Properties of Petroleum & Natural Gas Petroleum & Gas Refining Engineering

Quality Control Tests of Finished Petroleum Products

3- Diesel Fuel

Density
Pour
ASTM D86
Point

Diesel
Cloud
Flash Point
Point

Cetane
viscosity
Number

Super Diesel Fuel (C14 – C20) (boiling range 250-360 °C)

• Physical Description: A yellow viscous liquid.
• Chemical Description: 30% alkanes (paraffins), 45% cyclic alkanes (naphthenes) and 25%
aromatics.
• Density: 0.820-0.880
• Flash point (P.M.C.C.): 62 °C Min.
• Kinematic viscosity @40 °C: 2-4.5 cSt
• CFPP cold filter plugging point: -10 °C
• Copper corrosion @ 3hr and 50 °C: class 1 Max.
• Carbon residue: 0.15 mass%
• Ash content: 0.01 mass%
• Sulfur content: 0.7 mass%
• Cetane number: 51 Min.
Viscosity at 37.8°C (100°F) by ASTM D445 and by ASTM D446 at 99°C (210°F).
 Viscosity of a fluid is a measure of its resistance to gradual deformation by shear stress, i.e.
resistance (internal friction) to flow.
 More viscous oils create a greater pressure drop when they flow in pipes.
 Zero viscosity is observed only at very high temperatures. Otherwise, all fluids have positive
viscosity, and are technically said to be viscous.

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Types of viscosity:
Dynamic viscosity (μ) with units (poise or g / (cm · s)
Kinematic viscosity (υ) with unit (stoke or cm2 / s , cSt: mm2/s, or saybolt second)
 Dynamic (absolute) viscosity of a fluid expresses its resistance to shearing flows, where
adjacent layers move parallel to each other with different speeds.
 Kinematic viscosity is the resistance of fluid to flow under gravity
 Kinematic viscosity is also defined as the ratio of absolute viscosity (dynamic) to absolute
density (ρ) at the same temperature in the following form:
υ=μ/ρ
 The kinematic viscosity of oil is obtained by measuring the time required for a sample of the
oil to flow, under gravity, through a capillary viscometer at a known temperature.
 Viscometers have several sizes and differing designs.
 The configuration and size of the capillary must be calibrated and tested to provide a
constant value for particular viscometer.

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 The oil sample is introduced into the viscometer through tube L by tilting the viscometer to
about 30° from the vertical with bulb A below capillary R.
 Attach the viscometer into the holder and insert the viscometer into the oil bath so that it is
vertical. Allow the sample to reach the bath temperature, usually about 30 min before
starting the test.
 Using vacuum system, draw up the sample through bulb C to about 5 mm above the upper
timing mark E.
 Release the vacuum and allow the sample to flow by gravity.
 Measure the time for sample flow from mark E to mark F.
The kinematic viscosity can be measurement by viscometer (U-tube device) by using the
following equation:

υ : kinematic viscosity ( cSt. )

c : viscometer constant ( mm2/s2 ) .
t : time required to passing the oil through the limited marks in viscometer ( s ).
Time = 686 seconds , viscometer constant ( C ) = 0.035 mm2/s2 Density = 0.846 g/mL.

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Properties of Petroleum & Natural Gas Petroleum & Gas Refining Engineering
What is Viscosity Index?
The viscosity index is a number indicating the effect of change of temperature on the kinematic
viscosity of oil.
VI=100 for paraffinic base or light crude oil: small change of kinematic viscosity with
temperature.
VI=0 for naphthenic base or heavy crude oil: Low viscosity index is expected for naphthenic
base crude oil (large change in kinematic viscosity).
Prediction of Kinematic Viscosity at 38 and 99°C
The following equations can be used to calculate the liquid viscosities of petroleum fractions at
atmospheric pressure and at temperatures of 37.8°C (100°F) and 98.9°C (210°F).

Eq.43

Eq.44

The above relations cannot be applied to heavy oils and should be used with special care when Kw
< 10 or Kw > 12.5 and API < 0 or API > 80. Average error for these equations is in the range of
15-20%. They are best applicable for the viscosity ranges of 0.5 < v38 < 20 mm2/s and 0.3 < v99 < 40
mm2/s.
The Saybolt (SUS) universal second is related to the kinematics viscosity (v) in cSt by the relation
below:

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Properties of Petroleum & Natural Gas Petroleum & Gas Refining Engineering
Nomograph: used to find viscosity from API and Kw values

API 34
Kw 11.9

V100 =6
V210 =1.90

Exercise: Calculate the kinematic viscosities for oil which has a MeABP of 320 °C and API gravity
of 34. Compare the result with that calculated from the Nomograph.
Solution
MeABP SG cubic root Kw
1067.7 0.855 10.22076 11.9541

From the Nomograph V100 = 6.0 cSt and V210 = 1.90 cSt

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ASTM D 2500 – Cloud Point Test
 The cloud point is the lowest temperature at which wax crystals begin to form by a gradual
cooling of the oil sample.
 Low cloud point products are desirable under low-temperature conditions.
 Cloud points test measured for heavy fractions and no cloud point data are reported for
light fractions such as naphtha or gasoline.
 Cloud points usually occur at 4-5°C above the pour point.
 A clean sample is cooled at a specified rate and the temperature at which a haze is first
observed at the bottom of the test tube is the cloud point.

The following equation cab be used for predicting the cloud point:

where, CP = Cloud point °R. MeABP = mean average boiling point °R.
ASTM D 97 – Pour Point of Petroleum Products
The pour point is the lowest temperature in which the oil has ability to pour or flow when it is
cooled without stirring under cooling, below which the liquid loses its flow characteristics
 It indicates how easy or difficult is to pump the oil, especially in cold weather.
 It also indicates the aromatic or the paraffinic content of the crude oil or the fraction.
 A high pour point means that the paraffin content is high.
Pour point can be estimated for the petroleum fractions from viscosity, molecular weight, and
specific gravity by using the following form:
( )[ ][ ]
Oil Sample is first warmed and then cooled at a specified rate and observed at intervals of 3°C
(5°F).

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Cold filter plugging point (CFPP) ASTM D6371
 The lowest temperature at which a given volume of diesel fuel still passes through a
standardized filtration device in a specified time when cooled under certain conditions.
 This test gives an estimate for the lowest temperature that a fuel will give trouble free flow
in certain fuel systems.
Freezing Point
 Heavy oils contain heavy compounds such as waxes or asphaltenes. These compounds tend
to solidify at low temperatures, thus restricting flow.
 The freezing point is the temperature at which the hydrocarbon liquid solidifies at
atmospheric pressure.
Prediction of Freezing Petroleum Fractions

Where, FRP = Freezing point of petroleum fraction, °R

MeABP = mean average boiling point, °R
K = Watson K factor
SG = specific gravity of petroleum fraction, 60°F/60°F

Cloud and Pour Points Tester Diagram

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Properties of Petroleum & Natural Gas Petroleum & Gas Refining Engineering
Exercise: A kerosene sample has the boiling range of 150-204.4°C and API gravity of 48.7.
Estimate the cloud and pour points of this kerosene and compare with the experimental value of -
65°C and comment on your results.
Solution:
To find CP, we need MeABP and SG. Since Tb can be calculated and may be used as MeABP.

MeABP SG cubic root Kw

810.96 0.7852 9.325379 11.87644
( )

( )[ ][ ]

( )

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Cetane Number CN
 The cetane number measures the ability of fuel for auto ignition in internal combustion
engines (no spark) and is essentially the opposite of the octane number.
 Cetane number (CN) is the volume percent of cetane (C16H34) which has high ignition (CN
= 100) in a mixture with HMN which has low ignition quality (CN = 15).
 Cetane number (CN) is an inverse function of a fuel's ignition delay, the time period
between the start of injection fuel and the start of combustion is called Ignition Delay.
 In a particular diesel engine, higher cetane fuels will have shorter ignition delay.
Cetane Number ASTM D 613
 The method involves running the fuel in a single-cylinder engine with a continuously
variable compression ratio under a fixed set of conditions.
 In diesel engines, air and fuel are not pre-mixed
Four stroke ICE
 Intake & Compression: Air is inducted into the cylinder and compressed by piston to high
pressure and temperature (adiabatic compression T = 400 °C, 25:1 compression ratio).
 Fuel injection & Power: fuel is injected into the hot compressed air causing instant ignition
and generating high pressure torque to power the vehicle.
 Exhaust

 2,2,4,4,6,8,8-heptamethylnonane (HMN) CN = 15 (highly resistant to autoignition).

 N-hexadecane (cetane: C16), which burns well, was assigned a cetane number of 100.
 A fuel with a CN = 40 will perform the same in the engine as a blend of 40% C16 and 60%
(HMN).

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Predicting Cetane Number and Diesel Index
For diesel engines, the fuel must have a characteristic that favours auto-ignition (i.e. high CN).
The cetane number is defined as:
( )
ASTM D 976 (IP 218) proposed a method of calculation called calculated Cetane Index (CCI)
and can be determined from the following relation:
( )
Where T50 is the ASTM D 86 temperature at 50% point in °C.
Another characteristic of diesel fuels is called diesel index (DI) defined as.
( )
( )

DI is a function of API gravity and aniline point in °C.

 Diesel Index is just same as Cetane Number.
 The increase in both Diesel Index and Cetane Number indicates good quality fuel.
Cetane index is empirically correlated to DI, AP and normal paraffin content %NP in the Following
form:

Cetane number of diesel fuels can be improved by 3-5 points once 300-1000 ppm by weight 2-
ethyl-hexyl nitrate or other types of alkyl nitrates additives is added.
Why do diesel engines smoke?
Diesel engine smoke is caused by incomplete combustion.
White smoke is caused by tiny droplets of unburned fuel as a result of low engine temperature.
This smoke should disappear as the engine warms up.
Black smoke is caused by a faulty injector, insufficient air, and overloading and/or over fuelling the
engine.
Blue-gray smoke is the result of burning lubricating oil and is an indication of poor mechanical
condition.

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3
Exercise : A diesel fuel has a specific gravity of 820 kg/m and an average boiling point of 225 °C.
When the fuel tested in a standard test engine, the fuel is found to have the same ignition
characteristics as a mixture of 27% C16 and 73% HMN. Find CN of the fuel , % error if CCl was
used to calculate the cetane number.
Solution
( ) ( )
From eq. 1 find CCl
( ) ( ) ( )

Nomograph for Cetane Index

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Exercise: Diesel fuel have the below ASTM D86 distillation data. Calculate the following: CCI,
DI, kinematic viscosities, Cloud & Pour Points, and Flash point.
V% distilled IBP 10 30 50 70 90 95 EP
Diesel fuel ASTM D86 °C 216 243 268 284 304 318 327 334
Solution.
a b c T10 T50 SG
0.08342 0.10731 0.26288 516.15 557.15 0.859487
CCl calculated from eq. 49
SG T50 CCl
0.8623 284 42.39799

To find V100 & V210, we need API and Kw

API = 33

MeABP SG cubic root Kw

998.99 0.86 9.996632 11.62399

( )[ ][ ]
Find M.wt from equation in your notebook ( T mid =281.66 °C & SG = 0.860)
M.wt = 219.20

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