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Bubbling Nitrogen Techniques for Esterification of Nonionic Surfactant

for EOR Application

Ilham Ardatul Putra1*, Yani Faozani Alli1, Usman1, Didin Mujahidin2

1
LEMIGAS” R&D Centre for Oil and Gas Technology Jl. Ciledug Raya Kav.109, Cipulir,
Kebayoran Lama, Jakarta Selatan 12230
2
Laboratorium Kimia Organik, Institut Teknologi Bandung Jl. Ganesha No. 10, Lebak
Siliwangi, Coblong, Bandung 40132
Telephone : 022 – 250093
Email: [email protected]

Abstract reaction time (3, 4, 5, and 6 hours). The ester

product was identified by thin layer
Many industrial sectors, especially cosmetics,
chromatography test for optimum condition
food, and pharmaceuticals have high interest
determination. Confirmation the surfactant
in surfactants, due to the unique chemical
structure was performed by H1NMR. The
properties of the molecule which containing
optimized surfactant was further characterized
two groups with different polarity properties.
by an interface tension test (IFT) to see the
Petroleum industry also has an interest for
surfactant's ability to reduce IFT between
applying surfactants to increase oil production
water and oil. The results showed that the
in mature oil fields which experience a decline
optimum conditions for esterification of Oleate-
in oil production. This method is known as
PEG 400 which produced the best reaction
Enhanced Oil Recovery (EOR) technology. The
conversion was obtained with the equivalent
development of vegetable materials for
ratio oleic acid and PEG 1: 3 and reaction time
surfactant synthesis is preferably in association
of 6 hours. The surfactant structure has been
with the abundant availability, renewable and
confirmed using H1NMR and able to decrease
environmentally friendly raw materials. In this
the oil and water interfacial tension up to 10-4
research, surfactant synthesis was carried out
dyne/cm in brine salinity condition 18000 ppm
using vegetable materials as a hydrophobic
and oil 34,39 oAPI
group and polyethylene glycol as a hydrophilic
group that forming an ester. There are various
techniques to produce esters, such as reflux Introduction
technique using a condenser, the azeotrop
technique using dean-stark, enzymatic In spite of the recent worldwide interest for
alternative sources of energy,
techniques using enzymes from a bacterium,
with especial and strategic interest in fuels
and the bubbling technique using nitrogen gas.
derived from renewable products, the
Esterification of this nonionic surfactant was situation of petroleum in many countries stills
performed by nitrogen bubbling method with drives much concern. Brazil, for
the oleic acid and polyethylene glycol (PEG) example, is continuously advancing in the
400 as substrate. Since bubbling method are discovery of novel oil reservoirs and in the
environmentally friendly without the use of devise of potential ways to exploit oil both
onshore and offshore. Many research
organic solvents and economically efficient in
projects are joining industry and university
large scale applications, this method was personnel, aiming to improve the technology to
favorable to be conducted. enhance oil productivity. In addition to the
Reaction optimization was carried out primary recovery techniques and several
through equivalent variations of oleic acid and physical methods conceived as enhanced oil
PEG (1: 1.1; 1:2; 1:3; 1;4) and variations in recovery (EOR) methods, the development of
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EOR processes based on operations which Surfactants are the compounds which can
involve chemicals is greatly promising, reduce the surface tension (or interfacial
many of which employing surfactants. tension) of water by adsorbing at the
Knowledge on the interfacial properties water-air interface (or water-oil interface)
between oil, water and solid rock reservoirs, (Snell et all, 1958; Gushe et all, 1959;
especially under extreme conditions, with Schramm et all, 2003; O’Rear , 2015).
occasional presence of natural gas, is
important to better implement the EOR method There are many kinds of surfactants, and they
(Gurgel at all, 2008). are classified by use, properties and chemical
structure. The surfactant classification depends
In general, EOR chemical methods are
on water dissociation and the structure of
classified in terms of the main chemical agents
hydrophilic group (Schramm et all, 2003; .
used to modify the equilibrium established in
the reservoirs after recovery via conventional According to the water-soluble, surfactants can
or physical methods. We particularly focus our be classified into ionic surfactants and nonionic
attention on general EOR activities involving surfactants.Ionic surfactants can be divided
the use of polymers, surfactants, foams and into anionic surfactants, cationic surfactants
certain chemicals such as alkali, or suitable and amphoteric surfactant. Special features or
mixtures containing them, as in polymer-
new type surfactant is as special surfactant
alkaline, surfactant-polymer and alkaline
surfactant-polymer (ASP) flooding mixtures (Li (Wang et all, 2003; Zhang, 2001).
et al., 2000; Nedjhioui et al., 2005).
The hydrophilic group has common-COOH,-
Surfactant molecular structures consist of two SO3H, and a polyoxyethylene chain; lipophilic
parts. One is called the hydrophilic group which group has common-Si,-CF,-CF2, and a
is soluble in water and has hydrophilic nature. polyoxypropylene chain. The hydrophilia and
The other part is called the lipophilic group lipophilicity I surfactant molecules change with
which issoluble in oil but is not soluble in water molecule composition and structure. When the
and has lipophilic nature (Bhattacharya et all, hydrophilic is stronger that lipophilic, it is the
2011; Schramm et all, 2003; Czajka et all, water-soluble surfactant; when hydrophilic is
2015; Raffa et all, 2015). Two kinds of groups stronger than lipophilic, it is the oil-soluble
are in the opposite directions, and both ends surfactant. Water-soluble or oil-soluble reflects
are connected to bond in the same molecule, important physical and chemical parameters of
forming an asymmetric and polar structure.The surfactant application.It is an important basis
structure is usually referred to "parent for a reasonable choice of surfactant.
structure" (Amphiphilic structure) (Yuan et all,
2014). Surfactant molecules have amphiphilic Current development of the majority of novel
structure including an affinity for water and an substances/ chemicals, irrespective of their
affinity for oil (Figure 1). intended use, is based on the Green Chemistry
Program, established at the beginning
of 1990s (Shonnard et all, 2007). Since then,
the development of many green chemistry
approaches and environment-friendly chemical
syntheses have been driven by this program.
Green chemistry is defined as the design of
chemical products and processes that reduce
or eliminate the use or generation of
hazardous substances, whereas a hazard is
anything that could have a negative effect on
human health and the environment. Hence, a
permanent priority for both chemical industry
and academic community became the
development of greener or more
Figure 1. The structure of the surfactant environmentally benign processes and
materials (Jessop et all, 2015). Similar to

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other fields, industry needs are brought to the heated up to 100oC. Reaction was monitored
focus of academic work, which is achieved by TLC method and the structure was
through continual communication and confirmed by NMR 43 MHz.
collaboration between industry and academia
(Constable et all, 2007). In this manner, 3. Interfacial tension (IFT) measurement
research areas are tailored according to the
The ability of surfactant to decrease the IFT
actual needs.
of oil and water as the main function of
surfactant was evaluated by measuring the IFT
In the paper study the synthesis of vegetal-
using Spinning Drop Tensiometer TX-500 C/D.
based nonionic surfactants with catalytic
Surfactant solution with different concentration
reactions and without solvents. The solvent
at 18000 ppm salinity was prepared and filled
azeotropic technique using ethyl acetate to
into the IFT tube. Two microliters of oil was
reduce the concentration of water as a side-
added and put into the IFT unit. Setting the
product was replaced by nitrogen gas.
device at 60 oC and run the measurement at
Replacing the function of ethyl acetate with
6000 rpm.
nitrogen due to its non-toxic and environment-
friendly nature, and the application of
industrial-scale reactions will reduce production
costs. Ini mengacu pada Green Chemistry. Di Result and Discussion
mana reaksi kimia diarahkan pada efek
kesehatan dan lingkungan 1. Screening of Bubbling Nitrogen
The esterification reaction carried out is the
Data and Method development of the solvent azeotropic
Technical grade oleic acid from palm oil technique. The esterification reaction products
and PEG-400 were used as raw material of the not only produce esters, but also water as a
surfactant. Nitrogen technical grade were used side-product. The esterification reaction is a
as azeotropic agent with a by-product water. reversible reaction.
Sulfuric acid, sodium sulfate anhydrate, and
cerium sulfate pentahydrate with analytical A reversible reaction is a type of reaction
grade were used for product analysis. Crude oil that takes place in two directions when
“A” with 34.39 oAPI was used for IFT equilibrium is reached. Reaksi ketika
measurement. keseimbangan dapat terjadi terhadap
pembentukan produk, tetapi juga terhadap
1. Screening of Bubbling Nitrogen dekomposisi produk. To increase the
conversion of reactions can be done by several
Oleic acid with 70% purity was reacted with techniques following the principle of Le
PEG-400 by the mol equivalent ratio 1:1.1 as Chatelier which reads "When a system at
much as 7.05 grams and 11 grams of PEG-400 equilibrium changes in concentration,
in the presence of 10 % mol sulfuric acid (0.13 temperature, volume, or pressure, the system
mL) as catalyst. The reaction runs with adjusts itself to negate the effect of the
nitrogen flow and heated up to 100oC. Thin changes applied and the new balance is
layer chromatography (TLC) was used to achieved".
monitor the reaction with the cerium sulfate
tertahydrate (CeSO4.4H2O) as the staining Based on this theory, an increase in the rate
reagent. Esterification product was then of reaction towards product formation can be
identified by Spinsolve 43 MHz Proton Magritek done by reducing the amount of product
and . formed during the reaction. So that the
reaction equilibrium will shift towards the
2. Optimization of esterification formation of a product that will increase the
In order to obtain the highest yield, reaction conversion.
optimization were accomplished by varying
equivalent ration of oleic acid and PEG-400 as The esterification is the reaction between a
follows 1:1,1; 1:2; 1:3 and 1:4. The addition carboxylic acid and an alcohol with an ester as
of catalyst sulfuric acid and nitrogen flow with the main product and water as a by-product.

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Water produced as a side-product can be hour to the sixth hour it does not show
removed by the technique of flowing nitrogen significant substrate reduction and can be
gas into the mixture continuously. With the considered the same. Thus the reaction is
hope that the water formed will evaporate with stated to have reached its optimum condition
nitrogen. So it is expected that the reaction will with these conditions. Then the results of the
continue in the direction of product formation. work up a reaction using a salt solution to
The reaction was carried out with an equivalent remove the remaining unreacted PEG-400 and
ratio of oleic acid 1: 1.1 with PEG-400. The acid catalyst. The product of the subsequent
reaction is monitored every hour. It aims to reaction is measured 1H NMR to prove the
analyze esterification products by using product formed is the desired ester.
bubbling nitrogen to form esters and to
determine the optimum reaction time.

Figure 2. The Chromatogram of reaction for the 1st

hour (a) Oleic acid and (b) Crude reaction; Eluen n-
hexsane:ethyl acetate (8:2)

Figure 4. The spectrum of 1H NMR oleic acid and

Based on the TLC results (Figure 2) shows a PEG-400-oleate
new polar stain compared to the substrate of
oleic acid. PEG-400 stains cannot be seen
Combining the spectrum of measurement
using cerium sulfate stain. The TLC results of 1H NMR substrate and reaction
chromatogram shows the esterification products (Figure 4). The combined spectrum
reaction of oleic acid and PEG-400 can take shows the emergence of new peaks in the 3-
place using nitrogen bubbling. Then the
4.5 ppm area of the friction shift. The peak of
reaction is continued for up to 6 hours of
the chemical shift area 3-4.5 ppm is the peak
reaction. Every hour monitoring is carried out.
that shows the hydrogen atom bond on the
oxygenated carbon. This shows that oleic acid
and PEG-400 ester products have been
formed.

Because the esterification reaction between

oleic acid and PEG-400 is a chemoselective
reaction to the ester product formed. Two
possible ester products formed are PEG-400-
oleate and PEG-400-dioleate (Figure 5).
Because the desired ester product is a PEG-
400-oleic ester. Thus the amount of PEG-400
Figure 3. The Chromatogram of reaction for the 1st used in the reaction must be more than the
until 6th hour (s) Oleic acid and ( 1st until 6 th ) number of moles of oleic acid.
Reaction time; Eluen n-hexsane:ethyl acetate (8:2)

The results of monitoring using TLC showed

a significant change in reaction conversion per
hour to the fourth hour (Figure 3). This is
indicated by the thickness of the stain of the
oleic acid substrate which decreases from the
first hour to the fifth hour. But from the fourth

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protons (polyethylene glycol chain protons)

showing a ratio of 1: 18. This shows that the
ester product formed is a PEG-400-oleic ester.
The reaction product selectivity is also
influenced by the equivalence ratio between
oleic acid and PEG-400 used and not influenced
by reaction time (Abdullah et all, 2017).

2. Optimization of esterification
In order to obtain the highest yield,
optimization were accomplished by varying
equivalent ration of oleic acid and PEG-400 as
follows 1:1,1; 1:2; and 1:3. The addition of
catalyst sulfuric acid were at the same amount
with the previous reaction. Reaction was
monitored by TLC method.
Figure 5. Esterification of oleic acid and PEG-400
Based on the TLC results of each reaction
In the reaction screening, the mole for 6 hours, the most optimum reaction was
equivalent of oleic acid is 1: 1.1 with PEG-400. achieved with an equivalent ratio of 1: 3 oleic
To show the ester product formed is acid with PEG-400. The TLC chromatogram
monooleate or dioleate, it is necessary to showed a reaction with an equivalent ratio of
compare the integration between the alkene 1:3 and 1:4 oleic acid with PEG-400 having no
part and the region of the oxygenated protons substrate stain (Figure 7). This proves that the
that form the ester. If the ratio between alkene reaction lasts 100% towards the formation of an
integration and the integration of oxygenated ester product. This is in accordance with the
protons 1:18 shows that the formed ester is
PEG-400-oleate. Conversely, if the comparison
principle of equilibrium, where when increasing
between the integration of alkene protons and the mole of one substrate, the reaction will shift
oxygenated protons 1:36 shows the ester the equilibrium towards the opposite. Thus the
formed PEG-400-dioleate. number of products from the reaction will
increase. The increase in reaction conversion in
this way applies to reactions that are reversible.
Some other ways that can be done are like
using the nitrogen bubbling technique to reduce
the amount of water that is formed during the
reaction. While other ways can also be done to
optimize the reaction with variations in
pressure and volume.

Figure 6. The spectrum of 1H NMR PEG-400-oleate

Based on the results of the proton spectrum

analysis of the product (Figure 6) shows a
comparison between the alkene protons Figure 7. Profile results of TLC chromatograms
(protons in double bonds) and oxygenated

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O’Rear III, E.A., 2015, J. Chem. Educ., 92,

3. Interfacial tension (IFT) measurement 1779–1780.

Synthesized surfactants at optimum Gugel, A., M.C.P.A. Moura, T.N.C. Dantas, E.L.
conditions were tested for IFT values to see Barros N., A.A. Dantas N., 2008, Brazilian
their ability to reduce the interfacial tension of Journal of Petroleum and Gas, 2, 83-95.
water and oil. The results showed that
surfactant was able to decrease the IFT to the Gushee, D.E., O.L. Scherr, 1959, Ind. Eng.
ultralow level 10-3 dyne/cm in the range of Chem., 51, 798–804.
0.3-1.0% w/w (Figure 8), which indicating the
good performance of mixed PEG-400-Oleate Li, G., J.H. Mu, Y. Li, L.S. Yuan, 2000,
surfactant, and potential to be used as Physicochemical and Engineering Aspects,
chemical injection for chemical flooding EOR. 173, 219-229.

Nedjhioui, M., N.M. Moulai, A. Morsli, A.

Bensmaili, 2005, Desalination, 185,543–
550.

Raffa, P., D.A.Z. Wever, F. Picchioni, A.A.

Broekhuis, 2015, Chem. Rev., 115,
8504–8563.

Schramm, L.L., E.N. Stasiuk, D.G. Marangoni,

2003, Annu. Rep. Prog. Chem. Sect., C99,
3–48
Figure 8. IFT of esterification product PEG-400-
Oleate Snell, F.D., C.T. Snell, 1958, J. Chem. Educ.,
35, 271–278
Conclusions
The esterification reaction of the nitrogen Shonnard, D., Lindner, A., Nguyen, N.,
bubbling technique was successfully carried out Ramachandran, P. A., Fichana, D., Hesketh,
to obtain a PEG-400-Oleate Ester. The R., Slater, C. S. and Engler, R., 2007, Kent
optimum condition with the best conversion is and Riegel’s Handbook of Industrial
the equivalent ratio of 1: 3 oleic acid and PEG- Chemistry and Biotechnology 11th ed,
400 with 10% mol sulfuric acid as a catalyst. Springer Science+Business Media, 211;
The product of the reaction is identified using ISBN:978–0–387–27842–1.
1H NMR 43 MHz. The IFT measurement proved
that mixed-surfactant is having the ability to Wang, W.B., YF Liu, SC Sheng,2003, Chemical
lower the IFT of oil and water levels, which can Industry Press, 2003,1-2.
be used as a candidate for chemical flooding
EOR. Zhang, T.S., 2001, Chemical Industry Press, 2001, 2-
7
References

Abdullah, F. Z., A. Ma’amor, N. A. Daud, and Acknowledgements

S.B. A. Hamid, 2017, Quim. Nova,40, 506- This paper is the collaboration results of
512. Research Centre for Oil and Gas Technology
“LEMIGAS” and Organic Synthesis Laboratory
Bhattacharya, S., S.K. Samanta, 2011, J.Phys. of Chemistry, Bandung Institute of Technology.
Chem. Lett., 2, 914–920. Special thanks to Prof. Yana Maulana Syah for
NMR and MS measurement. The financial
Czajka,A., G. Hazell, J. Eastoe, 2015, Langmuir support from DIPA Research Center for Oil and
,31, 8205–8217. Gas Technology “LEMIGAS” is fully
acknowledged.

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