2nd International Conference on Agricultural, Environment and Biological Sciences (ICAEBS'2013) Dec.
17-18, 2013 Pattaya (Thailand)
Influence of Solvents on the Extraction of Oil
from Waste Lubricating Grease:
A Comparative Study
Motshumi Diphare, and Edison Muzenda
Abstract—In this study, the performance of six extracting
solvents (n-hexane, toluene, heptane, butane, 1-hexanol, and acetone)
was evaluated. The recovery of base oils from waste lithium based
lubricating grease was investigated using thermal degradation in an
aqueous caustic solution and solvent extraction. Waste grease was
initially dissolved in a basic solution at 80oC while being agitated.
During this stage most of the oil was recovered. The remaining
sludge was cooled to 45oC followed by addition of a solvent to
extract the remaining oil. This research further optimised the process
by studying the effect of various degrading agents (LiOH, NaOH and
KOH) and various solvents (n-hexane, toluene, heptane, butane,
hexanol and acetone) on oil recovery. KOH and Hexane produced the
highest recovery of 39% and 74.39% respectively.
Keywords—Base, Extraction, Oil Recovery, Solvent Extraction,
Waste Grease
I. INTRODUCTION
S OLVENT extraction is the ability of a solute to distribute
itself between an aqueous solution and an immiscible
organic solvent. The organic solvent separates and purifies the
solutes by extracting into the organic phase, leaving
undesirable substances in the aqueous phase [1]. Over the
years, fossil fuels have been the cheapest source for petroleum
and this led to the development of millions of petroleum based
products. However, fuel price and demand have reached
record high in recent times triggered by factors such as
depletion of easily accessible deposits and ever increasing
demand for energy by emerging economies [2].
Steady decline in valuable petroleum commodity against
ever-increasing demand has drove researchers to search for
alternative resources for energy and chemicals. This includes
recycling these hydrocarbons using sustainable methods.
Used lubricant contains a large proportion of valuable base
oil that may be used to formulate new lubricants if undesired
pollutants are removed [3].
Many processes [3] for recycling used lubricating oil
Motshumi Joseph Diphare is with the Department of Chemical
Engineering, Faculty of Engineering and the Built Environment, University of
Johannesburg, Doornfontein, Johannesburg 2028, (email:
dipharej@gmail.com).
Edison. Muzenda is a full Professor of Chemical Engineering, is with the
Department of Chemical Engineering, Faculty of Engineering and the Built
Environment, University of Johannesburg, Doornfontein, Johannesburg 2028,
South Africa, Tel: +27115596817, Fax: +27115596430, (Email:
emuzenda@uj.ac.za).
76
involve the use of vacuum distillation followed by a polishing
or decolorizing treatment. However, they present serious
problems related to coking and column fouling during
distillation and, therefore, some form of pre-treatment to
remove additives and contaminants from the oil is required.
Furthermore these types of processes are energy demanding
due to the high overpressures, deep vacuums and high
temperatures applied [4]. The use of extraction has been
studied as a low energy consuming alternative by a number of
researchers.
A solvent is used selectively to extract the base oil
component from the waste lubricant oil. The additives and
carbonaceous impurities that are normally present in used oil
should be rejected by the extracting solvent. These impurities
settle and flocculate based on gravity [5]. The solvent is then
recovered by distillation for reuse. However, a portion of this
solvent is lost due evaporation during treatment.
Hexane is the solvent of choice for oil extraction mainly
due to its efficiency and ease of recovery [4]. Reference [6]
reported that hexane is obtained from a non-renewable source
and is being consumed faster to the emergence of new sources.
It has become necessary to find alternative solvents for oil
extraction.
The extractability of oil depends on the nature of the solvent
and oil, extraction temperature, contact time between solvent
and the feed, pre-treatment conditions of the oil bearing
resource [7]. Key properties such as solubility are necessary to
evaluate the solvent performance [8]. Reference [9] reported
that an increase in solubility parameter difference further
enhances the solvent capability to extract the additives and
impurities from used oil.
Reference [10] compared the performance of several
solvents to extract fuel oil from oil sludge at room
temperature. They first used methyl ethyl ketone (MEK) and
then LPG condensate at solvent-to-sludge mass ratios ranging
from 1:1 to 6:1. The optimum ratio was found to be 4:1.
Additional solvents included heptane, hexane, iso-propanol,
and iso-butanol. Oil recovery ranged from 8% for the iso-
butanol to 39% for the MEK.
Reference [11] used supercritical ethane and
dichloromethane to extract hydrocarbons from petroleum
sludge using Soxhlet extraction. Recovery ranged from 16% to
55% for supercritical ethane and dichloromethane
respectively.
 2nd International Conference on Agricultural, Environment and Biological Sciences (ICAEBS'2013) Dec. 17-18, 2013 Pattaya (Thailand)
The objective of this study was to evaluate the oil recovery
through degradation-flocculation and solvent extraction. The
influence of various solvents and degrading agents on oil
recovery was investigated.
II. MATERIALS AND METHODS
A. Materials
Technical grade n-hexane, toluene, heptane, butane,
hexanol and acetone (95%), and analytical grade potassium
hydroxide (KOH), sodium hydroxide pellets and lithium
hydroxide (99.9%) were supplied by Laboratory Equipment
Supplies (Pty) Ltd. (Germiston, South Africa). The
contaminated high temperature metal bearing grease was
supplied by the Engine Petroleum (Pty) Ltd.
B. Method
A basic solution was heated to 80oC, followed by a slow
addition of 100g of waste grease while agitating at 1000 rpm.
After 12min of agitation, brownish oil started to float. The oil
was decanted and labelled stage 1 oil. The remaining sludge
was then left cool to 45oC. Subsequently a solvent was
introduced to extract the remaining oil while agitating. A
detailed description of the process was previously discussed
by the authors [12].
III. RESULTS AND DISCUSSION
A solvent should dissolve base oil and precipitate other
substances to form sludge. n-hexane, toluene, heptane, butane,
hexanol and acetone were selected due to their good solubility
parameters for base oil and good anti-solvent effect for
nonpolar or slightly polar polymeric additives, metals and
carbonaceous particles.
Fig. 1 shows variation of oil recovery with the use of
various solvents. n-Hexane gave the highest recovery of
74.39% while acetone gave the lowest of 7.43%. The
difference between them is related to the solubility of the base
oil in these solvents. The performance of the extraction agents
can also be related to the different interaction between the
solvent and oil molecules, due to the size of the main carbon
chain and the solvent molecules configuration [13]. Reference
[14] reported that the polarity of solvent is significant to the
extraction efficiency in removing oil contaminants. Thus, a
solvent has good dissolving ability when its polarity is similar
to that of oil.
The recovery increased with increase in solvent carbon
chain. This is mainly because carbon atoms lose hydrogen
ions and act as a carrier medium for the oil molecules.
However, this contradicts the findings in this work for n-
hexane and heptane. n-hexane extracts more oil because of its
favourable interaction and affinity for oil than heptane.
Previous studies [13, 15] have shown that n-hexane has
good oil extraction ability on used lubricants. Moreover other
factors such as physical properties of the solvent, particularly
its low boiling point attribute to the choice of n-hexane as the
optimum solvent [16]. Toluene was found to be the second
best extracting agent. Reference [17] compared extraction of
77
oil from lubricating grease using toluene and methyl-tert-
butyl-ether (MTBE). The tests results indicated that toluene
was most suitable for this application based on its higher 26
w/w% of oil recovery than 19.6% for MTBE.
Reference [18] reported that the extracting solvent must
have two important properties; they should be miscible with
the base oil contained in the waste oil being processed and
must reject from the solution the used oil impurities allowing
their aggregation to particle sizes big enough to separate from
the liquid by sedimentation.
75
70
65
60
55
Oil Recovery (%)
50
45
40
35
30
25
20
15
10
5
0
Solvent
Fig. 1 Effect of various solvents on oil recovery
Table I shows the various degrading agents investigated in
this study. Fig. 2 shows the influence of various degrading
agents on oil recovery. Reference [13] reported that addition
of a base promotes a fast flocculation of the impurities, which
are segregated from the base oil by the solvent. The
flocculation is enhanced in the presence of OH groups that
neutralize the electrostatic repulsion. This electrostatic
repulsion exists since alcohol groups are linked with the ions
from the additive. Furthermore, addition of a solution
containing ions that neutralize those charges, break this
stability. Participation of alcohol OH groups in ion exchange
reactions with the electrolyte ions helps to neutralize the
electrostatic repulsion.
Effective separation of thickening agent from primary base
oil in used grease is mainly influenced by the properties of the
degrading agent used such as solubility in water, concentration
and temperature. Alkali-hydroxides are highly soluble in water
compared to alkali-carbonates and they tend to have a strong
affinity of hydrolysing grease molecules in suspension [17].
At the molecular level, KOH is slightly smaller than NaOH,
therefore it can penetrate grease matrix faster than NaOH.
This makes KOH to ionize quickly in water and form stronger
nucleophile OH- ions for breaking polar bonds that holds the
thickener and base oil in grease.
LiOH is less basic, therefore it is unable to donate OH- ions
rapidly compared to sodium, potassium and other alkali
 2nd International Conference on Agricultural, Environment and Biological Sciences (ICAEBS'2013) Dec. 17-18, 2013 Pattaya (Thailand)

metals. The ability of strong inorganic degrading agent
depends on the base metal reactivity and concentration. A base
is a proton acceptor and the more readily willing it is to accept
a proton, the stronger it is. The base molecule, X-O-H,
dissociates in water forming X+ ions and OH-. The hydrogen
molecule in the oil molecule C-R-H (the C-R- represents a
carbon structure) attaches itself to the OH- in the aqueous
solution and forms water and the remaining C-R- oil molecule.
40
30
Oil Recovery (%)
experimental work. The department of Chemical Engineering
at the University of Johannesburg is acknowledged for
funding the research as well as conference attendance.
REFERENCES
[1] J. Rincon, P. Canizares, M.T. Garcia, “Regeneration of Used Lubricant
Oil by Polar Solvent Extraction,” Ind. Eng. Chem. Res., vol. 44, pp.
4373 – 4379, 2005
[2] W. W. Zmierczak, J. D. Miller, “Process for catalytic conversion of
lignin to liquid bio-fuels and novel bio-fuels,” U.S. Patent
20,080,050,792; 2008
[3] J. Rincon, P. Canizares, M. T. Garcia, “Regeneration of used lubricant
oil by ethane extraction,” J. of Supercritical Fluids, vol. 39, pp. 315-322,
2007
[4] J. Lucik, A. Orlovic, M. Spiteller, J. Jovanovic, D. Skala, “Re-refining
of waste mineral insulating oil by extraction with N-methyl-2-
pyrrolidone,” Seperation and Purification Technology, vol. 51, pp. 150-
156, 2006

[5] Al-Zahrani. S. M, Putra. M. D, “Used lubricating oil regeneration by

20 various solvent extraction techniques,” J. of Industrial and Enginnering
Chemistry, vol. 19, pp. 536-539, 2013
10 [6] W. Hamm, “Extraction, liquid-solid,” Kirk-Othmer Encyclopedia of
Chemical Technology, vol. 9, 3rd edition, Wiley Interscience Publishers,
New York, pp. 724, 1980
0 [7] S. D. Shulka, G. N. Pandey, “A Textbook of Chemical Technology,”
LiOH NaOH KOH vol. 2, Vikas, New Delhi, pp. 189-199, 1979
[8] N.O. Elbashir, “The Effect of Design Parameters on the Solvent
Base Solution Extraction Performance for Recycling of Used Oil,” M. Eng. Thesis,
University of Technology Malaysia, 1998
Fig. 2 Effect of various degrading agents on oil recovery [9] N.O. Elbashir, S.M. Al-Zahrani, M.I. Abdul Mutalib, A.E. Abasaeed,
“Chemical Engineering and Processing: Process Intensification,” vol. 41
Reference [19] reported that first ionization energy of group pp. 765, 2002
[10] D. M. Abouelnasr, E. Zubaidy, “Treatment and recovery of oil-based
1 alkali metals decreases down the group on the periodic table. sludge using solvent extraction,” Proceedings of the Abu Dhabi
When a metal reacts, it loses electrons to form ions with stable International Petroleum Exhibition and Conference, 2008
electron configurations. When a lot of energy is required for it [11] M. A. Ávila-Chávez, R. Eustaquio-Rincón, J. Reza, A. Trejo,
to lose electrons, it is going to be less likely to react than a “Extraction of hydrocarbons from crude oil tank bottom sludges using
supercritical ethane,” Separation Science and Technology, vol. 42, pp.
metal that easily sheds electrons. Therefore, the higher the 2327–2345, 2007
ionization energy for alkali metals, the lesser is the reactivity. [12] M.J Diphare, J. Pilusa, E. Muzenda, “The Effect of Degrading Agents
Also, as you go down the group, the distance between the and Diluents on Oil Recovery from Lithium Based Waste Lubricating
Grease, ICEAFS, Kuala Lampur (Malaysia), August 25-26, 2013
nucleus and the outer electrons increases. The electrons [13] R. M. Rafie, A.R. I. Inaam, H.T. Alladdin, M. Gordon, “Waste
therefore become easier to remove since the atoms get bigger lubricating oil treatment by extraction and adsorption,” Chemical
and the reactivity increases. There are more shells preventing Engineering Journal, vol. 220, pp 343–351, 2013
[14] L. Xingang, D. Yongliang, W. Guozhong, L. Zhongyuan, L. Hong, S.
the attraction between the positive nucleus and the negatively Hong, “Solvent extraction for heavy crude oil removal from
charged outer electron reducing the electrostatic force. Based contaminated soils,” Chemoshere, vol. 88, pp. 245-249, 2012
on this, KOH was found to be the optimum degrading agent. [15] L. Wang, M. Zhang, X. Wang, W. Liu, “The preparation of CeF3
nanocluster capped with oleic acid by extraction method and application
to lithium grease,” Material Research Bulletin, vol. 43, pp. 2220–2222,
2008
TABLE I [16] A. L. Ahmad, I. Norliza, I. Suzylawati, B. Subhash, “Coagulation-
PROPERTIES OF GROUP 1 ALKALI HYDROXIDES AS GREASE DEGRADING Sedimentation-Extraction Pretreatment Methods for the Removal of
AGENTS [17] Suspended Solids and Residual Oil from Palm Oil Mill Effluent
(POME), Engineering Journal, vol. 3, No. 1, pp. 25-30, 2008
Degrading Solubility H2O @ Basicity (pKb) Cost
[17] T.J. Pilusa, E. Muzenda, M. Shukla, “Thermo-chemical extraction of
reagent 30°C (g/100ml) (US$/kg)
fuel oil from waste lubricating grease,” Waste Management, vol. 33, pp.
12.8 -0.36 6.38 1509-1515, 2013
LiOH [18] SRS Engineering Corporation: Biodiesel Technology, Solvent
NaOH 111 0.2 1.42 Extraction. Accessed August 21 2013, from
KOH 121 0.5 2.11 http://www.srsengineering.com/SolventExtractors.aspx.
[19] Atomic and Physical Properties of Periodic Table Group 1 – Chemguide.
Accessed September 4 2013 from
http://www.chemguide.co.uk/inorganic/group1/properties.html
ACKNOWLEDGMENT
The The authors are grateful to the National Research
Foundation of South Africa (NRF), and the Council of
Scientific and Industrial Research (CSIR) for providing
bursaries to the first author. Boipelo Molotoane for her
significant contribution in planning and conducting of

78