Chapter Three Experimental Work
Chapter Three
EXPERMENTAL WORK
3.1 Introduction
There are several oil recovery methods exist for the treatment of used
lubricating oil. One of them was a solvent extraction process which will be
applied in this work. This section provides a description of the materials,
chemicals and equipment, as well as an experimental procedure applied to
re-refining of used lubricant oil and also those used to determine some
specific properties of used and re-refined lubricating oil.
3.2 Used Oil Sample - Chemicals and Equipment
3.2.1 Used Lubricating Oil Sample
The feedstock in this study was used lubricating oil, which was
supplied from Shell Company and used in electrical power generator in
University of Technology / Chemical Engineer Department, type 350 KVA
Perkin Company operating for 120 hr work as recommended by the supplied
company as, shown in figure 3.2. After this period of time, the oil was
drained and collected from electrical power generator for analysis, as shown
in figure 3.1.
Figure 3.1: Photographs of (A) Used lubricating oil, (B) Fresh lubricating oil.
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Chapter Three Experimental Work
Figure 3.2: Photographs of Electrical Power Generator.
3.2.2 Solvent and chemical materials
Some chemicals used in this work were provided by the Chemical
Engineering Department / University of Technology. Other solvents got
from Baiji Refinery/Iraq, such as (Toluene bottom, Raffinate, L.A.B,
Paraffin, Iso paraffin). Those not available were purchased from local
chemical stores. The chemicals and equipment specifications used in this
study are shown in Table 3.1, Table 3.2, Appendix B and Table 3.3.
Table 3.1: List of solvents used in this study and their properties.
Solvent Supplier Purity% Formula
No.
1 1-butanol RIEDEL-DE HAEN 99 C4 H9OH.
2 MEK SIGMA-ALDRICH 99 C4 H8O
3 2-butanol RIEDEL-DE HAEN 99 C4 H10 O
4 2- Propanol Scharlau 99.9 C3 H8O
5 Ethanol ROMIL 99.8 C2 H6O
6 Hexane BDH Chemicals 99 C₆H₁₄
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Chapter Three Experimental Work
7 1-Octanol RIEDEL-DE HAEN 99.5 C8 H18 O
8 Acetic acid GCC-Chemicals 99.9 C2 H4O2
9 Furfural SIGMA-ALDRICH 99 C5 H4O2
10 Methyl acetate HOPKIN&WILLAMS 99.5 C3 H6O2
11 2-methyl-2-butanol RIEDEL-DE HAEN 99.5 C5 H12 O
12 Pentane RIEDEL-DE HAEN 99 C5 H12
13 Cyclohexane HOPKIN&WILLAMS 99.97 C6 H12
14 Acetone HOPKIN&WILLAMS 99.9 C3 H6O
15 Acetonitral Biosolve-Chemicals 99.5 CH3 CN
16 1-Hexanol BDH Chemicals 99 C6 H14 O
17 Toluene bottom
18 Raffinate
19 L.A.B
20 Paraffin
21 Iso paraffin
Table 3.2: List of chemicals used in this Study.
Che micals Purity Manufacturer Uses
1 KOH 99 % EDUTEK Additive for solvent
2 NaOH 99 % EDUTEK Additive for solvent
3 MEA 99.5 % Scharlau Additive for solvent
4 H2 SO4 98 % SDFCL Activation of Clay
5 Bentonite In adsorption process
6 Attapulgite In adsorption process
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Chapter Three Experimental Work
Table 3.3: List of Equipments used in this study.
No. The device Manufacturer
1 Digital electronic Balance KERN & Sohn GmbH
2 Vacuum pressure pump PYE UNICAM (Germany)
3 Distillation Koehler (USA)
4 Homogenizer (Silent Crusher) Heidolph (USA)
5 Centrifuge GEMMY INDUSTRIAL CORP (Taiwan)
6 Burning furnace Kelvin (Italy)
7 Hot Plate Stirrer Heidolph (USA)
8 Ball milling
3.3 Characterization of Oil Samples
There are a series of tests were done on samples of used lubricating
oil, extract oil and the recovered base oil. The aim of the analysis was to
evaluate the properties of the oil samples.
3.3.1 Determination of kinematic viscosity, ASTM D-445
The Kinematic viscosity was calculated by measuring the time
needed for 10 ml lubricant oil to flow under gravity through a glass capillary
Viscometer multiplied by the calibration constant of the Viscometer
according to ASTM-D445 [28].
3.3.2 Viscosity Index calculation, ASTM D-2270
The viscosity index of lubricant oil was calculated according to
ASTM-D 2270-04, by applying the procedure for determination of
kinematic viscosity at 40 and 100 oC [31].
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Chapter Three Experimental Work
3.3.3 Determination of density, ASTM D-4052
0.7 ml of lubricant oil was set in the oscillating sample tube, and the
change in oscillating frequency caused by the change in the mass of the tube
was used in conjunction with calibrated data to determine the density of the
sample according to ASTM-D4052 [121].
3.3.4 Determination of Ash of Petroleum Products, ASTM D-482.
Ash content was evaluated according to ASTM-D 482-03, the
lubricant oil sample was weighed in a suitable crucible and carefully heated
and ignited by the flame until leaving a carbonaceous material only. Then,
the residual was heated in a furnace at 775 °C until the carbonaceous
material disappeared. The dish was removed from the furnace and placed in
desiccators where it was left to cool at room temperature. The ash content
was calculated by dividing the weights of ash produced to the original oil
sample.
3.3.5 Determination of Sulfated Ash of Petroleum Products,
ASTM D- 874.
Ash sulphur content was evaluated according to ASTM-D 874-00,
The crucible containing sample was ignited and burned until no further
smoke or fumes were evolved. Then, the remaining of the sample was
treated with sulfuric acid and then heated to 775 ± 25°C until oxidation of
the carbon was completed, the ash allowed to cool and retreated with
sulfuric acid again and then heated to 775 ± 25°C until the constant weight
[127]
. The sulphated ash was calculated by dividing the weight of ash
produced to the original oil sample.
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Chapter Three Experimental Work
3.3.6 Determination of TAN and TBN by Potentiometric titration,
ASTM D-664 and ASTM D-4739.
A suitable amount of the sample is dissolved in titrant solvent (mixture
of toluene and 2-propanol containing a small amount of distilled water) and
titrated potentiometrically with HCL or KOH, using combined glass indicating
electrode. The pH reading is plotted against the volume of titrating solution,
[92, 30]
and the end points are taken at the inflexions in the resulting curve . The
TAN and TBN were calculated according to ASTM D-664 and ASTM D-
4739 respectively.
3.3.7 Determination of flash point, ASTM D-92.
A sample of 70 ml of lubricating oil was put into a test cup by using
Cleveland open cup apparatus. The temperature of the test specimen is
increasing rapidly at first and then at a slower constant rate as the flash point is
approached. The lowest temperature of the ignition source caused the vapor
above the surface of the liquid to ignite was noted and recorded as the flash
point [128, 106].
3.3.8 Determination of Pour point, ASTM D-97
A suitable amount of the lubricating oil sample was put into a container
and cooled. Paraffin hydrocarbon (in the form of wax) will start to gather in
[106]
crystalline shape and separate. This temperature is called cloud point .
Further cooling leads to stop lubricating oil flow, this temperature is known as
the pour point [129].
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Chapter Three Experimental Work
3.3.9 Determination of water by distillation ASTM D-95
Water content in the used oil was determined by distillation, a
suitable amount of the sample was measured and transferred to the still. Heat
was applied to the still under reflux with the selected solvent -carrier liquid
(20 vol% toluene, 80 vol% xylene) which is a water-immiscible solvent. The
rate of boiling was adjusted, so that the condensed distillate and water in the
condenser to the graduated trap and the solvent is returning to the still [130].
3.3.10 Fourier-Transformed Infrared Spectra
FTIR spectroscopy is a technique that provides information about the
chemical bonds between molecules and the active groups grafted on used
oil, extracted oil and recovered base oil. The FT-IR instrument [Type:
Bruker –Tensor 27, Origin: Germany] was used as shown in Figure (3.3),
which is located in the University of Technology / Chemical Engineering
Department.
Figure 3.3: FTIR instrument.
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Chapter Three Experimental Work
3.3.11 Determination of metal analysis
The element concentration of used oil, extracted oil and recovered oil
is determined by using Inductively Coupled Plasma Atomic Emission
Spectrometry ICP-AES (Perkin Elmer Optima 5300 DV), ICP was done in
Dora Refinery, Baghdad / Iraq. Figure (3.4) shows the ICP instrument
photograph.
Figure 3.4: ICP instrument.
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Chapter Three Experimental Work
3.4 Re-Refining of used oil experimental procedure:
The used lubricating oil was re-refined by the following stages:
Used oil
Settling & Filtration
Dehydration
( by distillation )
Solvent
Sludge Solvent extraction
process
Extract oil
Solvent recovery
( by distillation )
Clay
Adsorption
process Recovered base oil
Spent clay
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Chapter Three Experimental Work
3.4.1 Filtration
The first step in the re-refining process of used lubricating oils settles
by gravity and then filtration to remove large contaminants. Filtration was
carried out by the filter paper type 542 Whatman to remove some impurities
and additives that formed as a result of exposure to high temperatures. A
vacuum pressure filter was used in Filtering process, and also filter paper
type 542 was used, as shown in figure (3.5).
Figure 3.5: Vacuum pressure filter
3.4.2 Dehydration (Vacuum Distillation)
300 ml of used lubricating oil was put in a simple batch vacuum
distillation as shown in Figure (3.7) to remove water and light fractions. The
light component in the used lubricating oil must be distilled off because their
presence changes the lubricating oil properties. This may affect the
efficiency of any pre-treatment step, especially the solvent extraction and
solvent recovery. The amount of used oil was heated at 200 Co by
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Chapter Three Experimental Work
[85]
atmospheric distillation to remove water and then, distilled up to 200 Co
under vacuum pressure (600 mmHg) [99] to eliminate the light hydrocarbon.
3.4.3 Solvent extraction process
In conical flask 20 ml of used oil sample (Woil ) was mixed with the
solvent (1-butanol and MEK) at a specified volume ratio of 0.05 to 4.9
solvent / used oil ratio, extraction temperatures from 7 to 72 oC and mixing
speed from 569 to 23431 rpm, as shown in figure (3.6). Mixtures were
prepared in different variable conditions as shown in table 3.4 by using
central composite design to get this set of experiment. Each system was then
being homogenized in a Homogenizer for about 10 minutes just to ensure
sufficient mixing in the flask and turned into a centrifuge. It was then left in
the centrifuge for 20 minutes at 4000 rpm, which is the time necessary for
formation and equilibrium of biphasic systems within which the oil
[124]
concentrated in the extract phase (solvent + recovered base oil) and
undesirable component such as sludge in the raffinate phase (lees).
Figure 3.6: Silent Crusher mixer
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Chapter Three Experimental Work
The following parameter (Percent Sludge Removal) was studied in
the extraction process experiment for comparison between the solvents used
in this work.
Percent Sludge Removal (P.S.R.)
After mixing, the solvent oil mixture was set into a centrifuge for 20
minutes at 4000 rpm, the sludge was separated, and then sludge was washed
with the same solvent to extract any remaining base oil. Then the sludge was
heated in an oven to 130 oC for 30 minutes to evaporate the solvent present
in the sludge as described in [99, 131]. And maintained at room temperature to
cool, then weighed as Dry Sludge (W dry ) and PSR was calculated by the
following equation [1].
Percent sludge removal (P.S.R) = × 100 % . . . . . . . . . (3-1)
Where:
PSR = Percent Sludge Removal.
Wdry = weight of dry sludge (gm).
Woil = weight of used oil (gm).
Table 3.4: Experimental design by central composite design (CCD)
Solvent / used oil ratio Temperature ( oC) Mixing speed (rpm)
Run
(vol / vol) (X1) (X2) (X3)
1 2.5 40 12000
2 1 60 5000
3 2.5 40 12000
4 4 20 5000
5 1 20 19000
6 4 60 19000
7 2.5 7 12000
8 2.5 40 12000
9 0.05 40 12000
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Chapter Three Experimental Work
10 2.5 40 569
11 2.5 40 23431
12 4.9 40 12000
13 2.5 72 12000
14 2.5 40 12000
15 4 20 19000
16 2.5 40 12000
17 1 20 5000
18 2.5 40 12000
19 1 60 19000
20 4 60 5000
3.4.4 Solvent Recovery
Solvent recovery is an important factor that must be calculated to
select the best economic solvent in the solvent extraction. The solvent
recovery for each system’s (base oil – solvent solution) was done by
distillation unit, as shown in figure (3.7). Taking into consideration the
boiling point of all solvents. Then, the base oil recovered was characterized
in accordance with the test methods stated.
Figure 3.7: Distillation unit
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Chapter Three Experimental Work
3.4.5 Adsorption process
3.4.5.1 Adsorbents.
Bentonite and Attapulgite clay were obtained from the Iraqi
National Company for Geological Survey and Mining and used as
adsorbents. The composition of clay was analysed by using X-Ray
fluorescence and BET. The analysis is shown in the table 3.5.
3.4.5.2 Clay activation.
The purpose of clay activation by acids is to increase the surface area
of clay and increase the ability of clay to remove contaminants and metal,
because the acid opens a clay crystal structure and releases Al+3, Mg+2,
Fe+3, Ca+2 ions to the solution of acid.
While dealing with acid, the replaced cation between clay layers by
hydrogen ions followed by partial crash aluminium Octahedral layers and
silicon Tetrahedral followed by dissolution of the cation of the crystal
structure. This process causes the crash stratified nature of the bentonite and
thus led to an increase in the specific surface area and pore volume, which is
leading to increasing the clay effectiveness to remove contaminants
The clay sample was ground by ball mill and then washed with
distilled water. The slurry was dried in a furnace at 110 oC for 4 hrs, then
the dried clay was grounded. The activation of clay was done by adding 100
grams of clay (after removing the dirt, and salt) with 400 ml of sulphuric
acid concentration 20% and left for 4 hrs in contact with clays at a
temperature 97 ± 3 oC under total reflux, as shown in figure (3.7). After this
time period, the mixture was cooled and filtered by using vacuum filter and
then washed with distilled water until neutralizing the pH of the mixture.
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Chapter Three Experimental Work
Then, the clay was dried in the oven for 4 hrs, grounded by ball milling
into fine particles and sieved to 200 mesh size by using a mechanical shaker.
Figures (3.8) and (3.9) show the clay activation and the clay before and after
activation, and table 3.5 show the raw and activation clay analysis.
Figure 3.8: Clay activation process.
Table 3.5: Analysis of the raw and activated clay.
SiO2 CaO Fe 2 O3 MgO Al2 O3 Surface Pore
area volume
m2 /gm cm3 /gm
Bentonite 56.77 4.48 5.12 3.42 15.62 52.2 0.0593
Activated 74.44 1.5 2.16 1.41 6.79 158.035 0.2144
bentonite
Attapulgite 41.6 18.1 4.4 3.8 13.36 23.729 0.02849
Activated 44.83 15.43 1.91 0.62 4.62 64.744 0.10585
attapulgite
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Chapter Three Experimental Work
Figure 3.9: Clay before and after activation
(A-bentonite, B- activated bentonite, C- attapulgite, D-activated attapulgite)
3.4.5.3 Clay adsorption procedure.
The main aim of the clay adsorption process is to remove the
resinous compounds, metal and poly aromatic hydrocarbons (PAHs) from
the extracted oil. The extracted oil was subjected to further purification by
adsorption processes, 20ml of the extract oil was put in contact with the
activated clay (bentonite, attapulgite) in different percentages of Clay/
extracted oil ratio, temperature and contact time, at 500 rpm mixing speed as
shown in figure 3.10. Then, the base oil separates from the adsorbent clay by
using filter paper type 542 Whatman, after that, the base oil produced was
analyzed by using physical and chemical tests. The limits of variables, which
were adopted during the adsorption process experiment are indicated by
Table (3.6).
Table 3.6: Variable values of batch adsorption process.
Variables Ranges
Clay/extract oil ratio wt/vol % 5 10 20 25
Temperature (o C) 30 60 90 120
Time (min) 30 60 90 120 150
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Chapter Three Experimental Work
Figure 3.10: Batch adsorption
3.5 Characterization of Clay
3.5.1 X-ray Fluorescence (XRF)
The chemical composition of clay and activated clay (bentonite and
attapulgite) was determined by using the X-ray fluorescence spectrometry
(XRF) (Shimadzu 1800), it was done in Iraqi Geological Survey Department
/ Ministry of Industry, Baghdad / Iraq. Figure (3.11) shows the XRF
apparatus photograph.
Figure 3.11: X-ray fluorescence (XRF).
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Chapter Three Experimental Work
3.5.2 Measurement of the specific surface area and pore volume
Specific surface area of clay and activated clay was determined
according to Brunauer, Emmett and Teller method, by using an Instrument
model Q-surf 9600 (USA) in Petroleum Research and Development Center
in Baghdad/ Iraq. Figure (3.12) shows The photograph of the surface area
measurement instrument.
Figure 3.12: Surface area measurement instrument.
64
