Petroleum Science and Technology

ISSN: 1091-6466 (Print) 1532-2459 (Online) Journal homepage: http://www.tandfonline.com/loi/lpet20

Optimization of separation of oil from oil-in-

water emulsion by demulsification using different
demulsifiers

V. K. Rajak, Inderpreet Singh, Amit Kumar & Ajay Mandal

To cite this article: V. K. Rajak, Inderpreet Singh, Amit Kumar & Ajay Mandal (2016)
Optimization of separation of oil from oil-in-water emulsion by demulsification using
different demulsifiers, Petroleum Science and Technology, 34:11-12, 1026-1032, DOI:
10.1080/10916466.2016.1181654

To link to this article: http://dx.doi.org/10.1080/10916466.2016.1181654

Published online: 12 Jul 2016.

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 PETROLEUM SCIENCE AND TECHNOLOGY
, VOL. , NOS. –, –
http://dx.doi.org/./..

Optimization of separation of oil from oil-in-water emulsion by

demulsification using different demulsifiers
V. K. Rajak, Inderpreet Singh, Amit Kumar, and Ajay Mandal
Department of Petroleum Engineering, Indian School of Mines, Dhanbad, India

ABSTRACT KEYWORDS
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Separation of oil from oil-in-water emulsion is a major challenge in petroleum Crude oil; demulsification;
industries during the producing and refining process. The authors investigated interface; oil-in-water
characterization of oil-in-water emulsion and subsequently separation of oil emulsion; oil separation
from emulsion using different chemical dimulsifiers. The effect of settling
time, pH, temperature, and demulsifier dosage on oil separation efficiency
has been studied. It was observed that as time, temperature, and chemical
dosage increased oil separation efficiency increased. Droplet size distribution
of emulsions illustrated that the demulsifier could lead to the breakup of crude
oil-in-water emulsions by flocculation and coalescence. More than 98% oil
separations were observed with some demulsifiers under optimum operating
conditions.

1. Introduction
Most oil fields are now mature, and produce a significant amount of water during oil production. The
produced water contains a significant amount of oil in the form of emulsions. Asphaltenes, resins, and
waxes present in crude oil are responsible for formation of stable emulsion (Yang et al., 2007). The oil-
in-water emulsions are stabilized by steric interaction or structural barriers and electrostatic repulsion
between oil droplets (Tadros and Vincent, 1983). Studies on stability and demulsification of crude oil
emulsions have been reported by many investigators (Auflem et al., 2001; Li et al., 2007; Qiao et al.,
2008). Other sources of oil-containing wastewaters include petroleum refineries, metal fabrication plants,
rolling mills, chemical processing plants, machine shops, and vehicle maintenance shops (Webb, 1991;
Bennett, 1998). There are different methods to separate oil from oil-water emulsion viz. air flotation
(Rajak et al., 2015), membrane filtration (Kumar et al., 2015), ultracentrifugation (Liu, 2014), coagulation
(Zhang et al., 2005), and flocculation (Bratskaya et al., 2006). However, chemical demulsification is the
most widely used method of treating oil-in-water emulsions as the chemical additives accelerate the
emulsion breaking process (Hao et al., 2016). Demulsifiers displace the natural stabilizers present in the
interfacial film around the dispersed oil droplets in emulsion. This displacement, occurring at the oil-
water interface, influences the coalescence of oil droplets through enhanced film drainage (Kang et al.,
2006). The efficiency of demulsifier is dependent on its adsorption at the oil-water or droplet surface.
The best demulsifiers are those that rapidly displace preformed rigid films and leave a mobile film in its
place.
In the present investigation an attempt has been made to study the influence of different chemical
demulsifiers on the destabilization of emulsions and hence separation of oil from wastewater. The effects
of settling time, pH, and temperature on the demulsification were also studied.

CONTACT Ajay Mandal mandal_ajay@hotmail.com Department of Petroleum Engineering, Indian School of Mines, Dhanbad,
India-.
Color versions of one or more of the figures in the article can be found online at www.tandfonline.com/lpet.
©  Taylor & Francis Group, LLC
 PETROLEUM SCIENCE AND TECHNOLOGY 1027

2. Experimental
Crude oil was collected from Digboi area (Oil India Limited, India) for preparation of emulsion. In
this study, eight different demulsifiers viz. ethylene glycol, polyethyleneoxide, polyethylene glycol-400,
polyethylene glycol-4000, polyethylene glycol 6000, polyethylene glycol 10000, n-hexylamine, and n-
octylamine were used for demulsification of oil-in-water emulsion. FT-IR analysis of crude oil was per-
formed to examine functional groups present in crude oil using Perkin Elmer FTIR (Spectrum 2, USA).
FT-IR spectra were collected over 40 scans in the 4000–450 cm−1 region. Emulsions were prepared with
crude oil as a dispersed phase and distilled water as continuous phase. Measured amount of crude oil
and distilled water was taken in a beaker and was kept in a sonication water bath (Model: FB15051 Make:
Fisherbrand) for 6 h at 27°C. The oil content in oil-in-water emulsion was determined by InfraCal TPH
analyzer (Wilks Enterprise Inc., USA). Initial concentration of oil in emulsion was kept 1000 mg/L for
each experiment.
To evaluate the effectiveness of demulsification, 150 mL of freshly prepared emulsion was thor-
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oughly mixed with demulsifier in a 250 mL separating funnel. The sample was collected from the bot-
tom of the separating funnel to measure the oil content. The efficiency of oil separation was inves-
tigated as a function of settling time, pH of the solution, dosage of demulsifier, and temperature of
demulsification.

3. Results and discussion

3.1. Characterization of crude oil

The properties of crude oil were determined experimentally and are given in Table 1. The properties
of the crude oil indicates that it is light oil with significant amount of asphaltene and resins, which are
responsible for emulsification in water. The acidic nature of the crude oil is evidenced by the total acid
number (0.038 mg KOH/g) of the crude oil. To understand the complexity of crude oil and chemical
groups responsible for emulsification, FTIR study was conducted. FTIR spectra of the crude oil used
in the present study were recorded between 450 and 4000 cm–1 and is shown in Figure 1. The typical
functional groups identified on the FTIR spectra of the crude oil include -CHn - stretching of the saturate
(2930–2856 cm–1 ), -CHn - deformation of the saturates (1460 cm–1 ), and -CHn - symmetric deformation
of the saturates (1380 cm–1 ) where n = 1 or 2. The peak at 722 cm–1 indicates the presence of long chain
alkyl groups. There is weak band at 1590 cm–1 because of the presence of C=C ring stretching. The peaks
of carboxylic acid O-H group (stretch) appear at 2670 cm–1 . The peaks around 2730 cm–1 correspond to
aldehyde due to stretching of = C–H group. The C–O group of carboxylic moieties (due to stretching)
appears in region between 1307 cm–1 and 1170 cm–1 , and O–H due to bending appears at 960 cm–1 . The
presence of acidic components in the fraction is indicated by the acidic carbonyl group absorption in
between 1634 cm−1− 1749 cm−1 . It may be concluded that carboxylic acids are available in the crude oil,
which are responsible for formation of surface active species.

Table . Compositions and characteristics of crude oil.

Sl. No. Parameter Value

 Density (.°C), kg.m− .

 Specific gravity (.°C) .
 API gravity (.°C), °API .
 Viscosity at °C, cp 
 Acid no., mg KOH/g .
 Pour point, °C 
 Saturates, %wt/wt .
 Aromatics, %wt/wt .
 Resins, %wt/wt .
 Asphaltenes, %wt/wt .
 1028 V. K. RAJAK ET AL.
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Figure . FTIR analysis of crude oil.

3.2. Effect of pH on separation of oil from emulsion

The demulsification occurs through flocculation and coalescence of dispersed oil droplets in emulsion.
The flocculation process is highly influenced by the pH of the system, which is also dependent on the
type of demulsifiers. Figure 2 shows the ability of different demulsifiers to separate oil from oil-in-water
emulsion under various pH values. The concentration of different demulsifiers was kept at 50 mg/L,
according to literature (Deng et al., 2005) and from an economic point of view. It may be seen from
the figure that with increase in pH oil separation efficiency first increases and then decreases passing
through a maxima. Oil removal increases from 79% at pH 7.5 to 95% at pH 10.5 for n-octylamine at
25°C and finally decreases at higher pH. The similar pattern was observed for other demulsifiers. Above
pH 12.5, the emulsion shows the greatest stability because only a little oil is separated out. Thus it may
be concluded that emulsions are stable at lower and higher pH, while at intermediate pH in alkaline

Figure . Effect of oil separation at various pH values. Experimental conditions: temperature = °C, demulsifier dosage =  mg/L,
initial oil concentration =  mg/L, time =  min.
 PETROLEUM SCIENCE AND TECHNOLOGY 1029
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Figure . Effects of demulsifier dosage on separation of oil from oil-in-water emulsion. Experimental conditions: initial concentration =
 mg/L, pH = ., time =  min, temperature = °C.

region the emulsions are unstable. The range and degree of emulsion stability are also dependent on the
crude oil from which the emulsion was formed. The stability of emulsions at low and high pH is because
of strong influence of asphaltene on the interfacial properties at the crude oil water interface (Poteau
et al., 2005). At these pH values, asphaltene functional groups become charged, leading to enhancing
surface activity (Tambe and Sharma, 1993). This is consistent with data obtained by Strassner (1968),
who studied crude oil emulsions at different pH values and found that Venezuelan crude oil emulsions
at pH >10 exhibit low stability or are highly unstable, although at pH = 13 the emulsions are very
stable.

3.3. Effect of demulsifier dosage on oil removal

From economic point of view the dosage of demulsifier for separation of oil from emulsion is very impor-
tant. Figure 3 illustrates the effect of demulsifier dosage on oil separation efficiency. The experiments
were conducted at 25°C and optimum pH of 10.5. It may be found from the figure that percentage of
oil removal increases with increase in demulsifier dosage due to neutralization of emulsion stabilizers.
After a particular concentration of demulsifier, the complete neutralization of the stabilizers occurred,
beyond which only marginal increase in efficiency is observed. The optimum dosage for n-Octylamine
is around 60 gm/L, where more than 96% oil separation is observed. For other demulsifiers the optimum
dosage varies from 60 to 80 gm/L. Polyethyne oxide and ethylene glycol show poor separation efficiency
compared to other demulsifiers.

3.4. Effect of settling time on separation of oil by different demulsifiers

The settling time after addition of demulsifier in the emulsion was found to have a strong effect on oil
separation. A minimum retention time should be provided for flocculation, coalescence, and separation
of dispersed oil droplets. Figure 4 shows the effect of settling or retention time on separation of oil at pH
10.5 and temperature of 25°C with demulsifier dosage of 60 mg/L. Oil separation efficiency increased
with increase in setting time and then remained almost constant after 60 min, as the dynamic equilibrium
of molecular motion at the interface is reached.
 1030 V. K. RAJAK ET AL.
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Figure . Effects of time on removal of oil from emulsion. Experimental conditions: initial concentration =  mg/L, pH = ., tem-
perature = °C, demulsifier dose =  mg/L.

3.5. Effect of temperature on oil separation

Figure 5 represents the oil removal efficiency with variation of demulsification temperature with 60 min
settling time, 10.5 pH, and demulsifier dosage of 60 mg/L. In all cases oil separation efficiency increased
with increase in temperature up to 70°C and then remained almost constant. At higher temperature
the instability of emulsions is due to increased Brownian motion and mass transfer across the interface.
The transportation of demulsifier molecules toward the surface of the oil droplets accelerates at higher
temperature, thus greatly enhancing the demulsification process. As temperature increases the interfacial
viscosity of the continuous phase decreases, which results increase in momentum and coalescence of
dispersed oil droplets. Different densities and polarities of the two phases of immiscible liquids make the
emulsion unstable.

Figure . Effect of oil separation at various temperatures. Experimental conditions: initial concentration =  mg/L, demulsifier
dose =  mg/L, pH = ., time =  min.
 PETROLEUM SCIENCE AND TECHNOLOGY 1031
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Figure . Oil droplet size distribution of different stages of oil-in-water emulsion.

3.6. Oil droplet size distribution of different stages of emulsion

The size of dispersed oil droplet in emulsion is a measure of breaking up of emulsion. Figure 6 shows
the oil droplet size distribution before and after demulsification using n-octylamine as demulsifier. The
average droplet size of fresh emulsion with oil content 1000 mg/L having pH 7.5 at 25°C was 111 nm,
which indicates that the fresh oil-in-water emulsion is highly stable. The same sample when measured
after 24 h, the average droplet size was changed to 145 nm. This means after natural gravity settling
the emulsion is also relatively stable. After 60 min demulsification with 50 mg/L of n-octylamine the
average oil droplet in separated water phase reduced dramatically to 68 nm with a relatively narrower size
distribution. So, after demulsification small amount of oil (∼35–40 ppm) remain in treated water in the
form of nanoemulsion. Thus it can be concluded that the n-octylamine destroys oil-in-water emulsion
stability and enhances oil droplet flocculation and coalescence, resulting faster separation.

4. Conclusion
A series of different demulsifiers for demulsification of the emulsion were studied, out of which n-
octylamine, n-hexylamine, and polyethylene glycol-400 were found to have good oil removal efficiency
from oil-in-water emulsion. It has been found that emulsions are stable both at lower and higher pH and
unstable around pH of 10.5. Oil removal efficiency increases with increase in settling time, demulsifica-
tion temperature and demulsifier dosage. However recommended values settling time and demulsifica-
tion temperature are 60 min, 70°C as after these optimum values the increase in separation efficiency is
only marginal. Optimum dosage of different demulsifiers vary from 60–80 mg/L. The size distribution
of dispersed oil in fresh emulsion and separated water after demulsification is an evidence of breaking
up of emulsions in presence of demulsifiers.

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