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Contents lists available at ScienceDirect

The Journal of Supercritical Fluids

journal homepage: www.elsevier.com/locate/supflu

Temperature effect on extraction and purification of used motor oil by

supercritical carbon dioxide
Svetlana Rudyk a,∗ , Pavel Spirov b
a
Oil and Gas Research Centre, Sultan Qaboos University, Oman
b
Petroleum Engineering Department, Soran University, Iraq

a r t i c l e i n f o a b s t r a c t

Article history: Supercritical carbon dioxide (SC-CO2 ) was used for the extraction of used motor oil (UMO) from two types
Received 19 September 2016 of contaminated sand (sieved and not sieved) at 70–80 ◦ C and 35–65 MPa. The presence of fine sand in
Received in revised form 1 March 2017 Sand 1 contributed to the increase of UMO recovery, decrease of outgassing losses and better purification
Accepted 2 March 2017
of extracted UMO samples. All samples extracted at 70 ◦ C from both sands were clean from engine wear
Available online xxx
residues and transparent while most of the samples extracted at 80 ◦ C were black.
This implies that the temperature has most significant effect on purification of UMO achieved by
Keywords:
depositing residues in the sand and extracting base oil fraction. Therefore, remediation of sands using
Used motor oil
Purification
SC-CO2 attained by removal of UMO can be obtained at higher temperatures, but the purification of UMO
Carbon dioxide requires lower temperatures.
© 2017 Elsevier B.V. All rights reserved.

1. Introduction long-term effects if they are allowed to enter the environment

Motor oil is used for the lubrication of all kinds of cars and
engines, which results in large quantities of used motor oil. 570 mil-
lion liters of used motor oil are produced every year in the United
States of America (USA) alone, and over 50% of it is recycled [1].
Improper disposal of used motor oil (UMO), such as pouring it onto
the ground, into storm drains or throwing it in the trash does still
occur. Oil spillages on soil can be observed at oil terminals, air-
ports, military areas, gasoline retail stations, and along roadsides.
The problem of soil contamination with UMO is even more pro-
nounced in developing countries where the waste is often dumped
directly onto the ground.
Used motor oil contains many contaminants, which are the
result of normal wear of engine components and the heating and
oxidation of lubricating oil during engine operation. These contam-
inants include metals, chemical elements, additives (detergents,
dispersants, oxidation inhibitors, rust inhibitors, and viscosity
improvers), a broad range of aromatic and aliphatic hydrocarbons
with chain lengths ranging from C15 to C50, dirt, ash, soot, and
water [2]. Used motor oil disposal can be more environmentally
damaging than crude oil pollution because of additives and con-
taminants. These carcinogenic materials can cause both short and
∗ Corresponding author.
E-mail address: snr@squ.edu.om (S. Rudyk).
through the soil. According to the US Environmental protection
agency, the UMO from one oil change can contaminate one mil-
lion gallons of fresh water which is one years’ supply for 50 people.
Over 40% of the USA’s oil pollution comes from improper disposal of
motor oil [1]. The most common method for treating contaminated
sites is still the excavation of contaminated soil and its transport to
a landfill which is considered safe from an environmental point of
view [3].
The UMO is a valuable product that can be refined into a base
stock for lubricating, transformer and hydraulic oil, or used for heat
generation. Jha (2005) concluded that the oil molecules of used
motor or lubricating oil are not degraded during use compared to
the additives [4]. 67 liters of raw crude oil produces 1 l of new motor
oil; 1.6 l of UMO makes 1 l of recycled oil [5]. The wider re-utilization
of UMO will contribute to the conservation of petroleum natural
resources, saving on energy and money used for their production.
The traditional acid-clay technology of used motor oil cleaning
is replaced by other technologies including propane de-asphalting,
hydrofinishing, atmospheric or vacuum distillation, and solvent
extraction, which are considered either to be too expensive or only
appropriate for treating large quantities of used oil [6,7]. The use
of propane makes it necessary for a hydrofinishing step because a
percentage of pollutants which are difficult to separate by vacuum
distillation, such as oxidation and metallic compounds, are soluble
in propane [8] and are, therefore, unavoidably co-extracted with
the base oil. To improve the process, ethane [6] was tested because

http://dx.doi.org/10.1016/j.supflu.2017.03.001
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Please cite this article in press as: S. Rudyk, P. Spirov, Temperature effect on extraction and purification of used motor oil by supercritical
carbon dioxide, J. Supercrit. Fluids (2017), http://dx.doi.org/10.1016/j.supflu.2017.03.001
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it is lighter than propane and dissolves preferentially the base oil
fraction of the lubricant oil and causes the particles, heaviest hydro-
carbons, and other undissolved compounds to precipitate more
easily than propane. However, propane and ethane are flammable
so this process is regarded as hazardous. The choice of treatment
technique also depends on the availability of solvents and cost of
equipment.
Carbon dioxide can be available in large quantities from natural
deposits or CO2 storages built in the efforts to curb global warming.
Extraction of used lubricating oils with supercritical carbon dioxide
(SC-CO2 ) has been proposed as an environmentally friendly process
[9]. The SC-CO2 was also applied [10] as a viscoreduction agent
for the removal of metals from used motor oil by ultrafiltration-
membrane separation at pressures of up to 18 MPa; it showed a
high potential for use in the cleaning of used motor oil. Contaminant
removal by SC-CO2 for soil remediation was broadly investigated
for the extraction of heavy metals, polycyclic aromatic (PAH), and
petroleum hydrocarbons (TPH) [11,12]. At conditions above critical
point, CO2 possesses a liquid-like density and gas-like penetrating
capability, enabling it to pass through minute gaps in the soil, inter-
act with contaminants, and transport them out of the matrix. The
recovery of contaminants has been determined at various pressures
and temperatures by displacement or extraction experiments car-
ried out in dynamic, static, or combination modes using various
types of high-pressure extractors [13–15]. An increase in pressure
causes an increase in the supercritical fluid density and viscos-
ity, which results in an increase in the solvating power of SC-CO2
and extraction recovery [13]. Yield increases, with increasing tem-
peratures at constant pressure, were reported by [16,17]. Higher
temperatures, however, can cause a decrease in the supercritical
fluid density and, consequently, a decrease in solvating power.
The objective of the study we present here was to investigate the
effect of temperature, pressure, and the sorting of sand grains on the
ability of pure CO2 , under supercritical conditions, to extract used
motor oil from the sand, aiming at two applications: remediation
of the contaminated sand by removal of the used motor oil and
purification of the used motor oil by removal of the engine waste
residues.
2. Experimental
2.1. Materials
Used motor oil (UMO) of an intense black colour was collected
from a motor-service center in the city of Ribe, Southern Denmark.
It consisted of a mixture of wastes of synthetic, semi-synthetic
and mineral oils. The sand was collected from the beach near Esb-
jerg city, Western Denmark. Strandmollen A/S, Denmark, supplied
99.9% pure carbon dioxide.
2.2. Samples preparation
In order to analyze the grain size of sand fractions, 100 g of
sand collected on the beach were wet sieved through sieves after
ultrasonic treatment in a solution of Na4 P2 O7 , using demineralized
water in order to remove the mud fraction and possible remains of
salt. The remaining sand fractions were dried in the oven at 90 ◦ C to
a constant weight. The content of each sieve was weighed with an
accuracy of 0.001 g. The sand grain size in the sieves distributed as
follows: (500–1000 ␮m) – 6%, (250–500 ␮m) – 26%, (125–250 ␮m)
– 32%, (63–125 ␮m) – 20%, (15–63 ␮m) – 15%, (0–15 ␮m) – 1%. The
density of sieved sand fractions was examined using a pycnome-
ter test. It was found that the density of sand was uniform in all
fractions and was similar to that of quartz (2.65 g/cm3 ).
Please cite this article in press as: S. Rudyk, P. Spirov, Temperature effect on extraction and purification of used motor oil by supercritical
carbon dioxide, J. Supercrit. Fluids (2017), http://dx.doi.org/10.1016/j.supflu.2017.03.001
Fig. 1. Experimental extractor, (1) CO2 gas balloon, (2) CO2 inlet valve, (3) CO2
cooler, (4) Pump, (5) Heater, (6) Oven, (7) Extractor, (8) Sample, (9) Pressure relieve
valve, (10) CO2 outlet valve, (11) Gas flow regulating valve, (12) Sample collection.
The samples for SC-CO2 extraction experiments were prepared
by mixing of above mentioned quartz sand with used motor oil
(density 0.8 g/cm3 ) in order to model contaminated sand. To sim-
ulate natural conditions, 2 kg of sand (Sand 1) was not sieved.
Another 5 kg of sand dried at 90 ◦ C were sieved through a 2 mm
sieve column and shaken for 20 min. 2 kg of coarser fraction (grains
>2 mm) were collected and designated as Sand 2.
The portions of Sand 1 and Sand 2 were put into the measuring
vessels and weighed. The 100 mL of used motor oil weighing 80.8 g
was added to the 519.2 g of each sand and mixed. The total weight
of the obtained portions of sand contaminated with used motor oil
was 600 g. The 98 g of contaminated sand was put in the extraction
cell of 100 mL volume and pressed. The calculations allow estimat-
ing that 98 g of sand sample consists of 84.8 g of sand and 13.2 g of
UMO.
2.3. Experimental procedure
The experiments were performed on a Spe-ed SFE extractor
shown in Fig. 1. The details of the experimental procedure can be
found in [18,19]. The sample consisting of 98 g UMO saturated sand
(8) was put in the extraction cell, which is a steel pipe (7) with a
100 mL volume, and heated. After the temperature reached a desig-
nated value, the gas valve (2) was opened and CO2 was injected until
the designed pressure was established. The extraction was carried
out in combination mode, which involved the interaction between
SC-CO2 and the UMO in static mode, followed by the extract collec-
tion in dynamic mode at the flow rate of 150 mL/min. The extracts
of oil were transported from the extraction cell along the steel pipe
of 0.3 mm diameter into the collecting test tube (12), the top of
which was covered with the cotton ball to minimize the escape of
extracted oil in vapor phase. The collecting test tubes were placed
in a vessel with water at a temperature of approximately 8 ◦ C for
cooling. After 15 min when the flow of UMO seized the inlet valve
(2) was closed to halt the CO2 injection, and the CO2 was released
from the extractor. The procedure described above comprised one
run.
In order to perform a second run, the gas was injected into the
extractor again at the same pressure value followed by collection
of the extracted UMO. In all, this procedure was repeated for three
sequential runs for each sand sample and at each pressure value.
When the extraction at a particular pressure over three runs was
over, the sand sample was removed from the vessel and measured,
then a new sand sample for investigation at the next pressure value
was placed in the extractor. Each run incorporated 20 min of oper-
ation in static mode followed by 15 min in dynamic mode.
The tests using the samples of contaminated sands were con-
ducted at (35, 45, 55 and 65) MPa at 70 ◦ C and 80 ◦ C. An additional
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test was performed using Sand 1 at 60 min in static mode followed
by 15 min in dynamic mode at 35 MPa and at 70 ◦ C in three runs
to determine if a higher recovery could be obtained after a longer
interval of interaction at static mode.
2.4. Numerical calculations
The collected UMO samples contained used motor oil and an
amount of fine beige sand on the bottom of some test tubes, in the
case of Sand 1 (not sieved), which passed through the 0.3 mm pipe
upon extraction. The interface between extracted motor oil and fine
sand was clearly seen. The test tubes with extracted motor oil were
weighed before and after the experiments to determine the weight
of the extracts after each run (Wrun ).
In order to exclude sand from calculations of the UMO recovery,
the weight of fine sand was calculated as:
Wsand = V · ,
where V is a volume in a test tube occupied by fine sand, sand
density  = 2.65 g/cm3 .
Recovery of used motor oil (R, %) was calculated as a ratio of
the weight of the collected UMO after each run corrected for the
presence of fine sand to the initial content of UMO in the sand Wi
= 13.2 g:
Wrun − Wsand
Rrun = × 100%,
Wi
The cumulative recoveries of UMO were calculated as the sum
of the recoveries after all three runs with the correction for fine
sand content:
 by SC-CO2 such as temperature, pressure, time of interaction with
CR = Rrun , %
The sand remaining in the extraction cell at the end of experi-
ment was also weighed. The total recovery (TR, %) of the UMO was
calculated as a ratio of the difference of the weight of sand sample
before (Wbefore ) and after the experiment (Wafter ) corrected for the
presence of sand in the test tube after the extraction from Sand 1
after three runs (˙Wsand ) at each pressure to the initial content of
UMO:
(Wbefore − Wafter ) − ˙Wsand
TR = × 100%
Wi
Outgassing losses (VR) were calculated as the difference
between the weights of each sand sample before and after the
experiment at specific pressure:
VR = TR − CR, %
The results of the experiments were plotted as recovery versus
the corresponding pressure (P, MPa).
2.5. GC–MS analysis
The chromatographic analysis was performed on a GC–MS sys-
tem consisting of gas chromatograph HP6890 GC and a mass
spectrometer Quattro Micro GC (Micromass MS Technology). Sep-
arations were performed on a Supelco SLB 5MS capillary column
(30 M × 0.25 mm × 0.25 ␮m film thickness). The initial flow was
0.6 mL/min. The initial temperature in the GC oven was 60 ◦ C for
2 min, followed by an increase of the temperature up to 320 ◦ C. The
total time was 45 min. Helium was used as the carrier gas at a pres-
sure of 20 psi. The MS was operated in electron ionization mode.
For the analysis, 100 ␮L sample was diluted by 10 mL hexane.
Please cite this article in press as: S. Rudyk, P. Spirov, Temperature effect on extraction and purification of used motor oil by supercritical
carbon dioxide, J. Supercrit. Fluids (2017), http://dx.doi.org/10.1016/j.supflu.2017.03.001
3
Fig. 2. Recovery of used motor oil after 20 and 60 min in static mode at 70 ◦ C and
35 MPa from Sand 1 (not sieved).
(1)
3. Results and discussion
In our previous experiments on extraction of grease obtained
from the windmill turbines, which was contaminated with dust
during several years of work, the purification of grease was
achieved by SC-CO2 without use of any filtering media. The
extracted samples of grease were light yellow compared to the
initial dark black [20]. The extraction of UMO from a simple car-
(2) rier, however, led to the unavoidable co-extraction of lees together
with the base oil [21]. The extraction of UMO described in the cur-
rent study was carried out from two types of sand used as filtering
media.
Several factors which influence UMO recovery and purification
(3) carbon dioxide, sand sorting, and number of runs, were investi-
gated. The theory of interaction of hydrocarbons and SC-CO2 , and
extraction of hydrocarbons by SC-CO2 from solid matrices can be
found elsewhere [6–17,22,24]. The present discussion is focused on
the most remarkable observation of this study, that is effect of tem-
perature on the separation of suspended solid particles from liquid
phase in the process of extraction from filtering media.
3.1. Selection of the optimal interaction time
(4)
Many investigations showed that 15–30 min of static mode
followed by a period of dynamic mode are sufficient to achieve
equilibrium and obtain the maximum recovery. Yang et al. [14] and
Al-Marzouqi et al. [15] extracted contaminants from sediments in
an interaction time at static mode followed by dynamic mode of
15× 15 min, respectively. Extracting hydrocarbons from oil shale
(5)
Jarboe et al. [22] applied 15× 60 min regimen while Akinlua et al.
[16] used 30× 50 min. To verify that the selected experimental reg-
imen provided the maximum recovery that can be obtained at the
given conditions of temperature and pressure, the results of two
tests carried out at 20 and 60 min of static mode (with each run)
at 35 MPa and 70 ◦ C, both followed by 15 min in dynamic mode,
were compared and are shown in Fig. 2. The difference in recov-
ery at 20 and 60 min after first runs is less than 3% while it is less
than 1% after both, second and third runs. This demonstrates that
the performance of the experiment during a longer time at static
mode would not have produced a higher recovery. Our previous
tests using naturally oil-saturated chalk samples showed that the
ultimate recovery of hydrocarbons during 30 and 90 min of static
mode followed by 15 min of dynamic mode in both cases did not
differ substantially [23].
The flow of extracted liquid ceased in less than 15 min in all
our experiments [18–20]. Therefore, the regimen of 20 min at static
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mode followed by 15 min at dynamic mode was chosen for all of
the described experiments.
3.2. Extraction of UMO from sand at specific runs
Most studies report extraction results of one run recovery. Typ-
ically, the recovery increases with the pressure increase to the
breakover point, above which it changes insignificantly. In case
of extraction from solid matrix or at high solute/solvent ratio the
recoveries after one run can be low, and the trend of recovery
change with the pressure can be unclear. This can lead to the con-
clusion that the extraction method is inefficient. In our previous
studies, we have observed that oil recovery from oil sand samples
can be similar or higher after the second runs [25,26]. We have
also observed lower oil recoveries after first runs when the extrac-
tion cell was filled with the oil sand at 75% of its volume compared
to that when it was filled at 50%. In the described experiment the
extractor was fully packed with the sand. Hence, the low recovery
after first runs could be expected.
The multiple extraction at specific pressure was performed in
three consecutive runs. Each experiment was repeated twice and
the average difference between the two independent measure-
ments was maximum 4%.
The recoveries of collected liquid phase of the UMO (LR) at 70 ◦ C
and 80 ◦ C from Sand 1 and from Sand 2 (sieved) were plotted after
each run in Fig. 3. The amount of co-extracted fine sand was shown
for Sand 1. The fine sand was co-extracted at 45 and 55 MPa at 70 ◦ C
and at all pressures at 80 ◦ C. The presence of water was observed at
the bottom of the samples extracted at 45 MPa and 65 MPa at 70 ◦ C
after the second runs.
At 70 ◦ C and 35 MPa, the liquid recoveries were less than 8% from
both sands after the first runs. After the first run, a maximum liquid
recovery of 31% was obtained at 55 MPa from Sand 1.
In similar experiments on the UMO extraction by SC-CO2 from
the towels performed in one run the recovery increased exponen-
tially from 1.4% at 35 MPa to 86.9% at 65 MPa [21]. Because the
density and solvating power of CO2 increased with increasing pres-
sure, the UMO recovery after the first runs at 70 ◦ C were greater at
55 and 65 MPa compared to the lower pressures for both sands. On
the contrary, the recovery did not increase at 80 ◦ C and 55 and 65
MPa for both sands. We have earlier observed the decrease of oil
recovery from oil sand at higher pressures but less sharp than that
for the Sand 1 [26]. This effect is often explained by the counter-
acting effects of volatility and solubility that lead to a cross-over
pressure below which the higher recovery is obtained at lower
temperature while lower recovery at higher temperature within
specific intervals of pressure [24].
It should be noted that the sand recovery after first runs were
also high from Sand 1 at 80 ◦ C and 55 and 65 MPa that could hin-
dered the UMO extraction.
The recoveries after the second runs increased in most cases. The
greatest recoveries above 40% were obtained from Sand 1 at 70 ◦ C
and at 45 MPa and 65 MPa after second runs. The recoveries after
the third runs were significantly lower than after the second runs
at 70 ◦ C but they were substantial at 80 ◦ C and at higher pressures
in comparison with the recoveries of previous runs.
At 70 ◦ C, the recovery from Sand 1 is greater than from Sand 2 at
all pressures after respective runs. The average difference between
the recoveries from Sand 1 and Sand 2 in the pressure range of
35–65 MPa was calculated as 6.6% after the first runs, 6% after the
second runs, and 5.2% after the third runs. At 80 ◦ C, the comparison
of recoveries after specific runs between Sand 1 and Sand 2 does
not lead to the similar straightforward conclusion.
In general, the recoveries of used motor oil after the first runs
were low, but they increased significantly after two additional
extractions at the same pressure values. It can be deduced that the
Please cite this article in press as: S. Rudyk, P. Spirov, Temperature effect on extraction and purification of used motor oil by supercritical
carbon dioxide, J. Supercrit. Fluids (2017), http://dx.doi.org/10.1016/j.supflu.2017.03.001
low recovery at one run is compensated by the higher recovery after
the other runs. In the experiments with oil sand [25,26], we have
also observed that the oil recovery after specific runs often varied
without clear dependency on pressure while cumulative recovery
of all three runs demonstrated more clear tendency. In order to esti-
mate the effects of temperature and sand sorting, the cumulative
recoveries of three runs were compared.
3.3. Comparison of cumulative, vapor and total recoveries
The cumulative recovery of all three runs was calculated by Eq.
(3) in order to make correction for the content of fine sand. At 70 ◦ C,
the cumulative fine sand content after three runs was 8.2% and
11.32% at 45 and 55 MPa, respectively, whereas almost no precipi-
tate was observed at 35 and 65 MPa. At 80 ◦ C, the fine sand content
was 10% on average at 35 and 45 MPa and about 6% on average at
55 and 65 MPa.
Cumulative recovery, total recovery and vapor recovery of used
motor oil at 70 ◦ C and 80 ◦ C from Sand 1 and Sand 2 (sieved) cor-
rected for the sand and water content were plotted in Fig. 4. The
cumulative recovery of UMO from Sand 1 varied from 42.6 to 75.6%
(64.1% on average) at 70 ◦ C and from 35.7 to 68.4% (50.7% on aver-
age) at 80 ◦ C. The CR at 70 ◦ C were substantially higher than at 80 ◦ C
at 45 and 55 MPa while they were close at 35 and 65 MPa. The CR
from Sand 2 varied from 14 to 60% (46% on average) at 70 ◦ C and
from 21 to 49% (42% on average) at 80 ◦ C, in the pressure range of
35–65 MPa. For 70 ◦ C, the average CR of UMO from Sand 1 was 17.2%
higher than from Sand 2 over the entire pressure range. The CR of
Sand 2 and Sand 1 at 80 ◦ C are close at 45 and 55 MPa. For Sand 2 at
both temperatures, the recoveries are lower than of Sand 1 at 80 ◦ C
at 35 and 65 MPa while they are close at 45–55 MPa.
All four curves of vapor recovery decline at increasing pressure
indicating that higher pressures suppress vaporization of UMO.
The vapor recoveries are very high at 35 MPa from Sand 2: 35%
at 70 ◦ C and 58% at 80 ◦ C. The VR from Sand 2 is higher for 80 ◦ C
at 35–45 MPa by 19% on average while they are very close at
55–65 MPa.
Similarly, the VR from Sand 1 is higher at 80 ◦ C than at 70 ◦ C by
5.5% on average at 35–45 MPa, and they are very close at 55–65 MPa.
This implies that the presence of fine sand in Sand 1 prevents high
vaporization of the UMO.
The high vaporization of UMO at lower pressures is unexpected
because volatility of motor oil is typically low. The SC-CO2 has a
strong ability to vaporize various liquids but the vapor phase trans-
ported by gas was not collected by existing collecting system after
the gas release. The solubility in SC-CO2 depends on volatility of the
compounds which increases with the temperature rise. The effect of
volatility prevails at lower pressures leading to higher vapor recov-
ery and lower liquid recovery [24]. As example, the vapor recovery
from oil sand reached 15–20% while the outgassing losses were
only 0.27% when it was heated at 120 ◦ C for 2 h [26].
We have shown earlier [18] that the deviations on the curves
of liquid phase recovery are influenced by the deviations of the
vapor phase recovery while the curves of the total recovery are
typically sustainable. The results of the current study confirm those
observations. The TR curve of Sand 1 at 70 ◦ C increased from 35 MPa
to the breakover point at 45 MPa with no substantial variations at
higher pressures. The decrease at 45 MPa was caused by high yield
of fine sand. The TR curve of Sand 2 at 70 ◦ C followed the TR curve
of Sand 1 at the same temperature lower by 15% on average. This
demonstrated better extraction of the UMO in the presence of fine
sand over entire pressure range, compared to sand having bigger
grains.
At 80 ◦ C, the TR curve of Sand 1 increased while it decreased
for Sand 2 at the increasing pressure, intercepting at about 55 MPa.
The decreasing trend of TR for Sand 2 at 80 ◦ C was caused by the
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Fig. 3. Recoveries of used motor oil and co-extracted sand after specific runs from Sand 1 and Sand 2 (sieved) at 70 ◦ C and 80 ◦ C.

Fig. 4. Recovery of used motor oil after three runs: a) cumulative recovery of liquid phase, b) vapor recovery and c) total recovery of used motor oil at 70 ◦ C and 80 ◦ C from
Sand 1 and Sand 2 (sieved). Sand recovery from Sand 1 is excluded.

decrease of VR, which reached above 30% at 35 MPa and declined
with the pressure rise. At higher temperature of 80 ◦ C, the vapor-
ization of the UMO from Sand 2 increased and was much higher
compared to Sand 1 in the absence of fine sand. The TR of Sand 1 at
80 ◦ C were close to those of Sand 2 at 45–55 MPa.
3.4. Effect of sand sorting on UMO recovery
As follows from Fig. 4, the CR and TR from Sand 1 is greater
than from Sand 2 (sieved) at 70 ◦ C at all pressures. The amount of
sand and UMO were equal in Sand 1 and Sand 2. Hence, the greater
recovery should be attributed to the presence of fine sand. With
Sand 1, the space between the sand grains is filled not only with
motor oil but also with fine sand particles. Reverchon and De Marco,
2006 noted that particle size plays a determining role in extraction
processes controlled by internal mass transfer resistances, since a
smaller mean particle size reduces the length of diffusion of the
solvent [27].
Experiments on extraction of essential oils from seeds, plants
and organic matters from oil shales [22,27,28] demonstrate that
the decrease of particle size increases the extraction rate due to an
increase in exposed sample surface area, which enhances accessi-
bility of the solvent to the extractable compounds and enhances
mass transfer through the sample matrix. Rincon et al. used glass
beads of 3 mm diameter to clean used motor oil by ethane [6]. The
fine sand probably increased the contact surface between SC-CO2
and UMO, which led to the higher recovery from Sand 1 at 70 ◦ C.
3.5. Visual observations of extracted UMO
A visual inspection of all of the investigated sand samples at the
end of the experiments at 70 ◦ C revealed that the sand was clean
at 55 and 65 MPa, as shown in Fig. 5. The dark black colour had

Please cite this article in press as: S. Rudyk, P. Spirov, Temperature effect on extraction and purification of used motor oil by supercritical
carbon dioxide, J. Supercrit. Fluids (2017), http://dx.doi.org/10.1016/j.supflu.2017.03.001
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Fig. 5. Photo of contaminated sand before (to the left) and after (to the right) SC-CO2 extraction.

Fig. 6. Photographs of the: a) typical fresh motor oil; b) and c) after SC-CO2 extraction at 70 ◦ C (water is on the bottom of the third test tube).

disappeared, the sand was dry, and even the smell of used motor oil
was no longer noticeable. However, because of the vertical position
of the samples in the extractor, the bottom part of the sand packs
still contained black engine-wear residues. At lower pressures at
70 ◦ C and at all pressures at 80 ◦ C, the sand samples were blacker
at the end of the experiments because of lower recovery.
Purification of UMO by vacuum distillation and hydro-treatment
involve difficulties and additional costs of sludge disposal. In the
described process the sand was not wet after SC-CO2 extraction at
70 ◦ C and higher pressures. The remaining soot and metal particles
can be washed out of the sand and collected on a filtering surface
in order to clean the sand completely.
Visual observation of the samples of motor oil collected in the
test tubes after extraction showed that most of them were of a
transparent reddish-brown colour (Fig. 6). The colour is similar to
that of the regenerated used motor oil obtained using the distilla-
tion method that has been described elsewhere [5].
All the samples recovered from Sand 1 at 70 ◦ C were transpar-
ently clean. All of the extracted samples from Sand 2 (sieved) at
70 ◦ C were also transparent and clean with the exception of the
sample extracted after the first run at 65 MPa.
The samples extracted from Sand 1 after all three runs at 35 MPa
and after the first run at 45 MPa at 80 ◦ C were black, with the consis-
tency of initial UMO. The rest of the samples extracted from Sand 1
at 80 ◦ C were clean, although they were darker than those extracted
at 70 ◦ C, which is indicative of the higher content of heavier hydro-
carbon fractions [19]. With extraction at 80 ◦ C, clean UMO samples
were obtained from Sand 2 only at 45 MPa and after a third run at
35 MPa. As a conclusion, better purification of UMO was obtained
at lower temperature of 70 ◦ C and from unwashed sand. Without
use of sand, the extracted UMO samples were similar to the original
UMO and contained lees [16].
3.6. GC–MS chromatography
The detailed analyses of typical motor oil can be found in sev-
eral recently published studies [29–31]. In this paper we present
results of GC–MS analysis of only three samples, which was made
in order to find out whether the extraction progression can be
observed comparing the fingerprints and compositions of the
extracts obtained after specific runs.
The chromatograms of UMO samples extracted at 45 MPa at
70 ◦ C from Sand 2 are shown in Fig. 7 and compositions are given in

Please cite this article in press as: S. Rudyk, P. Spirov, Temperature effect on extraction and purification of used motor oil by supercritical
carbon dioxide, J. Supercrit. Fluids (2017), http://dx.doi.org/10.1016/j.supflu.2017.03.001
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Table 1
Chemicals detected by GC–MS in the samples extracted from Sand 2 at 45 MPa and 70 ◦ C after Run 1, 2 and 3.
Chemicals Comments
1,2,3 Common chemicals for all three runs detected
in the samples
1 Additional substances detected in the sample
after Run 1.
2 Additional substances detected in the sample
after Run 2.
3 Additional substances detected in the sample
after Run 3.
Fig. 7. Example of GC–MS chromatograms of used motor oil samples extracted from
Sand 2 at 45 MPa and 70 ◦ C after run 1, 2 and 3.
Table 1 for example. The colours of the samples of first and second
runs are similar and lighter than after a third run.
The chromatograms have typical for used motor oil shape with
particularly pronounced areas of the unresolved humps (UCM),
examples of which can be found in [32–34]. The peaks of single
carbon number groups are short as a result of the solvent dewax-
ing which removes mainly the higher molecular weight of normal
paraffins [31].
The chromatograms of various runs unsubstantially differ
mainly by the areas of the unresolved humps (UCM). The compo-
sition of samples extracted after each of the run, however, differ
regardless a large number of similar components found in all sam-
ples (Table 1). Larger area of UCM hump of the sample of third run
and darker colour of this sample indicate its heavier composition. It
can be noticed that the number of components and an area of UCM
hump in a sample extracted after second run is less than after first
and third runs.
Biomarkers are one of the most important hydrocarbon groups
in petroleum for chemical fingerprinting used for characterization,
correlation, differentiation, and source identification in environ-
mental forensic investigations of oil spills [32].
Target biomarkers are abundant in lubricating oils compared
to crude oil from which they are produced. The biomarkers of
synthetic lubricating oil are usually low in abundance; they have
Please cite this article in press as: S. Rudyk, P. Spirov, Temperature effect on extraction and purification of used motor oil by supercritical
carbon dioxide, J. Supercrit. Fluids (2017), http://dx.doi.org/10.1016/j.supflu.2017.03.001
7
Run
Cyclohexane, dodecyclohexane, octane, nonane, decane, pentadecane,
hexadecane, hexacosanolnonadecane, heptadecane, nonadecane,
dodecane, triacontane, dotriacontane, tetracontane, tritetracontane,
tetratetracontane, tetrapentacontane pentatriacontane,
henriacontane, pentacosane, heneicosane, eicosane, squalane,
tridecanol, tetracosanol, hentetracontanol,
tetramethyldecahydrocyclopropa(d)naphthalene,tetradecanedulfonic
acid, disulfide, isobutyl.
Octadecane, nonadecane, tetraoxacyclododecane,
methyldotriacontane, cyclopentadecane, methylenesuccinate,
dioxolane, chloroasetic acid, benzenedicarboxylic acid, propanedioic
acid, hexacosanol, heptadecanol, isoheptadecanol, hentetracontanol,
trihexadecyl borate, dihydroxyisopropyl, butyl ester,
methylheptacosane, DL-Xylitol, norabietane
Undecane, tridecane, nonane, octacosane, nonacosane,
nonylcyclohexane, isopropenyl, nonadiene, 3-buten.
Biomarkers: stigmastane, coprostane (26.26 min), gammacerane,
baccharane (28.82 min).
Methoxyacetic acid, isooctyl mercaptopropionate,
tetraoxacyclododecane, nanocosane, octatriacontane, hexaacosanol,
triacontanol, ethanone, silane, methyldotriacontane, docosane,
nonylcyclohexane, benzenedicarboxylic acid, tridecane,
octadecanamide, hexatriacontane, octadecane, pregnan,
tetramethyl-dodecahydrobenzochromen, sclareol oxide, nonacosane,
dodecatrien, methanoazulen, oxaspirol, naphtalenemethanol,
carboxylic acid.
Biomarkers: stigmastane, cholestane, coprostane (26.26 min).
a different distribution and clearly pronounced UCMs [32–34].
Such biomarkers as stigmastane, coprostane, cholestane, gammac-
erane, baccharane were detected in the samples of first and second
runs by comparison with spectra available in NIST library (Fig. 8).
Spectra of gammacerane and baccharane are shown as example.
Gammacerane has frequently been associated with hypersaline
lacustrine environments to be a reliable geochemical indicator for
water column stratification in marine deposits [35]. Baccharane is a
rare biomarker associated with Impatiens balsamina, an indigenous
plant of southern Asia in India and Myanmar, also largely cultivated
in China [36].
4. Effect of temperature on UMO purification
The described experiment demonstrates the remarkable tem-
perature effect on the capability of SC-CO2 to dissolve preferentially
the base oil fraction of UMO and separate residues. The material
treated in the described investigation is a suspension consisting of
a liquid mixture (base oil) that contains solid compounds (lees) dis-
solved in it. The performed extraction process may be considered
as a flow of suspension through porous media, details of which can
be found in [37–39]. The liquid-solid separation by filtration can
be accomplished by retention of the suspended particles inside a
porous bed [39].
At least two counteracting forces act on particles contained in
UMO: advective particle transport by flow of SC-CO2 /UMO mix-
ture and particle retention [38]. The particles entrained by various
retention forces and capture processes are stabilized and retain
inside the porous media while fluid flows freely through the matrix.
The fine sand particles present in the Sand 1 increased filtering
efficiency of porous media. Partly they clogged the pores, enhanced
number of retention sites and increased capture of contaminants
particles.
Stabilization of particles can be distorted by the increasing
velocity of flow or changes of fluid viscosity. In the described case,
the increase of temperature caused the UMO viscosity decrease,
which led to the mobilization and movement of particles with the
carrier upon SC-CO2 release. In this regards, it needs to note that
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Fig. 8. Example of mass spectra and library match indicating biomarkers in the sample at 45 MPa and 70 ◦ C (Sand 2) after Run 2.
at some pressure and temperature conditions clean UMO was only
obtained after second or third runs. This shows that the destabi-
lized particles were removed after first runs while the rest particles
retained in the porous media. The similar effects were observed in
our experiments with oil sand. The extracted bitumen was black
after first runs and orange after subsequent runs when extracted
by pure SC-CO2 [25,26]. On the other side, at 70 ◦ C fine sand parti-
cles were extracted together with clean UMO while contaminants
particles retained in the porous media.
It can be deduced that the addition of other adsorbents, such as
powder, can provide better extraction and purification results.
5. Conclusions
The results of the SC-CO2 extraction experiments demonstrate
that by manipulating pressure and temperature, different aims can
be addressed. At higher temperature of 80 ◦ C, the base oil of UMO
is not separated from the contaminants, a factor which is relevant
for the purposes of sand remediation. On the other hand, extrac-
tion of motor-oil fractions being transparent and light in colour,
achieved at lower temperature of 70 ◦ C, suggests that this method
could be employed for the purification and regeneration of UMO
using SC-CO2 . The greater recoveries, lower outgassing losses and
better purification of used motor oil were obtained from the sand
containing fine sand.
The described method has great potential for use in the clean-
ing of used motor oil as independent method or in pre-cleaning
before vacuum distillation to avoid coking and column fouling [9].
Please cite this article in press as: S. Rudyk, P. Spirov, Temperature effect on extraction and purification of used motor oil by supercritical
carbon dioxide, J. Supercrit. Fluids (2017), http://dx.doi.org/10.1016/j.supflu.2017.03.001
The method seems to be fast, easy to manage, does not require a
great deal of space or special materials such as membranes, and it
is capable of treating small volumes of UMO.
The next steps of the investigation will be directed toward
upscaling of the extraction unit which must include the CO2 -
recycling process. The operation plant should be designed, built
and operated to verify whether the SC-CO2 extraction method can
be effectively applied on an industrial scale, and to obtain the data
necessary for accurate economic forecasts.
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