Chapter Two Literature Review

CHAPTER TWO

LITERATURE REVIEW

2.1 General overview

Lubricating oil is used to reduce friction between moving parts, and

it may also be used for the transfer of foreign particles and heat distribution.
[17]
It is known that the property to reduce friction is lubricity . Lubricants
have a wide range of applications, which include protecting the internal
combustion engines and the moving parts of other mechanical equipment
[18]
.

In general, lubricant oils contain about 71.5 – 96.2 wt% base oil
[1, 19, 20, 21, 56]
and additives about 28.5–3.8 wt% . The base oil is the main
ingredient in the composition of lubricating oils, If this base oil
manufactured from crude oil, it is called mineral oil and if it was synthesized
in the laboratory it is called synthetic base oil. Base oil mixed with some
additives to improve the base oil specification and work well during use in
engines.

During the use of lubricating oil in the engine, it becomes polluted

with some contaminants, such as metal scrapings, an oxidation product,
[17, 19]
broken down additive components, dirt and varnish . So, this
lubricating oil loses its lubricating properties. Therefore, it must be replaced
by a new lubricating oil to keep the engine [20].
The re-refining of lubricants (to get base oil) produces sludge as a
by-product. Sludge can be a main contributor to the problems in the engine

7
 Chapter Two Literature Review

and can necessitate the engine to be replaced if the harm was intense. Sludge
is usually caused by the existence of water, the light component in the oil
and other contaminant and can accumulate with use [109].

Synthetic oil, as the name suggests, is a lubricant made up of

chemical compounds that are artificially made (synthesized). In other words,
it is the base oil that is made by polymerization of hydrocarbons instead of
conventional crude oil refining. Synthetic lubricants are characterized by
specifications better than conventional mineral oils, for example, low pour
point, high viscosity index, high flash point, low volatility, excellent
oxidation stability [22].

2.2 Types of Lubricants

Lubricating oils generally consist mainly of base oil and mixed with
an amount of additives to impart desired properties on them. Sometimes
lubricants are one type of base oil or using a mixture of different base oil to
meet the performance requirements. Table 2.1, shows the various base oil
groups as designated by the American Petroleum Institute.

8
 Chapter Two Literature Review

Table 2.1: Types of base oil [25, 26].

Group I Group II Group III Group IV Group V

Saturates < 90% > 90% Over 90%

Sulfur > 0.03 % < 0.03% < 0.03%

Poly Each type
content
has not
Viscosity 103-108 113-119 >140 α-olefins
been
index
mentioned.
Methods Solvent Hydro Isohydro-
extraction, cracking, merization
hydro- solvent
finishing dewaxing

In North America. The group III, IV and V are classified as

industrial oils. In Europe, Group IV and V are classified as industrial oils.

Base oil can be classified according to the dominant composition into three
categories:

 Aromatic.
 Naphthenic.
 Paraffinic.

Lubricants can also be manufactured from vegetable oils and other

renewable sources, these are called biolubricants. Common sources include
sunflower seed oil, palm oil, etc. [27].

9
 Chapter Two Literature Review

2.3 Lubricating Oil Properties

The following properties are considered important properties for

lubricant oil.

Viscosity: This is one of the most important properties of the oil and used to
grade lubricants. The viscosity of the oil is a indicate of the fluid resistance
to flow. The viscosity must be high enough to maintain a lubricating film,
but low enough to flow around the engine parts under all conditions. It's
measured according to ASTM–D 445 [28].

Viscosity index (VI): It is one of the important properties of the lubricant oil,
which refer to how oils viscosity changes when the temperature changes. A
higher viscosity index is favoured and it's indicated that the viscosity
[32]
changes less with temperature than a lower viscosity index . Viscosity
index is measured according to ASTM-D2270 [31]. Some of additives such as
polyisobutylene and polymethacrylate are used as viscosity index improvers
for lubricating oil [106].

Flash and fire points: flash point is the lowest temperature at which
application of a flame causes specimen vapors to ignite. The flash point is
used to assess the overall risk of the substance in the field of maritime
transport and safety. Fire point is the minimum temperature at which a
[149]
specimen sustains burning for five seconds . Lubricant oil, which has a
high flash and fire point considered safer than low flash point when used in
the transportation of the lubricant. Flash point is evaluated according to
ASTM-D92 by Cleveland open cup [106].

10
 Chapter Two Literature Review

Pour point: The pour point is defined as a low temperature to flow, below
which the oil loses its fluidity and will not flow in the lubricating system. It
is a significant factor in cold weather start up. The pour point is evaluated
according to ASTM-D97 [106].
Total acid number (TAN): is a measure of the acidic components present in
the oil, which are present as additive degradation or an oxidation product. It
is the weight (in milligrams) of potassium hydroxide required to neutralize
1 gm of lubricant oil. The acid number is used to track the oxidative
degradation of oil in service. It is measured according ASTM-D644 [29].
Total base number (TBN): The total base number is an indicator of the oil's
ability to neutralize acidic component formed by oxidation processes, higher
TBN additive is more effective for neutralizing acids for longer periods of
time. It's measured according to ASTM- D664 [30, 34].

2.4 Functions of Lubricating Oil

Lubricating oil performs many functions, including the following:

1. Keep moving parts apart and guard against wear: Lubricants are
introduced between moving parts in the engines and other mechanical
equipment to prevent the metal-to-metal contact that would result in
wearing. This reduces friction and surface fatigue, less heat is generated
and noise reduced drastically by reducing the surface contact between
[17]
metal parts .

11
 Chapter Two Literature Review

2. Reducing friction: Often be a surface-to-surface friction in the system is

much more than a friction lubricants-to- surface. For this, the use of a
lubricant reduces friction in the system and this benefits in reducing
[17, 18].
heat generation as well as improves the efficiency of the process
3. Heat transfer function: Lubricating oils can transfer heat because of
their high specific heat capacity. Often, when the lubricant transmits
from the parts of the system, it heats or cools the parts of the system [18,
19, 17].

4. Draining contaminants and debris: Lubricant oil keeps all the deposit
forming materials in suspension and gets rid of them by the oil filter. It
leads this service through the transfer of all contaminants from the
[17, 18]
system to filter where it can be removed .
5. Application in high performance vehicles: Synthetic lubricants which
are used as lubricants in the sports car and high performance cars, help
in improving the overall engine performance, maintain better engine
[38, 19]
cleanliness and help in faster starting and better pick up of the vehicle .

2.5 Production of Mineral Base Oil from Crude Oils

Production of base oil from crude oil is done in several steps, firstly
by atmospheric distillation (ADU) of crude oil, the products of this unit are
many fractions which are distilled according to their boiling point, as shown
in Figure 2.1. The heaviest component, which did not distil in the
atmospheric unit, will distil in a vacuum distillation unit (VDU) to avoid the
thermal cracking that may occur in these compounds at high temperatures.
Figure 2.2 shows the output of the vacuum distillation unit, Lubricant
[42, 39]
feedstock which is the main feed in the mineral base oil production .

12
 Chapter Two Literature Review

Gases
Gas Gasoline
separator
Light naphtha

Atmospheric Heavy naphtha

Distillation
unit Kerosene

Light gas oil

Crude oil
Desalting Furnace Heavy gas oil
e

Residuum

Figure 2.1: Simplified block diagram of ADU process [39, 42].

Vacuum gas oil

Vacuum
Distillation
Unit Lubricant feed stock
(VDU) To separation process
Or conversion process

Residuum from ADU

Heating

V.R

Figure 2.2: Simplified block diagram of a vacuum distillation unit [39, 42].

2.5.1 Mineral Base Oils Production by Refining Processes

The raw lubricant feedstock can't be used directly without treatment
in the production of base oil because it contains components which are

13
 Chapter Two Literature Review

considered as undesirable characteristics of lubricant oil. There are two

methods for refining lubricating oils from lubricant feedstock [39].
1- Separation processes.
2- Conversion processes.

[Link] Separation processes

Separation processes are the way most widely used for the
production of base oil from crude oil. Lubricant feed stock which results
from VDU contains asphalt, resins and wax materials that are considered
undesirable in the composition of lubricating oils and therefore must be
removed.
 The first step in separation processes is to remove the asphalt.
Propane is most effective solvent to remove asphalt and resins due
to solubility difference between propane and asphalt. The
deasphalted oil is a long-chain hydrocarbon compounds (C+38)
which is a feed to production mineral base oil by several processes
[40, 42]
. Aromatic hydrocarbons in the lubricant feedstock and
deasphalted oil are also considered undesirable compounds in the
composition of base oils, so they must be removed.
 The second step in the separation processes includes extraction by
furfural solvent to remove the aromatic compounds from the
deasphalted oil.
 The third step involves removing the wax by using methyl ethyl
ketone (MEK), and then the final step is hydrofinishing to
[41]
saturation of the remaining unsaturated hydrocarbons . Figure
2.3 illustrates the separation process flow diagram.

14
 Chapter Two Literature Review

Lubricant feed stock from VD

Propane
desphalting
Desphalted Oil
Furfural
Aromatic extract extraction

Raffinate
MEK
Wax Dewaxing

Hydrogen
finishing

Mineral base oil

Figure 2.3: Separation process flow diagram [41].

[Link] Conversion processes

Conversion processes include hydro cracking, hydro dewaxing and
hydrofinishing. The conversion technology technique is quite different from
the separation technology; in separation processes, the aromatic compounds
are removed by using the solvent, while in conversion processes, these
aromatic compounds turn into saturated hydrocarbon compounds by using
hydro cracking and the presence of hydrogen [42]. Hydro dewaxing is used to
convert n-paraffin to iso-paraffin in the presence of hydrogen, and then the
final step is hydrofinishing to saturation of the remaining unsaturated
hydrocarbons as shown in figure 2.4.

15
 Chapter Two Literature Review

Lubricant feed stock

Propane
desphalting

Hydrocraking

Hydrodewaxing

Hydrofinishing

Mineral base oil

Figure 2.4: Conversion process flow diagram [42].

2.6 Lubricating Oil Additives:

The quality of lubricating oil depends on the quality of the base oil
and the lubricant additives. Modern lubricating oil mixed base oil about
(71.5-96.2 wt%) and the other is additives. Different types of additives must
be added to lubricating oils to improve their operational performances and
their quality, They include [44].

1. Detergent and depressants: These additives are used in the crankcase to

keep particulate matter dispersed in the oil and maintain engine cleanliness.
The detergents and depressants can prevent from causing corrosion,
plugging the oil pipe and filter screens, sticking and abrading the piston

16
 Chapter Two Literature Review

rings until the engine is out of work. Dispersants are more effective during
operation at low temperatures, while detergents are associated with high
temperature running. They both help with acid neutralization owing to their
basic nature. The commonly used detergents include calcium sulfonate,
calcium alkyl silicate, and Polybutylen succinimide which is a commonly
used ashless dispersant [43, 37, 42, 106].
2. Viscosity index improver: This characteristic is important for lubricating oils
because it refers to the appropriateness of lubricating oil to use in the engine,
and gaves an indication of the relationship between the change of viscosity
and temperature. In general, there is a reverse change between viscosity and
temperature. If the viscosity index is low this indicates the oil losses its
effectiveness and creates negative impacts on the engine, so it must be high
enough. The viscosity index improvers commonly used are polyisobutylene,
[43,
polymethacrylate, acrylates polymers and ethylene propylene copolymer
32, 106]
. Which add to base oil to improve the viscosity-temperature property
because these long-chain, high-molecular weight polymer additives have
the ability to stretch and then overlap, and this way keeps the viscosity of the
oil when the temperatures change.
3. Pour point depressant: It is used to decrease the freezing point of the
lubricant, for improving its low temperature fluidity. The commonly used
pour point reducers include naphthalene, alkyl phenol, polyalpha Olefin oil
and alkyaromatic polymers, These additives are working to interact with the
wax crystals and by this way impede wax crystals of expansion [42, 43, 47, 106].
4. Anti-oxidation additive: Mineral oils react with oxygen to form organic
acids. These oxidation reactions led to increase oil viscosity, formation of
sludge and the erosion of metal parts. This deterioration causes shortening

17
 Chapter Two Literature Review

service. The function of anti-oxidant additive is to retard the oxidation of

lubricants, slow down the oxidation rates and extend the service period of
the lubricants. When anti-oxidant is used, active sulfur can be produced. It
can corrode the metals, such as silver, copper and alloys. Therefore, anti-
[43]
corrosive additives should be added . Zinc diakyldithiophosphate is a
commonly used anti-oxidation and corrosion additive [106].
5. Anti Corrosion Additives: Metals are used in the manufacture of engine
parts, such as copper - lead or lead- bronze alloy, these metals easily
corroded with organic acids, which formed as a result of the oxidant through
exposure oil to high temperatures during use in the engine. Some additives
such as Amine succinate and alkaline earth sulfonates are used to protect the
metal surfaces from the impact of corrosion by forming a protective layer on
the metal surfaces and this is done in two ways, firstly, of these additives
adsorbed on the surface of the metal physically, secondly, chemically
bonding to the surface to form a hydrophobic film to prevent water and air to
[48, 42,
reach the surface. Therefore, these are used as anti corrosion additives
32, 106]
.
6. Antiwear additives: Friction that occurs between the moving parts in the
engine causing wear on the unprotected parts. Hard particle between two
contrariness surfaces is another form of wear. In order to overcome this,
[106]
materials adsorbed on surfaces and form a protective layer are used .
These additives are:
A - Polar organic compounds of type alcohols, fatty esters, fatty amines, or
acids with the risk of desorption beyond 150°C.
B - Organic compounds containing sulphur, phosphorus, chlorine, nitrogen,
[48, 37, 46]
oxygen, lead, or zinc

18
 Chapter Two Literature Review

7. Anti foam additive: Agitation and aeration that occur through using the
lubricant oil causes the formation of air bubbles in the lubricating oil, and
these bubbles improves the oil oxidation process and then cause the loss of
the lubricant oil's effect. To overcome this problem, antifoam additive such
as alkylated succinic acid, alkyl polymethacrylate, and dimethyl silicone oil
to reduce the formation of air bubbles or foam are used [43, 48, 42, 46, 106].

2.7 Used Lubricating Oil

According to the US EPA (Environmental Protection Agency), used
oil is defined as "any type of lubricating oils made from crude oil or any
synthetic source and as a result of the use it in equipment becomes
contaminated by chemical or physical component". Used engine oil refers to
oil that has been collected from oil changed workshops, garages and industry
[50, 49]
source . Unused oil is composed of base oil, which is a mixture of
hydrocarbon, 71.6 to 96.2 wt% and a group of various additives 28.4 to 3.8
wt% [1]. The main constituents of used engine oils are aliphatic and aromatic
hydrocarbon, such as phenol and naphthalene [40].
It is estimated that 45% of used oil was collected in worldwide, while
55% is disposed into the environment, as shown in figure 2.5 [35].

19
 Chapter Two Literature Review

Figure 2.5: Oil sales and used oil collection trends, 1994-2006, from CIWMB [36].

2.8 Used Lubricating Oil Composition

Generally used lubricating oil consists primarily of base oil and
sludge. Composition of base oil in used oil is different, this depends on the
type of crude oil (paraffinic or naphthenic), the way of production base oil,
the time of using lubricant oil and fuel type (gasoline or diesel). While,
sludge includes a mixture of contaminants, such as additive breakdown
products, metal particles from wear and incomplete combustion of fuel, light
component, water, etc. [55].
Used lubricating oil contains metal, such as Iron, Calcium,
Manganese, Copper, Lead, Aluminium, Nickel and Zinc. The reason of
presence these metals because of deterioration of additive was added to the
lubricating oil to improve its specifications as a result of using it in the
engine. These additive compositions contain elevated concentrations of

20
Chapter Two Literature Review

metals, such as barium and zinc. While, Nickel, cadmium, zinc, chromium is
a result of wear of engine parts. Used lubricating oil contains other metals
[56]
such as copper, iron, magnesium and Silicon . Polycyclic aromatic
hydrocarbons (PAHs) found in the new oil at low concentration, then
increasing the concentration of polycyclic aromatic hydrocarbons in used oil
during the operation of the engine [55, 57].
[52]
Cotton et al., 1977 studied the composition of 30 used oil samples and
then divided them into 4 groups, where they found that the used oil contains
76.7% saturates, 3.7% diaromatics, 13.2% monoaromatics and 6.5%
polyaromatics-polar material by using mass spectrum analysis and silica–
alumina gel adsorption chromatography.
[53]
Mohammed et al., 1984 used the elution adsorption chromatography
(EAC) to analyse Iraqi used oil for two samples. They found the Iraqi used
oil consists of 73.3-73.7% saturates, 21.5-18.9% aromatic and 5.5-7.4%
olefins for two samples respectively.
[46]
Elena et al., 2003 described the contaminants in used oil consisting of
aromatic hydrocarbon components, such as benzene and P-xylen, polycyclic
aromatic hydrocarbon (PAHs), aldehyde and ketone by using Fourier-
transformed infrared spectroscopy (FTIR), GC/MC, NMR.
Kupareva et al., 2013 [50] studied the chemical composition of fresh and
used oil by using multiple devices, such as GC/MS, FTIR, NMR. They
explained that the fresh oil consist in general of saturated compounds, but
after using it in the engine it will lose some properties, such as viscosity,
flash point and density, beside some of the contaminants will be produced
such as light component, aromatic ring, aliphatic component and phenolic
antioxidant.

21
 Chapter Two Literature Review

2.9 Lubricating Oil Degradation

Degradation of used oil can be one of the reasons for the engine
[106]
failure . The use of new oil in the engine means it goes from controlled
into uncontrolled condition inside the engine because it's exposed to
temperature from zero to greater than 816°C on the cylinder walls and high
[58]
pressure . The increase in oil temperature above its recommended stable
temperature will speed its oxidation, and the base oil molecules can break
down into smaller molecules which causes evaporation of light ends or
[115]
decomposition of oils and viscosity will be changed .

LOW TEMPERATURE OPERATION

During the operation of the engine in cold weather, the cooling water
does not exceed a temperature of 120°F and the lubricant oil crankcase not
warm enough. Therefore, the heavy fuel fractions in the form of liquid enter
into the combustion chamber and wash the cylinder wall. So this will be
exposed to the combustion chamber of many impurities as well as the result
of condensation on the walls of the cylinder. The effects of low temperature
can be reduced by insulating the outside surface of the crankcase oil [59].

HIGH TEMPERATURE OPERATION

At high temperature, the oil deterioration caused by oxidation is much
more than what is caused by contamination. When the oil is mixed with the
air, it tends faster to oxidation and the rate of oxidation increases doubled
whenever the temperature increases 18 oF [59]
. Oxidation is increased by the
presence of metallic contaminants that work as a catalyst. These minute
particles such as iron, which is scraped from the wall of the cylinder will
work to speed up the oxidation process oil at high temperature because its
work as a catalyst [59].

22
 Chapter Two Literature Review

On the other hand, the hydrocarbon composition of lubricant oil

contains a carbon-carbon multiple bonds. At high temperature these bonds
will react with oxygen molecules, and this will convert into smaller
molecules called carboxylic acids as shown [115].
R-CH=CH-R + 2O2 → R-COOH + HOOC-R (2-1)
This deterioration occurs in two steps, firstly, the molecule will divide into
smaller molecules that cause low viscosity for the oil. Secondly, these new
molecules are not simple hydrocarbon molecules, but acids, and these acids
[115]
are working on the corrosion of metal surfaces .
2 M + 2 R-COOH → 2 R-COO⁻M⁺ + H₂↑ (2-2)
If lubricating oil replacement in the engine is not regularly changed,
the carboxylic acids will increase its focus in the oil and cause to raise the
acidity of oil, This causes the excessive wear of the engine, and polluting
emissions will be released into the atmosphere [60].

2.10 Used Lubricating Oil Contaminates:

Lubricant oil loses its properties during use in the engine due to
contaminant formation. These contaminants are divided into :

2.10.1 Extraneous Contaminates

Extraneous contaminants are engine metallic particles or introduced
from the surroundings. Air may cause foaming of the oil so it can be
considered contaminated. Extraneous contaminants in the engine are divided
into:
A- Metallic particles produced due to wear.
B- Incomplete fuel combustion led to produce carbonaceous particles

23
 Chapter Two Literature Review

C - Corrosion product such as metal oxide particles

D - Water as a product of fuel combustion
E - Dust from atmospheric
F - Water from leakages of the cooling system of the engine
[110, 111]
G - Fuel and fuel additives might enter the crankcase of engines .

2.10.2 Products of Oil Deterioration

There are a large number of products that are formed during
deterioration, such as:
A- Sludge: This label releases a set of contaminants, such as dirt, carbon
particles and additives deterioration. The sludge deposited on the different
parts in the engine or remained in dispersion in the lubricant oil.

B – Coarse material: This deposited on the engine parts as a result of exposure

sludge to high temperatures
C - Oil – soluble products: They occur as a result of oxidation and remain in
[112, 113]
the oil and cannot be filtered, so these deposited on engine parts .

2.10.3 The effect of oil Contaminates

Lubricating oil's characteristics are affected by the presence of
contaminants, and the effects of contaminants are:
1- Water: Water is a very common contaminant in the oil system. It may come
from the burning of fuel in a cold engine or from condensation if the
temperature of the system rises and falls in a humid atmosphere. Water can
be easily driven off by evaporation if the system operates regularly at

24
 Chapter Two Literature Review

temperatures much higher than 100 oC. Water also helps to form water
sludge's (emulsion) and also leads to foaming problem.
2 –Solid particles: There are four main types of solid contaminant in an oil
system, wear debris, a breakdown product from the oil itself, combustion
product and external dust or dirt ingested or sucked into an engine. All of
these substances can be detected by various oil-monitoring techniques. This
type of contaminants causes immoderate wear and possible failure due to
metal fatigue.
3 - Lacquers: The sludge plugs the oil path. While, lacquer or varnish causes
affixing of the valve and leads to resist against an oil pump operation.
4 –Oxidation: The most important type of chemical reaction affecting oils in
service is oxidation, which very often determines the service life. The effect
of oxidation is to introduce oxygen atoms into some of the base oil
molecules at elevated temperatures, converting the hydrocarbon molecules
into aldehydes and then into acids. Because these products are less stable
than the original hydrocarbon molecules, they tend to be further attacked and
the final products may be highly oxidized gums and lacquers, or even solid
residues, such as carbonized materials [61, 62, 63].
5 – Soot: They form as the result of incomplete combustion, especially during
warm-up with a rich mixture and these make the oil go black. This occurs
when the ratio of air to fuel be rich during the beginning of a process
running in cold weather and intermittent operating in cold weather.
Impurities will be washed out of the cylinder wall to the piston ring and
crankcase. Oil ring is plugging due to soot mixing with the rest of
contaminates produced a smooth mass in the ring area [59].

25
 Chapter Two Literature Review

2.11 Used Lubricant Oil Impacts on Human Health and the Environment
Used oil is considered polluting substances according EPA Because of
their negative impact on human health, animal, plant and water.

1- Toxic Effects on Human Health

Used lubricating oils pose a threat to human health because they
contain carcinogens such as polycyclic aromatic hydrocarbons (PAHs), and
[64]
also contain metal, such as zinc, cadmium, zinc and sulphur . That
exposure to these dangerous compounds is either through skin contact or
through environmental pollution [65].

2 -Toxic Effects on Animals

Used oils pose a threat to animals, especially embryos and Newborn

animals. Where laboratory studies have shown that the used oil affects the
negative impact on ducks and bobwhite quail, where the mortality rate is
about 88-84% when exposed to low concentrations (0.003-0.015 ml) of used
oil for duck and bobwhite quail respectively [66, 67]. Other effects of used oils
[68, 67,70]
on animals are low growth and high mortality rate and birth defects .

Wasiu et al. 2015 [170] examined the effect of used engine oil on male rats,
concluded that the rats exposure to used oils led to decreasing in weight and
decreasing the proportion of motile sperm.

3- Toxic Effects on Plants

Used oils pose a threat to the plants. Studies have been conducted to
demonstrate the impact of used oil on the growth of vegetables. These

26
 Chapter Two Literature Review

studies conducted with different types of soil, such as clay loam and sandy
loam, and the results showed that the vegetables did not survive after nine
months for two types of soil and the growth is bad, such as the yellow
leaves and stalk yellow [71, 74, 67].

As well as the used oil's effect on the growth of corn in terms of growth rate
dropped to 45% of the soil contaminated by used oil, which concentration
about 1300 ml/m2 [72, 73, 67]
.

4 -Water Pollution:
Used lubricating oil can pollute water resource through the following
ways:
o Throw the used oil into sewers illegally
o Release used oil into waste such as garbage
Disposal of lubricating oils illegally in the stormwater sewer systems
causes environmental problems, because the used oil causes the oil film on
the water surface and this prevents photosynthesis process in the water and
[67]
impedes dissolved oxygen and thus affects negatively on the food chain
[114, 78]
aqueous . In addition, used lubricating oils contain a high
concentration of metal that may cause many problems for the aquatic
[115]
organisms . As well as, the disposal of this used oil into the sewer water
will damage to wastewater treatment because it contains metal, thus,
increasing the cost of the wastewater treatment [75, 76].
According to EPA, every one gallon of used lubricant can pollute
one million gallons of fresh waters and a half liter of used lubricating oils
can form the oil film on the water surface, which can cover nearly one acre
of water surface [114, 78].

27
 Chapter Two Literature Review

2.12 Benefits of Used Oil Re-Refining

There are several benefits of the used oil re-refining process, such as:

1- Conservation of Natural Resource

As explained previously, the used oils contain energy that can be
utilized in various fields, such as fuel and base oil production, thus, reduces
the dependence on crude oil in the production of these fractions and preserve
the natural resources.

[61]
Jia et al,. 2014 studied the possibility of using the used lubricating oils
in asphalt production. They used several types of asphalt binder mixed with
used oil and found that there is a marked improvement in asphalt binder
specifications.
[173]
Rathod et al,. 2014 used the catalytic cracking method to convert the
used oil to fuel, and they concluded can be obtained 11.7 wt% hydrocarbon
gases, 4.12 wt% residues and 84.16 wt% liquid products from this process.

2- Energy Conservation:
The chemical composition of used oils consists of hydrocarbons so
the advantage of them should be taken as an energy source. According to
(EPA), every gallon of used lubricant oil is enough to produce 0.75 gallons
of base lubricating oil, while producing the same amount needs 42 gallons
of crude oil. As well as, every gallon of used oil contains the energy of
about 140,000 BTU if it was converted into fuel [116]. Base oil production by
re-refining process consumes about one-third the energy of the process base
oil production from crude oil. This means the use of less energy and less

28
 Chapter Two Literature Review
[78]
emission of carbon, They can also recycle the used oils repeatedly .
Further motivated than 1 liter of used oil contains energy about 8000 KJ if
converts to fuel [11, 79].
Al-Omari et al,. 2008 [92] suggested the use of used oil as a source of energy
and proved this through the laboratory combustion unit. The mixing of a
small amount of used oil with the gases such as LPG led to the improvement
of the gaseous fuels flame radiation.

[94]
Orhan Arpa et al,. 2010 , developed a process using the pyrolitic
distillation method to produce Gasoline-Like Fuel (GLF). Fuels produced
were separated into two parts which were light fuel with 20 wt % and heavy
fuel with 60 wt% of the total waste lubricant oil.

Wisa Manasomboonphan et al,. 2012 [95], concluded that the waste lube oil
was pyrolyzed in Pyrolysis technique. Where it is possible to use this method
for the production of Liquid Fuels from Waste Lube Oils such as (Aromatics:
Benzene, Toluene, Xylene, Alkyl benzene). These studies, demonstrate that
pyrolysis generated an ≥ 50% yield of diesel oil product.
[171] [172]
Orabi et al,. 2015 and Lam et al,. 2010 , used the microwave
induced pyrolysis to convert the used oil to gaseous hydrocarbon, light
aliphatic and aromatic hydrocarbon, BTX and benzene derivatives.

3- Hazardous Waste Reduction:

Used lubricants are highly toxic to humans, animals, and plants.
Used lubricant regeneration can reduce a significant amount of hazardous
waste by extracting the toxic metals that are released into atmosphere
thought combustion.

29
 Chapter Two Literature Review

4- Environmental Protection:
Used oil re-refining process preserves the environment because it
prevents the release of these oils into the environment. Since the lubricating
oils are considered toxic and degrade slowly, the releasing of these oils into
the river water, causes a problem for the river life and then contamination of
drinking water [80].
According to the Environmental Protection Agency (EPA), only one
gallon of used oil can be million gallons of water unfit for drinking. When
used oils are coming into contact with water, they produce films that prevent
the oxygen circulation and sunlight and affect the process of photosynthesis
due to their low biodegradability, and prevent the renewal of dissolved
oxygen, which leads to the death of aquatic flora and fauna, also, there is a
possibility for the material that may enter into natural cycles through water
and it poses a threat to human health [78].
[93]
Boughton and Horvath,. 2004 studied the impact of used oil on the air
pollution in California state, they explained that the process of refining
lubricating oil is much better than burning it in terms of its effect on air
pollution.
[91]
Khelifi et al,. 2006 , explained through their research how to help the
process of recycling used oil to protect the environment and rely on these
used oils as a source for the production of new lubricating oil from the used
oil.

30
 Chapter Two Literature Review

2.13 Management of Used Oil

Lubricating oil may be used over and over again if it is getting rid of
its impurities. It loses some of lubricating properties throughout the heat and
stress of engine operation. Used oil will vary greatly in the level and types of
external and internal contamination it acquires. Some oils will contain only
excess water and dirt, while others will contain compounds that require
[81]
specialized techniques to separate them from the oil . Contaminants that
cause used oil management more problematic are heavy metals and chemical
additives. Heavy metals commonly present in used oil include cadmium,
calcium, arsenic, iron, calcium and zinc. These may arise from wear on the
metal engine parts or from their inclusion in oil additives that assure good oil
flow, prevent reactions between the oil and engine parts and avoid oil
breakdown at high temperatures. However, as the additives undergo use and
[82]
stress, they may produce hazardous chemicals .

The main objective of the waste management process is to ensure

[83]
safe, economical and effective process . Several treatments and recovery
strategies for used oil have been proffered. It is worthy of note that there are
no collection centers or recycle facilities in the country today.
As the country contemplates different options for the management of
used oil, lessons can be learned from countries that have made progress in
the field of used oil management system. There are three alternatives of used
oil management that related to the Iraqi reality:
o Reprocessing into fuel oil
o Re-refining into lube oil
o Destruction

31
 Chapter Two Literature Review

The advantages and disadvantages of these three management techniques are

highlighted below:
2.13.1 Advantages of re-processing used oil into fuel

1. It protects the environment from the indiscriminate disposal of used

oil into land and water resources.
2. It will boost the fuel production capacity of the country.
3. It will create jobs for teeming youths and thus ease the high rate of
unemployment prevalent in the country today.
4. Its reduces the environmental impacts resulting from the burning of
used oil.

2.13.2 Disadvantages of re-processing used oil into fuel

1- It is capital intensive.
2- It requires the sitting of collection centers in various locations in the
country to get raw materials for the plant.
2.13.3 Advantages of Re-refining of lubricating oil
1- It protects the environment.
2- It helps to create jobs in the country.
3- It reduces the import of lubricants and help in the development of the
oil industry.
2.13.4 Disadvantages of Re-refining of lubricating oil
1. It requires a disciplined system for collecting these oils in several
places.
2. It requires good marketing of these oils in the market to compete with
mineral oils.

32
 Chapter Two Literature Review

2.13.5 Advantages of Destruction

1- Economically useful when dealing with low volumes.
2- Cement plants using used oils therefore are willing to buy used oil
and used as fuel.
3- This method is characterized by less cost compared with the previous
options.
2.13.6 Disadvantages of Destruction
1- Emissions in the air, it will need to be addressed before it released.
2- Perhaps facing opposition from local residents.

2.14 Re-Refining of Used Lubricating Oil

Re-refining is the advanced process and commonly used to treat used
[106]
oil . The crude oil refining process produces base oil, lubricating oils
produced by mixing base oil with additives that give the required
specifications for lubricant oil, such as oxidation resistance, anti-foaming
characteristics and the minimum viscosity change with temperature. These
lubricant oils will be consumed after use in engines or other machines are
called used oils. These contain the base oil, additives consumed and light
petroleum products (naphtha, gasoil, etc.) and also contain other
contaminants during operations collected from garages, such as water [84, 85].
Therefore, the aim of re-refining is to provide a source of alternative
methods for the production of these oils without dependence on crude oil in
the process of manufacture. There are different ways to deal with used oil,
but the success of any method depends primarily on the quality of the
product which is produced in addition to market this product. Some methods
of treatment work to convert used oil into fuel and others converted it to a

33
 Chapter Two Literature Review

new base oil, but any method chosen depends mainly on the chemical
composition of used oil [85].
Also, all the methods in the treatment of used oil depended on the
steps, filtering, removing water, chemical or physical separation of
contaminants. There are several methods for re-refining of used oil such as:

2.14.1 Acid /clay process

Acid / clay process is one of the way used for the recovery of base oil
from used oil. However, its application is on the decline and is even
[106, 39]
prohibited in industrialized countries for environmental problems . But
it's low capital investment, yields about 45-65% and gives advantages in
small scale plants in the underdeveloped countries [97, 86, 98, 99].
During that process, the used oil is filtered to remove large
contaminants and then pumped to the distillation unit for the removal of
water and light component at a temperature of between 120 and 180 oC and
then cooled after that mixing with sulfuric acid at 98% concentration to
settling the contaminants and then separated but disposal of these sludge
causes environmental problems. Then, it is enter a clay treatment by mixing
with clay at a temperature of 270 oC to clarify the liquid and then filtered, as
shown in figure 2.6 [106].

34
 Chapter Two Literature Review

Water

Clay High temp Distillation

contactor
Water & light end
Light oil

Distillation Low temp. Settling Filter

mixer tank
Lube oil

Filtration
Slufuric acid Acid sludge Incinerator
Waste

Used oil feedstock

Figure 2.6: Flow diagram of Acid / Clay treatment process [106].

2.14.2 Distillation /hydro-treatment

During this process, used oils are distilled to separate off water and
light hydrocarbons, pumped to a vacuum tower to distillate many types of
base oil, and then distillates hydro-treated in the presence of catalyst to
remove the sulphur, chlorine and oxygenated organic components, as shown
in figure 2.7 [107, 108, 39]
.

35
 Chapter Two Literature Review

Water

Diesel oil
Hydrogen
waste
Preflash
oil
light fuel gas
Vacuum Medium Hydrotreating light
tower Heavy Medium
Heavy

Vacuum residue
(asphalt component or fuel oil)

Figure 2.7: Flow diagram of Distillation / hydro-treatment process [28].

Berry et al. 1981 [87] used the developer design consisting of several vacuum
distillations to reduce the coke formed during this process, but the problem
that encountered during this process is clogging the pipes in furnaces and
fractionators as a result of the resin material produced. This developer design
did not address the problem of the black colour of the base oil produced by
this process [88, 89].

2.14.3 Solvent extraction treatment:

Solvent extraction technology has been used a successful process and
[106]
better than the other methods for the treatment of used oils and
producing base oil because the base oil properties obtained by this method
are better than other methods, and side or hazard product such as acid sludge
be few. This method does not need a catalyst, and the re-refining process
[100, 101]
does not need high pressure and temperature . Many countries and

36
Chapter Two Literature Review

factories depend on this method at the present time, because this method has
been able to overcome the problems faced by the other methods, such as
environmental pollution, which faced its Acid/ clay process and cost that
[12]
faced the vacuum distillation process .
Solvent extraction process is working to separate base oil from the
rest of unwanted materials (sludge and metal) to easy base oil recovery, thus
will improve the recovered base oil characterization. Solvent extraction
process is a convenient way to treat multigrade oils that contain a high
amount of degraded compounds resulting of oil oxidation and additives
deterioration. Also, this process is the best way to improve the recovered
base oil colour [106].
In the process of solvent extraction process one type of solvent or
mixture of solvents can be used to achieve the aim of base oil recovery.
Therefore, the solvent must have the following specifications: Firstly, it
must be dissolved with base oil, secondly, it is insoluble with contaminants,
[164]
such as sludge and degraded additives , and thirdly, it must have the
suitable specifications, such as polarity, solubility, vapor pressure, viscosity
and easy to recover [102].
During this process, used oils are filtered to separate off large
contaminant and then mixed with solvent in solvent extraction to separate the
base oil and sludge. The sludge was disposed off, the base oil solvent
mixture pumped to distillation to recover the solvent, and then the base oil
treated with clay to improve its characterization and remove contaminants
that didn't remove in the solvent extraction process, as shown in figure 2.8.
Table 2.2 Comparison between the main processes used for re-refining of
used oil.

37
 Chapter Two Literature Review

used lubricant oil Sludge

Solvent Filtration Solvent

Extraction Recovery

Fresh solvent Recycled solvent

Clay
Spent Clay
Clean lube oil Adsoption
Filtration

Figure 2.8: Flow diagram of solvent extraction process [113].

Table 2.2: Comparison between the main processes used for re-refining of used oil.

Advantage Disadvantage
Method
Acid / Clay 1. Low investment and 1. Environmental pollution
method Maintenance cost 2. Create corrosion of
2. Treating Low quantities of equipment’s.
used oils 3. Low yield.
4. Unable to treat modern multi-
grade oils
5. Difficult to remove asphaltic
impurities.
Vacuum 1. Don’t use acid. 1. High cost technology
distillation 2. Good quality of produce base 2. Light base oil produces
method oil. 3. Operates at high temperature
& Very high vacuum pressure

Solvent 1. Improved base oil 1. Involves solvent losses

Extraction characteristics 2. Waste residue disposal may
method 2. The solvent selectively create problem
dissolves desired components 3. Economical only for high
3. Operates without extensive capacity Plants
heat or pressure
4. Relatively low operating and
capital costs
5. The Solvent is recyclable.

38
 Chapter Two Literature Review

2.14. 3.1 Solubility

Liquid substance, or the solvent, must overcome the intermolecular
stickiness of the solute molecules to be miscible and provide the similar
attraction between all molecules components (including solvent and solute
molecules). Solvent becomes immiscible with solute if attachment of the
solute molecules is stronger compared to the intermolecular stickiness
between solvent and solute.
The intermolecular stickiness between solutes (molecules) is called
Van der Waals force, and certain molecular geometries are known as a
polarity result from the deviations of the electron density. These forces are
responsible for ensuring the solubility between liquids or solids. Similar
polarities of substances will result in soluble mixtures. Consequently, in
vaporization, a certain amount of energy is added to a system of solution in
order to vaporize the liquid into vapor form. This amount of energy is
known as heat of vaporization.
[104]
According to (Burke, 1984) the heat of vaporization is similar to Van
der Waal’s forces that arrest the molecules of the liquid together, since the
same intermolecular attractive forces have to be overcome to vaporize the
liquid. In a case of mixing two liquids, the molecules of the liquid molecules
are separated physically by the molecules of other liquids, similar to the
separation that happens during vaporization. Therefore, the same
intermolecular Van der Waal’s forces must be overcome in both cases.

39
 Chapter Two Literature Review

2.14. 3.2 Solvent Selection

The main factor in solvent extraction is choosing a suitable solvent,
the solvent selection according to many specifications such as:

1. Polarity: It is one of the important characters in the solvent selection and

polarity of solvent selection carried out according to the rule (like dissolve
like). Where alcohol polarity is higher than ketone and hydrocarbon, so the
more efficient separation during the extraction process is when using
alcohols and then ketones and then comes hydrocarbons with less capacity,
according to their polarity. Solvent selection is based on their ability to form
[157]
hydrogen bonds .
The polar solvent choice is easy to reject nonpolar or low-polar
materials, such as sludge (polymeric additives, metal, carbonaceous
particles, etc.) thus prevents mixing with the solvent and base oil and then
will settle these impurities influences of gravity or by use centrifuge.
2. Solubility parameter: Latent heat of evaporation indicates the amount of
Van der walls forces holding the liquid molecules and for this, the chosen
solvent must overcome these forces in order to reach the base oil molecules,
solubility parameter gives an indication or a clear indication of this
behavior [158].
The good solvent should dissolve the base oil molecules, and at the
same time it must not dissolve sludge's (metal, polymeric additives,
carbonaceous particles) or it works as antisolvent to non polar material
found in used oil. Table 2.3 and Appendix B illustrate the solubility
[159]
parameter of the solvent selected .

40
 Chapter Two Literature Review
[159, 174]
Table 2.3: Solubility parameters of base oil and solvents .
δ (J/cm3) 1/2

Base oil 15.9

Additives 17
1-butanol 23.2
MEK 19.1

3. Viscosity: Low solvent viscosity works in a positive way more than high
solvent viscosity during the extraction process because the high solvent
viscosity needs more time to be separated into two phases (raffinate and
extract). Mass Transfer resistance is also low if the used solvent has low
viscosity. From the economic point, low solvent viscosity is easier to
transport and pumping.
[158]
EL-Halwagi et al,. 2013 , suggested the best solvents viscosity value
ranging between 0.5-3.5 CP. If viscosity is more than 3.5, the solution will
become very viscous and this increases the mass transfer resistance, and it
needs more time to be separated and thus costly.
4. Vapor pressure: Other economic characteristics must be taken into
consideration when choosing a solvent, the difference between the vapor
pressure of the solvent and base oil must be large in order to separate the
solvent easily in solvent recovery process and thus consumes low energy.
However, if the vapor pressure of the solvent is lower, this leads to
volatilization of the solvent during the extraction process and it becomes
difficult to complete the mass transfer [158].
[158]
EL-Halwagi et al,. 2013 , suggested the best vapor pressure of solvents
between 5 -15 torr However, if it is less than 5 torr, the solvent separating

41
 Chapter Two Literature Review

will be very expensive economically, and if it is more than 150 torr the
solvent will become volatiles.

2.14. 3.3 Effect of Flocculant Addition

Impurities in used lubricating oils often consist of: (a) oxidation
products, (b) metallic compound, (c) degradation additives, and (d)
[102]
carbonaceous particles . Therefore, substances (dispersed additives) are
added to prevent the deposition of these impurities and thus become with
the lubricant oil. In the extraction process at the suitable temperature, the
used oil will be mixed with the solvent, but because of electric repulsions,
[19, 21]
few quantities with these undesirable substances will precipitate.
Addition amount of flocculant (KOH, MEA) helps on the speedup of the
contaminant separation from the base oil molecules. The existence of a
hydroxyl group such as OH, helps to improve the flocculation process,
because this group neutralized the electrostatic repulsion. For this reason,
the flocculating agents are used. By a process of flocculation, these particles
[23,
will coagulate and obtained high molecular weight polymeric materials
24]
.
+
R– OH + X __________ R– OX + H ………… (2.3)
Where;
R–OH alcohol solvent
X is the ion flocculant
+
H is the ion of Hydrogen

42
 Chapter Two Literature Review

2.14. 3.4 Coagulation, Flocculation and Aggregation

Coagulation is a chemical destabilization of solution where the

electrolytes are added into a solution to reduce the charge on particles and
allow a close approach to aggregation. During coagulation, the lyophobic
colloid become unstable and flocculation by the addition of electrolytes. The
charge neutralization occurs when there is a strong ionic interaction between
the charge particle and the opposite charge of flocculant that is added for
effective flocculation. Initially, the charge particle is stabilized by electrical
repulsion, thus the presence of opposite charge of flocculant reduces or
eliminates the repulsive force and leads to flocculation. Excess amount of
[119]
flocculant will re-stabilize the particles .
Coagulation is usually achieved by the addition of chemicals, such as
(KOH, NaOH, MEA), and nullifies the repulsive force on the colloidal
particle surface. The flocculation is enhanced in the presence of OH group
that neutralize the electrostatic repulsion. This electrostatic repulsion exists
for alcohol group this are linked with the ions from the additive.
Furthermore, the addition of a solution containing ions that neutralize those
charge, breaks this stability. Participation of alcohol OH group in ion
exchange reaction with the electrolyte ions helps to neutralize the
electrostatic repulsion effect [ 120, 121].
Thus, the term coagulation-flocculation removes the non- settable
solid particles by sedimentation though transformation of the particle into
[122]
larger and heavier settable solid particles .

43
 Chapter Two Literature Review

2.15 Theory of Adsorption

Adsorption can be defined as the accumulation of ions at the solid -
liquid interface due to different types of forces, depending on their physical
and chemical properties. Where Physical adsorption is a deposition of
several layers of contaminants on the surface of the adsorbent, and the
attractive force by which molecules are linked with each other is the Van
Der Waals. As well as, the active site of this kind of adsorption is not equal
on the adsorbent surface. The effect of increasing the temperature in this
[33]
type of adsorption be inversely with the adsorption efficiency .
Chemisorptions defined the deposition of a single-layer of contaminants on
the adsorbent surface, where a molecule adheres to a surface through the
formation of a chemical bond, unlike physical adsorption method. This type
of adsorption is improving with increasing temperature [33].
Adsorption meets attention from researchers at present in different
processes, one of the ways in used oil treatment Also, the adsorption process
is considered economically useful because it is low-cost, so they are used in
many processes, such as wastewater treatment [77, 90].

2.15.1 Adsorbent
When choosing any type of adsorbent, the following specifications
must be available [105].
 High selectivity
 High adsorption capacity.
 Low cost.
 Easily regenerable.

44
Chapter Two Literature Review

Clay can be used in re-refining of used oil because it has a suitable

area reaching to 150-250 m2 /g after activation by acid, and the clay is
[120]
relatively inexpensive . These adsorbents were expected to adsorb
Polycyclic Aromatic Hydrocarbons (PAHs), metal, and carbon particle.

45