,82

Table 3
Statistical values of a flow rate of 4 liters per minute.
Pressure (PSI) Average volume of Standard Deviation Upper Confidence Limit Lower Confidence Limit
collected air (mL) (95%) (95%)

120 121,05 1,57 123,54 118,56

100 100,37 3,00 105,14 95,61
80 85,00 1,86 87,96 82,04
60 61,85 2,41 65,69 58,01

flow tests at 3 L/min and 4 L/min respectively, obtained through De-
pressurized air volume meter (Fig. 2):
With the confidence intervals for the results of depressurized air
volume, the graph shown in Fig. 6 was constructed, relating them to the
maximum saturation of air in water, under certain pressures, at the
temperature of 20 °C.
With this graph it is possible to observe that, for a limit of 95%
confidence, the two saturation curves, the first one 3 L/min and the
other one 4 L/min are statistically the same, since the confidence limits
of both lines overlap each other, so that there is no relevant difference
in the use of one of these two flow rates in conducting the tests at this
temperature, pressure and depressurizing valve.
The saturation efficiencies for each pressure in the temperature of
20 °C were obtained in relation to the maximum saturation curve for the
respective pressures tested at 20 °C, and can be seen in Table 4:
The saturation efficiency of the DAF System is between 73.24 and
81.24%, according to the tests performed.
3.6. Efficiency of oil removal using the flocculants proposed in the Jartest
In Fig. 7 we can observe the removal efficiency results for the ca-
tionic reference polymer, for the LW PEI used in conjunction with SDBS
and the HW PEI used in conjunction with the SDBS.
3.6.1. Reference cationic polymer in Jartest
The results show that the oil removal was higher at the 25 ppm
dosage of the reference cationic polymer, achieving removal effi-
ciencies of 30%. However, at higher concentrations of this flocculant,
the removal efficiency was lower. A possible explanation for this may
be the problem of electrostatic repulsion: if the polymer has a high
density of positive surface charge and there is excess of it in the
medium, it will saturate all the adsorption sites of the oil droplets,
forming a positive overcharged system, which will repel other oil dro-
plets in the same situation, increasing the difficulty of forming larger
flocs and consequent separation of the oil from the continuous phase.
This phenomenon is called electrostatic restabilization and is cited in
the work of Bratskaya et al. [21].
3.6.2. Efficiencies of PEI LW and PEI HW protonated in Jartest
When used in its protonated form, PEI LW and PEI HW achieved
near zero removal efficiencies. This is because the oil droplets are not
sufficiently negatively charged. The few naturally occurring negative
charges on the surface of the droplets are not enough for the polymer
chains to adsorb and flocs. Therefore, the polymer chains eventually
become dispersed in the solution, and the few chains that can adsorb
into the oil droplets may be causing a repulsion effect on the other
droplets that are in the same situation. Mutual repulsion between dis-
persed polymer chains and polymer chains adsorbed on the oil droplets

205
A.S. Santos et al. Colloids and Surfaces A 558 (2018) 200–210

Fig. 6. Graph of air saturation in water obtained in DAF system.

Table 4
Experimental values obtained at several pressures, with a flow rate of 3 liters per minute and 4 liters per minute.
Pressure (PSI) Maximum Saturation Saturation at flow rate Saturation efficiency Saturation at flow rate Saturation efficiency
(mililiter of air / liter 3 (mililiter of air / at flow rate 3 4 (mililiter of air / at flow rate 4
of water) liter of water) liter of water)

120,00 164,45 124,41 75,65 % 121,05 73,61 %

100,00 137,04 105,32 76,86 % 100,37 73,24 %
80,00 109,63 84,47 77,05 % 85,00 77,53 %
60,00 82,22 66,80 81,24 % 61,85 75,22 %

would explain the negative efficiencies results at different dosages.
Also the addition of the SDBS surfactant was carried out in the
absence of flocculants. The presence of SDBS further increased the
stability of the emulsion, since the removal efficiencies were all nega-
tive. This may have occurred because of the accumulation of the sur-
factant molecules at the oil / water interface, increasing the negative
charge on the surface of the droplets in such a way that they cannot
coalesce and remain efficiently dispersed in the emulsified form.
3.6.3. Efficiencies of PEI LW and PEI HW at 25 ppm concentration of SDBS
in Jartest
For the LW PEI, the first test was performed with the concentration
of 25 ppm of SDBS. The SDBS surfactant concentration selected for this
initial test was above its CMC (14.5 ppm) in the saline water prepared
for these tests. The choice of this surfactant concentration ensures that
the adsorption of the surfactant molecules is taking place in the oil
droplets dispersed in the medium as they begin to adsorb at the oil-
water interface between the droplet of oil and water. This interface did
not exist when the CMC test was performed, since it was performed only
in saline water. The high salt concentration in the medium reduces the
solubility of the surfactant, causing it to migrate rapidly to the oil /
water interface. The amount of cations present in the solution also fa-
cilitates the packaging of the surfactant molecules in the oil droplet,
preventing them from repelling [22].

Fig. 7. Graph of Oil Removal Efficiency x Flocculant Dosage.

206
A.S. Santos et al.
However, the efficiency of PEI LW remained relatively constant at the
various flocculant concentrations employed, in the range of 5–7% re-
moval efficiency. This means that a few droplets of oil were efficiently
saturated with negative charges, the low concentration of SDBS being
one of the limiting factors for flocculation. The PEI LW, with low molar
mass, has short chains and cannot attach electrostatically to a satisfactory
amount of oil droplets, which is another limiting factor. The neutralized
structures end up remaining dispersed without flocculating efficiently, so
much that no flocs were observed with the naked eye in the experiment.
For the HW PEI used in conjunction with the 25 ppm concentration
of SDBS, the removal efficiency was found to be in the range of
16–27%, substantially higher than the PEI LW performance, though still
lower than the efficiency of the cationic polymer. A possible explana-
tion for a greater efficiency of the PEI HW in relation to the PEI LW is
that the chains of the PEI HW are larger, i.e. the macromolecule of PEI
HW presents more positive charges quantitatively than a macro-
molecule of PEI LW. Thus, PEI HW is able to bind to several oil droplets
(although slightly charged negatively) and to form slightly larger ag-
gregates that can rise to the surface, without remaining dispersed as in
the case of PEI LW.
3.6.4. Efficiencies of PEI LW and PEI HW at 100 ppm concentration of
SDBS in Jartest
In the fixed concentration of 100 ppm of SDBS, there is an improve-
ment on the efficiency of the PEI LW, as it reaches an efficiency of 32% in
the concentration of 50 ppm. One possible explanation is that as there is a
greater amount of SDBS in the system, the oil droplets are more charged
and thus the demand for positive charges is greater. The PEI LW, even
with a shorter chain, can flocculate with a larger amount of oil droplets
because there is a greater supply of negative charges in the medium, al-
lowing the formation of many small flocs that rise to the surface.
The performance of PEI HW is similar to that of PEI LW, reaching
30% removal efficiencies at 75 ppm concentration. A possible reason
for PEI HW to exhibit slightly better removal efficiency than in the case
where 25 ppm of SDBS is used, and a performance similar to that of PEI
LW at the concentration of 100 ppm of SDBS is that most flocs formed
fail to rise to the surface alone, due to the larger chain size of the PEI
HW, if adsorbing into several different oil droplets. This causes most of
the flocs to remain dispersed in the medium, not contributing to effi-
cient separation.
3.6.5. Efficiencies of PEI LW and PEI HW at 150 ppm concentration of
SDBS in Jartest
The efficiency of PEI LW increases considerably when the con-
centration of SDBS is increased to 150 ppm, reaching separation
Fig. 8. Graph of Oil Removal Efficiency at DAF System x Flocculant Dosage.
207
Colloids and Surfaces A 558 (2018) 200–210
efficiencies of up to 67% when used at the concentration of 100 ppm.
An increase in removal efficiency of HW PEI is also observed for that
amount of SDBS employed, reaching removal efficiencies of up to
58% when using the PEI HW at a concentration of 100 ppm. Both
curves show practically the same tendency, as can be observed in
Fig. 7. A probable explanation for the increase in efficiency of the two
polyethylenimines is the increase in the negative charge of the oil
droplets, making them very compatible to be flocculated by some
cationic flocculant. However, the removal efficiency was higher in the
LW PEI than in the HW PEI, for the first time in all tests carried out
until then. One possible explanation for this is that a larger amount of
small flocs is formed with the PEI LW, whereas a larger amount of
large flocs is formed by the PEI HW. Small flocs alone can ascend the
surface more easily than large flocs, which are scattered in the solu-
tion. As PEI LW has a larger amount of small flocs formed, the se-
paration efficiency of the PEI HW ends up being greater than that of
the PEI HW in this case.
3.7. Efficiency of oil removal using the flocculants proposed in dissolved Air
Floating System
In Fig. 8 we can observe the removal efficiency results for the ca-
tionic polymer reference for the PEI LW used in conjunction with SDBS
and for the PEI HW used in conjunction with the SDBS, all of these tests
being performed in the dissolved air flotation system.
3.7.1. Reference cationic polymer in the dissolved air flotation system
The test with the cationic reference polymer carried out on the DAF
sytem showed a greater oil removal efficiency of the oily water than
that carried out in Jartest, with an average removal of up to 58%, as
shown in Fig. 8. Again, greater removal achieved at the lowest dosage
of flocculant used (25 ppm). The efficiency was much higher in the DAF
system than using only Jartest.
This indicates the coupling of the depressurized air bubbles in the
formed flocs, decreasing the density of the flocs, now aerated. A higher
density difference with respect to the continuous phase increases the
rate of ascent, as described in Stokes' Law [13].
3.7.2. Efficiencies of PEI LW and PEI HW at 25 ppm concentration of SDBS
in the dissolved air flotation system
In the case of PEI LW, the removal efficiency was similar to that
obtained using only Jartest. Flocs were not observed at the end of the
tests, which in a way explains the lack of efficiency increase using the
DAF system: in this case, the air bubbles cannot be coupled in the oil
droplets or in any flocs formed, because they are not large enough,
A.S. Santos et al.
Fig. 9. Influence of Jartest and DAF System on Flocculation.
making it impossible to reduce the density of the flocs (formation of
aerated flocs) and increase the water / oil separation efficiency.
In the graph of Fig. 8, it can be observed that in some moments the
efficiency in the DAF system is smaller than the one obtained when only
Jartest is used. This may indicate that the turbulence generated by the
depressurizing of the saturated water in the flotation chambers can
break the small flocs formed (not visible to the naked eye), dispersing
the oil and decreasing the removal efficiency, which is calculated from
an aliquot taken at a certain height of the flotation chamber. The tur-
bulence generated may be such that in some cases negative efficiency
results appear, and it can be seen more prominent on PEI HW curve
with 25 ppm of SDBS, although some results of PEI LW also had ne-
gative removal efficiency: this indicates that the turbulence generated
may even temporarily separate the coalesced oil by hydrophobic me-
chanisms. Coalesced oil droplets tend to rise more rapidly through the
same mechanisms as Stokes' law. If these oil droplets are separated,
there is a time required for them to coalesce again depending on the
stability of the emulsion. This may increase the concentration of dis-
persed oil at the height of the aliquot withdrawal valve, and thus results
in a decrease in removal efficiency, reaching negative values.
In the case of PEI HW the removal efficiency was lower compared to
the tests carried out in Jartest, as can be observed in Fig. 8. As explained
previously, one possible explanation could be that negative efficiencies
are a consequence of increased turbulence and the breaking of the small
flocs formed and the separation of the coalesced oil droplets into
smaller oil droplets, increasing the amount of oil dispersed at the point
of withdrawal of the oil aliquot. Also, there are few sites on the oil
droplet allowing PEI HW to attach electrostatically as the concentration
of SDBS is lower than the other conditions. As a result, another possible
explanation could be that most of sites created by SBDS allocation at the
surface of oil droplets are occupied by PEI molecules, leading to ca-
tionic repulsion because the positive charges of PEI could not attach to
other negative sites. This effect could maintain the oil droplets sepa-
rated from each other, preventing them to coalesce or flocculate and
ascending to the surface, increasing the concentration of the oil around
the oil aliquot withdrawal point. This effect of repulsion at lower do-
sages of SBDS, that increases with the increasing of flocculant, plus the
turbulence caused by dissolved air flotation could explain the negative
oil removal efficiency.
208
Colloids and Surfaces A 558 (2018) 200–210
Dissolved air flotation is known to cause smaller turbulences in the
flotation chambers when compared to other types of flotation, such as
induced air flotation [24]. However, the experiments of this work were
carried out on bench scale, where the flotation chambers have dimen-
sions much smaller than the industrial flotation chambers, where the
effects of the turbulence are much smaller.
3.7.3. Efficiencies of PEI LW and PEI HW at 100 ppm concentration of
SDBS in the dissolved air flotation system
In the case of PEI LW, oil removal efficiency results for systems with
SDBS concentration of 100 ppm in DAF system exhibited lower removal
efficiencies than at Jartest at most of the concentrations evaluated. This
leads us to believe that the chain extension of the PEI LW is a limiting
factor: even when there is a significant addition of SDBS to the system,
if there is turbulence in the medium, the oil droplets decouple from the
flocculating polymer and the removal efficiency is compromised.
However, the formation of small flocs could be distinguished in this
system.
In the case of PEI HW, it was finally possible to distinguish an in-
crease in the significant removal efficiency when using the DAF system:
the removal efficiencies doubled in almost all the dosages of PEI HW
flocculant, when compared with the test carried out in Jartest. The
results obtained for this system were much better than those obtained
when the polymer used was the LW PEI, with 100 ppm SDBS. The graph
of Fig. 8 when compared to the graph of Fig. 7 demonstrates the im-
provement in efficiency.
This result is important because it shows that the higher molar mass
of the HW PEI influenced the removal efficiency when the medium
became turbulent with the depressurizing of the saturated water. While
in the PEI LW + 100 ppm SDBS system showed worse efficiency than
Jartest, the PEI HW system practically doubled efficiency over Jartest at
all dosages. This leads one to believe that the polymer molecules are
more effectively trapped electrostatically to the oil droplets and,
forming flocs, are able to incorporate into these new structures the air
bubbles released from the saturated water, decreasing the density of the
agglomerate and causing it to rise faster.
A.S. Santos et al.
Fig. 10. Influence of polyethylenimine Concentration on Flocculation.
Fig. 11. SDBS Influence on Flocculation.
3.7.4. Efficiencies of PEI LW and PEI HW at the concentration of 150 ppm
SDBS in the dissolved air flotation system
In the case of PEI LW the tests in the DAF system presented values
worse than the analogous system realized in Jartest. Turbulent condi-
tions appear to be the major cause of decreased removal efficiency.
Flocs, in larger concentrations and larger in size, are also more sus-
ceptible to shear, and if they are weakly connected to each other, they
are easily split. Only for the lowest flocculant concentration (25 ppm)
the oil separation efficiency has increased in the DAF system.
In the case of PEI HW, it is possible to observe a small increase in
efficiency compared to that obtained by the PEI HW + 100 ppm SDBS
at the DAF system. This indicates that the PEI HW + SDBS system may
be reaching its maximum of removal, and that the increase in SDBS will
not impact large efficiencies from this flocculant concentration.
However, it can be seen that the increased removal efficiency is visible
when the air flotation system dissolved at these concentrations is
compared to the analogous system tested in Jartest.
3.8. Influence of SDBS and Molar Mass on efficiency of removal of Pei LW
and Pei Hw
With the results obtained, it is possible to first notice that there is
a great difference in the removal efficiency of the polyethyleneimines
when tested in Jartest system and dissolved air flotation system. The
dissolved air flotation system has caused turbulence in the flotation
chamber, so that if the polymer has not formed shear resistant flocs,
they break off and decrease the removal efficiency. If the formed
flocs are resistant, then the air bubbles released in the dissolved air
flotation system are coupled to the flocs, forming the aerated flocs,
with a density lower than the original flocs, increasing the rate of
ascent of the same towards the surface and Increasing the removal
efficiency.
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Colloids and Surfaces A 558 (2018) 200–210
By analyzing purely the system used for the oil removal treatment, it
is possible to notice that the PEI LW obtained better removal efficiency
in the Jartest, whereas the PEI HW obtained better removal efficiency
in the float system. Then the PEI LW flocs can be considered less re-
sistant to turbulence than the PEI HW flocs, as shown in Fig. 9.
Also, it is possible to observe that an increase of the molar mass
increased the stability of the flocs, which suggests a bridge flocculation
mechanism. This proposition is also indicated by the results obtained
with PEI LW in Jartest, which presented better removal efficiency than
the PEI HW in intermediate and high concentrations of SDBS. A lower
molar mass decreases the negative effect of the electro-static hindrance
(this phenomenon is represented in Fig. 10), so that the flocs tend to
meet by slow stirring of the medium and aggregate into larger flocs
more easily.
However, these results were only possible with the use of the SDBS
anionic surfactant. For all tests of both PEI LW and PEI HW, it was
observed that an increase in the concentration of SDBS in the medium
implies an increase in the removal efficiency of the polyethylenimines,
shown in Fig. 11.
The presence of SDBS is so important that at concentrations of
150 ppm PEI LW has been able to achieve removal efficiency values
comparable to those of the PEI HW even in the DAF system.
The more the oil droplets are negatively charged, the greater the
removal efficiency and the more stable the flocs formed. This can be
explained by the increase in the electrostatic interaction between the
polymer and the droplet of oil. The removal efficiency of the PEI HW
can already be observed in the DAF system from the concentration of
100 ppm of SDBS in the medium. This can be explained by the amount
of positive charges present in the PEI HW. If both PEI’s have 40% of
their protonated structures, this means that in absolute terms the PEI
HW presents more amount of positive charges than the PEI LW. This
implies that its structure can adsorb electrostatically in a larger amount
of oil droplets and formed primary flocs, increasing the removal effi-
ciency of the system. The influence of higher molar mass allowing the
flocculation of more colloidal particles is also reported by [25], when
PEI of higher and lower molar masses were evaluated as a flocculant for
kaolin slurries.
4. Conclusion
In this work the removal efficiency of high molar mass poly-
ethylenimine (PEI HW) and low molar mass polyethylenimine (PEI LW)
along with an anionic surfactant SDBS were evaluated, applied to the
produced water treatment. A cationic reference polymer was used as a
standard removal efficiency parameter. PEI LW and PEI HW were
evaluated in Jartest systems and in dissolved air flotation systems.
It was observed that the higher the concentration of SDBS in the
medium, the greater the removal efficiency of polyethylenimines. This
is because the oil droplets become more negative with the allocation of
SDBS surfactant molecules on their surfaces, increasing the cationic
demand. Because protonated polyethylenimines are strong polyelec-
trolytes, they are able to meet this demand by adsorbing electro-
statically to the surface of the oil droplets, forming flocs that are se-
parated from the medium. However, it has also been observed that the
molar mass of the polymer also influences the removal efficiency.
In Jartest systems and in low cationic demands, the polymer PEI
HW, of high molar mass, had the best removal efficiency. In inter-
mediate cationic demands (100 ppm SDBS), both the high mass
polymer PEI HW and the low mass polymer PEI LW performed simi-
larly, suggesting that the increased concentration of the SDBS favored
the LW PEI more than the PEI HW. In high cationic demands (150 ppm
SDBS), it was observed that the PEI LW low molecular weight polymer
has a better removal efficiency than the high molecular weight PEI HW
polymer. This suggests that the removal efficiency of the poly-
ethylenimines is governed by a balanced mechanism between the molar
mass of the polymer and the cationic demand of the oil droplets. The
A.S. Santos et al.
formation of a greater amount of large flocs by the PEI HW (due to the
high molar mass) in relation to PEI LW increases the electro-static
hindrance. However, the polymer of high molar mass can flocculate
systems of low cationic demand because they have a longer chain and a
molecule can reach a larger number of droplets of oil. Short chains such
as PEI LW cannot adhere to many oil droplets in cationic low-demand
systems, remaining adsorbed and dispersed in the medium without
flocculation.
In a DAF system, the PEI HW presented better results than the PEI
LW and high removal efficiency already from the intermediate con-
centration of 100 ppm of SDBS. SDBS has been shown to play a key role
in increasing the stability of the flocs formed by polyethylenimines: the
higher the concentration of SDBS in the medium, the greater the re-
moval efficiency of polyethylenimine. This is valid until the entire
surface of the oil droplets present in the system is saturated.
Removal efficiencies of the polyethylenimines also showed oil re-
moval efficiencies similar to the cationic reference polymer in low
concentrations of SDBS, and better removal efficiency than the re-
ference polymer at higher concentrations of SDBS.
Acknowledgments
This work was supported byConselho Nacional de Desenvolvimento
Científico e Tecnológico (CNPQ), by Coordenação de Aperfeiçoamento
de Pessoal de Nível Superior (CAPES), by Fundação Carlos Chagas Filho
de Amparo à Pesquisa do Estado do Rio de Janeiro (FAPERJ) and by
PETROBRAS.
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