INTERNATIONAL JOURNAL OF NEW CHEMISTRY, 2019, 6 (2), 76-86 M.

REZAEI ET AL

Int. J. New. Chem., 2019, Vol. 6, Issue 2, pp. 76-86.

International Journal of New Chemistry

Published online 2019 in http://www.ijnc.ir/.

Online ISSN 2383-188X

Open Access

Original Research Article

Synthesis of Liner Alkyl-benzene Sulfonate Nanoparticle Using Green

Promoter and High Efficiency

Meysam Rezaei*1, Reza Tarvirdi-zadeh2

1*
MA of Organic Chemistry, Responsible for Prototyping and Formulation, Raysun Oil Company,
Shams-Abad, Tehran, Iran
2
MA of Analytical Chemistry, Quality Control Manager, Raysun Oil Company, Shams-Abad, Tehran,
Iran

*Corresponding author Fax number: Tel.: +98 2156494659

*E-mail: rezaei_xy@yahoo.com

ABSTRACT
In this study, linear alkyl-benzene calcium sulfonate nanoparticles were made using linear
alkylbenzene. Calcium sulfonate nanoparticles are widely used as an additive in a variety of
engine oils and have cleansing, anti-wear and anti-oxidant properties and anti-corrosion
properties. In this method, a sulfonation set up was constructed and sulfonation reaction was
carried out both directly and indirectly with Oleum, which in the indirect method had better
yield and the amount of acid used was much less. Sulfonation was carried out on two types of
light and heavy alkylbenzene the calcification step was carried out with CaO, and then the
supernatural stage and carbonation with CO2 and CaO were performed for the first time with
Ethanol green promoter, and The Total Base Number amount of for calcium was measured at
different times. Carbonation time is very important and sensitive. In this research, residual
sediments were reused in the carbonation reaction, and excellent results were obtained. It was
also observed that the synthesis of linear calcium sulfonate nanoparticles with a high Total

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Base Number and a stable structure can only be carried out with heavy alkylbenzene C26. In
this work, linear calcium sulfonate alkylated benzene nanoparticles were made completely
transparent. (and) The Total Base Number 470, and the weight percent of calcium also
reached 17.4, and the nanoparticle stability was also tested using the standard ASTM D2273
method. This result compared with two commercially available linear calcium sulfonate
nanoparticles.

Keywords: Sulfonation, alkylbenzene, overbased, linear alkylbenzene calcium sulfonate,

Ethanol

1- Introduction
Linear alkylbenzenes (sometimes also referred as LABss) are a family(group) of organic
compounds with the (general) formula C6H5CnH2n+1. Typically, n lies between 10 and (to)
16, although generally supplied as a tighter cut, such as C12-C15, C12-C13 and C10-C13, for
detergent use. They are mainly produced as intermediate in the production of surfactants, for
use in detergent. Since the 1960s, LABs have emerged as the dominant precursor of
biodegradable detergents. Surfactants are usually organic compounds that are amphiphilic,
meaning they contain both hydrophobic groups (their tails) and hydrophilic groups (their
heads). Therefore, a surfactant contains both a water-insoluble (or oil-soluble) component
and a water-soluble component. Surfactants will diffuse in water and adsorb at interfaces
between air and water or at the interface between oil and water, in the case where water is
mixed with oil. A detergent is a surfactant or a mixture of surfactants with cleaning properties
in dilute solutions [1]. These substances are usually alkyl-benzene sulfonates, a group of
compounds that are similar to soap but are more soluble in hard water, because the polar
sulfonate (of detergents) is less likely than the polar carboxylate (of soap) to bind to calcium
and other ions found in hard water. Linear alkyl benzene sulfonate (LAS) is a highly
biodegradable surfactant that has been used in the United States (U.S.) since 1965 as a
replacement for branched alkyl benzene sulfonate. Linear alkyl benzene sulfonate represents
a mixture of homo-logs having alkyl chain lengths ranging from 10 to 15 carbon units with
isomers of varying phenyl position [2]. LAS is a conventional anionic detergent which is
used in about 80% of household detergent and can be considerably found in greywater [3].
LAS can be very toxic for marine life and result in foam formation in water resources [4].
Aromatic sulfonation is a very important chemical transformation of organic compounds [5].
Because of the diversity of feed stocks, no single process fits all needs. An acceptable

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sulfonation process requires [6] the proper reagent for the chemistry involved and the ability
to obtain high product yields; [7] consistency with environmental regulations such that
minimal and disposable by-products are formed; [8] an adequate cooling system to control
the reaction and to remove significant heat of reaction; [9] intimate mixing or agitation of
often highly viscous reactants to provide adequate contact time; products of satisfactory
yields and marketable quality; and acceptable economics [10]. So far, several methods have
been used for treatment of the greywater including physical approaches such as filtrations
[11] as well as chemical methods including photochemical oxidation [12] and
electrochemical process with iron oxides [13] and biological methods such as constructed
wetlands [14], membrane bioreactors (MBR) [15], Sequencing Batch Reactor (SBR) [16] and
Rotating Biological Contractors (RBC) [17]. For more than 100 years, for aromatics
sulfonation with SO3 in sulfuric acid or oleum or aprotic solvents a lot of experimental and
theoretical researches has been done and has formed a consensus popular mechanism in
organic chemistry textbooks [18]. Detergents are additives that are very important
components of engine oils. Since the 1950s, nanosized colloidal inorganic particles have been
widely used as detergents [19]. Detergent-dispersant agents consist, in different ratios, of
high molecular-weighted calcium (or barium) sulfonate, colloidal calcium carbonate, and
mineral oil (spindle oil) in accordance with the application area of lube oil [20] [21].
Sulfonates, well known for their high thermal stability, good detergency, rust inhibition, and
anti-wear properties [22, 23], are the most widely used surfactant for nanodetergents followed
by phenates, salicylates, phosphonates, and others [24] [25]. They are obtained from the
neutralization of corresponding organic acidic molecules using various readily available
alkaline or alkaline earth metals (sodium [Na], calcium [Ca], magnesium [Mg], and barium
[Ba]). Detergents with acid/base neutralization close to the same equivalent are called
“neutral” detergents. Ca salts are the most common detergent salts. Na salts are typically used
in industrial oil as emulsifiers. Mg salts have less sulfated ash than Ca salts for the same
alkaline reserve. This is desirable for low sulfated ash, phosphorous, sulfur (SAPS) engine
oils. MgCO3 is less basic and neutralizes acid slower than CaCO3, and Mg salts maintain the
alkaline reserve better than Ca salts [20] Mg salts are usually used in combination with Ca
salts as detergents in engine oils[26]. Mg salts are also used as fuel additives for corrosion
control for vanadium-containing fuels in gas turbines [27].

2. Materials and methods

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2.1 Chemicals and reagents

LAB (C18 & C26) Toluene, CaCl2, CaO, Oleum 65 % (SO3), Zero air cylinder. The
chemicals applied(used) in this work were obtained from Merck & Sigma-Aldrich companies
(and used) without further purification. Total Base Number of the products were recorded on
a Metrohm Swiss made 848 Titrino Plus and are uncorrected. FT-IR spectra were recorded on
a Perkin Elmer Model Spectrum Two. Elemental Analysis of the products were reported with
Spectro Scientific Model Spectroil Q100 (ASTM D 6595).
2.2 Method
In this study, sulfonation was initially performed on two samples of alkyl-benzene with
carbon-18 and 26 branches. The sulfonation process was initially performed with direct
addition of oleum. The reaction time and the amounts consumed in Table 1 and 2 are
presented. Elemental analysis of the samples before and after calcination and TBNs are listed
in the following tables.

Table 1. results of sulfonation and calcination

(Table a. results of sulfonation and calcination LAB C26 and Table b. results of sulfonation
and calcination LAB C18)
Table a Table b
Entry Oleum% ppm S ppm TBN Entry Oleum% ppm S ppm TBN
Ca Ca
1 6 3376 2100 0.4 1 5 3669 2301 0.61
2 10 4643 2907 0.59 2 10 4932 3079 0.73
3 15 5779 3618 1.05 3 15 6043 3762 1.07
4 30 11144 6948 2.6 4 20 11697 7301 1.89
5 40 22279 13900 4.7 5 25 23355 14600 3.78
6 50 41204 25706 9.01 6 40 44325 27695 5.74
7 60 60412 37680 13.43 7 50 64204 40108 6.83
8 70 60445 37504 13.45 8 55 64280 40104 6.65

As you can see, plenty of oleum is used to sulfone, and on the other hand it has a lot of waste.
Also, a large amount of solvent has to be used to purify it, so we decided to make a small
laboratory sulfonation set up, with a very low cost for it. All design and construction of this
set up was carried out inside the Raysun Oil Company. You will see the schema below.

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Air
Compressor
Acid Tank
Reducing (Oleum)
Valve
Pressure
Gauge

Air drier

SO3 And Air

Reactor Flow

Producer SO3 And Mix

With Air
Recycle
Flow

Shower

Product

Scheme 1. Sulfonation set up

The body of the tanks is all made of steel, because the oleum is a very bad environmental
substance. This set up was tested for sulfonation of LAB C26. In this study, SO3 sulfonation
method was used. The completion of the reaction was detected using TLC paper. As shown
in Fig. 2, this method has very low losses and can be said to be close to zero. The resulting
Calcination of LABS from this step was using CaO 10% higher than the stoichiometric value,
which was done to ensure that all LABS were used up in reaction complete. To calcify in
addition to CaO 1% CaCl2 was also added Because calcium oxide always contains some
impurities in the form of sodium magnesium and other metals that interfere with the reaction.
The best way to remove them is to use calcium chloride, which is used in the calcination
reaction.

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INTERNATIONAL JOURNAL OF NEW CHEMISTRY, 2019, 6 (2), 76-86 M. REZAEI ET AL

Scheme 2. Calcination of LABS

Times Roman, 12 font size, 1.5-spaced. Authors should be design manuscript in one-column
and space between columns must be 0.5.
First of all, to prepare calcium sulfonate from above. A sample of 18-carbon alkyl-benzene
was used and its calcium sulfonate content was 127.8 and which had the highest TBN in this
study, but the resulting product was turbid and was not soluble in mineral and synthetic oils.
The results are presented in the table.2 below.

Table 2. Results of time Vs. TBN from carbonation reaction (LABSCa C18)

Time
Entry TBN appearance
(min)
160
1 5 35.7 Opaque brown
120
10 67.1 Opaque brown
TBN

2 80

3 15 101.3 Opaque brown

40
4 20 127.8 Opaque brown
0
5 25 119.3 Opaque brown 0 10 20 30 40

30 77.1 Opaque brown Time (min)

6

7 35 64.9 Opaque brown

Then, to obtain the desired product, 21 gr of LABSC26 was digested and supplemented with
Nano Particle of alkylbenzene calcium sulfonate and again reacted with 3.5 gr CaO and CO2
gas in the presence of Ethanol as a promoter. At this stage the amount of CO2 injection is
very important because if it is too much the excess amount of CO2 will change the size of the
nanoparticles and thus reduce the TBN and the amount of calcium as well, and that is why the
color as become cloudy.

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Detergent Nanoparticle

CaCO3 Nanoparticle

CaCO3 Hard
Core

Scheme 3. Structure of linear alkyl-benzene calcium sulfonate nanoparticles

You can see in the table.3, the results of the above-mentioned reaction can be seen. This
reaction was performed with constant CaO and CO2 gas flow using a CO2 capsule using a
constant current flow meter of 6 Nl / h. In this process, we tested the samples at different
times and got the best time of 35 minutes.
Table 3. Results of time with total alkali by carbonation reaction (LABSCa C26)

Entry Time TBN Appearance

500
1 5 40 Transparent red
2 10 86.1 Transparent red 400

3 15 143.7 Transparent red 300

TBN

4 20 198.6 Transparent red

5 25 268.7 Transparent brown red 200

6 30 401.4 Transparent brown red 100

7 35 469.8 Transparent brown red
0
8 40 441.7 Transparent brown red
0 10 20 30 40 50 60
9 45 320.3 Transparent brown red
Time (min)
10 50 231.1 Opaque brown

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3. Results and Discussion

According to the results, it can be said that in alkylbenzene C18 is shorter than the length of
the chain, and the polarity of the molecule is high, which causes it to become clouded and not
mixed in the base oil, and also causes carbon dioxide injection the formation of the Micelle
structure becomes smaller and more unstable. But in alkylbenzene C26 due to the bonding of
the carbon chain and less polarity, there was no problem in the dissolution and instability of
the Micelle in this study, high efficiency sulfonation was performed and this method has the
least waste and good yield. There was no waste at the stage of making linear alkylbenzene
calcium sulfonate nanoparticles, and in this reaction for the first time, Ethanol was used as a
green promoter; in green chemistry, we are looking for ways to reduce and prevent pollution
in the environment. Green chemistry tries to develop a pathway to design and modernize
products and processes that eliminate or reduce environmental damage]28[. Research in
Green Chemistry to reduce energy use to produce manufactured products The requirement for
drugs, colors and other chemical products [29] or to reduce the damage to the materials and
processes used in the production of these products, in the book Anastas & Warner, the 12
principles referred to the 12 principles of Green Chemistry and one of its most famous
principles is the use of solvents and healthier reaction conditions ]30[ that the replacement of
green solvents rather than toxic organic solvents and volatilization is very important among
the Ethanol green promoters due to the cheap and easy to prepare and availability and non-
renewable, and has no pollution for the environment.
In this method, the TBN for the final product was 469.8 and the percentage of calcium was
also determined by elemental analysis (17.4%). As you can see in Table 4, the results of this
study are compared with several other studies.
Table 4: Comparison of several examples of research done
TBN % Ca
€Solvent reference
(mg KOH/g) (w/w)
274 30.4 Monoethanolamine ]31[
from 300 to 420 -- n-Butanol ]32[
416 about 15.5 (NH4)2CO3 ]33[
400 --- Methanol ]34[
469.8 17.4 Ethanol In this study

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The product was compared using a FT-IR device with two commercial samples (HY BASE
C-402) and (Chinese Sample, and it was found that the sample was made both in terms of
color and in terms of the spectrum given completely with the sample HY BASE C-402
(Chemtura) is the same. The product was also tested for stability. This test was carried out
using standard ASTM D2273 method, which showed no sediment.
Also, FT-IR spectrum was taken from them and compared with each other. Which shows that
the sample made with the Chemtura sample is very similar

Scheme 4. FT-IR spectrum

In this study, high efficiency sulfonation was performed and this method has the least waste
and good yield. There was no waste at the stage of making linear alkyl-benzene calcium
sulfonate nanoparticles, and the Ethanol was used as a green promoter, following the twelve
principles of green chemistry. In this study, we collected all waste deposits and placed them
in a furnace at 500 °C to remove water and organic compounds, and again used it for the

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reaction, and did not cause any disturbance in the final results and was like a pure CaO
sample.

Acknowledgments

In this research, we thank Mr. Seyed Ali Shahmoradi, CEO of Raysun Oil Co., for financial
support. We also appreciate the of the unit of repair and maintenance that helped us in
construction of sulfonation set up.

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