2.

0 Introduction to Base oil bitchessssss

Lubricating oils are prepared by blending different viscosity-based oils with suitable
proportion of additives (Pirro and Wessol, 2001). Base oil is the name given to lubrication grade
oils initially produced from refining crude oil (mineral base oil) or through chemical synthesis
(synthetic base oil) (Jha, 2005). Base oil is typically defined as oil with a boiling point range
between 550 and 1050 F, consisting of hydrocarbons with 18 to 40 carbon atoms. This o il can
be either paraffinic or naphthenic in nature depending on the chemical structure of the
molecules.
Base oils are used to manufacture products including lubricating greases, motor oil and
metal processing fluids. Different products require different compositions and properties in the
oil. One of the most important factors is the liquids viscosity at various temperatures
(Brussels, 200). Whether or not crude oil is suitable to be made into base oil would be
determined by the concentration of base oil molecules as well as how easily these can be
extracted. It produced by refining crude oil. This means that the crude oil is heated in order
that various distillates can be separated from one another. During the heating process, light
and heavy hydrocarbons are separated the light ones can be refined to make petrol and other
fuels, while the heavier ones are suitable for bitumen and base oils
Modern mineral base oils are the result of a long and complex distillation and refining
processes. The feed stock used is crude oil. This substance is not of uniform quality but consists
of several thousands of hydrocarbon compounds in which the elements carbon and hydrogen
are present in all molecules and, in part, are bound to other elements.
The hydrocarbons can be divided into three main groups: paraffinic, naphthenic and
aromatic. Paraffinic hydrocarbons can be further divided into two subgroups: normal
paraffinic and ISO- paraffinic. Paraffinic hydrocarbons are the best lubricants. The distillation
process in the refinery separates the hydrocarbons contained in the crude into cuts based on
the molecule size. Furthermore, as many unwanted substances as possible are removed in the
process, such as Sulphur, aromatic hydrocarbons, paraffin wax, etc. In other words, the mineral
oil production process is physical cleaning and the end product is so-called paraffinic base oil.
Most of the hydrocarbons in the base oil are paraffinic, but it also contains naphthenic and
aromatic molecules. When the finished lubricant, such as motor oil, is made of these, several
additive compounds are used to improve the base oil properties. The final outcome can also be
so-called naphthenic base oil, where most of the hydrocarbons are naphthenic. Their cold
properties are excellent.

2.1 Base Oil Classification

International standard body that handles base oil qualification is the American petroleum
institute (API). Currently API has categorized base oil into five categories. The first three groups
are derived from petroleum or mineral materials. Base oil I-IV is a group of full synthetic paos
(polyalphaolefin). Group V is for all other basic materials not included in groups I to iv. Like
esther, pag, etc.
Api classifies the quality of base oil based on the difference of hydrocarbon compound it
contains:% HC saturate (lots of carbon double-sleeved, facilitate it oxidized),% sulfur content
(impurities although functioning as anti-friction), and viscosity index (vi) as resistance to heat
temperature changes of its viscosity and flowability at cold temperatures (Ryan,1999).

It is important that in designing and operating a lubricating plant the base oil chosen should
be appropriate for the application, temperature range and conditions in your plant.

Group I

Group i base oils are classified as less than 90 percent saturates, greater than 0.03 percent sulfur
and with a viscosity-index range of 80 to 120. The temperature range for these oils is from 32 to
150 degrees f. Group I base oils are solvent-refined, which is a simpler refining process. This is
why they are the cheapest base oils on the market. The demand for group I oils is declining,
although they are still the largest single category in the global market (Anwar, etal., 2001) These
oils are falling out of favor because they contain too much sulfur and aromatics to be as stable as
hydro processed oils. They are commonly used in industrial and marine lubricants and in engine
oils for older engines.
 Solvent Freezing: Group 1 base oils are the least refined of all the groups. They are usually a mix
of different hydrocarbon chains with little or no uniformity. While some automotive oils on the market
use Group I stocks, they are generally used in less demanding applications.

Group II

Group ii base oils are defined as being more than 90 percent saturates, less than 0.03
percent sulfur and with a viscosity index of 80 to 120. They are often manufactured by
hydrocracking, which is a more complex process than what is used for group i base oils. Since all
the hydrocarbon molecules of these oils are saturated, group ii base oils have better antioxidation
properties. They also have a clearer color and cost more in comparison to group i base oils. Still,
group ii base oils are becoming very common on the market today and are priced very close to
group i oils (Anwar et al., 2002). This material is widely used by shell, total oil, bp, gulf, etc.

Most of Group II base oil manufacturers utilize Chevron based license. One of the biggest benefits
of the licensed technology is the ability to produce both Group II and III base oils. [23] More recently,
ExxonMobil has pushed forward the production of Group II oils with the patented technology. Patented
two-step, singlestage process includes first hydroconversion and then the cold hydrofinishing step.
Obtained effluent goes through catalytic or solvent dewaxing. [24] The process leaves an option to
produce also Group I oils [23, 24].

Group II - Hydro processing and Refining: Group II base oils are common in mineral based motor
oils currently available on the market. They have fair to good performance in lubricating properties such
as volatility, oxidative stability and flash/fire points. They have only fair performance in areas such as pour
point, cold crank viscosity and extreme pressure wear.
Group III

Group iii base oils are greater than 90 percent saturates, less than 0.03 percent sulfur and
have a viscosity index above 120. These oils are refined even more than group ii base oils and
generally are severely hydrocracked (higher pressure and heat). This longer process is designed to
achieve a purer base oil. Although made from crude oil, group iii base oils are sometimes described
as synthesized hydrocarbons. The group iiis are growing in use as fuel economy lubricants become
more important and car makers use 0w-20 oils for the factory fill of newly assembled engines.
0w-16 oil is already being used in some new engines and japanese car makers have expressed a
wish to see viscosity continue to drop to 0w-12, 0w-8 and even 0w-4. Group iii also includes gas-
to-liquid (gtl) oils made from natural gas using a process developed in the 1920s by the german
chemists franz fischer and hans tropsch. Shell is operating a large gtl plant in qatar, but the method
remains a complex one requiring a large investment in process equipment.

Group III - Hydro processing and Refining: Group III base oils are subjected to the highest
level of mineral oil refining of the base oil groups. Although they are not chemically engineered,
they offer good performance in a wide range of attributes as well as good molecular uniformity
and stability. They are commonly mixed with additives and marketed as synthetic or semi-
synthetic products. Group III base oils have become more common in America in the last decade.

Therefore, most original equipment manufacturers (OEMs) e.g. Ford, DaimlerCrysler, and
General Motors favor Group III base oils. [23]

Group IV
Group iv base oils are polyalphaolefins (paos). These synthetic base oils are made through
a process called synthesizing. They have a much broader temperature range and are great for use
in extreme cold conditions and high heat applications. Generally pao cannot mix with base oil
group v.
Fourth base oil group is limited to only polyalphaolefins (PAOs). PAOs are free of sulphur,
phosphorus, metals, and waxes. As a wax-free, Group IV oils are used in low temperature applications.
Viscosity index is quite high, between 170 and 300 but products with lower viscosity index range are also
available. PAOs are also well miscible with mineral oils. However, disadvantageously additive-free PAOs
have poor oxidation stability and there is also a risk that PAOs may shrink gaskets. These deficiencies can
be reduced by additives like antioxidants and esters. In addition, PAOs face tough competition from
cheaper base oils from Group III. [23]
 Group IV - Chemical Reactions: Group IV base oils are chemically engineered synthetic base stocks.
Polyalphaolefins (PAO's) are a common example of a synthetic base stock. Synthetics, when combined
with additives, offer excellent performance over a wide range of lubricating properties. They have very
stable chemical compositions and highly uniform molecular chains. Group IV base oils are becoming more
common in synthetic and syntheticblend products for automotive and industrial applications.

Group V
Group v embraces everything else, ranging from some very low-quality naphthenics all the
way up to some very exotic synthetic oils. Other occupants of this group are organic esters,
compressor oil, some biodegradable fluids and the polyalkylene glycols that are extremely non-
flammable and thus suited for use as high-temperature hydraulic fluid. This group is classified as
all other base oils, including silicone, phosphate ester, polyalkylene glycol (pag), polyolester,
biolubes, etc. These base oils are at times mixed with other base stocks to enhance the oils
properties. An example would be a pao-based compressor oil that is mixed with a polyolester.
Esters are common group v base oils used in different lubricant formulations to improve the
properties of the existing base oil. Ester oils can take more abuse at higher temperatures and will
provide superior detergency compared to a pao synthetic base oil, which in turn increases the hours
of use.

Group V, as described in Table I, is a collection of various, mainly synthetic base oil stocks. Usually
this group contains oils designed for very special applications which require extreme durability. For
example non-flammability, radiation resistance and chemical stability are properties that definitely raise
the price of Group IV oils. [23]

Group V - As Indicated: Group V base oils are used primarily in the creation of oil additives. Esters
and polyolesters are both common Group V base oils used in the formulation of oil additives. Group V oils
are generally not used as base oils themselves, but add beneficial properties to other base oils.
 Leavens (2012) has analyzed present and future global base oil demands on the economical
basis. In 2010, global demand of base oils from Groups I to IV was about 35 million tons. Group
I base oils have the predominant share, clearly over 50 % of the total demand. Due to steady
growth, global base oil demand is predicted to rise to nearly 44 million tons by 2030. During the
next decades, demand of Group I oils is estimated to decrease while demand of Group II and
especially the demand of Group III oils is going to increase. [28]
Although the global base oil demand is rising, demand in Europe and North America is
decreasing. Demand of Group I base oils will decline sharply by the year 2030 in these two regions
but these base oils still retain strong position in industrial and marine lubricants. Reformation of
automotive fleets in Europe and North America is shifting the demand towards mid- and top-tier
engine oils i.e. Group II and Group III. European mid-tier classification covers also the blends of
Group I and Group II or Group III. [28]
The growth in global base oil demand arises from the Asia following the rapid
industrialization and expansion of vehicle fleet. Group I base oils will hold its largest share,
because the quality requirements and legislation follow development of the Western world with a
delay. South Korea is already providing a large supply of Group III oils so the orientation is moving
towards mid- and top-tier lubricants at the same time with eventual modernization of automotive
fleets. [28]

2.3 Base Oil Properties

Base oils are described by physical properties that dictate how they will perform in service:

Cold flow properties

The cold flow properties are important in a cold climate. The N-alkanes in paraffinic oils
crystallise upon cooling which impedes the free flow of the oil. A differential scanning calorimeter
(DSC) can be used for measuring the amount of N-alkanes. When the cloud point occurs (i.e. The
crystallisation point), the oil is no longer a Newtonian fluid, but has become a two-phase system.
Naphthenic oils are virtually free from N-alkanes. This means that no yield stress is needed to start
moving the oil at low temperatures, which is important in many applications.
Pour point, the lowest temperature at which an oil flows, is measured according to ASTM
D 97. ) The lower is the temperature, the better quality is the oil. In a lubricant indicates the
paraffinic content, to lower with additives. Synthetic oil contains no paraffins. They dont need
pour point depressant additives. Most petroleum lubricant: > -34C even with additives Synthetic
lubricant without additives: -45 C Synthetic lubricant with additives: -60 C. CLOUD POINT =
the temperature at which the oil loses its clarity, i.e. Develops haze or cloudiness due to the start
of crystal formation

The pour point of petroleum is an index of the lowest temperature at which oil will flow under
specified conditions (Mortier et al., 2010). The maximum and minimum pour point temperatures provide
a temperature window where petroleum depending in its thermal history might appear in the liquid as
well as in the solid (lowest temperature at which movement of the test specimen is observed under the
conditions of test) (Speight, 2002). The pour point data can be used to supplement other measurements
of cold flow behaviour and the data are particularly useful for the screening of the effect of wax interaction
modifiers on the flow behaviour of petroleum. Most engine oils contain waxes and paraffins that solidify
at cold temperatures. Engine oils with high waxes and paraffins will have a higher pour point. Pour point
is highly affected by an oils viscosity and engine oils with high viscosity are characterized by having high
pour points. The oil must have the ability to flow into the oil pump and then be pumped to the various
parts of the engine, even at low temperatures. The pour point of a crude oil is an index of the lowest
temperature and handle ability of certain applications (Speight, 2002).

Viscosity
An oils resistance to flow defines the viscosity. Honey, for example, is more viscous than
water. The viscosity of an oil is important for its cooling and lubricity properties. The lower the
viscosity, the better the cooling. An increase in temperature reduces the viscosity. The rate of
change in viscosity with temperature can be expressed in terms of viscosity index (vi). A small
reduction in viscosity coupled with a large temperature changes indicates a high viscosity index.
Paraffinic oils have a higher vi than naphthenic oils. A high vi is required in certain applications.
Automotive lubricants are one example where lubrication is needed at both high and low
temperatures. However, for cooling applications, such as metal working or quenching, a low vi is
better because of the lower viscosity (better heat transfer) at operating temperatures. Viscosity
(kinematic) is measured according to astm d 445.
Viscosity index Viscosity index is a measure of the effect of temperature on the viscosity of a
lubricant. Ideally the viscosity should vary as little as possible with temperature so that the lubricant can
perform adequately over a wide range of engine operating conditions. VI is used as a convenient measure
of the degree of aromatic removal during base oil manufacturing process and also a useful tool in
comparing base oils only if they are derived from the same distillate feedstock (Mortier et al., 2010). The
viscosity indexes of the used and regenerated oils were calculated according to ASTM-2270 by the
application of the procedure for oils of 0-100 VI. In this procedure, the kinematic viscosity of the lube oil
at 40 and 100C were measured and the equation 4 below was used accordingly. VI = 100
.4 Where: U is the kinematic viscosity at 40C of the oil whose viscosity index
is to be calculated (cSt). L is the kinematic viscosity at 40C of an oil of zero viscosity index having the same
kinematic viscosity at 100C as the oil whose VI is to be calculated (cSt). H is the kinematic viscosity of an
oil of 100 viscosity index having the same kinematic viscosity at 100C as the oil whose VI is to be calculated
(cSt). The values of L and H are obtained from tables. For oils having viscosity index greater than 100,
another viscosity index formular exists. For this index, the oil is only compared with a reference oil of the
H family having the same viscosity at 100C, and by applying Equation 5, VI = 10 1 0.00715 + 100
4 N = 1 + . .5
B is the kinematic viscosity of the oil at 100C.

Purity
Constituents of many lubricants such as sulfur, nitrogen and polycyclic aromatic
compounds must be held within strict limits

Flash point
The flash point of an oil is specified for safety reasons, but also because it indicates how
volatile the oil is. Light parts of the oil determine the flash point which is extremely sensitive to
contaminants from lighter oils, such as gas oil or gasoline. The flash point is reached when the oil
releases enough gases to make the gas mixture above the oil ignitable in the presence of an open
flame. The pm (pensky marten) closed cup method (astm d 93) gives the best repeatability. Another
method is the coc (cleveland open cup) astm d 92, which, generally, gives 5- 10c higher flash
point values.
 It is a function of the apparatus design, the condition of the apparatus used, and the
operational procedure carried out. Flash point can therefore only be defined in terms of a standard
test method, and no general valid correlation can be guaranteed between results obtained by
different test methods, or with test apparatus different from that specified (ASTM D93).
The flash point of engine oil is the lowest temperature to which the oil must be heated under
specified conditions to give off sufficient vapour to form a mixture with air that can be ignited
spontaneously by a specific test flame (ASTM, 2004). Flash point measures the tendency of the specimen
to form a flammable mixture with air under controlled laboratory conditions. It is only one of a number
of properties used to evaluate the overall flammability hazard of a substance. It gives a rough indication
of the lubes oil boiling range and is significant in high temperature duties where vapourization of
lubricants is unacceptable. Flash point can indicate the possible presence of highly volatile and
inflammable materials in a relatively non-volatile or non-flammable material. Also, the degree of
contamination of lube oil can be evaluated using this parameter. A substantially low flash point is an
indicator that the oil has become contaminated with volatile products such as gasoline. This implies that
if a lubricant has already been in use, a low flash point will indicate dilution by a fuel. A low flash point of
lube oil from a plant can also be traced to insufficient stripping out of solvent used in the stripping process
(Gary and Handwerk, 2001; Hamawand et al., 2013).
Density
Specific gravity Density is defined as the mass per unit volume and specific gravity is the ratio of
mass of a volume of a specified material at a specified temperature to the mass of the same volume of
distilled water at a standard temperature.
Density increases with the aromatic and naphthenic content. A standard coefficient,
0.00065/C, can be used in most cases for calculating the density at other temperatures than those
already measured. Density is measured according to ASTM D 4052

Kinematic viscosity Viscosity is a measure of the internal friction of a fluid and numerous methods
have been formulated for its determination (Chiyoda, 1980). Usually these methods involve the
measurement of the flow of fluid through an orifice or capillary tube at a carefully controlled temperature.
These methods are usually dependent on the specific gravity of the fluid under test in which the kinematic
viscosity is obtained (measured in centistoke cSt).
The kinematic
viscosity was then calculated by applying the formula;
 = . .3
Where:
k is a constant factor for the calibrated viscometer.
t is the time taken by the oil to flow through the
viscometer in seconds.
v is the kinematic viscosity measured in mm2
/s
(centistoke cSt) (ASTM, 2004).

Solubility
The solubility properties of an oil are important in areas such as grease manufacturing. It
is also important for keeping oxidation products in solution and for seal swell. Viscosity Gravity
Constant (VGC) is an indication of solubility. A high VGC value means good ability to dissolve
polymers, additives and oxidation products. VGC can be calculated from density and kinematic
viscosity (ASTM D 2501). Aniline point is also a property that indicates the solubility of an oil. It
is defined as the lowest temperature at which a mineral oil is completely miscible with an equal
volume of aniline (ASTM D 611). The lower the aniline point, the better the solubility. In the past,
low refined oils, such as aromatic oils or distillates, were used where high solubility was needed.
Due to health and safety reasons, these products are now banned in most countries. Due to
sophisticated refining techniques, Nynas naphthenic oils are label-free, and yet retain low aniline
scores i.e. Good solubility. Nynas T-grades have the best solubility properties

The pour point of petroleum is an index of the lowest temperature at which oil will flow under
specified conditions (Mortier et al., 2010). The maximum and minimum pour point temperatures provide
a temperature window where petroleum depending in its thermal history might appear in the liquid as
well as in the solid (lowest temperature at which movement of the test specimen is observed under the
conditions of test) (Speight, 2002). The pour point data can be used to supplement other measurements
of cold flow behaviour and the data are particularly useful for the screening of the effect of wax interaction
modifiers on the flow behaviour of petroleum. Most engine oils contain waxes and paraffins that solidify
at cold temperatures. Engine oils with high waxes and paraffins will have a higher pour point. Pour point
is highly affected by an oils viscosity and engine oils with high viscosity are characterized by having high
pour points. The oil must have the ability to flow into the oil pump and then be pumped to the various
parts of the engine, even at low temperatures. The pour point of a crude oil is an index of the lowest
temperature and handle ability of certain applications (Speight, 2002).

Colour Determination of colour of petroleum products is used mainly for manufacturing control
purposes and is an important quality characteristic since colour is readily observed by the product user.
In some cases colour may serve as the degree to which a material has been refined (Speight, 2002). When
the colour range of a particular product is known, a variation outside the established range may indicate
possible contamination with other products. These contaminants are mainly those generated as a result
of use of the oil. However, colour is not always a reliable guide to product quality and hence should not
always be used indiscriminately in product specification.

Boiling point The boiling point of a liquid is defined as the temperature at which the vapour
escaping from the surface of the liquid has a pressure equal to the pressure existing above the liquid
(Scodellaro, 2008). The boiling point of the used oil was determined with the help of an adequately
calibrated thermometer by taking the temperature of the oil on heating, immediately physical boiling was
observed.

Refrences

S.q.a. Rizvi, lubricant chemistry, technology, selection and design (a

comprehensive review), astm publication mnl 59, 2009 isbn 978-0-8031-7000-1
L.r. Rudnick (eds), synthetics, mineral oils, and bio-based lubricants chemistry
and technology, 2nd ed, crc press, 2013 isbn 978-1-4398-5538
https://www.astm.org/Standards/D611.htm
Jha, M.K., 2005. Re-refining of used lube oils: An intelligent and eco-friendly option. Indian
Chem. Eng., 47(3): 209-211.
Brussels, S. and Luxembourg, R. 2001. Recycling of used Mineral Oil. Journals of
Mechanical Engineering and Processing Technology, 8(12):67-81.
 Pirro, D.M. and Wessol, A.A. (2001). Lubrication Fundamentals, 2nd Edition, Revised and
Expanded. Marcel Dekker, Inc., USA, ISBN 0-8247-0574-2.
Ryan, H. (1999). Use of Group II, Group III base stocks in hydraulic and industrial
applications. Industrial Lubrication and Tribology, 51, pp. 287293.
Anwar, M., Kaushik, R.S., Srivastava, M., Kumar, M., and Garg, M.O. (2002). Basics:
Current base oil quality and technological options for its improvement - an overview.
Lubrication Science, 14, pp. 425434.