Petroleum Refining Fourth Year Dr.Aysar T.

Jarullah

8- Octane number
An octane number is a measure of the knocking tendency of gasoline fuels in spark ignition
engines. The ability of a fuel to resist auto-ignition during compression and prior to the spark
ignition gives it a high octane number. Two octane tests can be performed for gasoline. The
motor octane number (MON) indicates engine performance at high way conditions with high
speeds (900 rpm). On the other hand, the research octane number is indicative of low-speed
city driving (600 rpm).
RON of a fuel may be estimated from the pseudocomponent techniques in the following
form:

…………….(1)
where x is the volume fraction of different hydrocarbon families i.e., n-paraffins (NP),
isoparaffins (IP), olefins (O), naphthenes (N), and aromatics (A). RONNp, RONIp, RONo,
RONN, and RONA are the values of RON of pseudocomponents from n-paraffin,
isoparaffins, olefins, naphthenes, and aromatics families whose boiling points are the same
as the mid boiling point or the ASTM D86 temperature at 50% point of the fraction and
can be determined from Figure:

Figure 2: Research octane number of different families of hydrocarbons.

There is another graphical relation for estimation of RON of naphthas in terms of Kw

characterization factor or paraffin content (wt%) and mid boiling point as given in
Figures below
Petroleum Refining Fourth Year Dr.Aysar T. Jarullah

Figure 3: Research octane number of naphthas

Figure 4: Research octane number versus paraffin content

Petroleum Refining Fourth Year Dr.Aysar T. Jarullah

RON for these various hydrocarbon groups have been correlated to normal boiling
point, Tb in the following form:

……………………..(2)

Where RON is the clear research octane number and T = (Tb-273.15)/100 in which Tb is the
boiling point in kelvin. Based on the data taken from the API-TDB, the coefficients a - e
were determined and are given in Table below:

Coefficients of eq. 2 for estimation of RON

Example: A naphtha sample from an Australian crude oil has the following characteristics:
boiling point range 15.5 – 70°C specific gravity 0.6501, n-paraffins 49.33%, isoparaffins
41.45%, naphthenes 9.14%, aromatics 0.08%, clear RON 69.6, and MON 66.2. a) Estimate
RON from the pseudocomponent method using experimental composition, b) Estimate RON
from Fig.4.

Solution:
For this fraction: Tb = (15.5 + 70)/2 = 42.8°C, SG = 0.6501, xp = 0.4933, xw = 0.4145,
xN = 0.0914, xA =0.008:
a) RON can be estimated from Eq.(1) through pseudocomponent method using RON values
for pure hydrocarbons calculated from Eq. (2) and Table above with Tb= 315.9K. Results
of calculation are (RON)np =54.63, (RON)Ip = (90.94 + 104.83 + 88 + 87.05)/4 = 92.7,
(RON)N = 55.57, and (RON)A =125.39. In calculation of (RON)w, an average value for
RON of 4 families in Table above is calculated. From eq.2, clear RON can be calculated as:

In comparison with the reported value of 69.6 the error is 70.55 - 69.6 = 0.95.

b) To use Fig. 4 we need total paraffins which is % = 49.33 + 41.45 = 90.78 and Tb = 109F.
In this case Tb is outside the range of values on the curves, but with extrapolation a value of
about 66 can be read. The error is about = 3.6.
Petroleum Refining Fourth Year Dr.Aysar T. Jarullah

9- Aniline Point
The lowest temperature at which an equal volume mixture of the petroleum oil and aniline
are miscible is the aniline point. Since aniline is an aromatic compound, petroleum fractions
with high aromatic content will be miscible in aniline at ambient conditions.
Aniline point can be estimated using the following relation:

where AP is in °C Tb is the mid boiling point in kelvin and API is API gravity.

10- Cetane number

The cetane number measures the ability for auto ignition and is essentially the opposite of the
octane number. The cetane number is the percentage of pure cetane (n-hexadecane) in a blend
of cetane and alpha methyl naphtha-lene which matches the ignition quality of a diesel fuel
sample. This quality is specified for middle distillate fuels.
Since determination of cetane number is difficult and costly, ASTM D976 (IP 218) proposed
a method of calculation. Calculated number is called calculated cetane index (CCI) and can
be determined from the following relation:

WhereT50 is the ASTM D 86 temperature at 50% point in °C Another characteristic of diesel

fuels is called diesel index (DI) defined as:

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

11- Smoke Point

The smoke point is a test measures the burning qualities of kerosene and jet fuel. It is defined
as the maximum height in mm, of a smokeless flame of fuel.
The smoke point (SP) can be calculated using the following equation:

Where AP is the aniline point in °C and SG is the specific gravity at 15.5°C. Equation above
estimates SP according to the IP test method. To estimate SP from the ASTM D1322 test
method, 0.7 mm should be subtracted from the calculated IP smoke point.

Example: A Nigerian kerosene has an API gravity of 41.2, aniline point of 55.6°C. Estimate
the smoke point of this fuel and compare with the experimental value of 20 mm.

Solution:
From API gravity, SG = 0.819, AP=55.6°C, the calculated SP is SP = 20 mm. The ASTM
smoke point is then 19.3 mm which is in very good agreement with the experimental value of
20 with deviation of -0.7 mm.
Petroleum Refining Fourth Year Dr.Aysar T. Jarullah

12- Freezing Point

Petroleum fractions are mostly liquids at ambient conditions. However, 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. It is one of the important property
specifications for kerosene and jet fuels due to the very low temperatures encountered at high
altitudes in jet planes.

13- Reid Vapor Pressure (RVP)

Is a common measure of the volatility of gasoline. It is defined as the absolute vapor
pressure exerted by a liquid at 100 °F (37.8 °C) as determined by the test method ASTM-D-
323. The matter of vapor pressure is important relating to the function and operation of
gasoline powered, especially carbureted, vehicles. High levels of vaporization are desirable
for winter starting and operation and lower levels are desirable in avoiding vapor lock during
summer heat. Fuel cannot be pumped when there is vapor in the fuel line (summer) and
winter starting will be more difficult when liquid gasoline in the combustion chambers has
not vaporized. Thus, oil refineries manipulate the Reid Vapor Pressure seasonally specifically
to maintain gasoline engine reliability.
RVP data on 52 different petroleum products (light and heavy naphthas, gasolines, and
kerosenes) from the Oil and Gas Journal data bank have been used to develop a simple
relation for prediction of RVP in terms of boiling point and specific gravity in the following
form:

Where Tb is the mid boiling point and Tc is the pseudocritical temperature of the fraction in
kelvin. Pc is the pseudocritical pressure and RVP is the Reid vapor pressure in bars.

Example: Estimate RVP of a gasoline sample has molecular weight of 86 and API gravity of
86 and Tb=388K, Tc=501.2K, Pc=28.82bar.

Solution:
Tr = 0.6205, X = 1.3364, and Y = -3.7235. Thus we calculate RVP = 0.696 bar or 10.1 psia.
The experimental value is 11.1 psia
Petroleum Refining Fourth Year Dr.Aysar T. Jarullah

14- Molecular Weight

Molecular weight (M) is perhaps the most important characterization parameter for
petroleum fractions and many physical properties may be calculated from this parameter.
M can be pridicted by using the following equation:

This equation can be applied to hydrocarbons with molecular weight ranging from 70 to 700,
which is nearly equivalent to boiling point range of 300-850 K (90-1050F) and the API
gravity range of 14.4-93. For heavy petroleum fractions based on the molecular weight of
heavy fractions in the range of 200-800:

The three input parameters are kinematic viscosities (in cSt) at 38 and 98.9°C (100 and 210F
shown by v38(100) and v99(210), respectively, and the specific gravity (SG) at 15.5°C.

15- Distillation Range

The boiling range of the crude gives an indication of the quantities of the various products
present. The most useful type of distillation is known as a true boiling point (TBP) distillation
and generally refers to a distillation performed in equipment that accomplishes a reasonable
degree of fractionation. (See Fig. and Table below)
Petroleum Refining Fourth Year Dr.Aysar T. Jarullah

Table 1: Oil fractions destinations and ultimate products with their boiling ranges
Oil Fractions Approx. Boiling Next Destination Ultimate Products
Ranges (0C)

LPG -40 to 0 Sweetener Propane fuel

Light Naphtha IBP - 85 Hydrotreating Gasoline
Heavy Naphtha 85 – 200 Cat. Reformer Gasoline, aromatics
Kerosene 170 – 270 Hydrotreating Jet fuel, diesel No.1
Gas Oil 180 – 240 Hydrotreating Heating oil, diesel No.2
Vacuum Gas Oil 340 - 566 FCC Gasoline, LGO, gases
Hydrotreating Fuel oil, FCC, feed
Lube Plant Lube basestock
Hydrocracking Gasoline, jet fuel, diesel,
FCC feed, basestock
Vacuum Residue > 540 Coker Coke, coker gas oil,
Visbreaking Visbreaker gas oil, resid
Asphalt Unit Deasphalted oil, asphalt
Hydrotreating FCC feed