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

involve the use of vacuum distillation followed by a polishing

Abstract—In this study, the performance of six extracting or decolorizing treatment. However, they present serious
solvents (n-hexane, toluene, heptane, butane, 1-hexanol, and acetone) problems related to coking and column fouling during
was evaluated. The recovery of base oils from waste lithium based distillation and, therefore, some form of pre-treatment to
lubricating grease was investigated using thermal degradation in an remove additives and contaminants from the oil is required.
aqueous caustic solution and solvent extraction. Waste grease was
initially dissolved in a basic solution at 80oC while being agitated. Furthermore these types of processes are energy demanding
During this stage most of the oil was recovered. The remaining due to the high overpressures, deep vacuums and high
sludge was cooled to 45oC followed by addition of a solvent to temperatures applied [4]. The use of extraction has been
extract the remaining oil. This research further optimised the process studied as a low energy consuming alternative by a number of
by studying the effect of various degrading agents (LiOH, NaOH and researchers.
KOH) and various solvents (n-hexane, toluene, heptane, butane, A solvent is used selectively to extract the base oil
hexanol and acetone) on oil recovery. KOH and Hexane produced the
highest recovery of 39% and 74.39% respectively. component from the waste lubricant oil. The additives and
carbonaceous impurities that are normally present in used oil
Keywords—Base, Extraction, Oil Recovery, Solvent Extraction, should be rejected by the extracting solvent. These impurities
Waste Grease settle and flocculate based on gravity [5]. The solvent is then
recovered by distillation for reuse. However, a portion of this
I. INTRODUCTION solvent is lost due evaporation during treatment.
Hexane is the solvent of choice for oil extraction mainly
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
due to its efficiency and ease of recovery [4]. Reference [6]
reported that hexane is obtained from a non-renewable source
solutes by extracting into the organic phase, leaving and is being consumed faster to the emergence of new sources.
undesirable substances in the aqueous phase [1]. Over the It has become necessary to find alternative solvents for oil
years, fossil fuels have been the cheapest source for petroleum extraction.
and this led to the development of millions of petroleum based The extractability of oil depends on the nature of the solvent
products. However, fuel price and demand have reached and oil, extraction temperature, contact time between solvent
record high in recent times triggered by factors such as and the feed, pre-treatment conditions of the oil bearing
depletion of easily accessible deposits and ever increasing resource [7]. Key properties such as solubility are necessary to
demand for energy by emerging economies [2]. evaluate the solvent performance [8]. Reference [9] reported
Steady decline in valuable petroleum commodity against that an increase in solubility parameter difference further
ever-increasing demand has drove researchers to search for enhances the solvent capability to extract the additives and
alternative resources for energy and chemicals. This includes impurities from used oil.
recycling these hydrocarbons using sustainable methods. Reference [10] compared the performance of several
Used lubricant contains a large proportion of valuable base solvents to extract fuel oil from oil sludge at room
oil that may be used to formulate new lubricants if undesired temperature. They first used methyl ethyl ketone (MEK) and
pollutants are removed [3]. then LPG condensate at solvent-to-sludge mass ratios ranging
Many processes [3] for recycling used lubricating oil 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-
Motshumi Joseph Diphare is with the Department of Chemical
Engineering, Faculty of Engineering and the Built Environment, University of butanol to 39% for the MEK.
Johannesburg, Doornfontein, Johannesburg 2028, (email: Reference [11] used supercritical ethane and
[email protected]). dichloromethane to extract hydrocarbons from petroleum
Edison. Muzenda is a full Professor of Chemical Engineering, is with the
Department of Chemical Engineering, Faculty of Engineering and the Built sludge using Soxhlet extraction. Recovery ranged from 16% to
Environment, University of Johannesburg, Doornfontein, Johannesburg 2028, 55% for supercritical ethane and dichloromethane
South Africa, Tel: +27115596817, Fax: +27115596430, (Email: respectively.
[email protected]).

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 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 oil from lubricating grease using toluene and methyl-tert-
through degradation-flocculation and solvent extraction. The butyl-ether (MTBE). The tests results indicated that toluene
influence of various solvents and degrading agents on oil was most suitable for this application based on its higher 26
recovery was investigated. w/w% of oil recovery than 19.6% for MTBE.
Reference [18] reported that the extracting solvent must
II. MATERIALS AND METHODS have two important properties; they should be miscible with
the base oil contained in the waste oil being processed and
A. Materials
must reject from the solution the used oil impurities allowing
Technical grade n-hexane, toluene, heptane, butane, their aggregation to particle sizes big enough to separate from
hexanol and acetone (95%), and analytical grade potassium the liquid by sedimentation.
hydroxide (KOH), sodium hydroxide pellets and lithium
hydroxide (99.9%) were supplied by Laboratory Equipment
Supplies (Pty) Ltd. (Germiston, South Africa). The 75
contaminated high temperature metal bearing grease was 70
65
supplied by the Engine Petroleum (Pty) Ltd. 60
B. Method 55

Oil Recovery (%)

50
A basic solution was heated to 80oC, followed by a slow 45
addition of 100g of waste grease while agitating at 1000 rpm. 40
After 12min of agitation, brownish oil started to float. The oil 35
was decanted and labelled stage 1 oil. The remaining sludge 30
was then left cool to 45oC. Subsequently a solvent was 25
introduced to extract the remaining oil while agitating. A 20
detailed description of the process was previously discussed 15
10
by the authors [12]. 5
0
III. RESULTS AND DISCUSSION
A solvent should dissolve base oil and precipitate other
substances to form sludge. n-hexane, toluene, heptane, butane, Solvent
hexanol and acetone were selected due to their good solubility Fig. 1 Effect of various solvents on oil recovery
parameters for base oil and good anti-solvent effect for
nonpolar or slightly polar polymeric additives, metals and Table I shows the various degrading agents investigated in
carbonaceous particles. this study. Fig. 2 shows the influence of various degrading
Fig. 1 shows variation of oil recovery with the use of agents on oil recovery. Reference [13] reported that addition
various solvents. n-Hexane gave the highest recovery of of a base promotes a fast flocculation of the impurities, which
74.39% while acetone gave the lowest of 7.43%. The are segregated from the base oil by the solvent. The
difference between them is related to the solubility of the base flocculation is enhanced in the presence of OH groups that
oil in these solvents. The performance of the extraction agents neutralize the electrostatic repulsion. This electrostatic
can also be related to the different interaction between the repulsion exists since alcohol groups are linked with the ions
solvent and oil molecules, due to the size of the main carbon from the additive. Furthermore, addition of a solution
chain and the solvent molecules configuration [13]. Reference containing ions that neutralize those charges, break this
[14] reported that the polarity of solvent is significant to the stability. Participation of alcohol OH groups in ion exchange
extraction efficiency in removing oil contaminants. Thus, a reactions with the electrolyte ions helps to neutralize the
solvent has good dissolving ability when its polarity is similar electrostatic repulsion.
to that of oil. Effective separation of thickening agent from primary base
The recovery increased with increase in solvent carbon oil in used grease is mainly influenced by the properties of the
chain. This is mainly because carbon atoms lose hydrogen degrading agent used such as solubility in water, concentration
ions and act as a carrier medium for the oil molecules. and temperature. Alkali-hydroxides are highly soluble in water
However, this contradicts the findings in this work for n- compared to alkali-carbonates and they tend to have a strong
hexane and heptane. n-hexane extracts more oil because of its affinity of hydrolysing grease molecules in suspension [17].
favourable interaction and affinity for oil than heptane. At the molecular level, KOH is slightly smaller than NaOH,
Previous studies [13, 15] have shown that n-hexane has therefore it can penetrate grease matrix faster than NaOH.
good oil extraction ability on used lubricants. Moreover other This makes KOH to ionize quickly in water and form stronger
factors such as physical properties of the solvent, particularly nucleophile OH- ions for breaking polar bonds that holds the
its low boiling point attribute to the choice of n-hexane as the thickener and base oil in grease.
optimum solvent [16]. Toluene was found to be the second LiOH is less basic, therefore it is unable to donate OH- ions
best extracting agent. Reference [17] compared extraction of rapidly compared to sodium, potassium and other alkali

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 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 experimental work. The department of Chemical Engineering
depends on the base metal reactivity and concentration. A base at the University of Johannesburg is acknowledged for
is a proton acceptor and the more readily willing it is to accept funding the research as well as conference attendance.
a proton, the stronger it is. The base molecule, X-O-H,
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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

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