Journal of Industrial and Engineering Chemistry 23 (2015) 154162

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Journal of Industrial and Engineering Chemistry

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Application of Iranian nano-porous Ca-bentonite for recovery of

waste lubricant oil by distillation and adsorption techniques
Shiva Salem a, Amin Salem b,c,*, Aylin Agha Babaei d
a

Faculty of Chemical Engineering, Urmia University of Technology, Urmia, Iran

Mineral Processing Research Center, Chemical Engineering Department, Sahand University of Technology, Tabriz, Iran
c
Center of Excellence for Color Science and Technology, Tehran, Iran
d
Faculty of Engineering, Islamic Azad University South Tehran Branch, Tehran, Iran
b

A R T I C L E I N F O

Article history:
Received 9 February 2014
Accepted 4 August 2014
Available online 13 August 2014
Keywords:
Waste lubricant oil
Adsorption
Bentonite
Acidication
Nano-pores

A B S T R A C T

The nano-porous adsorbents were initially produced by acid treatment of natural clay. The effects of
some important factors such as acid type, concentration and residence time were evaluated on porous
structure of adsorbent. A reduction about 2.7 A was observed in the distance of montmorillonite layers
due to replacement of hydrogen ions in the presence of sulfuric acid. The number of nano-pores, 12 nm,
was preferable for removal of contaminations from spent engine oil, depending on the activation agent
type in the treatment process. The results are very promising for reduction of adsorbent content in the
regeneration of waste lubricant oil.
2014 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights
reserved.

Introduction
Engine oil is an important lubricant that is extensively used in
the cars for lubrication, cooling and sealing of motor. The chemical
analysis of lubricant oil depends on the source of crude oil and
manufacturing method. The technical characteristics of oil are
controlled by blending base oil with a few percent polymers such
as polyalphaolenes and polyisobutene [1,2]. Moreover, the other
additives are used in composition of engine oil to neutralize acids
generated during the combustion and reduce corrosion [1].
Though, the modern cars have only a very small loss of oil under
normal operation condition, a certain amount of lubricant is
degraded, limiting the life time of oil consequently.
The waste oil is contaminated by impurities obtained from
undesirable oxidation product, sediment, metallic wear particles
and water, degraded additive and hazardous substances from lead
compound [3]. During operation of engine, the oil temperature
increases leading to degradation and change in the important
properties such as density, viscosity, ash point, etc. Regardless of

* Corresponding author at: Mineral Processing Research Center, Chemical

Engineering Department, Sahand University of Technology, Tabriz, Iran.
Tel.: +98 4123459159; fax: +98 4123454335.
E-mail address: salem@sut.ac.ir (A. Salem).

these variations in the oil characteristics, the metal particles are

deposited in the oil. As time passes, the engine oil loses the
functional properties and it must be replaced with fresh oil.
The contaminants in waste oil can induce a variety of diseases in
humans through inhalation, ingestion and skin contact. The waste
oil causes different type of illness, especially skin cancer. These
effects can be related to the presence of toxic materials.
Particularly harmful metals that remain in the waste oil include
lead, cadmium and chromium. Some of the impurities are formed
by incomplete combustion of organic matter. Combustion of fuel
containing carbon and chlorine can produce a wide range of
organo-chlorine compounds. The pollution of natural water,
accumulation in the agriculture products and foods result in
adverse effects on human health [4].
Due to the high cost of crude oil, the countries try to nd out the
alternative ways for fuel production. Thus, there is a great scope to
manufacture fuel from waste engine oil which would help to
decrease environmental problems, save waste oil disposal fees and
reduce burden of fuel import [5,6]. By considering the quantity of
waste oil produced daily in the world, it is necessary to develop the
recovery processes. The engine oil is a very important material and
the recovery process for recycling of oil is an efcient technique [7].
On comparing characteristics of rened base oil with waste, it is
observed that the recovery of used oil is responsible with respect to
producing fuel. Recovery of waste engine oil is a regeneration

http://dx.doi.org/10.1016/j.jiec.2014.08.009
1226-086X/ 2014 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights reserved.

Sh. Salem et al. / Journal of Industrial and Engineering Chemistry 23 (2015) 154162

process in which the obtained oil can be used again. The choice of
regeneration technique to achieve base oil is determined by the
nature of waste, cost and environmental considerations. Usually,
both mechanical and physico-chemical processes are required for
deep purication. The physical method includes removal of dirt,
sand and metal particles. The centrifugation, settling and ltrations are classied into mechanical techniques. Regarding physicochemical techniques, many advance methods such as supercritical
separation [8], microwave pyrolysis [9,10] and catalytic process
[11] can be used for the removal of toxic materials from used oil. All
these procedures have signicant disadvantages because of
incomplete removal, high energy requirements and inapplicability
in the industrial scale. These techniques also have different yield
and product quality, construction and operational cost.
Waste engine oil usually is collected in garages. In some cases
gasoline is used for cleaning the transmission parts. Therefore,
mixing gasoline with waste oil into the same container is
unavoidable. Even small amounts of gasoline or other solvents
may result in a low ash point and increase in the explosion risk
during rening process. Before storing waste oil in tank, the water
content, solids, ash and pour points, etc should be tested.
Distillation, solvent extraction, adsorption and hydro-treating
are preferred process because of high efciency and low cost as
well as applicability in practice compared to advance techniques
[11]. Optimization of recovery factors should be considered to
achieve either maximum sludge removal or minimum oil losses.
Water is removed from the waste oil by dehydration. Thus, the
waste oil is distilled up to 100 8C. The vacuum distillation is used to
eliminate the light hydrocarbons. The pre-treatment process for
rening waste oil consists of two steps. In the rst step water and
light hydrocarbons are evaporated. After this step the dehydrated
oil is treated by vacuum distillation [7].
Traditionally, the automobile waste oil can be rened through
vacuum distillation, acid and bleaching treatment [12,13]. As the
chemical treatment creates environmental problems, distillation,
adsorption and solvent extraction were proposed as alternate
methods. The solvent extraction treatment has received considerable attention in recent years, because it overcomes the problems
associated with acid sludge produced from chemical treatment.
Solvent could be recovered by distillation, but the regeneration
process is expensive and huge content of liquid should be
distillated to separate oil and solvent. Recently, waste oil has
been rened by vacuum distillation with chemical treatment or
clay adsorption due to low manufacturing cost [13].
The characteristics of rened base oil obtained by vacuum
distillation and solvent extraction showed that these processes are
good techniques for the removal of contaminants from used oil and
to enhance the desired properties [14,15]. The performance of
2-propanol, 1-butanol and methyl-ethyl-ketone, MEK, in recycling
used oil was evaluated experimentally [1618]. The results show
that the solvent extraction technique is efcient process in
recovery of waste oil. The lowest percent oil loss as well as the
best performance was achieved by the use of MEK. Extraction by
MEK and n-hexane followed by adsorption on magnesite gives the
lowest color index oil. This system however uses two solvents and
thus requires two solvent recovery steps [19,20]. The color of oil is
related to the nitrogen, sulfur and oxygen compounds and
impurity fractions. The amounts of saturated compounds are
increased due to hydro-treating of oil and this process can be
considered as nal stage for stabilization the color of product [13].
Several materials have been used for regeneration of waste
engine oil as an adsorbent [21,22] such as magnesite [19], silica gel
[23], charcoal [24], date palm kernel powder [25], kaolin [26] and
natural and activated bentonites [27,28]. It is important to note
that the removal efciency of low cost adsorbents depends on the
material characteristics and surface modication. Overall, the

155

technical applicability and cost effectiveness are two key factors in

the selection of suitable adsorbent for treating waste oil.
Calcium bentonite is widely used in clarifying and purication
of liquids such as liquors and oils due to their large specic surface
area. This material is preferred to use as an adsorbent because of its
porous structure and maintaining impurities. The properties of
bentonite are function of montmorillonite amount which determines quality of raw material as well as the specic surface area
[29]. Also, the other crystals, which exist in natural bentonite such
as cristobalite and opal CT, inuence the adsorption capacity. The
control of bentonite composition is necessary to get reliable
performance in the industrial applications. The montmorillonite
structure is classied as dioctahedral, having two-thirds of
octahedral sites occupied by trivalent cations. The charge of
dioctahedral montmorillonite is originated from the substitution
of Mg2+ in the octahedral sheet. The idealized structural formula
for montmorillonite is M+ynH2O(Al2yMgy)Si4O10, where M is a
cation [30]. The negative charge is balanced by cations intercalated
between structural units. These cations may be alkali earth ions
such as Ca2+ or the alkaline metals such as Na+. When Ca2+ cations
are exclusively exchanged in montmorillonite, the clay is known as
Ca-montmorillonite.
The application of bentonites in production of selective
adsorbents, bleaching earth, catalyst beds, carbonless copy paper
and medication depends on the pore structure of montmorillonite.
If the pore diameters are smaller than 2 nm, these are called micropores. If their sizes are between 2 and 50 nm, these are called
meso-pores. Also, the material is named macro-porous if their sizes
are larger than 50 nm. The adsorption capacity of the macroporous materials is at a negligible level compared to that for the
micro- and meso-porous adsorbents [31].
The most commercial used process for manufacturing Cabentonite with high specic surface area is acid treatment. The
activated bentonites are usually used as an adsorbent in the above
applications [32]. Activation is the chemical treatment applied to
certain types of clay to develop their capacity to absorb coloring
matters and other impurities in the oils. The acid treatment of
bentonite is carried out in a continuous stirred tank reactor at low
temperatures between 70 and 110 8C. During the activation
process, considerable amount of Ca2+ located between the layers
were substituted by H+ [33]. This variation in montmorillonite
layers leads to signicant changes in cation exchange capacity,
CEC. Also, the specic surface area of bentonite can be affected by
acid solution due to decomposition of clay mineral structure. As
bentonite is held in the acid solutions, the pores are developed
within the clay microstructure [33]. The formation of new pores
allows increasing the specic surface area compared to its original
value [31]. As activation progresses, Al3+, Mg2+and Fe3+ leave the
octahedral layers and the cationic spaces remain empty [34].
Because of the favorable physicochemical characteristics, the
activated bentonite is widely used in regeneration of waste
lubricating oils.
The commercial interest in treatment of waste engine oil is
accompanied by a scarcity of knowledge about relationship
between bentonite activation factors and adsorption in recovery
process. Although it is possible to nd in the literature several
papers on used oil treatment as explained above, they are mainly
focused on processing feasibility of different techniques and
adsorbents. The relationship between the activation factors and
technological properties of rened oil has not been well-studied
and the articles were focused on yield and efciency of different
low cost adsorbents. The effect of activation factors on technological properties of oil rened by distillation and adsorption process
has not been previously investigated, leaving signicant opportunities for research in this area. The present work is part of a more
extensive study with two main objectives. First, is to establish the

156

Sh. Salem et al. / Journal of Industrial and Engineering Chemistry 23 (2015) 154162

effect of activation factors on physical and technological characteristics of Iranian Ca-bentonite and, second, to study the effect
of activation factors on the regenerated oil characteristics. For this
purpose, it is very important to have knowledge about the behavior
of natural bentonite during acid treatment. With this aim, the
following criteria were considered. The selected natural adsorbent
is a conventional composition that is applied by Iranian oil
recovery factories without activation. From the environmental
point of view, the increase in content of used adsorbent has a high
hazardous potential. The optimization of acidication process
should lead to the minimum consumption of adsorbent. For this
reason, the natural bentonite was activated with different
concentrations of nitric and sulfuric acids. Also, the effect of
residence time was evaluated on activation and regeneration
processes.

The adsorption ratio was determined from the amounts of

MB need to reach the end point for activated and natural clays
[36].
In order to characterize the chemical composition of natural
and activated clays, the inductive coupled plasma atomic emission
spectroscopy (Model 785, Varian Inc, Santa Clara, CA, USA) was
applied. The crystalline phase evaluation was carried out by X-ray
diffraction analysis using a diffractometer (Model D-5000,
Siemens, Karlsruhe, Germany) with Cu-Ka radiation. The molecular vibrations of the resulting powders were evaluated by Fourier
transform infrared spectroscopy (Model Unicam Mattson 1000,
Philips, Almelo, The Netherlands). The specic surface area, pore
volume and average pore size of powders were measured from
low-temperature nitrogen adsorption isotherms, using a Quantachrome instrument (Model Chem-BET 3000, Boynton Beach, FL,
USA).

Experimental
Distillation of waste engine oil
Clay activation process
The natural clay used in this study is from Soltaniyeh situated
on the highlands in the Western region of Iran. Soltaniyeh is a
district in Abhar county, Zanjan province. The raw material, which
is widely used as a bleaching earth in Iranian food and petroleum
industries, was procured in ground form with the maximum grain
size of 75 mm. The activation process was carried out in a smallscale batch setup. For this purpose nitric, 65.0 wt.%, and sulfuric,
98.0 wt.%, acids were applied as received. Dry bentonite powder
and acid solutions with concentrations of 0.5, 1.0, 1.5 and
2.0 mol l1 were separately prepared and heated up to 80 8C into
three-neck ask. The experimental setup consisted of a 1000 ml
ask equipped propeller mixer, condenser and thermometer.
Eighty grams of dry bentonite was added to 500 ml acid solution
and mixed thoroughly into the ask. The samples prepared as
explained above, were activated during 15, 30, 45, 60, 90 and
180 min. The ask containing suspension was heated using
laboratory water bath and the temperature was controlled by a
thermometer. The zero time was counted when the suspension
temperature reached to desired temperature. The temperature of
activation environment was continuously monitored to keep it in
80  1 8C. After acidication, the mixture was ltrated and washed
with de-ionized water in order to remove any excess acids and
released ions. Finally, the washed clay was dried in an oven at 60 8C
for 1 day and ground to obtain particles smaller than 75 mm.
The adsorption ratio of activated powders was measured by
methylene blue, MB, adsorption as the following procedure
[35,36]. MB powder (Merck 6045 Germany) was used in this
study. The chemical formula of MB is C16H18ClN3S with a
corresponding molecular weight of 319.86 g mol1. MB molecules dissolve in aqueous solution as cationic dye, C16H18N3S+,
which is a large polar organic cation and is absorbed onto the
negatively charged surfaces of clay minerals. Hence, the
adsorption ratio can be determined by the amount of MB
absorbed onto natural and activated clays. The amount of MB
absorbed by given mass of clay depends on negative sites on the
clay particles. The MB solution was prepared by mixing 1.0 g of
dry powder with 200 ml of de-ionized water. The clay
suspension was also obtained by mixing 2.0 g of oven-dry clay
with 120 ml of de-ionized water. The MB solution was added to
the clay suspension in 0.5 ml increments. After mixing suspension, 1520 min for the each addition of MB, a small drop of it
was removed and placed in Fisher brand lter paper P5. MB ions
coat the clay mineral surfaces and the end point is obtained
when the unabsorbed MB forms a permanent light blue halo
around the clay aggregate spot. The entire experimental
procedure was found to give satisfactory reproducible results.

Waste motor lubricating oil was collected from different local

garages and service stations in Tabriz city. The lubricating oils of
cars were changed after at least 6000 km in use and mixed in a
single container, industrially. It was stored for several days for
sedimentation of suspended particles by gravity. Waste oil
treatment using dehydration and distillation causes the removal
of volatiles at low temperatures. Distillation is adequate to produce
the volatiles as a fuel from waste. Also, this technology can
signicantly reduce water and fuel content in the waste oil to limit
the ash content seriously. Along with settling, decanting and
ltering, distillation is used to treat waste oil in the most of
regeneration units. The dehydration of waste oil was performed in
a simple batch distillation to eliminate water and light hydrocarbons. Water and gasoline fractions were separated at 200 8C.
Distillation was carried out at 400 8C until no further distillate was
produced. The obtained oil was sent to the next steps that involve
the adsorption and ltration for further treatment.
Waste engine oil recovery
For regeneration of distillated oil and evaluation of activation
factors, the adsorption was performed by mixing different content
of natural and activated clays from 30.0 to 45.0 wt.%. Adsorption
was carried out to improve color and technical characteristics of
oil. Different content of adsorbents were added to 80 g distillated
oil and mixed for 1 h by magnetic vibrating mixer. The suspensions
were left at room temperature for 1 h to allow gravity for
sedimentation. The decolorized oils were separated from the
adsorbent by a lter paper (Whatman, 40).
The color evaluation was conducted using UVVisible spectroscopy (Model UV-1700 Pharma Spec, Shimadzu, Kyoto, Japan)
by scanning the rened oils at the visible region. The structures of
the resulting oils also were evaluated by Fourier transform infrared
spectroscopy (Model Unicam Mattson 1000, Philips, Almelo, The
Netherlands) in the wave number of 4004000 cm1.
Specic gravity of regenerated oils was measured by a
pycnometer. The kinematic viscosity of oils was determined by
a capillary viscometer at 40 and 100 8C [37]. The temperature of
instrument was controlled by the parafn bath at mentioned
values.
The ash point is the lowest temperature in which the ignition
of produced vapor is observed. Fifty milliliters of regenerated oil
was placed into an open cup and the temperature was increased
slowly, near the ash point. At specied intervals, a ame was
passed across the cup. This temperature is the ash point [38]. For
the measurement of pour point, the oil was cooled at a constant
rate and examined at the specied intervals to observe the ow.

Sh. Salem et al. / Journal of Industrial and Engineering Chemistry 23 (2015) 154162

1.2
Activated by H2SO4
Activated by HNO3
1
Adsorption ratio

It is the lowest temperature in which the movement of oil is

recorded [39].
For the measurement of ash content, the rened oil was
contained in a ceramic cup and heated up to 775 8C in an electrical
kiln, allowed to burn until only ash and carbon remained. It was
cooled and weighed to calculate the ash percentage [40].
Total acid number, TAN, is the weight of potassium hydroxide
required to neutralize the rened oil. The usual major components
of such materials are organic acids. TAN is an important factor for
lubricant engine oil quality for denition oxidation. Fifty milliliters
of ethanol was weighed into a baker in which a phenolphthalein
indicator was added and heated to 40 8C. The used alcohol was
neutralized with potassium hydroxide solution, 0.50 N. The
neutralized alcohol was added to 10.0 g oil and then stirred to
ensure complete extraction of acid by alcohol. Two drops of
phenolphthalein solution was added and the mixture was titrated
with potassium hydroxide solution, again. TAN can be calculated
by the following equation:

157

0.8

0.6

0.4
0

0.5

1.5

2.5

-1

Acid concentration (mol.l )

NA V KOH
W Oil

(1)

where NA is the normality of KOH solution, VKOH the volume of KOH

solution used and WOil the weight of oil [41].
The alkaline base materials are added to engine oil for
neutralizing the acidic products. The total base number, TBN, is
a factor for the replacement of oil after specic time. TBN
measurement involves titration of lubricant oil dissolved in a
mixture of solvent such as chlorobenzene and glacial acetic acid
with a titrant such as perchloric acid in glacial acetic. Hundred
milliliters of rened oil was weighed into a beaker and 2.0 g
titration solvent was added. After mixing oil and solvent, the
mixture was titrated with perchloric acid in glacial acetic acid,
0.10 N. For visual determination, two drops of para-naphtholbenzein indicator is added to the mixture before titration. The end
point of titration is identied if the orange color changes to green
or brown green. A blank titrant is prepared by adding 10 ml of
titration solvent into a beaker without any sample and then
titrated. TBN can be calculated as follows:
TBN 56:1

N T V T  V B
W Oil

Fig. 1. The adsorption ratios of activated clays versus acid concentration.

1.1
Activated by H2SO4: 1.00 mol.l-1
1

Activated by HNO3: 1.00 mol.l-1

0.9
Adsorption ratio

TAN 56:1

0.8
0.7
0.6
0.5
0.4
0

(2)

30

60

90

120

150

180

210

Residence time (min)

where NT is normality of the titrant, which is equal to 0.0641 in this

research, VT the volume of titrant used for titration of rened oil
and VB the volume of titrant used for blank titration [41].

Fig. 2. The adsorption ratios of activated clays versus residence time, acid
concentration: 1.00 mol l1.

Results and discussion

reduces to minimum value. The adsorption of MB rapidly falls

down initially and then remains constant between 30 and 60 min.
Beyond 60 min, the adsorption ratio decreases slowly and there is
no signicant reduction in the MB uptake. The maximum
adsorption ratio was achieved during 15 min and it is independent
on activation agent type. The adsorption of MB onto modied
adsorbent surface is favored when the clay is treated by nitric acid.
Based on the above results, the activation time plays a vital role in
this system. In general, an increase in the time leads to reduce in
MB adsorption.
The chemical analysis of natural bentonite is reported in
Table 1. The clay consists of silica and alumina. In particular, the
material shows the low Al2O3/SiO2 ratio, 0.18, while it is
characterized by comparable amount of CaO + MgO, 7.57 wt.%.
This material is Ca-bentonite since the content of calcium is higher
than the amount of sodium. The used clay also displays the low
proportion of alkali oxides, 1.06 wt.%. Also, the low content of iron
oxide was found in raw material. The noteworthy amounts of other
elements are observed in bentonite. The effect of acid type on
leaching process is also investigated by obtaining chemical

Natural and treated clays characterization

The adsorption ratios of activated clays versus acid concentration were plotted in Fig. 1. As the sulfuric acid concentration rises,
the value of adsorption ratio decreases linearly up to a minimum
value. As the concentration of acid increases from 0.50 to
1.00 mol l1, the acid attacks the structure of clay minerals;
therefore, the reduction in adsorption ratio is observed. This
phenomenon shows that the concentration of acid is a very
important parameter in the acidication. The identical behavior in
the nature of the plots is observed when activation is carried out in
the presence of nitric acid. The adsorption is highly dependent on
activation agent type, which affects the clay structure.
The effect of residence time on the adsorption ratio was also
investigated in the range of 15180 min as presented in Fig. 2. For
evaluation of residence time effect, the acid concentration kept
constant at level of 1.00 mol l1. When the time is increased, the
adsorption ratio of clays treated by sulfuric acid non-linearly

Sh. Salem et al. / Journal of Industrial and Engineering Chemistry 23 (2015) 154162

158

Table 1
The chemical composition of natural and activated clays (wt.%).
Adsorbent

SiO2

Al2O3

K2O

Na2O

CaO

MgO

Fe2O3

L.O.Ia

Natural bentonite
Activated clay by HNO3
Activated clay by H2SO4

67.72
70.95
67.21

11.89
12.53
11.69

0.77
0.38
0.55

0.29
0.19
0.24

4.20
0.89
2.59

2.50
1.68
1.60

0.83
0.84
0.61

11.57
12.38
15.33

Loss on ignition.

analyses of activated bentonite as reported in Table 1. The

activation was performed by acid solutions in which the
concentration was 1.00 mol l1. Also, the residence time was
considered to be 30 min. The acid treatment modied the structure
of bentonite as indicated by the change in the chemical
composition. The both acids showed signicant effects on chemical
composition. Higher acid concentration enhances the removal of
alkaline earth elements, but nitric acid exerts a major inuence on
Ca content. When the nitric acid solution is applied for activation,
the chemical composition is affected signicantly. The application
of sulfuric acid in activation process did not promote the extraction
of Ca in comparison to that by nitric acid solution. It is expected
that the exchangeable cations such as Ca2+ and Mg2+ are removed
during the acid treatment. However, some parts of these elements
remain in the activated clays. The increase in SiO2 and Al2O3
content, in the clay activated by nitric acid, is accompanied by
decrease in content of CaO + MgO. H2SO4 is inefcient in removal
of Ca from clay mineral structure in comparison to HNO3. The iron
oxide content of clay activated by HNO3 is very low compared to
that for natural clay. It is obvious that the amount of Mg in
octahedral sheet decreases considerably in the presence of acids.

It is assumed that the chemical changes occurred in the structure of

clay minerals due to acid treatment lead to vacancies in the crystal
lattice. It is expected that the number of empty spaces in the clay
activated in the presence of nitric acid is higher than that in the
clay activated by sulfuric acid. In order to provide charge
equilibrium, the protons of acids are replaced with the exchangeable cations, such as Ca2+, which are presented between the layers.
However, the protons cannot ll all the empty spaces left by ions
such as Mg2+ that had occupied the octahedron positions; hence,
the number of vacancy increases considerably.
The mineralogy of the natural bentonite and activated clays is
shown in Fig. 3. The acid treatment was carried out by
concentrated nitric and sulfuric acids, 1.00 mol l1, during
30 min. The XRD pattern of natural clay indicates the substantial
amount of montmorillonite in the bulk material. The raw material
predominantly consists of cristobalite as a major impurity, as well
as trace amounts of feldspar. The term cristobalite is used because
the international diffraction data for the silica admixture shows
that the sample is more indicative for cristobalite than the
other silica phases. The activation by nitric and sulfuric acids
was unsuccessful in removing cristobalite. The acid treatment

Fig. 3. The XRD patterns of natural bentonite and clays treated by concentrated nitric and sulfuric acid solutions.

Sh. Salem et al. / Journal of Industrial and Engineering Chemistry 23 (2015) 154162

introduces some changes into the crystal structure of bentonite.

The main reection is observed in the region of 48 < 2u < 88. This
peak corresponds to diffraction angle of 5.968, in which the interlamellar distance was found to be 8.7 A. The intensity of
montmorillonite peak decreases due to acid treatment by H2SO4
and yields peak spacing, which was absent in the XRD pattern of
clay activated by HNO3. After activation by sulfuric acid, the
position of mentioned peaks (0 0 1) is shifted. This implies changes
in the regular pattern of the montmorillonite along with partial
destruction compared to the original material. The decrease in the
interlayer region, 2.7 A resulting from the acid treatment, can be
attributed to the exchange of Ca2+ with H+. The increment in loss on
ignition, L.O.I in Table 1, is due to substitution of H+ in interlayer
spaces. It can also be observed that the characteristic peaks
corresponding to gypsum appeared after acid activation by sulfuric
acid, whereas feldspar is not destroyed, indicating that feldspar is
resistant to acid attack. The XRD characterizations show that the
structural properties of montmorillonite are not fundamentally
inuenced by treatment with HNO3.
The FTIR spectra of raw and activated clays were carried out in
the range of 4004000 cm1 to study the effects of acids on the clay
structure. The FTIR spectra of natural and activated bentonites are
illustrated in Fig. 4. In the OH stretching region, the natural clay
shows that the two prominent bands at 3632 cm1 correspond to
AlOH and MgOH vibrations. The hydroxyl groups, lying between
the tetrahedral and octahedral sheets give the absorption around
3632 cm1. The wide band observed at 3454 cm1, assigned to the
high amount of water physically absorbed by the clays. The peak at
wave number of 1640 cm1 is related to the bending vibration of
physically absorbed water. The infrared spectrum of the natural
clay reveals the presence of SiO2. The band at 798 cm1 can be
ascribed to cristobalite. The spectrum shows intensive band at
1090 cm1 attributed to the hydrous SiO stretching vibrations.
The band at 626 cm1 is identied as a vibration in the octahedral
layers such as AlOSi and MgOSi. The bands at 520 and
477 cm1 were assigned to SiOAl and SiOSi bending,
respectively. There are no considerable changes in the FTIR spectra
of clays activated by nitric and sulfuric acids.
The physical properties of natural bentonite and activated clays
are presented in Table 2. The measured value indicates a very low
specic surface area and volume for untreated bentonite and these
properties are improved when activation is carried out in the
presence of HNO3. Although the specic surface area of activated

Fig. 4. The FTIR spectra of natural bentonite and clays treated by concentrated nitric
and sulfuric acid solutions.

159

Table 2
The physical properties of natural and activated bentonites.
Adsorbent

Specic
surface
area (m2 g1)

Pore
volume
(cm3 g1)

Average
pore
size (nm)

Natural bentonite
Activated clay by HNO3
Activated clay by H2SO4

31.8
81.6
76.9

0.093
0.230
0.220

11.7
11.3
11.5

clay is higher than untreated clay, the difference is approximately

50 m2 g1. It returns to reactivity of acid with clay crystal in which
the surface area increases mainly in the edge area of crystals. The
rises in specic surface area and volume are result of unoccupied
octahedron spaces remaining from Mg2+ cations that leave the
layers of montmorillonite. As the activation progresses, the empty
spaces grow larger and micropores are transformed into mesopores, 12 nm. It is obvious that the average pore size approximately remained constant but the number of nanopores is higher
in the treated clays. This factor is the main reason, entailing
considerable increase in empty spaces when HNO3 is used.
Therefore, the adsorption of MB is remarkably affected by acid
type. The predominant MB retention mechanism is due to cation
exchange [42]. The broken MgOH bonds of clay crystals results in
the increment of negative charge in the clay structure and the MB
cations can easily adsorbed on clay surface, consequently.
Regenerated oils evaluation
For the regenerated oils, the UVVisible spectra were obtained
between 200 and 1200 nm. The comparison between the UV
absorbance peaks is made to determine which oil was well rened.
Fig. 5 indicates the effect of adsorbent content on the colorant
behavior of rened oil. Different amounts of natural clay were
added to distillated oil. The adsorption is highly dependent on
adsorbent content which affects the UV absorbance. A peak at
wavelength of 530 nm was observed in the spectrum of oil
regenerated by 30 wt.% natural clay. The maximum absorbance at
wavelength of 510 nm is seen in the patterns of oils rened by 40.0
and 45.0 wt.% bentonite. The peak intensity of oil recovered by
maximum content of bentonite is lower than the others. As shown
in Fig. 5, the oil color was not changed signicantly and remains
dark when the content of natural clay is less than 40.0 wt.%. The
blackness of oil could be due to the formation of small carbon

Fig. 5. The UV patterns of oils rened by different content of natural bentonite.

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Sh. Salem et al. / Journal of Industrial and Engineering Chemistry 23 (2015) 154162

particles during thermal cracking and oxidation. The oil may be

contaminated with soot resulting from an incomplete combustion
in motor. The presence of contaminants in used oil will be
discussed later. By contrast, the color of oil was effectively changed
when it was mixed with 45.0 wt.% clay. The selected bentonite
shows a low reactivity with the contaminants because the
distillated oil needs high amount of adsorbent for recovery. It is
obvious that the base oil resulting from clay treatment is brighter
and has a clear reddish color.
The inuence of acid concentration of activation environment
on UV absorbance of rened oils was investigated by obtaining the
peak intensity at maximum wavelength, lmax. When the oil color
changes from reddish to yellow, the maximum wavelength
remains constant at approximately 510 nm. If the acid concentration is increased from 0.50 to 1.00 mol l1, the absorbance
decreases sharply (Fig. 6(a)). These data indicate that the acid
concentration plays an important role in the adsorption capacity.
The UV absorbance of regenerated oil by bentonite treated in the
presence of sulfuric acid, 1.00 mol l1, is comparable with other
data. The maximum removal of contaminants was observed when

the activation is carried out in the presence of sulfuric acid

(Fig. 6(b)).
The effect of residence time on UVVisible absorbance was also
studied at the range of 15120 min (Fig. 7). For evaluation of
residence time effect on UV absorbance, the activation environment concentration kept constant at level of 1.00 mol l1. When
the activation time was increased, the UV absorbance was not
changed remarkably. The removal of contamination by clays
activated in the presence of sulfuric acid is rapid in comparison to
that for clays treated by nitric acid. The signicant variation in the
absorbance is not observed when activation time is less than
60 min. The sharp change occurs in UV absorbance beyond 60 min
and there is no signicant variation in the absorbance for oils
rened by clays activated above 90 min. The adsorption of
contaminations by activated clay is also affected by acid type.
The clay modied by sulfuric acid favors for recovery process,
because the UV absorbance of oils rened by clays activated in the
presence of nitric acid is always higher than that for oils recovered
by clays activated in the presence of sulfuric acid at the same
condition. In conclusion, not only the high specic surface area, but
also interlayer spacing of montmorillonite has substantial effect on
regeneration of waste oil. The relation between MB adsorption
level and removal of contaminations were not observed in the
regeneration of waste oil.
The adsorbent content is the most important factor, affecting
the regeneration process. In order to study the inuence of
activated clay content on adsorption, the UV absorbance is plotted
versus adsorbent content in Fig. 8. It is clear that the adsorption is
highly dependent on adsorbent content. Maximum removal of
contaminations is carried out by clay activated by sulfuric. When
the amount of clays is increased, the absorbance decreases linearly.
Conversely, a lower adsorption is observed by natural clay. The
uptake of contaminations by clay activated in the presence of
sulfuric acid increases considerably, which indicates 17 wt.%
reduction in the adsorbent content to achieve the same absorbance, approximately.
In order to determine the chemical composition of regenerated
oils, FTIR technique was used as shown in Fig. 9. The same
information, regarding to the most important bands, were
observed in the spectra of examined oils. By recording the oil
spectrum after recovery, it is possible to understand the changes
occurring in oil composition. The rened oils are a mixture of
hydrocarbons. The bands related to CH vibrations appear in the
2737, 2860 and 2961 cm1. The intense band occurred at wave
number of 1465 cm1 shows CH plain bending vibration.

3
Activated by H2SO4

Absorbance

2.5

Activated by HNO3

2
1.5
1
0.5
0

Fig. 6. (a) The UV absorbance of oil versus acid concentration. (b) The UV patterns of
oils rened by clays treated by concentrated nitric and sulfuric acid solutions,
1.00 mol l1.

20

40

60

80

100

120

Activation time (min)

Fig. 7. The UV absorbance of oil versus residence time.

140

Sh. Salem et al. / Journal of Industrial and Engineering Chemistry 23 (2015) 154162

3
Raw bentonite
2.5

Activated by
H2SO4
Activated by
HNO3

Absorbance

1.5

0.5

0
25

30

35
40
Adsorbent content (wt.%)

45

50

Fig. 8. The UV absorbance of oil versus adsorbent content.

Fig. 9. The FTIR spectra of oils regenerated by natural bentonite and clays treated by
concentrated nitric and sulfuric acid solutions.

Generally, hydrocarbons containing methyl, CH3, groups indicate

vibration at 13701380 cm1. Also, CH2 rocking is observed at
wave number of 721 cm1. The peaks in wave number of 816, 970,
1310 and 1611 cm1 are related to C5
5C bond in aromatic ring. The
FTIR spectra display limited amount of aromatic components in the
regenerated oils.
The most common contaminations found in the degraded oil
are fuel, glycol pollutions, oxidation, nitrating and sulfating
components, soot and water accumulation [43]. Fuel contaminations coming from combustion chamber or line leakage have the
lower boiling point. The condition in engine causes the change of
fuel composition, due to incomplete combustion and distillation of
lighter fractions. Since the lubricating base oil is derived from
crude oil distillation cuts, they are very similar in chemical
composition and physical nature. The FTIR technique is a more fast
and simple way for identication fuel contaminations. The main
difference between the fuel and base oil is the boiling range and the
percentage of aromatic materials. Fuel has a lower boiling range
and signicantly higher amount of aromatic compositions. The
vibrations at the range of 570800 cm1 are used for this purpose.
Gasoline contamination detection is very easy because of the

161

higher aromatic content in gasoline. The absence of aromatic

material peaks at 570800 cm1 show that the oils are well
distillated.
Water is a very strong FTIR absorber and is very easy to detect. It
also appears in the region that few bands appear in infrared
spectrum of oil. Water is detected as a broad feature, centered on
3400 cm1. Glycol has a characteristic peak around 880 cm1 as
well as peaks at 1040, 1080 and 3400 cm1. The other peaks in the
spectrum related to glycol are used to conrm its presence. The
peak at 880 cm1 is used to identify glycol because it is not subject
to interferences with the other bands. The related peaks show the
absence of glycol and limited amount of water. The distillation at
400 8C removed the water and glycol satisfactorily.
Sulfur by-products such as SO2 and SO3 are the result of sulfur
compound oxidation in fuel during combustion as well as
oxidation of additives. These compounds increase the production
of varnish and sludge in the degraded oil. They also react with the
water formed during combustion to produce powerful inorganic
acids such as sulfuric acid. Sulfates can be identied by monitoring
their characteristic infrared bands, found at wave number of
1150 cm1. The vibration in this wave number is not detected.
When organic compounds are exposed to high temperatures
and pressures in the presence of oxygen, the nitrogen oxides are
formed. These products cause the increase in acidity, varnish and
sludge due to the formation of higher molecular weight
compounds. These are generally in the form of nitrogen oxides
such as NO, NO2 and N2O4. In addition, the nitration products are
the major reason for build-up of varnish. They have a characteristic
peak between 1600 and 1650 cm1. The infrared spectra show the
absence of nitration products in rened oils.
When the organic compounds of engine oil are exposed to the
high temperatures and pressures, these materials partially react
with the oxygen. There is a wide variety of by-products produced
during the combustion process such as carboxylic acids. Some of
these compounds are dissolved or dispersed in the oil. Carboxylic
acids contribute to increase the acidity of oil. The chemical effect of
oxidation is corrosion and the increment in viscosity also occurs
simultaneously. The oxidation can be identied by FTIR. If
oxidation is carried out in the oil, a general response for carbonyl
(C5
5O) is observed between 1670 and 1800 cm1 and around
2360 cm1. In this region, infrared energy is absorbed due to the
carbonoxygen bonds in the waste oil. The above vibrations are not
observed in the oil spectra rened by activated bentonite but a
negligible amount of carboxylic acid was found in oil recovered by
natural bentonite.
When fuel and air mixture is burned, soot particles are formed.
Soot build-up is a problem, causing the change of oil viscosity. The
FTIR analysis of soot is different than the methods used for
identication of other contaminants, because specic infrared
bands are lack for soot. The soot particles cause a general scattering
of the infrared radiation, which is more severe at higher wave
numbers. Soot is identied by taking to account the intensity at
wave number of 2000 cm1. The absence of soot in the rened oils
is conrmed by FTIR spectra.
The technical characteristics of oils regenerated by industrial
raw material and treated clays are reported in Table 3. The density
of oils rened by natural clay is higher than that for oil regenerated
by treated bentonites. The kinematic viscosity at 40 8C rises when
regeneration is carried out by activated clays, indicating the better
removal of contaminants from oil. Furthermore, regeneration of
waste oil by activated clay cannot signicantly change the
viscosity at 100 8C. It is very interesting that the ash point of
oil recovered by raw materials is higher than that for oils
regenerated by clays treated in the presence of nitric and sulfuric
acids. Also, the pour point of studied oils remained constant,
approximately. The reported ash content is favorable that satises

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Sh. Salem et al. / Journal of Industrial and Engineering Chemistry 23 (2015) 154162

Table 3
The technical characteristics of oils regenerated by natural and activated clays.
Property

Natural
bentonite

Activated
by H2SO4

Activated
by HNO3

Density (g cm3) at 27.5 8C

Kinematic viscosity at 40 8C (cSt)
Kinematic viscosity at 100 8C (cSt)
Flash point (8C)
Pour point (8C)
Ash content (wt.%)
Total acid number (mg KOH/g oil)
Total base number (mg HCl/g oil)

0.923
38.9
7.2
198
1
Nil
0.1
0.1

0.908
46.5
7.4
170
2
Nil
Nil
Nil

0.891
46.8
7.4
183
1
0.014
Nil
0.6

the standard limitation. The results also show that the total acid
number of oils regenerated by modied clays is negligible while
the TAN of oil rened by natural clay is higher than the standard
value, <0.03. The reduction in the TAN is due to adsorption of
contaminants. The lower total acid number shows the greater
stability of oil. The acidity of oil may be due to the presence of
carbonyl components. These compounds are present in low
quantity after recovery. The total base number of regenerated
oil by clay modied in the presence of sulfuric acid is negligible.
The color of the oils rened by natural material and modied clay
in the presence of nitric acid was reddish while the color of the
regenerated oil by clay modied in the presence of sulfuric acid
was yellow. The clay activated by sulfuric acid was observed to be a
better adsorbent than the other studied cases. The improvement in
oil color and characteristics can be achieved by hydro-treating
process due to decrease in the content of unsaturated components
[11]. Because the additives were degraded during the serves or
eliminated from the oil by distillation and adsorption, the viscosity,
ash point, pour point and TBN of oil can be improved by mixing
the suitable additives to satisfy the standard requirements.

Conclusions
The present study demonstrated the feasibility of Iranian
activated bentonite, from Soltaniyeh in Zanjan province, for
regeneration of used lubricant oil by clay treatment process. The
acidication of natural clay was carried out by concentrated HNO3
and H2SO4 solutions and the conclusions can be summarized as
follows:
1 The acid treatment results in re-organization of the pore
structure by leaching Mg from octahedral sheet, creating
vacancies. The concentrated nitric acid, 1.00 mol l1, is efcient
in the removal of Mg from the montmorillonite structure but
sulfuric acid affects the interlayer spacing by substitution of
hydrogen ions. The nitrogen adsorption isotherms indicated that
the average pore size, 12 nm, is independent on acid type. The
increase in number of nano-pores due to treatment by nitric acid
is more prominent in comparison to that by sulfuric acid.
2 The methylene blue adsorption tests conrm that the structural
changes in clay due to acidication. The MB uptake by treated
clays is directly related to specic surface area.
3 The uptake of oil contaminants on the treated clays is affected by
acid treatment condition. It continuously increases with acid
concentration until the clay destruction is observed. The acid
type and concentration are two important factors that inuence
the oil regeneration process. The activation of bentonite by
sulfuric acid, 1.00 mol l1, yields an adsorbent material that is
efcient in removal of color from waste oil and is better than the
natural one. The decolorizing power of clay treated by nitric acid
at the same condition was shown to be inefcient for the
recovery of used lubricant oil.

4 A clear relationship between the MB adsorption and UVVisible

absorbance was not observed. Although the higher specic
surface area is necessary for removal of contaminants from used
lubricant oil, the interlayer spacing should be considered in
evaluation of activated bentonite.
Acknowledgment
The distillation of waste engine oil was carried out by Shahab
Gatran Company. The authors would like to thank this company for
providing the distillated oil in the industrial scale.
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