Fig.1. Comparison of viscosity by different instruments.(Viscosity must be at the same T.

)
Figure 2: Research octane number of different families of hydrocarbons.
Figure 3: Research octane number of naphthas
Figure 4: Research octane number versus paraffin content
Fig. 5. TBP cut point versus ASTM end point
Fig. 6. Crude distillation curve
Fig. 7. TBP and gravity-mid-percent curves
Fig. 8. Molal average boiling point of petroleum fractions
Fig.9. Mean average boiling point of petroleum fractions
Fig. 10. Relationships between the slopes of various distillation curves
Fig. 11. Relationships between distillation temperatures at 50% vaporized and the flash
(E.F.V.) Temp. at 50%
Fig. 12. Sulfur content of products from Middle East crude oils
Fig. 13. Specific heat of Mid liquids oils with a correction factor for other bases of oils
Fig. 14. Specific heat of Mid oil vapors with a correction factor for other bases of oils
Figure 15. Gross heats of combustion of liquids petroleum hydrocarbons
Fig. 16. Approximate change of specific gravity of intermediate- base oils with T.
Fig. 17. Atmospheric latent heat of vaporization as a function of molecular weight or API
gravity
Fig. 18. Temp. correction to heat of vaporization
Fig. 19. Molecular weight, pseudo critical temp., characterization factors and gravities of
petroleum fractions
Fig. 21.Vapor Pressure and B.P. corrections for normal paraffins hydrocarbons and petroleum
fractions
Fig. 26: Viscosity index
Fig. 27: relation between the V.I, k and the amount of wax
Distillation column with trays
Process flow diagram of the vacuum distillation unit
Light End Fractionation

Coil Visbreaker
Soaker Visbreaker
Role of Hydrocracking
One stage HDC Process
Solvent dewaxing
 Ministry of Higher Education
and Scientific Research

University Of Tikrit
College of Engineering

Chemical Engineering Department

Petroleum Refining Fourth Year Dr.Aysar T. Jarullah

University of Tikrit
College of Engineering - Chemical Engineering Department

Petroleum Refining
Fourth Year - B.S. Syllabus

Objectives
• To impart the basic concepts of petroleum processing and manufacture of Petrochemicals
• To develop understanding about refining and post refining operations

Course Description
This course presents a comprehensive introduction to petroleum refining technology and
calculations. The focus is on transportation fuels refineries is also discussed. The program
includes an overview of crude oil supply and petroleum product demand. This is followed
with a description of refinery process technology. Major refining technologies are described
such as crude oil distillation, heavy oil conversion options, hydrotreating, and catalytic
reforming.

Learning Outcomes
Understanding of oil refining and associated downstream processing technologies,
operations and calculations; process safety, oil products – properties and Specifications,
operations integrity; and methods for oil productions with their calculations.

No Topics Hours
1 Classification of Crude Oils, Composition of Crude Oils 4

2 Physical and Chemical Properties of Crude oil and Oil Products 10

3 Evaluation of Crude Oil 4

4 Crude Oil Pre-treatment, Fractionation of Crude Oil (Atmospheric and 8

Vacuum Distillation, Light End Fractionation, Process Description)
5 Thermal Cracking and Coking Processes 6

6 Catalytic Operations (Processes and calculations) - (Fluid Catalytic 26

Cracking, Hydrocracking, Hydrotreating, Catalytic Reforming,
Isomerization, Alkylation, Catalytic Dewaxing)

7 Chemical Treatment of Oil Products 4

8 Lubricating Oils (Specifications, Production Process, Calculations) 4

9 Solvent Refining (Solvent Deasphalting, Solvent Extraction, Solvent 6

Dewaxing, Wax Deoiling)

10 Oil Products – Properties and Specifications, Description of Process Flow 12

and Calculations- (Oil Gases, Gasoline, Kerosene, Jet Fuel, Gas Oil, Diesel
Oil, Fuel Oil, Asphalt, Greases and Wax)

11 Safety and Environmental Aspects in Refining (Air Quality, Sulfur 6

Recovery, Wastes in Refinery Units, Fugitive Emissions)

Text Book
1- Fahim, M.A.; Al-Shahhaf, T.A. and Elkilani, A.S., Fundamentals of Petroleum
Refining, Elsevier.

References
2- Hsu, Ch.s. and Robinson, P.R., Practical Advances in Petroleum Processing,
Springer.
3- Riazi, M. R., Characterization and Properties of Petroleum Fractions, ASTM
International.
4- Nelson, W.L., Petroleum Refinery Engineering, McGraw-Hill.
Petroleum Refining Fourth Year Dr.Aysar T. Jarullah

Introduction
Petroleum refining plays an important role in our lives. Most transportation vehicles are
powered by refined products such as gasoline, diesel, aviation turbine kerosene (ATK) and
fuel oil. Petroleum has remained an important aspect of our lives and will do so for the next
four or five decades. The fuels that are derived from petroleum supply more than half
of the world s total supply of energy. Gasoline, kerosene, and diesel oil provide fuel for
automobiles, tractors, trucks, aircraft, and ships. Fuel oil and natural gas are used to heat
homes and commercial buildings, as well as to generate electricity. Petroleum products are
the basic materials used for the manufacture of synthetic fibers for clothing and in plastics,
paints, fertilizers, insecticides, soaps, and synthetic rubber. The uses of petroleum as a source
of raw material in manufacturing are central to the functioning of modern industry.

Composition and Classification of Crude Oils

Crude oil is a complex liquid mixture made up of a vast number of hydrocarbon compounds
that consist mainly of carbon and hydrogen in differing proportions. In addition, small
amounts of organic compounds containing sulfur, oxygen, nitrogen and metals such as
vanadium, nickel, iron and copper are also present (See Table below).

There are three main classes of hydrocarbons. These are based on the type of carbon–carbon
bonds present. These classes are:
 Saturated hydrocarbons contain only carbon–carbon single bonds. They are known as
paraffins (or alkanes) if they are acyclic, or naphthenes (or cycloalkanes) if they are
cyclic.
 Unsaturated hydrocarbons contain carbon–carbon multiple bonds (double, triple or
both). These are unsaturated because they contain fewer hydrogens per carbon than
paraffins. Unsaturated hydrocarbons are known as olefins. Those that contain a
carbon–carbon double bond are called alkenes, while those with carbon–carbon triple
bond are alkyenes.
 Aromatic hydrocarbons are special class of cyclic compounds related in structure to
benzene.
Petroleum Refining Fourth Year Dr.Aysar T. Jarullah

1- Paraffins

General formula: CnH2n+2 (n is a whole number, usually from 1 to 20), straight or branched-
chain molecules, can be gasses or liquids at room temperature depending upon the molecule.
For example, methane, ethane, propane, butane, isobutane, pentane, hexane

2- Olefins (also known as alkenes)

General formula: CnH2n (n is a whole number, usually from 1 to 20), linear or branched chain
molecules containing one carboncarbon double-bond, can be liquid or gas. For example:
ethylene, butene, isobutene

3- Naphthenes (cycloalkanes)

General formula: CnH2n (n is a whole number usually from 1to 20), ringed structures with one
or more rings, rings contain only single bonds between the carbon atoms, typically liquids at
room temperature. For example: cyclohexane, methyl cyclopentane

4- Aromatics

General formula: C6H5 - Y (Y is a longer, straight molecule that connects to the benzene
ring), ringed structures with one or more rings, rings contain six carbon atoms, with
alternating double and single bonds between the carbons,typically liquids. For examples
benzene, naphthalene
Petroleum Refining Fourth Year Dr.Aysar T. Jarullah

Crude oils from various origins contain different types of aromatic compounds in different
concentrations. Light petroleum fractions contain mono-aromatics, which have one benzene
ring with one or more of the hydrogen atoms substituted by another atom or alkyl groups.
Examples of these compounds are toluene and xylene.

More complex aromatic compounds consist of a number of benzene rings. These are known
as polynuclear aromatic compounds. They are found in the heavy petroleum cuts, and their
presence is undesirable because they cause catalyst deactivation and coke deposition during
processing, besides causing environmental problems when they are present in diesel and fuel
oils. Examples of polynuclear aromatic compounds are shown below.

5- Sulfur Compounds

The Sulfur content of crude oils varies from less than 0.05 to more than 10 wt% but generally
falls in the range 1–4 wt%. Crude oil with less than 1 wt % sulfur is referred to as low sulfur
or sweet, and that with more than 1 wt% sulfur is referred to as high sulfur or sour. Crude oils
Petroleum Refining Fourth Year Dr.Aysar T. Jarullah

contain sulfur heteroatoms in the form of elemental sulfur S, dissolved hydrogen sulphide
H2S, carbonyl sulphide COS, inorganic forms and most importantly organic forms, in which
sulfur atoms are positioned within the organic hydrocarbon molecules. Sulfur compounds
lead to environmental pollution, decreases the life of machinery, corrodes of pipes, machines
and equipment, affecting the additives used for the purpose of increasing the octane number,
reduce the activity of Tetra Ethyl Lead (TEL) added to gasoline. As a result, the engine metal
will erode and leads to destruct the metallic parts. Also, their emissions are very dangerous to
human safety and environment. In addition, these impurities cause catalyst poisoning and
reduce the catalyst activity. Sulfur containing constituents of crude oils vary from simple
mercaptans, also known as thiols, to sulphides and polycyclic sulphides (Mercaptans (R–SH),
sulphides (R–S–R'), disulphides (R–S–S–R'), Thiophenes)

6-Nitrogen Compounds

Crude oils contain very low amounts of nitrogen compounds, less than 1%, The nitrogen
compounds in crude oils may be classified as basic or non-basic. Basic nitrogen compounds
consist of pyridines. The greater part of the nitrogen in crude oils is the non-basic nitrogen
compounds, which are generally of pyrrole types. The decomposition of nitrogen compounds
in catalytic cracking and hydrocracking processes forms ammonia and cyanides that can
cause corrosion.

7- Oxygen Compounds

Less than 1% (found in organic compounds such as carbon dioxide, phenols, ketones,
carboxylic acids) occur in crude oils in varying amounts.
Petroleum Refining Fourth Year Dr.Aysar T. Jarullah

8- Metals Compounds
Metallic compounds exist in all crude oil types in very small amounts. Their concentration
must be reduced to avoid operational problems and to prevent them from contaminating the
products. Metals affect many upgrading processes. They cause poisoning to the catalysts used
for hydroprocessing and cracking. Even minute amounts of metals (iron, nickel and
vanadium) in the feedstock to the catalytic cracker affect the activity of the catalyst and result
in increased gas and coke formation and reduced gasoline yields. Burning heavy fuel oils in
refinery furnaces and boilers can leave deposits of vanadium oxide and nickel oxide in
furnace boxes, ducts, and tubes. It is also desirable to remove trace amounts of arsenic,
vanadium, and nickel prior to processing as they can poison certain catalysts.

9- Asphaltenes and Resins Compounds

Asphaltenes are dark brown friable solids that have no definite melting point and usually
leave carbonaceous residue on heating. They are made up of condensed polynuclear aromatic
layers linked by saturated links. The presence of high amounts of asphaltenes in crude oil can
create tremendous problems in production because they tend to precipitate inside the pores of
rock formations, well heads and surface processing equipments. They may also lead to
transportation problems because they contribute to gravity and viscosity increases of crude
oils.

Resins are polar molecules have high molecular weight, which are insoluble in liquid propane
but soluble in n-heptane. It is believed that the resins are responsible for dissolving and
stabilizing the solid asphaltene molecules in petroleum.
Petroleum Refining Fourth Year Dr.Aysar T. Jarullah

Products Composition
To understand the diversity contained in crude oil, and to understand why refining crude oil is
important in our society, look through the following list of products that come from crude oil:

 Liquefied Petroleum Gas (LPG)

 used for heating, cooking, making plastics
 small alkanes (1 to 4 carbon atoms)
 commonly known by the names methane, ethane, propane, butane
 boiling range < 90 degrees Fahrenheit / < 27 degrees Celsius
 often liquified under pressure to create LPG (liquefied petroleum gas)
 Gasoline
 motor fuel
 liquid
 mix of alkanes and cycloalkanes (5 to 7 carbon atoms)
 boiling range = 90-220 degrees Fahrenheit / 27-93 degrees Celsius
 Kerosene
 fuel for jet engines and tractors; starting material for making other products
 liquid
 mix of alkanes (10 to 15 carbons) and aromatics
 boiling range = 315-450 degrees Fahrenheit / 177-293 degrees Celsius
 Diesel Fuel
 used for diesel fuel and heating oil, starting material for making other products
 liquid
 alkanes containing 13-18 carbon atoms
 boiling range = 450-650 degrees Fahrenheit / 293-315 degrees Celsius
 Lubricating oil
 used for motor oil, grease, other lubricants
 liquid
 long chain (20 to 50 carbon atoms) alkanes, cycloalkanes, aromatics
 boiling range = 572 to 700 degrees Fahrenheit / 300 to 370 degrees Celsius
 Fuel oil
 used for industrial fuel; starting material for making other products
 liquid
 long chain (16 to 40 carbon atoms) alkanes, cycloalkanes, aromatics
 boiling range = 650-800 degrees Fahrenheit / 315-565 degrees Celsius
 Residual oil
 coke, asphalt, tar, waxes; starting material for making other products
 solid
 multiple-ringed compounds with 40 or more carbon atoms
 boiling range = greater than 800 degrees Fahrenheit / 565 degrees Celsius
Petroleum Refining Fourth Year Dr.Aysar T. Jarullah

Evaluation of Crude Oils

Base of Crude Oil
The crude oil can be classified into:
1) Paraffinic base crude (P)
2) Intermediate bas crude (IN)
3) Naphthenic base crude (N)

Classification Methods

1- Composition of Residue
paraffin 5%  P
2  5%paraffin  IN
parrafin 2%  N
2- Sp.gr of two cuts.

API fraction 1 API fraction 2 Crude Base

≥ 40 ≥ 30 P
33 - 40 20 - 30 IN
≤ 33 ≤ 20 N
≥40 20 - 30 PIN (mix)
30 - 40 ≥ 30 INP (mix)
Petroleum Refining Fourth Year Dr.Aysar T. Jarullah

3- Watson Factor (Kw)

Where
Tb = mean average boiling point (MeABP) K
SG = specific gravity at 15.5°C

Kw Crude Base
10.5 - 11.5 P
11.5 – 12.1 IN
12.1 – 12.5 N
12.08 NIN
11.47 PIN

4- Correlation index (CI)

87552
CI   473.7 SG  456.8
Tb

CI Crude Base
0 – 15 P
15 – 50 IN
50 - 00 N

5- Viscosity Gravity Constant (VGC)

Where
V38 = viscosity at 38°C (100F in SUS (Saybolt Universal Seconds)
V99 = Saylbolt viscosity (SUS) at 99°C (210F)

VGC Crude Base

< 0.82 P
0.82 – 0.9 IN
> 0.9 N
Petroleum Refining Fourth Year Dr.Aysar T. Jarullah

Physical and Chemical Properties of Crude Oil and Oil Products

1- Density, Specific Gravity, and API Gravity
Density is defined as mass per unit volume of a fluid. Density is a state function and for a
pure compound depends on both temperature and pressure and is shown by ρ. Liquid
densities decrease as temperature increases but the effect of pressure on liquid densities at
moderate pressures is usually negligible.
Liquid density for hydrocarbons is usually reported in terms of specific gravity (SG) or
relative density defined as

Since the standard conditions adopted by the petroleum industry are 60°F (15.5°C) and 1 atm,
specific gravities of liquid hydrocarbons are normally reported at these conditions. Water
density at 60°F is 0.999 or almost 1 g/cm3, thus

The American Petroleum Institute (API) defined the API gravity (degrees API) to quantify
the quality of petroleum products and crude oils. The API gravity is defined as

Crude Oils API = 10 – 50, crude oils can generally be classified according to API as shown

The definition of specific gravity for gases is somewhat different. The specific gravity of a
gas is proportional to the ratio of molecular weight of gas (Mg) to the molecular weight of air
(28.97)

2- Viscossity
The viscosity of oil is a measure of its resistance to internal flow and an indication of its
oiliness in the lubrication of surfaces. There are two types of viscosity: dynamic and
kinematics viscosity.
Kinematic viscosity (υ) = dynamic viscosity (µ) / density (ρ)

The unit of dynamic viscosity is poise (0.1 Pa·s). It is more commonly expressed, particularly
in ASTM standards, as centipoises (cP). While the kinematics viscosity as centiStokes -cSt
(10 −6m2·s−1). 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)
Petroleum Refining Fourth Year Dr.Aysar T. Jarullah

where v100 and v210 are the kinematic viscosities at 100 and 210 °F, in centistokes. The
viscosity can be measured by several instruments (U-tube Viscometer, Saybolt Universal
Viscosity (SSU), thermo-viscosity, Red wood viscometer and Englar)

Thermo. = 15 + 148.5 kinematic Vis. = 46 SSU - 1183

The comparison of viscosity by different instruments is shown in Figure 1>

Ex) Calculate the kinematic viscosities for oil which has a MeABP of 320 °C and API
gravity of 34.

Sol.:

The boiling point is 593.15 K or 1067.7 R. the specific gravity is 0.855 and the Watson K
factor is 11.95.

v100= 5.777 cSt and v210 = 1.906 cSt

Petroleum Refining Fourth Year Dr.Aysar T. Jarullah

Fig.1. Comparison of viscosity by different instruments.(Viscosity must be at the same T.)

3- Pour Point
The pour point is defined as the lowest temperature at which the sample will flow and is a
rough indicator of the relative paraffinicity and aromaticity of the crude. A lower pour point
means that the paraffin content is low and greater content of aromatics.
To estimate the pour point of petroleum fractions from viscosity, molecular weight, and
specific gravity, the following form is used for this purpose:

where Tp is the pour point (ASTM D 97) in kelvin, M is the molecular weight, and
v38(100) is the kinematic viscosity at 37.8°C (100F) in cSt. This equation was developed
with data on pour points of more than 300 petroleum fractions with molecular weights
ranging from 140 to 800 and API gravities from 13 to 50 .
Petroleum Refining Fourth Year Dr.Aysar T. Jarullah

4- Carbon Residue, wt%

Carbon residue is determined by distillation to a coke residue in the absence of air. The
carbon residue is roughly related to the asphalt content of the crude and to the quantity of the
lubricating oil fraction that can be recovered. In most cases the lower the carbon residue, the
more valuable the crude. This is expressed in terms of the weight percent carbon residue by
either the Ramsbottom (RCR) or Conradson (CCR).

Crude distilled (%) at 1100°F= 100 – 3*CCR, CCR is the Carbon residue for whole crude oil

5- Salt Content, lb/1000 bbl

If the salt content of the crude, when expressed as NaCl, is greater than 10 lb/1000 bbl, it is
generally necessary to desalt the crude before processing. If the salt is not removed, severe
corrosion problems may be encountered. If residua are processed catalytically, desalting is
desirable at even lower salt contents of he crude. Although it is not possible to have an
accurate conversion unit between lb/1000 bbl and ppm by weight because of the different
densities of crude oils, 1 lb/1000 bbl is approximately 3 ppm.

6- Sulfur Content, wt%

Sulfur content and API gravity are two properties which have had the greatest influence on
the value of crude oil, although nitrogen and metals contents are increasing in importance.
The sulfur content is expressed as percent sulfur by weight and varies from less than 0.1% to
greater than 5%. Crudes with greater than 0.5% sulfur generally require more extensive
processing than those with lower sulfur content.

7- Flash point
Flash point TF, for a hydrocarbon or a fuel is the minimum temperature at which vapor
pressure of the hydrocarbon is sufficient to produce the vapor needed for spontaneous
ignition of the hydrocarbon with the air with the presence of an external source, i.e., spark or
flame. From this definition, it is clear that hydrocarbons with higher vapor pressures (lighter
compounds) have lower flash points. Generally flash point increases with an increase in
boiling point. Flash point is an important parameter for safety considerations, especially
during storage and transportation of volatile petroleum products (i.e., LPG, light naphtha,
gasoline) in a high-temperature environment.
The flash point can be estimated using the following equation:

Where T10 is normal boiling point for petroleum fractions at 10 vol% distillation temperature.
Both temperatures (T10 and flas point (TF) in Kelvin).

Example: A kerosene product with boiling range of 175-260°C from Mexican crude oil has
the API gravity of 43.6 and T10 is 499.9K. Estimate its flash point and compare with the
experimental value of 59°C.

Solution:
By using the last equation, TF = 60.4°C, which is in good agreement with the experimental
value of 59°C.
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
Petroleum Refining Fourth Year Dr.Aysar T. Jarullah

Types of Distillation Curve

1- True Boiling point(TBP) Distillation

2- ASTM Distillation
3- Semi-fractionating Distillation
4- Equilibrium Flash Vaporization(EFV)

1) TBP: This type of distillation is commonly used due to the accuracy of the results obtained
by this method which is very close to that obtained via real distillation or industrial
distillation. In this distillation, there is a fractionation column located between the condenser
and the flask. In general, this type of distillation is carried out by two steps: firstly, under
atmospheric pressure until 300°C (1% distilled very 2 min), secondly under vacuum pressure
(to prevent cracking process and to reduce the boiling point) at 40mmHg (1% distilled every
3-5 min). In this process, the vapor press. temp. is plotted vs. distilled(%) to get TBP curve.

2) ASTM: In this type of distillation there is on fractionation column located between the
condenser and the flask. On the other hand, the raised vapor will not be fractionated in this
process. This distillation is used with fractions having short range of the boiling point.

3) Semi-fractionating distillation: In this type of distillation, their will be some

fractionating process on the raised vapor via package located between the condenser and the
flask.

4) Equilibrium Flash Vaporization (EFV): Is a single stage separation technique. A liquid

mixture feed is pumped through a heater to raise the temperature and enthalpy of the mixture.
It then flows through a valve and the pressure is reduced, causing the liquid to partially
vaporize. Because the vapor and liquid are in such close contact up until the "flash" occurs,
the product liquid and vapor phases approach equilibrium.
Petroleum Refining Fourth Year Dr.Aysar T. Jarullah

Fig. 5. TBP cut point versus ASTM end point

Petroleum Refining Fourth Year Dr.Aysar T. Jarullah

Fig. 6. Crude distillation curve

Fig. 7. TBP and gravity-mid-percent curves

Petroleum Refining Fourth Year Dr.Aysar T. Jarullah

Average Boiling Point

1- Volume Average Boiling Point (VABP)

T20%  T50%  T80%

VABP 
3
Ti% = Temp. at i vol. % distilled

For short cut Boiling Point (having short B.P)

VABP  T50%
2- Weight Average Boiling Point (WABP)

T10%  T20%  T30%  ..........T90%

WABP 
9
Ti% = Temp. at i weight. % distilled

3- Molal Average Boiling Point (MABP)

Tx1  Tx 2  Tx 3  ..........
MABP 
x1  x 2  x3 ................
Tix = Temp. at i mol. x distilled, x is the no. of mole

MABP  VABP  T

4) Slope of Distillation Curve

T70%  T10%
Slope 
60
If the slope  2  Short Cut (T50% )  VABP  WABP  MABP

Fig. 10 is used to convert Distillation Curve from any type to any type.

Figure 11 is used to find T50% for EFV ( y axix  T50%( ASTM or TBP)  T50%( EFV ) )
Petroleum Refining Fourth Year Dr.Aysar T. Jarullah

Fig. 8. Molal average boiling point of petroleum fractions

Fig.9. Mean average boiling point of petroleum fractions

Petroleum Refining Fourth Year Dr.Aysar T. Jarullah

Also, Differential (Δ) can be estimated from the following eq.

Fig. 10. Relationships between the slopes of various distillation curves

Petroleum Refining Fourth Year Dr.Aysar T. Jarullah

Fig. 11. Relationships between distillation temperatures at 50% vaporized and the flash
(E.F.V.) Temp. at 50%

Ex) Find T100% and T0% for EFV if T 50%(TBP) = 570 and Slope = 9.4.

Sol.: From Fig.10, the slope of EFV curve = 6.6 (at 9.4 TBP)

From Fig. 11, ΔT = 65 (at T50%(TBP) = 570)

 T50%( EFV )  T50%( ASTM or TBP)  T  570  65  505

y T100%  505
slope    6.6  T100%  835
x 50  0
y 505  T0%
Slope    6.6  T0%  175
x 100  50
Petroleum Refining Fourth Year Dr.Aysar T. Jarullah

Fig. 12. Sulfur content of products from Middle East crude oils
Petroleum Refining Fourth Year Dr.Aysar T. Jarullah

Home work

For a given crude oil; 1- Draw a TBP curve, 2- Evaluate the crude, 3- Find the value of Kw if
API=43, 4- Draw a EFV on the same Figure, 5- Find the vol. dis. At 1100F if CCR= 1.8%
then draw it, and 6- Find the vol. of the distilled at 1000F.

Vol. Distilled 0 10 20 30 40 50 60 70 80
Temp. (F) 160 270 335 400 480 560 610 680 820 1100
Sp.gr 0 0.72 0.75 0.78 0.80 0.82 0.835 0.85 0.87
Petroleum Refining Fourth Year Dr.Aysar T. Jarullah

Conversion between Distillation Curves

A) API Method
1- TBP vs ASTM

TBP  a ( ASTM )b

(T should be in R for ASTM or TBP)

2- ASTM vs EFV

EFV  a (ASTM)b ( sp.gr ) c

(T should be in R for ASTM or TBP)

B) Daubert Method.
More recently, Daubert (1994) published a new method for distillation curves interconversion
using the following equations:
Petroleum Refining Fourth Year Dr.Aysar T. Jarullah

The symbols stands for ASTM D86 and TBP temperatures, respectively, both in
F. The subscripts 0 and f stand for the initial and final temperatures, respectively. Ai and Bi
are constants given in Table below.

Thermal Properties

1) Specific Heat (cp): The specific heat is the amount of heat per unit mass required to raise
the temperature by one degree Celsius. It depends on the temp., where it increases with
increasing in temp. and decreasing in density. The following eq. can be used to estimate cp

 0.415 
c Lp  4.1868   0.0009 T  288.15
  15.6 
 L 
Petroleum Refining Fourth Year Dr.Aysar T. Jarullah

cp in J/g.K , T in K, and  15
L
.6
is the density of oil at 15.6 0C, g/cm3.

Also Fig. 13 is used to find cp. For hydrocarbons gasses, Fig.14 is used for this purpose.

Fig. 13. Specific heat of Mid liquids oils with a correction factor for other bases of oils

Ex: How much heat is required to heat 100 bbl of crude oil (API = 40) from 100 to 200 F.

Sol: Note: Appendix A is used to convert vol. to weight of Oil materials.

From Appendix A, at API 40, lb/bbl = 288.54
From Fig. 13, cp at 100F = 0.465 Btu/lb.F and at 200F = 0.54 Btu/lb.F
Average cp = (0.465+0.54)/2 = 0.52 Btu/lb.F
m = 288.54 lb/bbl * 100 bbl = 28200.54 lb
Q = 0.52 * 28200.54 * (200 – 100) = 1466428.08 Btu
Petroleum Refining Fourth Year Dr.Aysar T. Jarullah

Fig. 14. Specific heat of Mid oil vapors with a correction factor for other bases of oils

2) Heat of Combustion: The amount of heat released per unit mass or unit volume of a
substance when the substance is completely burned under standard conditions.
For crude oil or oil fractions, the heat of combustion increases with increasing in temp., API
and hydrogen content, and decreases with increasing in sulfur, ash and water content.

Heat of combustion  43434  93.2(API - 10), kJ/kg

Petroleum Refining Fourth Year Dr.Aysar T. Jarullah

Figure 15. Gross heats of combustion of liquids petroleum hydrocarbons

Petroleum Refining Fourth Year Dr.Aysar T. Jarullah

3) Coefficient of Heat Expansion: is the tendency of matter to change in volume in response

to a change in temperature, or the change amount in density. It depends on API, where
decreases with decreasing in API. This property is an important issue in desining of fuel
tanks. The following Table is used for this purpose.

API Coefficient of Expansion

0 – 14.9 0.00035
15 – 34.9 0.00040
35 – 50.9 0.00050
51 – 63.9 0.00060
64 – 78.9 0.00070
79 – 88.9 0.00080
89 – 93.9 0.00085
94 - 100 0.00090

Also Fig. 12. is used to find the change amount via changing in density.

Fig. 16. Approximate change of specific gravity of intermediate- base oils with T.
Petroleum Refining Fourth Year Dr.Aysar T. Jarullah

Ex: One barrel at 19 API oil is to be heated from 60 to 400 F. What volume will it occupy?
Sol: From Table above, Coeff. of Expansion = 0.0004,
Increase in vol. = 1bbl * (400-60) *0.0004 = 0.136bbl
Total vol. = 1+0.136 = 1.136 bbl

Using Fig. 16,

Sp.gr at 60 F (19 API) = 0.942, sp.gr at 400F (19 API)= 0.83
Vol. at 400F = 1bbl *(0.94/0.83) = 1.13

4) Latent Heat of Vaporization: is the amount of energy in the form of heat released or
absorbed by a substance during a change of phase (i.e. solid, liquid, or gas), or the heat
required to complete vaporization under atmospheric pressure.

Fig. 17. is used to find the latent heat of vaporization under atmospheric pressure.

Fig. 17. Atmospheric latent heat of vaporization as a function of molecular weight or API
gravity
Petroleum Refining Fourth Year Dr.Aysar T. Jarullah

It can also be calculated at any temp. or press. from the following eq.

T
L  LB
TB

L = is the latent heat of vaporization at any T or P

LB = is the latent heat of vaporization at normal B.P
γ = correction factor (from Fig. 18)
T = any temp. (R)
TB = normal B.P (R)

Also, Fig. 19 can be used to find MABP (normal B.P)

Fig. 18. Temp. correction to heat of vaporization

Petroleum Refining Fourth Year Dr.Aysar T. Jarullah

Fig. 19. Molecular weight, pseudo critical temp., charactrization factors and gravities of
petroleum fractions
Petroleum Refining Fourth Year Dr.Aysar T. Jarullah

Ex: A mixed base has a gravity of 35 API. The latent heat of this fraction at atmospheric
press. and also at 500F is required. Kw =11.9.

Sol.:
From Fig. 19, at API = 35 and Kw=11.9, the MABP = 580F
From Fig. 17 at API = 35 and MABP = 580F, Latent Heat = 92 Btu/lb
In order to estimate La at 500 F, additional factors must be set down

From Fig. 19, Tc = 900F (1360R), TR=T/TC= ((500+460)/1360)=0.706, TB/TC = 0.765

From Figure 18, γ = 1.16

500  560
 L  1.17  92   98 Btu / lb
1040

If T = Tc, γ will be zero and then L = 0

5) Heat Content (or Enthalpy): refers to the required heat to rise the substance temperature.
Figure 20 is used to find the heat content.

Ex: A sample of gasoline (API = 56) at 60F and Kw=11.4 is to be heated, vaporized and
superheated to 500F at 200psia. Calculate the heat required 2) specific heat of vapor.

Sol.: From Fig. 20,

Heat content at 60F = 28 Btu/lb
Heat content at 500F = 397 Btu/lb
Correction of pressure (upper left Fig within Fig.20) = 8 Btu/lb
Correction of Kw (upper center Fig. within Fig. 20) = 0.97 Btu/lb
Heat content at 60F corrected = 0.97 * 28 = 27 Btu/lb
So the heat required (difference between the heat of vapor and the heat of the liquid) =
397 – 27 – 8 = 385 Btu/lb
2) cp for vapor will be between 400 and 500F, So we need the value of TB (can be calculated
from Watson law or from Fig. 19)
TB = 190F
Then we have to find the temp. under 200psia, which is estimated from Fig. 21
TB.P = 400F
Then from Fig. 14 at TB.P and API
cp = 0.55
Petroleum Refining Fourth Year Dr.Aysar T. Jarullah

Fig 20: Heat content of petroleum fractions

Petroleum Refining Fourth Year Dr.Aysar T. Jarullah

Fig. 21.Vapor Pressure and B.P. corrections for normal paraffins hydrocarbons and petroleum
fractions
Petroleum Refining Fourth Year Dr.Aysar T. Jarullah

Generalized Equation for Thermophysical Properties

Riazi and Al-Sahhaf (1996) presented a method for the calculation of different properties
such as the NBP, density, refractive index, critical temperature, pressure and density,
acentric factor, solubility parameter and surface tension given only the molecular weight and
using the following general equation

…………………… (A*)
Petroleum Refining Fourth Year Dr.Aysar T. Jarullah

Crude Oil Pre-treatment (desalting)

When the crude oil enters the unit, it carries with it some brine in the form of very fine water
droplets emulsified in the crude oil. The salt content of the crude measured in pounds per
thousand barrels (PTB) can be as high as 2000. Desalting of crude oil is an essential part of
the refinery operation. The salt content should be lowered to between 5.7 and 14.3 kg/1000m3
(2 and 5 PTB). Poor desalting has the following effects:

 Salts deposit inside the tubes of furnaces and on the tube bundles of heat exchangers
creating fouling, thus reducing the heat transfer efficiency;
 Corrosion of overhead equipment; and,
 The salts carried with the products act as catalyst poisons in catalytic cracking units.

The two most typical methods of crude-oil desalting, chemical and electrostatic separation,
use hot water as the extraction agent. In chemical desalting, water and chemical surfactant
(demulsifiers) are added to the crude, heated so that salts and other impurities dissolve into
the water or attach to the water, and then held in a tank where they settle out. Electrical
desalting is the application of high-voltage electrostatic charges to concentrate suspended
water globules in the bottom of the settling tank. Surfactants are added only when the crude
has a large amount of suspended solids. Both methods of desalting are continuous. A third
and less-common process involves filtering heated crude using diatomaceous earth.

In both methods, the feedstock crude oil is heated to between 150° and 350°F to reduce
viscosity and surface tension for easier mixing and separation of the water. The temperature
is limited by the vapor pressure of the crude-oil feedstock. In both methods other chemicals
may be added. Ammonia is often used to reduce corrosion. Caustic or acid may be added to
adjust the pH of the water wash. Wastewater and contaminants are discharged from the
bottom of the settling tank to the wastewater treatment facility. The desalted crude is
continuously drawn from the top of the settling tanks and sent to the crude distillation
(fractionating) tower.
Petroleum Refining Fourth Year Dr.Aysar T. Jarullah

Fractionation of Crude Oil

1- Atmospheric Distillation
Crude distillation unit (CDU) is at the front-end of the refinery, also known as topping unit,
or atmospheric distillation unit. It receives high flow rates hence its size and operating cost
are the largest in the refinery. The capacity of the CDU ranges from 10,000 barrels per stream
day (BPSD) or 1400 metric tons per day (tpd) to 400,000 BPSD (56,000 metric tpd). The
economics of refining favours larger units. A good size CDU can process about 200,000
BPSD.
These towers can be up to 150 feet (50 meters) high and contain 20 to 40 fractionation trays
spaced at regular intervals. Before entering the column distillation, desalted crude oil pass
through a network of pre-heat exchangers in order to heat it initially with hot material drawn
from the bottom of the distillation tower to raise its temperature up to 450°F and then to a
heating furnace, which brings the temperature up to about 650°F. This part of process is
essential because the carbon will be deposited inside the pipes and equipment through which
it flows when the oil gets much hotter. The hot crude oil enters the column distillation and
most of it vaporizes. Unvaporized heavy oil cuts and residue will drop to the bottom of the
column, where it is drawn off. Inside the tower distillation column, there are the so-called
trays (Figure 22 below), which are working mainly in the separation of crude oil to light the
required derivatives. These trays permit the vapors from below to pass from it and contact
with the condensed liquid on top of the tray that provides excellent contact between vapor
and liquid. Condensed liquid flows down through a pipe to the hotter tray below, where the
higher temperature causes re-evaporation. A given molecule evaporates and condenses many
times before finally leaving the tower.
Products are collected from the top, bottom and side of the column. Side draw products are
taken from trays at which the temperature corresponds to the cut point for a desired product.
In modern towers, a portion of each side draw stream is returned to the tower to control tray
temperatures and further enhance separation. Part of the top product is also returned; this
“reflux” plays a major role in controlling temperature at the top of the tower.

Figure 22: Distillation column with trays

Petroleum Refining Fourth Year Dr.Aysar T. Jarullah

Fractionation process depends on

1- Number of Trays
2- Reflux ratio
3- Quantity of steam added to the column

As increasing in trays no. and reflux ratio, the efficiency of separation process is increasing
Typical designs have the trays distribution between products as shown in Table below.

The degree of separation process inside the distillation column depends on

1- Degree of difficulty of separation (represents the difference between T50% for two
consecutive cuts, i.e. an increasing in T50% means that the range of the cut becomes
wide and easy to separate). On the other hand, needs low reflux ratio and less no. of
trays.
2- Degree of separation (is called ASTM Gab, which is represents the difference
between T5% and T95% for two consecutive cuts). Whenever a big difference,
separation between to cuts becomes small and as a result required more trays and high
reflux ratio.

Operation of Crude Distillation Units

In this section, the factors which affect the design and operation of the unit are explored.

1) Fractionation or separation (mentioned above)

2) Cut Points: The cut points in the CDU are controlled by the overhead vapour
temperature which determines how much vapour goes to the condensers to produce
light naphtha and by the flow rate of the various products straight from the column or
the side stream strippers. The atmospheric residue level control inside the column
determines its flow rate and thus its initial cut point. The amount of light naphtha is
determined by the dew point of the naphtha at its partial pressure, which is close to the
overhead temperature.

3) Overflash: In order to fractionate the crude oil into the various products, it has to be
heated to a temperature between 330 and 385 °C (626 and 725 °F), depending
Petroleum Refining Fourth Year Dr.Aysar T. Jarullah

on the crude composition. The partially vaporized crude is transferred to the flash
zone of the column located at a point lower down the column. The furnace outlet
temperature should be enough to vaporize all products withdrawn above the flash
zone plus about 3–5 vol% of the bottom product. This overflash has the function of
providing liquid wash to the vapors going up the column from the flash zone, and
improving fractionation on the trays above the flash zone, thereby improving the
quality of the HGO and reducing the overlap with the bottom products below the flash
zone.

4) Column Pressure: The pressure inside the CDU column is controlled by the back
pressure of the overhead reflux drum at about 0.2–0.34 bar gauge (3–5 psig). The top
tray pressure is 0.4–0.7 bar gauge (6–10 psig) higher than the reflux drum. The flash
zone pressure is usually 0.34–0.54 bar (5–8 psi) higher than the top tray.

5) Overhead Temperature: The overhead temperature must be controlled to be 14–17

°C (25–31 °F) higher than the dew point temperature for the water at the column over-
head pressure so that no liquid water is condensed in the column. This is to prevent
corrosion due to the hydrogen chloride dissolved in liquid water (hydrochloric acid).

6) Pre-flash Columns and Crude Column Capacity: The crude flow rate to the CDU
determines the capacity of the whole refinery. A crude column is typically designed
for 80% loading, which means that the unit can be operated at 20% throughput more
than the design value. The capacity of the column is limited by the vapour flow rate
with a velocity between 2.5 and 3.5 ft/s (0.76 and 1.07 m/s). The vapour flow rate
increases as the vapours rise from the flash zone to the overhead.
Petroleum Refining Fourth Year Dr.Aysar T. Jarullah

Steam Quantity Required

The vapor is usually pumped to the down distillation column located below flash zone (i.e.
below the reign where the crude oil enters). The aim of pumping the vapor is
1- Remove the remaining gas oil from reduced crude (un-vaporized)
2- Reduce the partial pressure leading to boiling the compounds at low temp.

The water vapor or the steam is pumped due to the following reasons:
1) Available
2) Cheap
3) Don't mix with crude oil
4) Good heat transportation

The steam quantity is calculated by using the following equation:

ns p
 s
nt pt
ns: is the no. of moles of vap.
nt : is the total moles
ps: is vap. press.
pt: is the total press.

ps  pt  pn
( pt  pn )
ns  nt
pt
pn: is the press. of H.C

Ex: Estimate the no. of moles of steam required to add to the distillation column to reduce the
boiling temperature from 400 to 350F.

Sol.:
400 at 760mmHg
From Fig. 17, (by connection 350 with 400F) so pn=400mmHg
Let n t =100 mol
(760  400)
 n s  100   47.38 moles
760

Reflux and Reflux Ratio

Reflux is the ratio between the amounts of material that returned to the distillation column to
the material that result at distillation. In order to increase the degree of separation and high
purity, amount of liquid is returned to the column in addition to getting rid of heat making the
column in thermal equilibrium case.
Petroleum Refining Fourth Year Dr.Aysar T. Jarullah

Types of Reflux
1) Top tray reflux. In this type, the steam from the top of distillation column is
condensed then some of it is returned to the distillation column. This method
is easy to design and operate, but create big quantity of steam inside the
distillation column and the amount of reflux is not enough. The quantity of
heat drawn is calculated as (mcpT  L.H ) (m for every lb).
2) Pump back reflux. In this arrangement, reflux is provided regular intervals.
This helps every plate to act as a true fractionator. The vapor load in the tower
is fairly uniform and hence a uniform and smaller diameter tower will do. The
rejected heat at the reflux locations can be effectively utilized. This method
provides enough liquid at different points along distillation column and hence
good separation, but so difficult to design and operate. The quantity of heat
drawn is calculated as (mcpT ) (m for every lb).
3) Pump around reflux. In this way, reflux from a lower plate is taken, cooled
and fed into the column at a higher level by 2 to 3 plates. This method needs
column distillation with high plates because the whole cut will be on one plate.
The quantity of heat drawn is calculated as (mcpT ) (m for every lb).

Products from ADU

The product obtained from a top of ADC under atmospheric pressure is gasoline having B.P.
from C5 to 190F. This fraction withdrawal as a vapor then is condensed and a part of it will
be returned to the atmospheric column as a reflux, while a stabilization process is carried out
on the remaining part. The stabilization process is removing the compounds that have low
B.P. (from C2 to C4), where these compounds cause high vapor pressure.
The stabilization process is carried out by passing the feed through fractionating column
containing many trays and reflux ratio (10 to 1) in order to make the separation process at
high accuracy. These light compounds are regarded as a source to produce liquefied gas.
Other products will withdrawal from several points along atmospheric column as a liquid.
These products are cooled and a part of them will be returned to the column as a reflux and
the remaining parts send to the stripper towers (small fractionating column like column
distillation having 4-8 trays placed on each other – beside the distillation column). These
stripper towers are aimed to remove the light compounds that effect on the flash point.
F .P  0.64T  100, for distilled fraction
F.P  0.57T  110 , for crude oil
The other products are: T in F
Heavy straight naphtha (190 – 400F)
Kerosene (380 500F)
Light gas oil (500 – 600F)
Petroleum Refining Fourth Year Dr.Aysar T. Jarullah

The remaining part at the bottom of atmospheric distillation will be sent to the vaccum
distillation tower.

2- Vacuum Distillation Column

The residue from an atmospheric distillation tower can be sent to a vacuum distillation
tower, which recovers additional liquid. The furnace outlet temperatures required for
atmospheric pressure distillation of the heavier fractions of crude oil are so high that thermal
cracking would occur, with the resultant loss of product and equipment fouling. These
materials are therefore distilled under vacuum because the boiling temperature decreases with
a lowering of the pressure. Distillation is carried out with absolute pressures in the tower flash
zone area of 25 to 40 mmHg (Fig. 23). To improve vaporization, the effective pressure is
lowered even further (to 10 mmHg or less) by the addition of steam to the furnace inlet and at
the bottom of the vacuum tower. Addition of steam to the furnace inlet increases the furnace
tube velocity and minimizes coke formation in the furnace as well as decreasing the total
hydrocarbon partial pressure in the vacuum tower.

Fig.23. Process flow diagram of the vacuum distillation unit

The main products from this unit are:

1- Heavy gas oil (600 – 800F)
2- Lubricant – base stokes (B.P. >700F), Non-viscous (50 – 100SUU), viscous (100 –
200SUU) and mid (>200SUU) at 100F.
3- Asphalt or vacuum residue (B.P > 1000F)

Yield Estimation of Crude Oil

1- Draw the curve between Vol.% dis. Vs. TBP.
2- Extrapolate the curve to the final point (EBP) of the distillation (100%) by fitting the
curve to a suitable polynomial function and extrapolating the results. From the curve,
we cal find the IBP if it is not given.
Petroleum Refining Fourth Year Dr.Aysar T. Jarullah

3- Find the intervals, ((EBP - IBP)/ no. of pseudo compounds)

4- Find the EBP of each pseudo comp. (intervals + IBP of the cut)
5- Find the normal BP (NBP) or average B.P ((EBP +IBP (EBP of the last cut))/2)
6- Read the yield% or vol.% from the curve at NBP.

Example: A petroleum cut has the following ASTM D86 Distillation data:

Divide the TBP curve of the petroleum cut into 20 pseudo-components. Calculate the liquid
volume percentage of each pseudo-component.

Sol:
Firstly, the temperatures should be converted from ASTM to TBP, as given previously. The
results will be as follow

Vol. % 0 10 30 50 70 90 95
ASTM (°C) 36.5 54 77 101.5 131 171 186.5
TBP (°C)-API 14.1 33.4 69 101.6 135.2 180.5 194.1
TBP (°C). Duabert -5.3 27.5 66.7 101.7 138.1 184.6 201.1

The TBP curve obtained extends to 95 volume percent distilled only. In order to obtain the
average boiling point of the last cuts, the curve is extrapolated to the final point of the
distillation (100%) by fitting the curve to a suitable polynomial function and extrapolating the
results. An Excel spreadsheet program was used to fit a fifth order polynomial function, as
shown Figure below for TBP temperature versus volume% using Duabert method.
Petroleum Refining Fourth Year Dr.Aysar T. Jarullah
Petroleum Refining Fourth Year Dr.Aysar T. Jarullah

Ex.: Plot the true boiling point curve for the kerosene product from Table below

Sol.:
The cumulative vol% at the IBP of kerosene = 1.33 + 7.27 + 16.56 = 25.16%
The cumulative vol% at the EBP of kerosene = 25.16 + 10.05 = 35.21%
The cumulative vol% at the 10% of kerosene cut = 0.1(10.05) + 25.16 = 26.17%. At vol% of
26.17% the estimated TBP is 186.73 °C (via drawing TBP curve directly or from the
polynomial fit equation of the Fig.). The procedure is repeated at 20% of kerosene volume
which yield 27.17% and TBP of 189.26 °C. Figure below shows the TBP curve for kerosene
which starts at IBP of 180 °C and ends at EBP of 240 °C.
Petroleum Refining Fourth Year Dr.Aysar T. Jarullah

Distillation Tower Temperature

1- Top Temp.
The temperature at the top should be high up to the temperature where all the top product are
vaporized with out any condensation for any part of it, and avoid vaporization process for the
compounds having temperature higher than the temperature of the top product.
If the pressure inside the column equals to atmospheric pressure and there is no vapor is fed
to the column, the temperature will be
Top temp. = 100% EVF
If the pressure is not equals to the atmospheric pressure and there is vapor inside the column,
the temperature should be corrected according to the following steps:

Steps of Calculations
1) Estimate the amount of heat that should be removed from the column to make
it in thermal equilibrium (in Bt/hr)
2) Divide the heat in part 1 on the heat that can remove 1lb of reflux to calculate
the amount of reflux (i.e. Btu/hr / Btu/lb = lb/hr)
3) Estimate the no. of moles of hydrocarbons at the top of column (i.e. Reflux +
Product) by weight / M.wt.
4) Estimate the no. of moles of vapor by the same way.
5) Estimate the total no. of moles (3+4).
n hy
6) Estimate the partial pressure of hydrocarbons by Phy  Pt 
nt
7) Correct the temperature (100%) of product by using Fig. 17.

2- Side- temperature
Estimation of temperature at side points is the same of that at top temp., except the following
differences: a) correct EVF (0%) for the product, b) the no. of moles of hydrocarbons is
estimated for the hydrocarbons that pass to the higher tray in addition to this tray.

Ex: The amount of heat that should be removed from the distillation column is 100000 Btu/hr
in order to make the column in thermal equilibrium. The top product (gasoline) has a yield of
2000 lb/hr (M.wt = 110 lb/lb mol) and Evf 100%=230 F and the pressure is 272.5 psia. The
quantity of steam that should fed inside the column is 500 lb/hr, hot L.H = 100 Btu/lb.

Sol:
The amount of reflux = 100000/100 = 1000 lb/hr
The no. of moles of hydrocarbons at the top of column = (1000 + 2000) /110=27.273lbmol/hr
The no. of moles of vapor 500 / 18 = 27.778 lbmol/hr
The total no. of moles = 27.273 + 27.778 = 55.051 lbmol/hr
The partial pressure of hydrocarbons = 272.5 * (27.273/55.051) = 135 psia
From Fig. 17 the correct temp = 400 F.

Note: if the reflux is cold reflux, the amount of heat = L.H + Cp.ΔT
Petroleum Refining Fourth Year Dr.Aysar T. Jarullah

Light End Fractionation

Within refineries there are numerous other, smaller distillation towers called columns,
designed to separate specific and unique products. Columns all work on the same
principles as the towers described above. For example, a depropanizer is a small column
designed to separate propane and lighter gases from butane and heavier components in
the light end unit.

 The light end gases are the top cut of crude distillation. Iso and normal butanes
(C4H10) and lighter gases such as methane (CH4), ethane (C2H6), propane (C3H8) and
hydrogen (H2) are then recovered and separated in the refinery gas plant. Typically:
Hydrogen, methane and sometimes ethane are diverted to the refinery fuel gas
header for use in site heaters and furnaces
 Ethane is used as the chemical feedstock for ethylene upon transfer to a petrochemical
complex
 Propane is used for liquefied petroleum gas (LPG) sales or as the chemical
feedstock for propylene
 N-butane is used for motor gasoline blending. Iso-butane is used as feedstock to the
alkylation

Fig. 24: Light End Fractionation

Petroleum Refining Fourth Year Dr.Aysar T. Jarullah

Thermal Cracking and Coking

Thermal cracking is the cracking of heavy residues under severe thermal conditions. The
liquid products of this process are highly olefinic, aromatic and have high sulfur content.
They require hydrogen treatment to improve their properties.
Coking is the process of carbon rejection from the heavy residues producing lighter
components lower in sulfur, since most of the sulfur is retained in the coke.
There are three classes of industrial thermal cracking processes. The first is mild cracking (as
in visbreaking) in which mild heating is applied to crack the residue just enough to lower its
viscosity and also to produce some light products. The second process is delayed coking in
which moderate thermal cracking converts the residue into lighter products, leaving coke
behind. The third process involves severe thermal cracking: part of the coke is burned and
used to heat the feed in the cracking reactor, as in fluid coking.

Visbreaking Process
Visbreaking is a mild thermal cracking of vacuum or atmospheric residues to produce light
products and 75–85% cracked material of lower viscosity that can be used as fuel oil.

Feed Sources
The feed to visbreaker can be either
 Atmospheric residue (AR)
 Vacuum residue (VR)
Vacuum residue is the heaviest distillation product and it contains two fractions: heavy
hydrocarbons and very heavy molecular weight molecules, such as asphaltene and resins.

Visbreaking Reactions
The possible reactions in visbreaking are:
 Paraffinic side chain breaking which will also lower the pour point;
 Cracking of naphthens rings at temperature above 482 °C (900 °F);
 Coke formation by polymerization, condensation, dehydrogenation and dealkylation; and
Petroleum Refining Fourth Year Dr.Aysar T. Jarullah

 Further cracking will be the result of asphaltene and coke leaving the
liquid phase (delayed coking).

Product Yield and Properties

Four products are produced in the visbreaking process: gases (C4), Naphtha C5 - 166 °C (C5 -
330 F), gas oil 166–350 °C (330–660 F) and residue or tar 350+ °C (660+ F). Typical yields
are given in Table below.

Prediction of Visbreaking Yields

Products yields:
Petroleum Refining Fourth Year Dr.Aysar T. Jarullah

Example: A vacuum residue is fed into a coil visbreaker at a rate of 200,000 lb/h. It has an
API = 8.5 and sulphur content of 3%. Assume 6 wt% conversion. Make a material balance
for the visbreaker.

Sol.:
The solution of this example is summarized in Table below.

Process Description
There are two types of visbreakers: coil visbreaking, in which thermal cracking occurs in the
coil of the furnace, and the soak visbreaker, in which cracking occurs in a soak drum.

Coil Visbreaker
Vacuum or atmospheric residue feedstock is heated and then mildly cracked in the visbreaker
furnace. Reaction temperatures range from 850 to 900 F (450 to 480 °C), and operating
pressures vary from as low as 3 bar to as high as 10 bar. As shown in Figure A, coil furnace
visbreaking is used and the visbroken products are immediately quenched to stop the
cracking reaction. The quenching step is essential to prevent coking in the fractionation
tower. The gas oil and the visbreaker residue are most commonly used as quenching streams.
Petroleum Refining Fourth Year Dr.Aysar T. Jarullah

After quenching, the effluent is directed to the lower section of the fractionator where it is
flashed. The fractionator separates the products into gas, gasoline, gas oil and visbreaker tar
(residue).

Soaker Visbreaker
The process scheme described above is usually referred to as furnace or coil cracking. Some
visbreakers employ a soaker between the visbreaker furnace and the quenching step, similar
to the conventional thermal cracking processes. This type of operation is termed soaker
cracking as shown in Figure B.

Both process configurations have their advantages and applications. Coil cracking yields a
slightly more stable visbreaker product, which are important for some feedstocks and
applications. It is generally more flexible and allows the production of heavy cuts, boiling in
the vacuum gas oil range. Soaker cracking usually requires less capital investment, consumes
less fuel and has longer on-stream times.

Ex.: It is required to decoke a visbreaker coil with an inside diameter = 9 cm and 700 m long
with a coke layer of 0.35 cm thickness. This is done in two steps:
a) Air is introduced to combust the coke layer whose density is 1202 Kg/m3.
b) Steam at 450  C and flow rate of 1000 Kg/hr is introduced to the coil to remove
debris and cleaning-up. The exit temperature is 700 °C. Coke contains 92 wt% carbon
and 8 wt% sulphur.

For how long should steam be switched on, in hours?

Data: specific heat of steam = 2.13 kJ/(Kg °C) heat of carbon combustion = 32,770 kJ/Kg,
heat of sulphur combustion ¼ 9300 kJ/Kg.
Petroleum Refining Fourth Year Dr.Aysar T. Jarullah

Delayed Coking
Delayed coking is a type of thermal cracking in which the heat required to complete the
coking reactions is supplied by a furnace, while coking itself takes place in drums operating
continuously on a 24 h filling and 24 h emptying cycles.
The feed to coker is usually vacuum residue which is high on asphaltenes, resins, aromatics,
sulphur and metals. The deposited coke contains most of the asphaltenes, sulphur, and metals
present in the feed, and the products are unsaturated gases (olefins) and highly aromatic
liquids.

Process Description
A schematic flow diagram of the delayed coking is shown in Figure below. The process
includes a furnace, two coke drums, fractionator and stripping section. Vacuum residue
enters the bottom of the flash zone in the distillation column or just below the gas oil
tray. Fractions lighter than heavy gas oil are flashed off and the remaining oil are fed to the
coking furnace.

Steam is injected in the furnace to prevent premature coking. The feed to the coker drums is
heated to just above 482 °C (900 F). The liquid–vapour mixture leaving the furnace passes to
one of the coking drum. Coke is deposited in this drum for 24 h period while the other drum
is being decoked and cleaned. Hot vapors from the coke drum are quenched by the liquid
feed. Vapors from the top of the coke drum are returned to the bottom of the fractionator.
These vapors consist of steam and the products of the thermal cracking reaction (gas, naphtha
and gas oils). The vapors flow up through the quench trays of the fractionator. Steam and
vaporized light ends are returned from the top of the gas oil stripper to the fractionator. Eight
to ten trays are generally used between the gas oil draw and the naphtha draw or column top.
Petroleum Refining Fourth Year Dr.Aysar T. Jarullah

Delayed Coking Variables

There are three classes of variables affecting coking. They are related to process operating
variables, feedstock characterization and engineering variables as shown in Table below.

Temperature is used to control the severity of coking. In delayed coking, the temperature
controls the quality of the coke produced. High temperature will remove more volatile
materials. Coke yield decreases as temperature increases. If the furnace temperature is high
this might lead to coke formation in the furnace. A low inlet furnace temperature will lead to
incomplete coking. Short cycle time will increase capacity but will give lower amounts of
liquid products and will shorten drum lifetime. Increasing pressure will increase coke
formation and slightly increase gas yield. Recycle ratio is used to control the endpoint of the
coker gas oil. It has the same effect as pressure. Feedstock variables are the characterization
factor and the Conradson carbon which affect yield production. Sulphur and metal
content are usually retained in the coke produced. Engineering variables also affect the
process performance. These include mode of operation, capacity, coke removal and
handling equipment.

Delayed Coker Yield Prediction

Estimation of product yields can be carried out using correlations based on the weight
percent of Conradson carbon residue (wt% CCR) in the vacuum residue.

The naphtha can be split in light naphtha (LN) and heavy naphtha (HN). The split in wt% is
33.22 and 66.78, respectively, respectively. The gas oil (GO) can be split also into light cycle
gas oil (LCO) and heavy cycle gas oil (HCO). The spilt in wt% is 64.5 and 35.5, respectively.
Typical sulphur distribution in the products for delayed coking is presented in Table below.
Petroleum Refining Fourth Year Dr.Aysar T. Jarullah

Ex.: A vacuum residue of Conradson carbon (wt% CCR = 15) is fed into a delayed coker at a
rate of 200,000 lb/h, of API = 8.5 and with a sulphur content of 3.0 wt%. Find the amount of
yield (lb/h) and their sulphur content. Calculate yield of liquid products in BPD.

Sol.: The solution of the example is summarized in Table below.

Petroleum Refining Fourth Year Dr.Aysar T. Jarullah

Gas composition
The gas produced is fuel gas, which can be sent to a fuel gas network after amine washing.
The gas can also be used in the alkylation unit because of its high olefin content. A typical
coker gas composition is given in Table below.

Fluid Coking
Fluid coking is a thermal cracking process consisting of a fluidized bed reactor and a
fluidized bed burner as shown in Figure below. Vacuum residue is heated to 260 °C (500 F)
and is fed into the scrubber which is located above the reactor for coke fine particle recovery,
and it operates at 370 °C (700 F). The heavy hydrocarbons in the feed are recycled with the
fine particles to the reactor as slurry recycle. The reactor operating temperature is 510–566
°C (950–1050 F). The heavy vacuum residue feed is injected through nozzles to a fluidized
bed of coke particles. The feed is cracked to vapor and lighter gases which pass through the
scrubber to the distillation column.

Flexicoking
The flexicoking process is a development of the fluid coking process where only 2 wt% of
coke is produced, thus most of the coke is used to heat the feed. A fluidized bed is added to
the process which acts as a gasifier in which steam and air are injected to produce synthesis
gas called Low Btu Gas (LBG) as shown in Figure below.
Petroleum Refining Fourth Year Dr.Aysar T. Jarullah

Yield Correlations for Flexicoking

Petroleum Refining Fourth Year Dr.Aysar T. Jarullah

Catalytic Operations
Fluidized Catalytic Cracking
The fluidized catalytic cracking (FCC) unit is the heart of the refinery and is where heavy
low-value petroleum stream such as vacuum gas oil (VGO) is upgraded into higher value
products, mainly gasoline and C3/C4 olefins, which can be used in the alkylation unit for
production of ultra-clean gasoline (C7 – C8 alkylates). The FCC unit mainly depends on
circulating a zeolite catalyst with the vapor of the feed into a riser-reactor for a few seconds.
The cracked products are disengaged from the solids and taken out to a distillation column
for separation of the desired products. The catalyst is circulated back into the regenerator
where coke is burned and the catalyst regenerated.

Feedstock and Products

The main feedstock used in a FCC unit is the gas oil boiling between 316 °C and 566 °C (600
F and 1050 F). This gas oil can be considered mixtures of aromatic, naphthanic and paraffinic
molecules. Gas oil from residue and conversion processes (predominantly coking) can be fed
to catalytic cracking units. They must be hydrotreated before catalytic cracking to separate
aromatics and remove sulphur.
The principal limitation on charge stocks are the Conradson Carbon Residue (CCR) and
metal contaminants. The effect of Conradson carbon is to form a deposit on the catalyst. This
deposit could be beyond the burning capacity in the regenerator. For atmospheric residue, it
is desulphurized first in the ARDS unit. Vacuum residue must also desulphurized and may be
deasphalted before used in the FCC.
Some possible feedstocks are atmospheric distillates, coking distillates, visbreaking
distillates, VGO, atmospheric residue (desulphurized) and vacuum residue (desulphurized,
deasphalted). Typical feedstock properties are given in Table A1. In addition, products with
their corresponding yields and characteristics are shown in Table A2.
Petroleum Refining Fourth Year Dr.Aysar T. Jarullah

FCC Reactions
The main reaction in the FCC is the catalytic cracking of paraffin, olefins, naphthenes and
side chains in aromatics. The main reactions in the FCC reactor can be summarized as
follows:
Petroleum Refining Fourth Year Dr.Aysar T. Jarullah

FCC Catalyst
The main catalyst which is used in a FCC reactor is the zeolite type. It is in a powderform
with an average particle size of 75 µm and an average surface area of 800 m2/g.

Process Description
The basic configuration of the FCC unit is a reactor (riser) and a regenerator. The catalyst is
circulated between them where it is deactivated in the riser and regenerated in the
regenerator. The process flow diagram for FCC unit is shown in Figure below. Steam and
VGO heated up to 316–427 °C (600–800 F) are fed to the bottom of the riser, which is a long
vertical pipe. The regenerated hot catalyst at 649–760 °C (1200–1400 F) is also fed to the
bottom of the riser. The riser is the main reactor in which the endothermic reactions take
place. The residence time in the riser is 2–10 s. At the top of the riser, the gaseous products
flow into the fractionator, while the catalyst and some heavy liquid hydrocarbon flow back in
the disengaging zone. Steam is injected into the stripper section, and the oil is removed from
the catalyst with the help of some baffles installed in the stripper. The oil is stripped in this
way from the catalyst and the spent catalyst is sent to the regenerator at a temperature of 482–
538 °C (900–1000 F). The coke in the spent catalyst is burned off in the regenerator by
introducing excess air, which is used to ensure the efficient combustion of coke.
In both the reactor and the regenerator, hydrocyclones are installed to catch any solid
particles carried out in the overheated stream. The product gases from the reactor are sent to
the fractionator which produces light gases, heavy gasoline (main product), light cycle gas oil
(LCO), heavy cycle gas oil (HCO) and decant slurry. The light gases are sent to the gas
concentration unit where flue gas, propane, butane, LPG and light gasoline are produced. The
operating conditions are usually adjusted to produce the maximum amount of gasoline from
the VGO.
Petroleum Refining Fourth Year Dr.Aysar T. Jarullah

FCC Yield Correlations

The yield correlations given in Table below require target conversion (LV%), feed API and
sulphur in the feed. Conversion is defined as the percentage of the oil fed that has been
cracked into lighter fractions than gasoline and lighter products:

The recycle stock is the portion of the feedstock which is not cracked to fractions lighter than
gasoline. For example, for 75% conversion, the cycle stock is 25%.

Example:
A feed of 20,000 BPD of AGO (650–850 F) having an API of 24 and a sulfur content of 0.2
wt%, is mixed with another of feed of 15,000 BPD of VGO (850–1050 F) that has an API of
15 and a sulfur content of 0.35 wt%. They are used as a feed to FCC unit. Use the FCC
correlations to find the material balance around the reactor unit. Assume a conversion of 75
LV%.
Petroleum Refining Fourth Year Dr.Aysar T. Jarullah

This gives feed API = 20.02. The results and product properties can be calculated as shown in
Table below.
Petroleum Refining Fourth Year Dr.Aysar T. Jarullah

Hydrotreating
Hydrotreating achieves the following objectives:
 Removing impurities, such as sulphur, nitrogen and oxygen for the control of a final
product specification or for the preparation of feed for further processing (naphtha
reformer feed and FCC feed);
 Removal of metals, usually in a separate guard catalytic reactor when the organo-
metallic compounds are hydrogenated and decomposed, resulting in metal deposition
on the catalyst pores (e.g. atmospheric residue desulphurization (ARDS) guard
reactor); and,
 Saturation of olefins and their unstable compounds.

Role of Hydrotreating
Hydrotreating units are needed in the refinery to clean streams from material such as
sulphur, nitrogen or metals harmful to the catalysts. That is why they are located before the
reformer, hydrocracker and FCC as shown in Figure below.
Petroleum Refining Fourth Year Dr.Aysar T. Jarullah

They are also needed to adjust the final product specification for various streams, such as
light naphtha, kerosene and low sulphur fuel oils (LSFOs).
Hence, the main role of hydrotreating can be summarized as follows:

1. Meeting finished product specification.

 Kerosene, gas oil and lube oil desulphurization.
 Olefin saturation for stability improvement.
 Nitrogen removal.
 De-aromatization for kerosene to improve cetane number, which is the percentage
of pure cetane in a blend of cetane and alpha-methyl-naphthalene. The
latter matches the ignition quality of kerosene sample.

2. Feed preparation for downstream units:

 Naphtha is hydrotreated for removal of metal and sulphur.
 Sulphur, metal, polyaromatics and Conradson carbon removal from vacuum gas oil
(VGO) to be used as FCC feed.
 Pretreatment of hydrocracking feed to reduce sulphur, nitrogen and aromatics.

Hydrotreating reactions
1. Desulphurization
a. Mercaptanes:
Petroleum Refining Fourth Year Dr.Aysar T. Jarullah

Hydrotreating Catalysts
The hydrotreating catalyst is a porous alumina matrix impregnated with combinations of
cobalt (Co), nickel (Ni), molybdenum (Mo) and tungsten (W). The reactivities of each
catalyst are given in Table below:
Petroleum Refining Fourth Year Dr.Aysar T. Jarullah

Hydrotreating Processes
Hydrotreating processes are similar in common elements and in general can be represented as
shown in Figure below. The liquid feed is mixed with hydrogen and fed into a heater and the
mixture is brought to the reaction temperature in a furnace and then fed into a fixed bed
catalytic reactor. The effluent is cooled and hydrogen-rich gas is separated using a high
pressure separator. Before the hydrogen is recycled, hydrogen sulphide can be removed using
an amine scrubber. Some of the recycle gas is also purged to prevent the accumulation of
light hydrocarbons (C1 – C4) and to control hydrogen partial pressure. The liquid effluent for
the reactor is introduced to a fractionator for product separation.

Make-up Hydrogen
A certain hydrogen partial pressure should be maintained in the reactors by recycling un-
reacted hydrogen and adding a make-up hydrogen to compensate for the amount consumed.
The make-up hydrogen can be calculated by the following expression:

Make-up hydrogen = hydrogen in feed - hydrogen consumed for chemical requirement

- hydrogen purged - amount of hydrogen dissolved in product

Hydrogen purge is the amount of hydrogen lost with the purging of light hydrocarbons (C1-
C4) and hydrogen sulphide (if not removed by amine treatment). This hydrogen can be
predicted using flash calculation, or using the purge gas ratio. The purge ratio is defined as:

Operating Conditions
The operating conditions of the hydrotreating processes include pressure, temperature,
catalyst loading, feed flow rate and hydrogen partial pressure. The hydrogen partial pressure
must be greater than the hydrocarbon partial pressure. Increasing hydrogen partial pressure
improves the removal of sulphur and nitrogen compounds and reduces coke formation.
Higher temperatures will increase the reaction rate constant and improve the kinetics.
Petroleum Refining Fourth Year Dr.Aysar T. Jarullah

However, excessive temperatures will lead to thermal cracking and coke formation. The
space velocity is the reverse of reactor residence time. High space velocity results in low
conversion, low hydrogen consumption and low coke formation. The range of operating
conditions for hydrotreating of different feed fractions is given in Table below.

Naphtha and Gas Oil Hydrotreating Correlations

The standard cubic foot of hydrogen per barrel of feed (SCFB) required for complete sulphur
removal is calculated as:

Where Sf is the sulphur wt% in feed.

The increase in the API gravity of a product is calculated as:

Where p and f refer to product and feed, respectively. In some cases, if it is required to
saturate aromatics and naphthenes to the corresponding paraffin, a set of correlations for PNA
analysis is required to predict the naphtha composition. These are:

Where Kf is the feed Watson characterization factor.

Example:
It is required to hydrotreate naphtha which has 1 wt% S and API = 50. Find: a) How much
hydrogen is required to remove all the sulphur in the feed by empirical correlations? b) How
much of this H2 is used for chemical requirements. c) If the mean average boiling point of
this naphtha is 135 F and assuming that the naphthene and aromatic present in the naphtha are
cyclohexane and benzene, respectively. Find the volume of hydrogen (SCFB) to convert all
cyclohexane and benzene into hexane.
Petroleum Refining Fourth Year Dr.Aysar T. Jarullah

Thus the following Table can be constructed for the calculation of the volume of H2 required
to convert cyclohexane and benzene to hexane.
The final amount of H 2 required can be summed up as:

It can be seen that the amount of hydrogen for naphthenes and aromatics saturation is much
higher than that needed for other requirements such as sulphur removal.
Petroleum Refining Fourth Year Dr.Aysar T. Jarullah

Middle Distillate Hydrotreating Correlations

The amount of hydrogen required can be calculated as:

Where Sf is the wt% sulphur in the feed and HDS% is the percent of hydrodesulphurization
required (degree of severity). The increase in product API is calculated as:

This equation is used for feed sulphur content of 0.5–6.0 wt%.

Example:
Gas oil has an API of 30, and a sulphur content of 1.5 wt% is fed into a hydrotreater. It is
required to carry out HDS at a severity of 90%. Calculate the hydrogen required and the
product API.
Petroleum Refining Fourth Year Dr.Aysar T. Jarullah

Hydrocracking
Hydrocracking is a catalytic hydrogenation process in which high molecular weight
feedstocks are converted and hydrogenated to lower molecular weight products.
Hydrogenation removes impurities in the feed such as sulphur, nitrogen and metals. Cracking
will break bonds, and the resulting unsaturated products are consequently hydrogenated into
stable compounds.

Role of Hydrocracking in the Refinery

Hydrocracking plays an important role as one of the main conversion processes in the
refinery as shown in Figure below. It is mainly used to produce middle distillates of low
sulphur content such as kerosene and diesel. If mild hydrocracking is used, a LSFO can be
produced. More recently, it has been used to remove wax by catalytic dewaxing and for
aromatic removal by hydrogen saturation. This has been applied to the lube oil plants and is
gradually replacing the old solvent dewaxing and aromatic solvent extraction.
Petroleum Refining Fourth Year Dr.Aysar T. Jarullah

Feeds and Products

VGO is the main feed for hydrocrakers, however a variety of feeds can be used as shown in
Table below. The feedstock type has an important influence on the final products.

Hydrocracking Reactions
Petroleum Refining Fourth Year Dr.Aysar T. Jarullah

Hydrocracking Catalysts
Hydrocracking catalysts have a cracking function and a hydrogenation-dehydrogenation
function (Figure below). The cracking function is provided by an acidic support,
whereas the hydrogenation–dehydrogenation function is provided by active metals.
Petroleum Refining Fourth Year Dr.Aysar T. Jarullah

Hydrocracking Factors
The following factors can affect operation (product quality), yield (quantity), and the total
economics of the process:
 Process configuration: one stage (once-through or recycle) or two stages
 Catalyst type
 Operating condition-depends on process objective (Conversion level, Maximization
of certain product, Product quality, Catalyst cycle, Partial hydrogen pressure, Liquid
hourly space velocity, Feed/hydrogen recycle ratio

Process Configuration
The one-stage process shown in Figure below can be used for light feeds with once through
or recycle process. In commercial hydrocrackers, a conversion of 40–80% of the feed can be
achieved. However if high conversion is required the product from the bottom of the
distillation tower is recycled back to the reactor for complete conversion. This configuration
can be used to maximize a diesel product, and it employs an amorphous catalyst.

One stage HDC Process

The two-stage operation is shown in Figure below. The effluent from the first stage reactor is
sent to a separator and fractionator. The fractionator bottoms are sent to the second reactor. In
both configurations, the hydrogen is separated inthe high pressure separator and recycled
back to the reactor. The hydrocracking catalyst in the first stage has a high
hydrogenation/acidity ratio, causing sulphur and nitrogen removal. In the second reactor, the
catalyst used is of a low hydrogenation/acidity ratio in which naphtha production is
maximized.
Petroleum Refining Fourth Year Dr.Aysar T. Jarullah
Petroleum Refining Fourth Year Dr.Aysar T. Jarullah

Catalytic Dewaxing
Catalytic dewaxing is a particular hydrocracking process used to improve cold flow
properties of middle distillates and lubricants by cracking normal paraffins. Dewaxing can be
achieved by isomerization, as carried out by Chevron’s isodewaxing process. Isoparaffins
have lower melting points than normal paraffins. The properties targeted for improvement are
pour point and viscosity of middle distillates and lubricants, the cloud point of diesel fuel,
and the freeze point of jet fuel. Due to their high melting points, long-chain normal paraffins
have the most detrimental effect on low temperature properties of middle distillates and lube
oils. By reducing the amount or chain length of normal and minimally branched paraffins in
these fuels and lubricants, their cold flow properties are improved. This can be accomplished
by using a catalytic dewaxing process. Such a process can also be used to improve the flow
properties of gas oils. A single-stage, once through hydrocracking process can be used for
catalytic dewaxing, with or without hydrotreating, depending on the sulphur and nitrogen
content of the feedstock. The catalytic process is carried out as a trickle bed reactor over a
bifunctional zeolite catalyst under hydrogen flow. A non-noble metal (e.g. nickel) supported
on a medium-pore zeolite, such as ZSM-5 can be used. The medium-pore zeolite ZSM-5
appears to be particularly suitable to obtain a high selectivity.

Hydrocracking Correlations
Yield Correlations
The yield correlations in conventional hydrocracking depend on feed properties, hydrogen
severity and mode of operation. There are three modes of operation: maximum gasoline
mode, maximum ATK mode (jet fuel) and maximum diesel fuel. In all these modes, gasoline
yield is used to correlate other yields. Using mild hydrocracking (low severity) will add a
fourth mode of operation, maximum low sulphur fuel oil (LSFO). The hydrogen severity
ranges between (1.5 – 4) wt% of feed. In mild hydrocracking it can be assumed as 1.5 wt%
and in conventional hydrocracking as 3.0 wt%. In high severity (high aromatic feeds) it can
be assumed as 4.0 wt% of feed. ATK mode is frequently used because of the high demand for
aviation fuels

Maximum ATK Correlations

The ATK mode yield correlations are given here as an example. These correlations are
developed from plant data. The following is the calculation procedure for ATK yields:
Petroleum Refining Fourth Year Dr.Aysar T. Jarullah

Example:
A feed of VGO of 37,500 BPCD is hydrocracked to maximize the ATK production. The API
of the feed is 20 and the mean average boiling point TB = 575 F. Make material balance
around this hydrocraker.
Petroleum Refining Fourth Year Dr.Aysar T. Jarullah
Petroleum Refining Fourth Year Dr.Aysar T. Jarullah

Catalytic Reforming
Catalytic reforming is the process of transforming C7 –C10 hydrocarbons with low octane
numbers to aromatics and iso-paraffins which have high octane numbers. It is a highly
endothermic process requiring large amounts of energy. A schematic presentation of the
feedstock, products and process condition is shown in Figure below. The process can be
operated in two modes: a high severity mode to produce mainly aromatics (80–90 vol%) and
a middle severity mode to produce high octane gasoline (70% aromatics content).

Role of Reformer in the Refinery and Feed Preparation

The catalytic reformer is one of the major units for gasoline production in refineries. It can
produce 37 wt% of the total gasoline pool. Other units such as the fluid catalytic cracker
(FCC), the methyl ter-butyl ether (MTBE) production unit, alkylation unit and isomerization
unit, also contribute to this pool. These units will be covered in other chapters of the book.
The straight run naphtha from the crude distillation unit is hydrotreated to remove sulphur,
nitrogen and oxygen which can all deactivate the reforming catalyst. The hydrotreated
naphtha (HTN) is fractionated into light naphtha (LN), which is mainly C5 –C6, and heavy
naphtha (HN) which is mainly C7 –C10 hydrocarbons. It is important to remove C6 from the
reformer feed because it will form benzene which is considered carcinogenic upon
combustion. Light naphtha (LN) is isomerized in the isomerization unit (I). Light naphtha can
be cracked if introduced to the reformer. The role of the heavy naphtha (HN) reformer in the
refinery is shown in Figure below. Hydrogen, produced in the reformer can be recycled to the
naphtha hydrotreater, and the rest is sent to other units demanding hydrogen.

Research Octane Number

The research octane number (RON) is defined as the percentage by volume of iso-
octane in a mixture of iso-octane and n-heptane that knocks with some intensity as the fuel is
being tested. A list of the RON of pure hydrocarbon is given in Appendix D. It is seen from
this appendix that the RON of paraffins, iso-paraffins and naphthenes decrease as the carbon
number of the molecule increases. Aromatics have the opposite trend.
Petroleum Refining Fourth Year Dr.Aysar T. Jarullah

Reforming Reactions
Petroleum Refining Fourth Year Dr.Aysar T. Jarullah
Petroleum Refining Fourth Year Dr.Aysar T. Jarullah

Coke Deposition
Coke can also deposit during hydrocracking resulting in the deactivation of the catalyst. The
catalyst in this case has to be re-activated by burning off the deposited coke. The catalyst is
selected to produce a slow hydrocracking reaction. Coke formation is favoured at low partial
pressures of hydrogen. Hydrocracking is controlled by operating the eaction at low pressure
between 5–25 atm (74–368 psia), not too low for coke deposition and not too high in order to
avoid cracking and loss of reformate yield.

Catalytic Reforming Catalysts

Catalytic reforming catalysts contain highly dispersed platinum (Pt), the activity of which is
inhibited by sulfur. Therefore, an upstream hydrotreater lowers the sulfur content of reformer
feeds to <1 wppm. In addition to Pt, modern multi-metallic catalysts contain highly dispersed
rhenium (Re) and in some cases tin (Sn).

Process Technology
There are several commercial processes available for reforming. These include Platforming
(UOP), Powerforming (Exxon), Magna forming (Engelhard), Catalytic reforming (IFP),
Rheniforming (Chevron) and Ultra forming (Amoco). The old technologies are fixed bed
configuration. Moving bed technology has also recently been introduced.

Semi-regenerative Fixed Bed Process

The schematic flow diagram of this process is shown in Figure below. The name semi-
regenerative comes from regeneration of the catalyst in the fixed bed reactors after shut down
by burning off the carbon formed on the catalyst surface. Reactions such as dehydrogenation
of paraffins and naphthenes which are very rapid and highly endothermic occur in the first
reactor, with high temperature drop. Reactions that are considered rapid, such as paraffin
isomerization and naphthens dehydroisomerization, give moderate temperature decline in the
second reactor. Furthermore, slow reactions such as dehydrocyclization and hydrocracking
give low temperature decline in the third reactor.
Petroleum Refining Fourth Year Dr.Aysar T. Jarullah

To prevent catalyst coking, the hydrogen partial pressure is maintained at a level such that the
H2-to-hydrocarbon ratio by weight (H2/HC) is greater than 25 for monometallic catalyst. This
is done by recycling some of the hydrogen produced. Some light hydrocarbons (C1 –C4) are
separated from the reformate in the stabilizer. At the top of the stabilizer residual hydrogen
and C1 to C4 are withdrawn as condenser products, which are then sent to gas processing, and
part of the liquid product (C3 and C4) is returned from the reflux drum back to the stabilizer.
The main product of the column is stabilized reformate, which is sent to the gasoline blending
plant. A slight modification to the semi-regenerative process is to add an extrareactor to avoid
shutting down the whole unit during regeneration. Three reactors can be running while the
forth is being regenerated. This modified process is called the ‘‘cyclic fixed bed’’ process.
Petroleum Refining Fourth Year Dr.Aysar T. Jarullah

Continuous Regenerative (moving bed) CCR Platforming - UOP Process

In this process, three or four reactors are installed one on the top of the other. The schematic
flow diagram of the continuous regenerative process (CCR) is shown in Figure below. UOP
has licensed this process under the CCR Platforming process. The effluent from each reactor
is sent to a common furnace for heating. The catalyst moves downwards by gravity from the
first reactor (R1) to the forth reactor (R4). The catalyst is sent to the regenerator to burn off
the coke and then sent back to the first reactor R1. The final product from R4 is sent to the
stabilizer and gas recovery section. The process can be operated at lower hydrogen partial
pressure (PH2 = 3 bar) compared to the semi-generative process (PH2 = 35 bar), with a
reformate yield gain of nearly 10 vol%. Table below gives a comparison of the operating
conditions for the three reforming processes.
Petroleum Refining Fourth Year Dr.Aysar T. Jarullah

Material Balance in Reforming

Material Balance Using Empirical Correlations
Catalytic reforming data base compiled by Maples (1993) were correlated using multiple
regression. Yield correlations for the reformer were developed as given in Table below. The
correlation coefficients were in the range of 0.990 – 0.999.

Material Balance Using Conversion Criteria

If detailed analysis of the reformer feed is known, the feed conversion can be calculated from
the conversion data for each class of compounds as shown in Tables below.
Petroleum Refining Fourth Year Dr.Aysar T. Jarullah

Example:
100 m3 /h of heavy naphtha (HN) with specific gravity of 0.778 has the following
composition: A = 11.5 vol%, N = 21.7 vol% and P = 66.8 vol% is to be reformed to naphtha
reformate of RON = 94. Calculate the yields of each product for that reformer.

Solution:
Given RON R = 94 and N þ 2A = 44.7%,

The yields for the other products can then be calculated from the correlations in Table above.
The material balance for the reformer is presented in the following table:
Petroleum Refining Fourth Year Dr.Aysar T. Jarullah

Example:
Heavy naphtha, which has the following detailed analysis in mol%, is fed to a reformer unit.

Find the composition of the products.

Solution:
The data, given in Tables above, are used to estimate the composition of the products as
follows:
Petroleum Refining Fourth Year Dr.Aysar T. Jarullah

Isomerization Process
Isomerization is the process in which light straight chain paraffins of low RON (C6, C5 and
C4) are transformed with proper catalyst into branched chains with the same carbon number
and high octane numbers. The hydrotreated naphtha (HTN) is fractionated into heavy naphtha
between 90–190 °C (190–380 F) which is used as a feed to the reforming unit. Light naphtha
C5 - 80 °C (C5 - 180 F) is used as a feed to the isomerization unit. There are two reasons for
this fractionation: the first is that light hydrocarbons tend to hydrocrack in the reformer. The
second is that C6 hydrocarbons tend to form benzene in the reformer. Gasoline specifications
require a very low value of benzene due to its carcinogenic effect.

Isomerization Catalysts
The most common catalyst for isomerising n-butane is platinum (Pt) on alumina
promoted by chloride. The high activity of this catalyst allows operation at relatively low
temperature. This is beneficial because the reaction is controlled by equilibrium; at low
temperature, equilibrium favors isobutane. Pt/alumina catalysts can’t be regenerated, and
they are highly sensitive to water and other contaminants.
In units that isomerize n-pentane and n-hexane, the reactions are catalyzed either by
Pt/alumina or Pt on zeolite. The zeolite catalysts require higher temperatures, but they are
less sensitive to water. As with butane isomerization, the reactions are controlled by
equilibrium, so lower reaction temperatures favor branched isomers. The high temperatures
required by zeolite catalysts reduce the octane of the product relative to products made at
lower temperatures with chlorided alumina catalysts. A comparison of the operating
conditions for the alumina and zeolite processes is shown in Table below

Isomerization Reactions
Isomerization is a reversible and slightly exothermic reaction:

The conversion to iso-paraffin is not complete since the reaction is equilibrium conversion
limited. It does not depend on pressure, but it can be increased by lowering the temperature.
However operating at low temperatures will decrease the reaction rate. For this reason a very
active catalyst must be used.
Petroleum Refining Fourth Year Dr.Aysar T. Jarullah

Process Flow: C 5 C6 Isomerization

Pentane/hexane (C5C6) isomerization processes increase the octane of light gasoline. In a
typical unit, dried, hydrotreated feed is mixed with a small amount of organic chloride and
recycled hydrogen, then heated to reaction temperature. Process objectives determine whether
one or two reactors are used. In two-reactor units (Figure below), the feed flows first to a
saturation reactor, which removes olefins and (to a large extent) benzene. After saturation, the
feed goes to an isomerization reactor, where normal paraffins are converted to isoparaffins.
The reactor effluent flows to a product separator, where hydrogen is separated from the
other reaction products. Recovered hydrogen can go to a recycle compressor, which returns it
to the reactors, or it can be treated and sent to the fuel gas system. Separator liquids go to a
stabilizer column, which removes light gases and remaining dissolved hydrogen. The
stabilized liquid goes to storage or gasoline blending. If sent to a fractionator, n-pentane and
n-hexane can be recycled to the isomerization unit for increased conversion.

Isomerization Yields
The reformate yield from light naphtha isomerization is usually very high (>97 wt%). Typical
yields are given in Table below:

Example:
Light naphtha with a specific gravity of 0.724 is used as a feed to the isomerization unit at a
rate of 100 m3 /h. Find the product composition.
Petroleum Refining Fourth Year Dr.Aysar T. Jarullah

Solution:
Appling the yield guidelines of Table aboves, the product composition are presented in Table
below.
Petroleum Refining Fourth Year Dr.Aysar T. Jarullah

Alkylation Process
Alkylation is the process of producing gasoline range material light olefins (primarily
propylene and butylene) with isobutane in the presence of a highly acidic catalyst, either
sulfuric acid or hydrofluoric acid. The product (alkylate) contains a mixture of high-octane,
branched-chain paraffinic hydrocarbons.
Refinery gases produced from different units are collected and sent to the gas plant. Olefins
and isobutanes are separated and used as a feed to the alkylation plant to produce gasoline
which can be sent to the gasoline pool.

Alkylation Processes
Alkylation is catalyzed by a strong acid, either sulphuric (H2SO4) or hydrofluoric (HF). In the
absence of catalysts, alkylation between isobutene and olefin must be run under severe
conditions such as T = 500 °C (932 F) and P = 200–400 bars (2940–7080 psia). In the
presence of an acid catalyst, the reaction temperature will be lower than 50 °C (122 F), and
the pressure will be lower than 30 bars (441 psia). The major difference in using either acid is
that isobutane is quite insoluble in H2SO4 but reasonably soluble in HF. This requires the use
of high isobutane/olefin ratios to compensate for low solubility in H2SO4. Furthermore, the
reaction must occur at low temperature. The alkylation process consists of running the
hydrocarbons in liquid form (enough pressure is used to ensure that) and at low temperature
and with a high isobutane (iC4) to olefin (such as C4) ratio. The reaction products are sent to
an acid settler where the acid is recycled back to the reactor. Products are then separated into
gaseous LPG propane and n-butane and the desired product of alkylate. A block diagram of
the process is shown in Figure below:

Process Flow: Sulfuric Acid Alkylation

In sulfuric acid (H 2 SO 4 ) alkylation units, the feeds – propylene, butylene, amylene, and
fresh isobutane – enter the reactor and contact sulfuric acid with a concentration of 85 to
95%. The reactor is divided into zones. Olefins are fed through distributors to each zone,
and sulfuric acid and isobutanes flow over baffles from one zone to the next.
The reactor effluent goes to a settler, in which hydrocarbons separate from the acid. The acid
is returned to the reactor. The hydrocarbons are washed with caustic and sent to fractionation.
The fractionation section comprises a depropanizer, a deisobutanizer, and a debutanizer.
Alkylate from the deisobutanizer can go directly to motor-fuel blending, or it can be
reprocessed to produce aviation-grade gasoline. Isobutane is recycled. A block diagram of the
process is shown in Figure below.
Petroleum Refining Fourth Year Dr.Aysar T. Jarullah

Hydrofluoric Acid Alkylation

Figure below shows a process schematic for hydrofluoric acid (HF) alkylation. Olefins and
isobutane are dried and fed to a reactor, where the alkylation reaction takes place over the HF
catalyst. The reactor effluent flows to a settler, where the acid phase separates from the
hydrocarbon phase. The acid is drawn off and recycled. The hydrocarbon phase goes to a
deisobutanizer (DIB). The overhead stream, containing propane, isobutane, and residual HF,
goes to a depropanizer (DeC3). The DeC3 overhead goes to an HF stripper. It is then treated
with caustic and sent to storage. Isobutane from the DIB main fractionator is recycled. The
bottom stream from the debutanizer goes to product blending.

AlkyClean Process
Lummus technology has developed a solid acid catalyst gasoline alkylation technology. The
AlkyClean process employs a zeolite catalyst coupled with a novel reactor processing to yield
a high quality alkylate product. The process shown in Figure below consists of four main
sections: feedstock pretreatment, reaction, catalyst regeneration and product distillation. An
olefin feed is preheated and fed with the isobutane recycle to the reactor. The reactor operates
Petroleum Refining Fourth Year Dr.Aysar T. Jarullah

at 50–90 °C (122–194 F) with liquid phase conditions. Multiple reactors are used to allow for
the catalyst regeneration cycle. During regeneration, olefin addition is stopped and hydrogen
is added to achieve a low reactor concentration of dissolved hydrogen while maintaining
liquid phase alkylation reaction conditions. This minimizes energy consumption during the
switching of the operation. The swing reactor coupled with long catalyst life allows the
refiner to work without the need of taking the reactor off-line for moderate temperature
regeneration that restores the catalyst activity completely.

Effect of Operating Conditions

 Olefin Type
The presence of propylene or pentene with butane will lower the octane number and increase
the acid consumption. The octane number of alkylates produced from light olefins is given in
Table below:

 Isobutane Concentration
Petroleum Refining Fourth Year Dr.Aysar T. Jarullah

 Acid Strength
An optimum value of acid strength of 90 wt% H2SO4 is maintained by adding fresh
concentrated acid (98–99 wt%). As the strength of the acid decreases, the acid consumption
increases with the octane number decreases. The minimum acid strength required to operate
the system should not be lower than 85 wt%. To provide a sufficient margin of safety, acid
strength is kept around 90 wt%. The acid strength decreases because of the formation of
gums and other products resulting from the reaction with other impurities. Thus, acid make-
up has to be added.

 Degree of Agitation
When the hydrocarbons are dispersed in sulphuric acid, the speed of the impeller determines
the dispersed phase size (droplet diameter) and hence, the interfacial contact area. The
reaction rate of iC4 and C4 is quite fast, and the reaction is controlled by mass transfer. Side
reactions cause the formation of heavy alkylates as given by the following equation

where [iC4] h is the concentration of iC4 in hydrocarbon phase, N is the impeller speed (rpm),
Ha is the fractional acid hold-up, (SV)o is the space olefin velocity (1/h), RHeavy alkylate is the
rate of formation of the undesirable heavy alkylate, and RiC8 is the rate of formation of the
target alkylateiC8 .

 Space Velocity
The olefin space velocity is defined as:

The residence time in the reactor is (1/(SV)o ) and is defined as the residence time of the fresh
feed and externally recycled isobutane in the reaction mixture. Since the alkylation reaction is
very fast, the residence time is not a limiting parameter. However, as the space velocity
increases, the octane number tends to decrease while acid consumption tends to increase.
Residence time for sulphuric acid is usually from 5 to 40 min, and for hydrofluoric acid, it is
5–25 min.
Petroleum Refining Fourth Year Dr.Aysar T. Jarullah

 Reaction Temperature
The reaction thermodynamics and kinetics are favoured at low temperatures. Sulphuric acid
alkylation units are operated at 5–10 °C (40–50 F). Above 10 °C, oxidation and side reactions
are promoted, and the deteriorate-alkylate yield and quality while acid consumption
increases. It is impossible to run the reaction below 0 °C (32 F) because acid viscosity will be
too high and agitation becomes difficult.Above 21 °C (70 F), the polymerization of olefin
will occur, and thevoctane number of alkylate decrease. For HF alkylation, the reaction
temperature is less significant and is between 21 and 38 °C (70 and 100 F).

Performance of Alkylation Process

A schematic diagram of the alkylation process is shown in Figure below

The feed to the reactor consists of olefin V1 (BPD) and a fresh acid make-up of m×1000
(lb/day). The product alkylate yield is V4 (BPD). Therefore, the external isobutane/olefin
ratio (I/O)F = x1 which can be expressed as

The recycled isobutane (V2) can be calculated, since (I/O)F is assumed to be 5–15. The
alkylate yield V4 can be expressed in term of (I/O)F as

If we assume a volumetric shrinkage in alkylate formation from olefin and isobutane of 22%,
thus:
Petroleum Refining Fourth Year Dr.Aysar T. Jarullah

Hence the make-up isobutane (V5) is:

The acid strength weight percent, x2, could be derived from the acid addition rate m (strength
of 98%), alkylate yield V4 and the acid dilution factor x4 as:

where x4 is the dilution ratio

where F is the performance number and is defined below.

Petroleum Refining Fourth Year Dr.Aysar T. Jarullah
Petroleum Refining Fourth Year Dr.Aysar T. Jarullah

Chemical Treatment of Petroleum Products

The aims of chemical treatment is to remove the impurities, such as sulfur, nitrogen, oxygen,
asphaltene, unsaturated compounds and some aromatics compounds at low temperature.
Treatment processes for the removal of impurities compounds are much less severe than the
hydrotreating processes. In fact, it is generally recognized that the removal or conversion of
theses compounds in distillates by treatment processes is usually limited to the lower
molecular weight compounds.

Methods of Chemical Treating

1- Oxidative Processes
2- Caustic Processes
3- Acid Processes
4- Solvent Processes, having three types
 Solvent Deasphalting
 Solvent extraction
 Solvent dewaxing

1- Oxidative Processes
Oxidative treatment processes are, in fact, processes that have been developed to convert the
objectionable-smelling mercaptans to the less-objectionable disulfides by oxidation.
However, disulfides tend to reduce the tetraethyl lead susceptibility of gasoline, and recent
trends are toward processes that are capable of completely removing the mercaptans. These
reactions are carried out on the light products (such as gasoline and kerosene) because the
mercaptans are concentrated within these cuts.
There are many methods for oxidative treating (for example, Bender process, Copper
Sweetening Process, Doctor Process, Hypochlorite Sweetening Process, Merox Process).

 Merox Process
Merox is a proprietary catalytic chemical process for mercaptans oxidation developed
by UOP used in oil refineries and natural gas processing plants to remove mercaptans
from LPG, propane, butanes, light naphthas, kerosene and jet fuel by converting them to
liquid hydrocarbon disulfides.
Processes within oil refineries or natural gas processing plants that remove mercaptans
and/or hydrogen sulfide (H2S) are commonly referred to as sweetening processes because
they results in products which no longer have the sour, foul odors of mercaptans and
hydrogen sulfide. The liquid hydrocarbon disulfides may remain in the sweetened products,
they may be used as part of the refinery or natural gas processing plant fuel, or they may be
processed further. The Merox process is usually more economical than using a
catalytic hydrodesulfurization process for much the same purpose.

Types of Merox Process Units

UOP has developed many versions of the Merox process for various applications:
 Conventional Merox for extraction of mercaptans from LPG, propane, butanes or light
naphthas.
 Conventional Merox for sweetening jet fuels and kerosenes.
 Merox for extraction of mercaptans from refinery and natural gases.
Petroleum Refining Fourth Year Dr.Aysar T. Jarullah

 Minalk Merox for sweetening of naphthas. This process continuously injects just a
few ppm of caustic into the feed naphtha.
 Caustic-free Merox for sweetening jet fuels and kerosenes. This process injects small
amounts of ammonia and water (rather than caustic) into the feed naphtha to provide the
required alkalinity.
 Caustic-free Merox for sweetening of naphthas. This process also injects small amounts
of ammonia and water (rather than caustic) into the feed naphtha to provide the required
alkalinity.
In all of the above Merox versions, the overall oxidation reaction that takes place in onverting
mercaptans to disulfides is:
4 RSH + O2 → 2RSSR + 2H2O

Conventional Merox for Sweetening Jet Fuel or Kerosene

The conventional Merox process for the removal of mercaptans (i.e., sweetening) of jet fuel
or kerosene is a one-step process. The mercaptan oxidation reaction takes place in an alkaline
environment as the feedstock jet fuel or kerosene, mixed with compressed air, flows through
a fixed bed of catalyst in a reactor vessel. The catalyst consists of charcoal granules that have
been impregnated with UOP's proprietary catalyst. The oxidation reaction that takes place is:

4 RSH + O2 → 2RSSR + 2H2O

The jet fuel or kerosene sweetening process also requires that the feedstock be prewashed to
remove any H2S that would interfere with the sweetening. The reaction that takes place in the
batch caustic prewash vessel is:
H2S + NaOH → NaSH + H2O
Petroleum Refining Fourth Year Dr.Aysar T. Jarullah

The Merox reactor is a vertical vessel containing a bed of charcoal granules that have been
impregnated with the UOP catalyst. An alkaline environment is provided by caustic being
pumped into reactor on an intermittent, as needed basis.
The jet fuel or kerosene feedstock from the top of the caustic prewash vessel is injected with
compressed air and enters the top of the Merox reactor vessel along with any injected caustic.
The mercaptan oxidation reaction takes place as the feedstock percolates downward over the
catalyst. The reactor effluent flows through a caustic settler vessel where it forms a bottom
layer of aqueous caustic solution and an upper layer of water-insoluble sweetened product.
The caustic solution remains in the caustic settler so that the vessel contains a reservoir for
the supply of caustic that is intermittently pumped into the reactor to maintain the alkaline
environment.
The sweetened product from the caustic settler vessel flows through a water wash vessel to
remove any entrained caustic as well as any other unwanted water-soluble substances,
followed by flowing through a salt bed vessel to remove any entrained water and finally
through a clay filter vessel. The clay filter removes any oil-soluble substances,
organometallic compounds (especially copper) and particulate matter, which might prevent
meeting jet fuel product specifications.
The pressure maintained in the reactor is chosen so that the injected air will completely
dissolve in the feedstock at the operating temperature.

2-Caustic Processes
The process consists of mixing a water solution of lye (sodium hydroxide or caustic soda)
with a petroleum fraction. The treatment is carried out as soon as possible after the petroleum
fraction is distilled, as contact with air forms free sulfur, which is very corrosive and difficult
to remove. The lye reacts with any hydrogen sulfide present to form sodium sulfide, which is
soluble in water.
There are many methods for caustic process (such as Dualayer Process, Mercapsol Process,
Polysulfide Treatment, Sodasol Process, Unisol Process)

Unisol Process
The Unisol process is a regenerative method for extracting not only mercaptans but also
certain nitrogen compounds from sour gasoline or distillates. The gasoline, free of hydrogen
sulfide, is washed countercurrently with aqueous caustic-methanol solution at about 40°C
(100F). The spent caustic is regenerated in a stripping tower (145°C to 150°C, 290°F to
300°F), where methanol, water, and mercaptans are removed.

3- Acid Treatment
Treating petroleum products with acids is, like caustic treatment. Various acids, such as
hydrofluoric acid, hydrochloric acid, nitric acid, and phosphoric acid, have been used in
addition to the more commonly used sulfuric acid, but in most instances there is little
advantage in using any acid other than sulfuric.

Sulfuric Acid Treatment

Sulfuric acid treatment is a continuous or batch method that is used to remove sulfur
compounds. The treatment will also remove asphaltic materials from various refinery stocks.
The acid strength varies from fuming (>100%) to 80%; approximately 93% acid finds the
Petroleum Refining Fourth Year Dr.Aysar T. Jarullah

most common use. The weakest suit able acid is used for each particular situation to reduce
sludge formation from the aromatic and olefin hydrocarbon s. The use of strong acid dictates
the use of a fairly low temperature (-4°C to 10°C, 25°F to 50°F), but higher temperatures
(20°C to 55°C, 70F to 130F) are possible if the product is to be redistilled.

4- Solvent Treating
Distillation splits a mixture into fractions according to the boiling points of the mixture
constituents. In contrast, solvent refining segregates compounds with similar compound
types, such as paraffins and aromatics. The three main types of solvent refining are solvent
deasphalting, solvent extraction, and solvent dewaxing.

Solvent Deasphalting
Solvent deasphalting takes advantage of the fact that aromatic pounds are insoluble in
paraffins. Propane deasphalting is commonly used to precipitate asphaltenes from residual
oils. Deasphalted oil (DAO) is sent to hydrotreaters, FCC units, hydrocrackers, or fuel-oil
blending. In hydrocrackers and FCC units, DAO is easier to process than straight-run residual
oils. This is because asphaltenes easily form coke and often contain catalyst poisons such as
nickel and vanadium, and the asphaltene content of DAO is (by definition) almost zero.
In traditional solvent deasphalting, residual oil and propane are pumped to an extraction
tower at 150 to 250°F (65 to 120°C) and 350 to 600 psig (2514 to 4240 kPa). Separation
occurs in a tower, which may have a rotating disc contactor (Figure below). Liquid products
are evaporated and steam stripped to recover the propane solvent, which is recycled.
An advanced version of solvent deasphalting is “residuum oil supercritical extraction
(ROSE),” In this process, the oil and solvent are mixed and heated to above the critical
temperature of the solvent, where the oil is almost totally insoluble. Advantages include
higher recovery of deasphalted liquids, lower operating costs due to improved solvent
recovery, and improved energy efficiency. The ROSE process can employ three different
solvents, the choice of which depends upon process objectives:
Propane: Preparation of lube base stocks
Butane : Asphalt production
Pentane: Maximum recovery of liquid
Petroleum Refining Fourth Year Dr.Aysar T. Jarullah

Solvent Extraction
Solvent extraction is used to remove aromatics and other impurities from lube and grease
stocks. The feedstock is dried, then contacted with the solvent in a counter-current or rotating
disk extraction unit (Figure above). The solvent is separated from the product stream by
heating, evaporation, or fractionation. Remaining traces of solvent are removed from the
raffinate by steam stripping or flashing. Electrostatic precipitators may be used to enhance
separation of inorganic compounds. The solvent is then regenerated and recycled.
Today, phenol, furfural, and cresylic acid are widely used as solvents. In the past, some
refiners installed the Edeleanu process, in which the solvent is liquid sulfur dioxide, but the
hazards of potential leaks made it undesirable. Chlorinated ethers and nitrobenzene also have
been used.

Solvent Dewaxing
Solvent dewaxing removes wax (normal paraffins) from deasphalted lube base stocks. The
main process steps include mixing the feedstock with the solvent, chilling the mixture
to crystallize wax, and recovering the solvent. Commonly used solvents include toluene
and methyl ethyl ketone (MEK). Methyl isobutyl ketone (MIBK) is used in a wax deoiling
process to prepare food-grade wax.
Petroleum Refining Fourth Year Dr.Aysar T. Jarullah

Oil Products
1- Gaseous Fuels.
Natural gas, which is predominantly methane, occurs in underground reservoirs separately or
in association with crude oil. The principal types of gaseous fuels are oil (distillation) gas,
reformed natural gas, and reformed propane or liquefied petroleum gas (LPG).
LPG is the term applied to certain specific hydrocarbons and their mixtures, which exist in
the gaseous state under atmospheric ambient conditions but can be converted to the liquid
state under conditions of moderate pressure at ambient temperature. The most common
commercial products are propane, butane, or a mixture of the two, and are generally extracted
from natural gas or crude petroleum. Mixed gas is a gas prepared by adding natural gas or
LPG to a manufactured gas, giving a product of better utility and higher heat content.

1.1 Compositions
The principal constituent of natural gas is methane. Other constituents are paraffinic
hydrocarbons such as ethane, propane, and the butanes.

1.2 Manufacture
Unless produced specifically as a product (e.g., LPG ), the gaseous products of
refinery operations are mixtures of various gases. Each gas is a by-product of a refining
process. Thus, the compositions of natural, manufactured, and mixed gases can vary so
widely, no single set of specifications could cover all situations.

1.2 Properties and Uses

As already noted, the compositions of natural, manufactured, and mixed gases can vary so
widely, no single set of specifications could cover all situations. The requirements are usually
based on performances in burners and equipment, on mini mum heat content, and on maxi
mum sulfur content. Gas utilities in most states come under the supervision of state
commissions or regulatory bodies an d the utilities must provide a gas that is acceptable to all
types of consumers and that will give satisfactory performance in all kinds of consuming
equipment.

2- Gasoline
Gasoline, also called gas (United States and Canada), or petrol (Great Britain) or benzene
(Europe) is a mixture of volatile, flammable liquid hydrocarbons derived from petroleum and
used as fuel for internal-combustion engines. It is also used as a solvent for oils and fats.
Gasoline became the preferred automobile fuel because of its high energy of combustion and
capacity to mix readily with air in a carburetor. Gasoline is a mixture of hydrocarbons that
usually boil below 180°C or, at most, below 200°C. B.p (35 – 180°C) and sp.gr (0.7 – 0.78).

2.1 Compositions
Gasoline is manufactured to meet specifications and regulations and not to achieve a specific
distribution of hydrocarbons by class and size. Automotive gasoline typically contains about
almost 200 (if not several hundred) hydrocarbon compounds. The relative concentrations of
the compounds vary considerably depending on the source of crude oil, refinery process, and
product specifications. Typical hydrocarbon chain lengths range from C4 through Cl2 with a
general hydrocarbon distribution consisting of alkanes (4–8%), alkenes (2–5%), iso-alkanes
25–40%, cycloalkanes (3–7%), cycloalkenes (l–4%), and aromatics (20–50%). However,
these proportions vary greatly. The majority of the members of the paraffin, olefin, and
Petroleum Refining Fourth Year Dr.Aysar T. Jarullah

aromatic series (of which there are about 500) boiling below 200°C have been found in the
gasoline fraction of petroleum.

2.2 Manufacture
 Gasoline produced by distillation (light straight run (LSR)), simply separating the
volatile, more valuable fractions of crude petroleum (O.N ≈ 65).
 Catalytic reforming (O.N = 90)
 Thermal racking of heavy cuts higher than kerosene.
 Catalytic cracking (O.N > 90).
 Alkylation process (O.N > 95).
 Haydrocracking.

2.2 Properties
2.3.1 Octane Number
In a spark-ignition engine, some compounds start to burn before they reach the spark plug.
This premature ignition causes knocking, which reduces the power of the engine, increases
engine wear, and in some cases causes serious damage. Octane number is a measure of the
propensity of fuels to knock in gasoline engines. It is based on an arbitrary scale in which the
octane number of n-heptane is zero and the octane number of isooctane (2,2,4-
trimethylpentane) is 100. When a fuel is tested in a standard single-cylinder engine, mixtures
of isooctane and n-heptane are used as standards. ASTM D2699 and ASTM D2700 describe
methods for measuring research octane number (RON) and motor octane number (MON),
respectively. The engine speed for the RON test is 600 rpm, while 900 rpm is used for the
MON test. RONC and MONC are sometimes used instead to RON and MON.
Aromatics, olefins, and branched isomers have higher octane numbers than straight-
chain isomers with similar carbon numbers. Octane numbers for naphthenes are substantially
lower than those for aromatics.

2.3.2 Reid vapor pressure

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 test method applies to volatile crude oil and volatile nonviscous
petroleum liquids, except liquified petroleum gases. 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. The Reid
vapor pressure (RVP) differs slightly from the true vapor pressure (TVP) of a liquid due to
small sample vaporization and the presence of water vapor and air in the confined space of
the test equipment. RVP various from winter to summer.

2.3.3 Low - Sulfur Gasoline

In recent years, the U.S. Environmental Protection Agency (EPA) and the European
Parliament promulgated clean-fuel regulations that are lowering the sulfur content of gasoline
Petroleum Refining Fourth Year Dr.Aysar T. Jarullah

and diesel fuel. New sulfur-content standards for several developed countries are shown
in Table below, which also shows the target dates for implementation.

2.4 Gasoline Additives

Table below lists the kinds of additives used to prepare finished gasoline. Additive
packages vary from season-to-season, region-to-region, and retailer usually are more
concentrated. They are packaged so that they can be added b consumers to the fuel tanks of
individual automobiles.

3- Kerosene and Jet Fuel

Kerosene is a flammable pale-yellow or colorless oily liquid with a characteristic odor. It is
obtained from petroleum and used for burning in lamps and domestic heaters or furnaces, as a
fuel or fuel component for jet engines, and as a solvent for greases and insecticides. Kerosene
is intermediate in volatility between gasoline and gas=diesel oil. It is a medium oil distilling
between 150°C and 300°C. Kerosene is widely used to power jet engines of aircraft (jet fuel)
and some rocket engines, but is also commonly used as a cooking and lighting fuel and for
fire toys.
Petroleum Refining Fourth Year Dr.Aysar T. Jarullah

Jet fuel is a light petroleum distillate that is available in several forms suitable to use in
various types of jet engines. Jet fuel comprises both gasoline and kerosene type jet fuels
meeting specifications for using in aviation turbine power units and is often referred to as
gasoline-type jet fuel and kerosene-type jet fuel.

3.1 Compositions
Chemically, kerosene is a mixture of hydrocarbons; the chemical composition depends on its
source, but it usually consists of about 10 different hydrocarbons, each containing from 10 to
16 carbon atoms per molecule; the constituents include n-dodecane (n-C12H26), alkyl
benzenes, and naphthalene and its derivatives. Kerosene is less volatile than gasoline; it boils
between about 140°C and 320°C.

3.2 Manufacture
 Distillation of petroleum.
 Cracking process.

3.3 Properties
The key product properties are:
• Flash point
• Freezing point
• Sulfur content
• Smoke point

The flash point is the lowest temperature at which a liquid gives off enough vapor to
ignite when an ignition source is present.
The freezing point is especially important for jet aircraft, which fly at high altitudes
where the outside temperature is very low. Sulfur content is a measure of corrosiveness.
The measurement of smoke point goes back to the days when the primary use for kerosene
was to fuel lamps. To get more light from a kerosene lamp, you could turn a little knob to
adjust the wick. But if the flame got too high, it gave off smoke. Even today, per ASTM
D1322, smoke point is the maximum height of flame that can be achieved with calibrated
wick-fed lamp. The smoke point of a test fuel is compared to reference blends. A standard
40%/60% (volume/volume) mixture of toluene with 2,2,4-trimethylpentane has a smoke
point of 14.7, while pure 2,2,4-trimethylpentane has a smoke point of 42.8. Clearly,
isoparaffins have better smoke points than aromatics. Table below shows specifications for
five grades of jet fuel, otherwise known as aviation turbine fuel. The JP fuels are for military
aircraft.
Petroleum Refining Fourth Year Dr.Aysar T. Jarullah

4- Diesel Oil
Diesel fuel oil is also a distillate fuel oil that distills between 180°C and 380°C. Several
grades are available depending on their uses: diesel oil for diesel compression ignition (cars,
trucks, and marine engines) and light heating oil for industrial and commercial uses.
Diesel fuel, many possible combinations of characteristics (such as volatility, ignition quality,
viscosity, gravity, stability, and other properties) exist. To characterize diesel fuels and
thereby establish a framework of definition and reference, various classifications are used in
different countries.

4.1 Compositions
Petroleum-derived diesel is composed of about 75% saturated hydrocarbons (primarily
paraffins including n, iso, and cycloparaffins), and 25% aromatic hydrocarbons (including
naphthalenes and alkylbenzenes). The average chemical formula for common diesel fuel is
C12H23, ranging approximately from C10H20 to C15H28.

4.2 Properties
Sulfur, cetane number, and (in some countries) aromatics and density are regulated for
environmental reasons. Sulfur contributes heavily to particulate emissions from diesel
engines, and cetane number is a measure of burning quality in a diesel engine. As with octane
number, cetane number measures the tendency of fuels to auto-ignite in a standard test
engine. It is easier to start a diesel engine when the cetane number of the fuel is high.
Diesel index is a simpler calculation based on density and aniline point. The streams listed in
Table belows are typical candidates for making diesel fuel.

Catalytic converters led to the elimination of lead from gasoline, because lead poisons the
converter catalyst. Similarly, sulfur poisons catalysts that may be used on future vehicles.
Hence, the reduction of sulfur in gasoline and diesel fuel to ultra-low levels is a key
requirement of Auto Oil. Around the world, the transportation and fungibility of ultra-clean
fuels is a major concern. For common-carrier pipelines, which transport various products
made by different refiners, cross-contamination is a major concern.
Other important diesel-fuel properties include flash point, cloud point, pour point,
kinematic viscosity, and lubricity. Cloud point and pour point indicate the temperature at
which the fuel tends to thicken and then gel in cold weather. In addition to providing energy,
diesel fuel also serves as a lubricant for fuel pumps and injectors, which prolongs the life of
the engine. Viscosity measures the tendency of a fluid to flow. In a diesel engine, viscosity
indicates how well a fuel atomizes in spray injectors. It also measures its quality as a
lubricant for the fuel system. Lubricity measures the fuel’s ability to reduce friction between
solid surfaces in relative motion. It indicates how the engine will perform when loaded.
Petroleum Refining Fourth Year Dr.Aysar T. Jarullah

4.3 Diesel Additives

Chemical additives improve the performance and extend the tank-life of diesel fuels. Typical
types of additives are shown in Table bellows.

5. Fuel Oil
Fuel oil is classified in several ways but generally may be divided into two main types:
distillate fuel oil and residual fuel oil. Distillate fuel oil is vaporized and condensed during a
distillation process and thus has a definite boiling range and does not contain high-boiling
constituents. A fuel oil that contains any amount of the residue from crude distillation of
thermal cracking is a residual fuel oil. The terms distillate fuel oil and residual fuel oil are
losing their significance, as fuel oil is now made for specific uses and may be either distillates
or residuals or mixtures of the two. The terms domestic fuel oil, diesel fuel oil, and heavy fuel
oil are more indicative of the uses of fuel oils.
Domestic fuel oil is fuel oil that is used primarily in the home. This category of fuel oil
includes kerosene, stove oil, and furnace fuel oil; they are distillate fuel oils. Heavy fuel oil
comprises all residual fuel oils (including those obtained by blending). Heavy fuel oil
constituents range from distillable constituents to residual (nondistillable) constituents that
must be heated to 260°C or more before they can be used. The kinematic viscosity is above
10 cst at 80°C. The flash point is always above 50°C and the density is always higher than
0.900. In general, heavy fuel oil usually contains cracked residua, reduced crude, or
cracking coil heavy product, which is mixed (cut back) to a specified viscosity with
cracked gas oils and fractionator bottoms.

6. Asphalt/ Bitumen
It is a sticky, black and highly viscous liquid or semi-solid form of petroleum. It may be
found in natural deposits or may be a refined product; it is a substance classed as a pitch.
Until the 20 th century. The primary use of asphalt/bitumen is in road construction, where it is
used as the glue or binder mixed with aggregate particles to create asphalt concrete. Its other
main uses are for waterproofing products, including production of roofing felt and for sealing
flat roofs.
Asphalt (or asphalt cement) is the carefully refined residue from the fractional
distillation of crude oil boiling at 525°C.

6.1 Compositions
Asphalt is the residue of mixed-base and asphalt-bas e cru de oils. It can not be distilled even
under the highest vacuum, because the temperatures required to do this promote formation of
coke. Asphalt have complex chemical and physical compositions that usually vary with the
Petroleum Refining Fourth Year Dr.Aysar T. Jarullah

source of the crude oil and are considered dispersions of particles, called asphaltenes, in a
high-boiling fluid composed of oil and resins.
Asphalt/bitumen can be separated from the other components in crude oil (such
as naphtha, gasoline and diesel) by the process of fractional distillation, usually
under vacuum conditions. A better separation can be achieved by further processing of the
heavier fractions of the crude oil in a de-asphalting unit, which uses
either propane or butane in a supercritical phase to dissolve the lighter molecules which are
then separated.

6.2 Properties and uses

Nowadays, a good portion of the asphalt produced from petroleum is consumed in paving
roads; the remainder is employ ed for roofing, paints , varnishes, insulating, rust-
protective compositions, battery boxes, and compounding material s that go into rubber
products, brake linings, and fuel briquettes. How ever, asphalt use s can be more popularly
divided into use as road oils, cutback asphalt, asphalt emulsions, and solid asphalt. The
properties of asphalt are defined by a variety of standard tests that can be used to define
quality and viscosity specifications.
Petroleum Refining Fourth Year Dr.Aysar T. Jarullah

6- Lubricating Oils
The remaining part at the bottom of the atmospheric distillation - above 350 0C is regarded
the source for base lubricating oils extraction via vacuum distillation in order to prevent
cracking process.

6.1 Compositions
Lubricating oil is distinguished from other fractions of crude oil by their usually high
(>400 0C) boiling point, as well as their high viscosity. Materials suit able for the
production of lubricating oils are comprised principally of hydrocarbons containing from 25
to 35 or even 40 carbon atoms per molecule. The composition of lubricating oil may be
substantially different from the lubricant fraction from which it was derive d, as wax (norm al
paraffins) is remove d by distillation or refining by solvent extraction and adsorption
preferentially removes non hydrocarbon constituents as well as poly nuclear aromatic
compounds and the multiringcyclo paraffins.

6.2 Manufacture
The production of lubricating oils is well established and consists of four basic processes: (1)
distillation to remove the lower-boiling and lower-molecular weight constituents of the
feedstock, (2) solvent refining, such as deasphalting, and hydrogen treatment to remove the
nonhydrocarbon constituents and to improve the feedstock quality, (3) dewaxing to remove
the wax constituents and improve the low-temperature properties, (4) and clay treatment or
hydrogen treatment to prevent instability of the product.

6.3 Properties
Lubricating oil may be divided into many categories according to the types of service they
are intended to perform. However, there are two main groups: (1) oils used in intermittent
service, such as motor and aviation oils, and (2) oils designed for continuous service, such as
turbine oils. This classification is based on the SAE (Society of Automotive Engineers) J 300
specification and shown in Table below. The single grade oils (e.g., SAE 20, etc.) correspond
to a single class and have to be selected according to engine manufacturer specifications,
operating conditions, and climatic conditions. At -20°C, a multigrade lubricating oil such as
SAE 10W -30 possesses the viscosity of a 10W oil and at 100°C, the multigrade oil possesses
the viscosity of a SAE 30 oil.
Petroleum Refining Fourth Year Dr.Aysar T. Jarullah

The main properties of lubricants, which are usually indicated in the technical characteristics
of the product, are:

Viscosity
 This indicates the resistance of a liquid to flow.
 Oil with higher viscosity can stand greater pressure without being squeezed out of the
lubricating surfaces. However, the high internal friction of the oil may offer greater
resistance to the movement of the lubricating parts. An oil of lower viscosity offers less
resistance to the moving parts but the oil can be easily squeezed out of the lubricating
surfaces. It is therefore important to select a lubricating oil of appropriate viscosity to
achieve optimum lubrication effect.
 Viscosity changes with temperature. Hence, the measuring temperature must be
specified whenever the viscosity of a liquid is stated. When temperature rises, a liquid
becomes less viscous. Similarly, a liquid becomes thicker when temperature drops.
 Viscosity Index (VI) is an indication of how the viscosity of a liquid varies with
temperature. A high VI means the liquid does not thin out so much when temperature
rises. VI improver additives that are usually high molecular weight polymers can
increase the VI of lubricating oil. Figure 26 below is used to find the V.I.
 Increase in oil viscosity achieved by addition of polymers can be partially lost again
through degradation of the polymer molecules by shear stress such as heavily loaded
gears. Oil that can resist viscosity change due to shear are said to have high shear
stability.

Fig. 26: Viscosity index

Petroleum Refining Fourth Year Dr.Aysar T. Jarullah

Pour Point
The pour point refers to the minimum temperature at which a lubricant continues to flow
when cooled. Below the pour point, the oil tends to thicken and to cease to flow freely.
There is term is called (zero %wax), which is the amount of oil that should be removed to
reach 0 °F. The following Table is used for this purpose (C.F is k).

The following Figure (27) is shown the relation between the V.I, k and the amount of wax
that should be removed.

Fig. 27: relation between the V.I, k and the amount of wax
Petroleum Refining Fourth Year Dr.Aysar T. Jarullah

Ex: Oil has B.P = 40 F and k=12.2. Find V.I?

Sol.
From Table above, the amount of wax = 8,
From Fig. above, V.I = 73.

Flash Point
The flash point is the minimum temperature at which vapours from lubricants mixed with air
and progressively heated in a standard laboratory receptacle, becomes inflammable. There is
a closed flashpoint (Penskin Martens) and an open flashpoint (Cleveland). In addition to
defining the limits of use and the precautions to be taken for moving or storage it is also
useful as an indication of possible contamination from fuels (which have lower flashpoints
than lubricants).

6.4 Additives
A large number of additives are used to impart performance characteristics to the lubricants.
The main families of additives are:

 Antioxidants
 Detergents
 Anti-wear
 Metal deactivators
 Corrosion inhibitors, Rust inhibitors
 Friction modifiers
 Extreme Pressure
 Anti-foaming agents
 Viscosity index improvers
 Demulsifying/Emulsifying
Petroleum Refining Fourth Year Dr.Aysar T. Jarullah

Product Blending
Refining processes do not generally produce commercially usable products directly, but
rather semi-finished products which must be blended in order to meet the specifications of the
demanded products. The main purpose of product blending is to find the best way of mixing
different intermediate products available from the refinery and some additives in order to
adjust the product specifications. For example, gasoline is produced by blending a number of
components that include alkylate, reformate, FCC gasoline and an oxygenated additive such
as methyl tertiary butyl ether (MTBE) to increase the octane number.

1- Reid Vapour Pressure Blending

RVP is the vapour pressure at 100 F of a product determined in a volume of air four times the
liquid volume. RVP is not an additive property. Therefore, RVP blending indices are used. A
commonly used RVP index is based on an empirical method, which is

……………………… (1)

where BI RVPi is the RVP blending index for component i and RVPi is the RVP of component
i in psi. Using the index, the RVP of a blend is estimated as

……………………… (2)

where xvi is the volume fraction of component i.

Petroleum Refining Fourth Year Dr.Aysar T. Jarullah

Additives, such as propane, i-butane and n-butane can be added to the gasoline blend to
adjust the RVP requirements. Example E9.2 illustrates how the amount of an additive is
calculated using the method of RVP index.
Petroleum Refining Fourth Year Dr.Aysar T. Jarullah

2- Flash Point Blending

If the flash point of a petroleum product does not meet the required specifications, it can be
adjusted by blending this product with other fractions. Flash point is not an additive property
and flash point blending indices are used, which blend linearly on a volume basis. The flash
point of a blend is determined using the following equation:

……………………(3)
where xvi is the volume fraction of component i, and BIFPi is the flash point index of
component i that can be determined from the following correlation

……………………(4)

FPi is the flash point temperature of component i, in K, and the best value of x is -0.06.
Another relation to estimate the flash point blending index is based on the flash point
experimental data

………….(5)

FPi is the flash point temperature of component i, in F. The flash point blending index is
blended based on wt% of components.
Petroleum Refining Fourth Year Dr.Aysar T. Jarullah
Petroleum Refining Fourth Year Dr.Aysar T. Jarullah

3- Pour Point Blending

The pour point is the lowest temperature at which oil can be stored and still capable of
flowing or pouring, when it is cooled without stirring under standard cooling conditions. Pour
point is not an additive property and pour point blending indices are used, which blend
linearly on a volume basis. The pour point of a blend is determined using the following
equation:

……………………(6)
where xvi is the volume fraction of component i, and BIPPi is the pour point index of
component i that can be determined from the following correlation

……………………(7)
where PPi is the pour point of component i, in °R. The pour point of the product, PP Blend ,
is then evaluated using the reverse form of equation (7).
Another relation to estimate the pour point blending index is the same formula for the flash
point with different value of the exponent:

………………………(8)
PPi is the pour point temperature of component i, in K, and the best value of x is 0.08.
Petroleum Refining Fourth Year Dr.Aysar T. Jarullah

4- Aniline Point Blending

The aniline point indicates the degree of aromaticity of a petroleum fraction. It is the
minimum temperature at which equal volumes of the aniline and the oil are completely
miscible. Aniline point is not an additive property, and aniline point blending indices are
used, which blend linearly on a volume basis. The aniline point of a blend is determined
using the following formula:

…………………….(9)

where xvi is the volume fraction of component i, and BIAPi is the aniline point index of
component i that can be determined from the following correlation

…………………(10)
APi is the aniline point of component i, in °C

5- Viscosity Blending
Viscosity is not an additive property; therefore, viscosity blending indices are used to
determine the viscosity of the blended products. A number of correlations and tables are
available for evaluating the viscosity indices. The viscosity index of the blended product is
determined using the following equation:
Petroleum Refining Fourth Year Dr.Aysar T. Jarullah

…………………………(11)

where xvi is the volume fraction of component i, and BIvisi is the viscosityvindex of
component i that can be determined using the following correlation

…………………………..(12)

where vi is the viscosity of component i, in cSt.

The viscosity of the blended product is then calculated using

……………………..(13)

6- Gasoline Octane Number Blending

If the octane number of a blend is calculated by the linear addition of an octane number for
each component, the following equation can be obtained:

…………………(14)

Where xvi is the volume fraction of component i, and ONi is the octane number of comp. i.
Petroleum Refining Fourth Year Dr.Aysar T. Jarullah

Many alternative methods have been proposed for estimating the octane number of gasoline
blends since the simple mixing rule needs minor corrections. The following octane index
correlations depend on the octane number range as follows:

(15)

(16)

(17)

(18)

where xvi is the volume fraction of component i, and BIONi is the octane number index of
component i that can be determined from equation (15, 16, 17).

(14)
Petroleum Refining Fourth Year Dr.Aysar T. Jarullah

To solve for RONBlend, equation (16) is solved for RON, when IRON equals 60.98. The
resulted RONBlend is 88.09.

(18)

Depending on the availability of olefin and aromatic contents in the blended components, the
octane number of the blend can be calculated using the linear mixing rule method with a
correction

(19)

(20)
Petroleum Refining Fourth Year Dr.Aysar T. Jarullah

(a) Calculate the RON and MON for the blend using equation (19) and (20), then compare
with the reported experimental value.
(b) Calculate the RON of the blend using the blending index method (equations (15-19)) and
compare with the reported experimental value.
Petroleum Refining Fourth Year Dr.Aysar T. Jarullah
Petroleum Refining Fourth Year Dr.Aysar T. Jarullah

Safety and Environmental Aspects in Refining

The evolution of petroleum refining from simple distillation to today’s sophisticated
processes has created a need for environmental, health and safety management procedures
and safe work practices. The safe processing of crude oil into flammable gases and liquids at
high temperatures and pressures using vessels, equipment and piping requires considerable
control technologies to avoid damage to the environment. Environment andhealth
professionals assure that potential physical, mechanical, chemical and health hazards are
recognized and therefore, provisions are made for safe operating practices and appropriate
protective measures. These procedures should be established to assure compliance with
applicable regulations and standards such as hazard communications, emission rates
regulations, waste management and waste minimization.

1-Air Quality
In the 1970s and 1980s, environmental laws compelled refineries to reduce emissions of SOx,
NOx, CO2, and hydrocarbons. In the atmosphere, SOx reacts with water vapor to make
sulfurous and sulfuric acids, which return to earth as acid rain. Volatile hydrocarbons react
with NOx to make ozone. CO2 is a major “green-house” gas. To reduce these pollutants, the
industry tightened its operation by:

• Reducing fugitive hydrocarbon emissions from valves and fittings

• Removing sulfur from refinery streams and finished products
• Adding tail-gas units to sulfur recovery plants
• Reducing the production of NOx in fired heaters
• Scrubbing SOx and NOx from flue gases
• Reducing the production of CO2 by increasing energy efficiency

1.1 Sulfur Recovery

Conversion processes, hydrotreaters, and sweetening units remove chemically bound
sulfur from petroleum fractions. That’s a good thing, but where does the sulfur go? The
answer depends upon the form in which it is produced.
SOx Abatement. Fuel-oil fired heaters and the regenerators of FCC units are major sources
of refinery SOx and NOx emissions. The most obvious way to reduce SOx emissions
from a heater is to use low-sulfur fuels. Unfortunately, although that solution
requires no investment, it is probably the most expensive due to the relatively high cost of
buying low-sulfur fuel oil or hydrotreating high-sulfur fuel oil. A large fraction of the sulfur
in the feed to an FCC unit ends up in coke on the catalyst. SOx is formed in the regenerator
when the coke is burned away. Therefore, removing sulfur from the feed decreases SOx
emissions. As stated previously, using a hydrotreater or hydrocracker for feed HDS
eliminates or minimizes the cost of post-FCC desulfurization equipment. Removing basic
nitrogen decreases deactivation of acid sites on the FCC catalyst, which allows the
FCC to reach a given conversion at lower temperatures. The saturation of aromatics in
the feed pretreater provides the biggest benefit, because it converts hard-to-crack aromatics
into easier-to-crack naphthenes. This alone can justify the installation of an FCC feed
pretreater. Therefore, in addition to abating SOx, hydrotreating the feed to an FCC can
generate a substantial return.

SOx Transfer Additives. Arguably, SOx transfer additives are the most cost-effective
way to lower SOx emissions in an FCC unit. These materials, first developed by Davison
Petroleum Refining Fourth Year Dr.Aysar T. Jarullah

Chemical, react with SOx in the FCC regenerator to form sulfates. When the sulfated
additive circulates to the riser/reactor section, the sulfate is reduced to H2S, which is
recovered by amine absorption and sent to the sulfur plant. In some units, these additives
reduce FCC SOx emissions by more than 70%. Consequently, if a pre-treater or post-treater
still must be installed, its size can be reduced.

Flue-Gas (Stack-Gas) Scrubbing. Flue-gas scrubbing is a refiner’s last chance to keep NOx
and SOx out of the air. In wet flue-gas desulfurization, gas streams containing SOx react with
an aqueous slurry containing calcium hydroxide Ca(OH)2 and calcium carbonate CaCO3 .
Reaction products include calcium sulfite (CaSO3) and calcium sulfate (CaSO4), which
precipitate from the solution.
NOx removal is more difficult. Wet flue-gas scrubbing removes about 20% of the NOx from
a typical FCC flue gas. To remove the rest, chemical reducing agents are used. In the
Selective Catalytic Reduction (SCR) process, anhydrous ammonia is injected into the flue gas
as it passes through a bed of catalyst at 500 to 950°F (260 to 510°C). The chemical reaction
between NOx and ammonia produces N2 and H2O.

Hydrogen Sulfide Removal. When sulfur-containing feeds pass through hydrotreaters or

conversion units, some or most of the sulfur is converted into H2S, which eventually ends up
in off-gas streams. Amine absorbers remove the H2S, leaving only 10 to 20 wppm in the
treated gas streams. H2S is steam-stripped from the amines, which are returned to the
absorbers. The H2S goes to the refinery sulfur plant.

2.1 Waste Water Treatment

Waste water treatment is used to purify process water, runoff, and sewage. As much as
possible, purified waste-water steams are re-used in the refinery. Wastewater streams may
contain suspended solids, dissolved salts, phenols, ammonia, sulfides, and other compounds.
The streams come from just about every process unit, especially those that use wash water,
condensate, stripping water, caustic, or neutralization acids.

2.1.1 Primary Treatment

Primary treatment uses a settling pond to allow most hydrocarbons and suspended
solids to separate from the wastewater. The solids drift to the bottom of the pond,
hydrocarbons are skimmed off the top, and oily sludge is removed. Difficult oil-in-water
emulsions are heated to expedite separation. Acidic wastewater is neutralized with
ammonia, lime, or sodium carbonate. Alkaline wastewater is treated with sulfuric acid,
hydrochloric acid, carbon dioxide-rich flue gas, or sulfur.

2.1.2 Secondary Treatment

Some suspended solids remain in the water after primary treatment. These are removed by
filtration, sedimentation or air flotation. Flocculation agents may be added to consolidate
the solids, making them easier to remove by sedimentation or filtration. Activated
sludge is used to digest water-soluble organic compounds, either in aerated or anaerobic
lagoons. Steam-stripping is used to remove sulfides and/or ammonia, and solvent
extraction is used to remove phenols.

2.1.3 Tertiary Treatment

Tertiary treatment processes remove specific pollutants, including traces of benzene and other
partially soluble hydrocarbons. Tertiary water treatment can include ion exchange,
Petroleum Refining Fourth Year Dr.Aysar T. Jarullah

chlorination, ozonation, reverse osmosis, or adsorption onto activated carbon. Compressed

oxygen may be used to enhance oxidation. Spraying the water into the air or bubbling air
through the water removes remaining traces of volatile chemicals such as phenol and
ammonia.

3.3 Solid Waste

Refinery solid wastes may include the following materials:
• Spent catalyst and catalyst fines
• Acid sludge from alkylation units
• Miscellaneous oil-contaminated solids
All oil-contaminated solids are treated as hazardous and sent to sanitary landfills.
Recently, super-critical extraction with carbon dioxide has been used with great success to
remove oil from contaminated dirt.

Wastes in Refinery Units

1- Desalter
Hydrogen sulphide is emitted to a atmosphere from the desalter when treating sour crude.
Demulsifiers and other chemicals, which are used in the pretreatment process, are considered
chemical hazards either during processing or in disposal. Safe material handling will
minimize human exposure to these chemicals. The wash water from the desalter unit contains
a large amount of chlorides, sulphides, ammonia, hydrocarbons and suspended solids. The
best practices should be followed to deal with this hazardous waste.

2- Crude Distillation
Low boiling point hydrocarbons can escape to the atmosphere from the leaky connections
during distillation. Hydrogen sulphide is emitted when sour crude is processed. Wastewater
contains soluble hydrocarbons, mercaptans, antifoam and anticorrosion additives.

3- Catalytic Reforming and Isomerization

Benzene is one of the most carcinogenic compounds that may be formed in an undesired
reaction in catalytic reforming. Small emissions of carbon monoxide and hydrogen sulphide
may occur during regeneration of a catalyst. Appropriate catalyst handling will prevent dust
emissions during loading. In isomerization, there is a potential for exposure to hydrogen gas,
hydrochloric acid, and hydrogen chloride and to dust when solid catalyst is used.

4- Thermal Cracking and Coking

In delayed coking units, the main point sources for air quality concerns are the coker furnace
stack emissions and the flare system where off gas is rejected from the unit and burned.
Complete combustion in both the furnace and the flare assures minimum hydrocarbon
emissions to the atmosphere. To reduce furnace stack emissions, it is important to operate
coker furnaces at optimum conditions; installing air pre-heaters and advanced process
controls can increase the overall furnace efficiency. Water, which is used for cooling, is
considered waste since it contains coke and hydrocarbons. Wastewater may be highly
alkaline and contain oil, sulphides, ammonia, and/or phenol. Large quantities of water are
Petroleum Refining Fourth Year Dr.Aysar T. Jarullah

used during coke drum cleaning. Coke handling and dewatering operations use the optimum
water quantities to reduce water pollution. Typically, all coke handling water is recycled
within the unit.

5- Hydrocracking
Low boiling point hydrocarbons, hydrogen and hydrogen sulphide can leak during
hydrocracking. Improper catalyst regeneration may lead to carbon monoxide and
hydrocarbon emissions. Steam stripping and regeneration of the catalyst create waste streams
containing sour water and ammonia.

6- Hydrotreating
Hydrogen sulphide and ammonia are hazardous emissions that are released into the
atmosphere during hydrotreating. The hydrogen required in hydrotreating reactions should be
handled with care to avoid explosions.

7- Fluid Catalytic Cracking (FCC)

Catalyst regeneration produces emissions to the atmosphere upon burning the deposited coke.
When the catalyst is stripped with steam, condensate is produced that needs to be treated
before disposing since it contains heavy metals such as nickel and vanadium. Carbon
monoxide (CO) results from the incomplete combustion of coke in the regenerator.
Combustion promoters with a noble metal base (Pd or Pt) are added to the catalyst.
Particulate matters emissions are controlled by applying more resistant catalyst and improve
cyclone designs as well as installing third stage cyclone, electrostatic precipitations and wet
scrubbers downstream from the FCC regenerator.

8- Alkylation
Sulphuric acid and hydrofluoric acid are potentially hazardous chemicals. Material handling
should be based on available material safety data sheets for both acids. Water contamination
with these acids is hazardous and may lead to an explosion. Furthermore, appropriate skin
and respiratory personal protective equipment is needed for potential exposure to liquid
spillage of the acids.

9-Asphalt Production, Solvent Extraction and Dewaxing

Phenol, amines and other solvents used in deasphalting processes are considered hazardous
chemicals. If a spill or release occurs, there is a potential for exposure to residues and asphalt.
The potential for exposure to hydrogen sulphide and sulphur dioxide exists in the production
of asphalt. Solid waste effluent should be treated with care since it contains large quantities of
hazardous chemicals.

Fugitive Emissions
Valves, flanges and fittings can emit hydrocarbons into the atmosphere. These emissions are
usually the result of improper fit, wear and tear, and corrosion. The hydrocarbon emissions
can be estimated for existing facilities using a factor that is multiplied by the number of
active equipment pieces. Generally, fugitive emissions are less than 1% of the total emissions
from tanks and flares. Where no screening values are available for particular equipment
types, average emission factors should be used. This methodology involves applying the
following equation to estimate emissions from all sources in a stream:
Petroleum Refining Fourth Year Dr.Aysar T. Jarullah

where EVOC is the emission rate of VOC from all sources in kg/year, FA is the applicable
average emission factor, WFVOC is the average weight fraction of VOC in the stream, and N
is the number of pieces of equipment grouped in the relevant category according to weight
fraction of VOC. The following steps for fugitive emission calculation are:
1. Develop an inventory of the number and type of fugitive sources: The number and
service type of each equipment in the refinery must be determined.
2. Group the inventory into streams: To simplify calculations, it is recommended that the
equipment/service mode combinations identified in Step 1 (i.e. valves in gas service) be
grouped into streams according to the approximate weight fraction of VOC in each stream.
3. Note operational hours: The number of operational hours needs to be estimated.
4. Use emission factors to estimate emission rates: Use the relevant emission factors and the
equation given above to calculate the emissions from each equipment type. These emissions
should then be added to derive a total emission rate for all equipment pieces quantified using
this methodology.
Table below presents the emission factors required to estimate emissions using the steps
discussed above.

Example
In the calculations of fugitive emissions from a refinery site, the following inventory steps are
carried out:
1. A particular section of a refinery has a count of 300 valves (Step 1)
2. It is ascertained that 200 of these are in gas service (Step 1)
3. Within these valves in gas service, it is ascertained that 100 (N =100) valves are with 80
wt% (non-methane hydrocarbons) (WFVOC = 0.8) and 20 wt% methane. Therefore, the rest
of the valves do not emit any VOCs and will not be included (Step 2)
4. It is estimated that this group of valves operates for 5500 h/year (Step 3)
5. The appropriate emission factor for valves in gas service is FA = 0.0268 kg/h/source
(from Table above) (Step 4). Calculate the emission rate of VOC.
Petroleum Refining Fourth Year Dr.Aysar T. Jarullah

Solution:
The final emission estimate for the group of 100 valves specified above is calculated from
equation above
EVOC = (0.0268) (0.8) (100) (5500) = 11,790 kg VOC/year.

Emission Estimation
Mass balance involves the quantification of total materials into and out of a process. The
differences between their inputs and outputs are accounted for in terms of releases to the
environment or as part of the facility waste. Mass balance is particularly useful when the
input and output streams can be quantified, and this is most often the case for individual
process units and operations.
In general, emission factors are developed for emission rate estimation. The emission rate is
calculated by multiplying the emission factor by the flow rate of the activity. The formula is

Table below lists typical emission factors for refinery units.

Petroleum Refining Fourth Year Dr.Aysar T. Jarullah