oil refinary dr adndn 2016-مهمة PDF

Fourth Year - Chemical Process Eng.
Branch
Petroleum Refinery Eng. Lectures
By
Dr. Adnan A. Abdul Razak
Petroleum Processing Overview
 Actually, crude oil straight from the ground has some
value, but not a lot.
Table 1 shows the history of petroleum before 1861.
 Before 1859, oil that was mined or that simply seeped
up out of the ground was used to water-proof ships, as an
adhesive in construction, for flaming projectiles, and in a
wide variety of ointments.
 After 1859, petroleum became more and more important
to the world’s economy, so important that today, without a
steady flow of oil.
It provides fuels and lubricants for our trucks, trains,
airplanes, and automobiles. Ships are powered by fuel oil
derived from petroleum. Bottom-of-the-barrel petroleum
derivatives pave our roads and provide coke for the steel
industry.
 At the end of 2003, the world was consuming 78 million
barrels of oil per day.
In August 2005, that volume of petroleum was worth $4.6
billion per day, or $1.7 trillion per year.
The availability of kerosene got a sudden boost on
August 27, 1859, when Edwin L. Drake struck oil with the
well he was drilling near Titusville, Pennsylvania.
History of Petroleum Processing
Modern Petroleum Processing
All refineries are different.
Oil refining separates everything into useful substances.
The petroleum refining industry converts crude oil into
more than 2500 refined products, including liquefied
petroleum gas, gasoline, kerosene, aviation fuel, diesel
fuel, fuel oil, lubricating oil and petrochemical industry
feedstock.
Most refineries perform the seven basic operations
named
Petroleum Refinery Feed-Stocks and Products
• What is Petroleum or Crude Oil?
–Petroleum (Latin Petroleum derived from Greek πέτρα (Latin petra) - rock + έλαιον
(Latin oleum ) - oil) or crude oil is a naturally occurring liquid found in formations in
the earth consisting of a complex mixture of hydrocarbons (mostly alkanes) of various
lengths
– The approximate length range is C5H12 to C18H38. Any shorter hydrocarbons are
considered natural gas or natural gas liquids, while long-chain hydrocarbons are
more viscous, and the longest chains are paraffin wax.
–In its naturally occurring form, it may contain other nonmetallic elements such as
sulfur,
oxygen, and nitrogen.
–Crude oil vary from light coloured volatile liquids to thick, dark oils-so viscous that
difficult to pump.
– To use the different parts of the mixture, they must be separated – refining.
• What is natural gas?

– A mixtures of hydrocarbons with small molecules.
– These molecules are made of atoms of C and H i.e. CH4.
• Why are oil and gas so useful?
– Oil is a liquid. Meaning that oil may be transported and delivered through pipes.
– Compare oil to coal-coal is a solid, which comes in lumps. To get it, miners have to work
underground.
– HC with small molecules makes good fuels. Methane (smallest molecules, gas) used for
cooking, heating and generating electricity. Gasoline, diesel, jet fuel and fuel oil are all
liquid fuels.
– HC molecules can be split up into small ones, built up into bigger ones, altered in shape or
modified by adding other atoms.
– Even the thick black tarry residue left after distillation is useful – bitumen (for road
surfacing and roofing).
• Due to its
􀂃􀂃 high energy density
􀂃􀂃 easy transportability
􀂃􀂃 relative abundance
It has become the world's most important source of energy since the mid-1950s. Petroleum is
also the raw material for many chemical products, including pharmaceuticals, solvents,
fertilizers, pesticides, and plastics; the 16% not used for energy production is converted into
these other
materials.
Origin of Petroleum
Theories broadly classified into non-biogenic & biogenic :
• Non-biogenic : from inorganic sources
Metal carbides + H2O…..> Hydrocarbons
CaCO3 --->CaC2--->Acetylene--->Petroleum hydrocarbons
Reaction of CO2, in presence of alkali and alkaline earth metals, with water is also
postulated to form hydrocarbons
Theory did not receive much recognition
•Biogenic : from organics, by bacterial transformation :

Organic matter (carbohydrates/proteins//lipid/ ligninboth from plant & animal origin
-------->Decay in presence and/or absence of air into HC rich sediments which in
presence of micro organism undergoes biological/physical and chemical alterations
to form Kerogen (geopolymer) which may be coaly or sapropelic
Sapropelic Kerogen under high pressure and temperature further gets converted into
Oil & Gas.
Widely accepted theory
Formation of Oil and Gas
• Where have crude oil and natural gas come from?

Accumulation of Oil and Gas
• The oil, gas, and salt water occupied the pore spaces between the grains of the
sandstones.
• Whenever these rocks were sealed by a layer of impermeable rock, the cap rock, the
petroleum accumulating within the pore spaces of the source rock was trapped and
formed the petroleum reservoir.
Fourth Year - Chemical Process Eng. Branch
By
Refinery Feedstocks and
Products
Chemical Composition of Petroleum
 Petroleum is a mixture of hundreds of hydrocarbons of all type with
water, salts, sulfur and nitrogen containing compounds and some metal
complexes.
The elementary composition of crude oil usually falls within the following
Table 2.1 Elemental composition of crude oils
ranges.
The proportion of hydrocarbons in the mixture is highly variable and

ranges from as much as 97% by weight in the lighter oils to as little as
50% in the heavier oils and bitumens.
Four different types of hydrocarbon molecules appear in crude oil. The
relative percentage of each varies from oil to oil, determining the
Paraffins
The paraffin series of hydrocarbons is characterized by the rule that the
carbon atoms are connected by a single bond and the other bonds are
saturated with hydrogen atoms. The general formula for paraffins is
CnH2n+2. The simplest paraffin is methane, CH4, followed by the
homologous series of ethane, propane, normal and isobutane, normal,
iso-, and neopentane, etc. (Fig. 1).
Figure( 1 ) Paraffins in crude oil.

 Saturated alkanes: (n-alkane and i-alkane)
 General formula CnH2n+2
 Boiling point and density increase with increasing no. of C atoms.
 Branched alkanes (iso-alkanes) is very small in quantity
 Boiling point of straight chains > iso-alkanes with the same # of C
Naphthenes or cycloparaffins
Cycloparaffin hydrocarbons in which all of the available bonds of the
carbon atoms are saturated with hydrogen are called naphthenes. Typical
examples of these are cyclopentane, cyclohexane, etc. (Figure 2). General
formula CnH2n for one ring compounds
Figure 2: Naphthene compounds

Aromatics
The aromatic series of hydrocarbons is chemically and physically very
different from the paraffins and cycloparaffins (naphthenes). Aromatic
hydrocarbons contain a benzene ring which is unsaturated but very stable
and frequently behaves as a saturated compound. Some typical aromatic
compounds are shown in (Figure 3).
Figure 3: Aromatic compounds

Olefins
Olefins do not naturally occur in crude oils. However, they are formed during its
processing. They are very similar to paraffins, but they exhibit double bonds,
usually one per molecule (Figure 4), although some di-olefins (two double
bonds in the same molecule, ( Figure 5) can be found.
Figure 4: Olefin compounds
Figure 5: Di-olefin compounds

Sulfur Compound
(might be present in inorganic and organic forms)
 (hydrogen sulfide, sulfides, disulfides, elemental sulfur).
 Each crude oil has different amounts and types of sulfur
compounds (sulfur concentration can range from 0.1 to more than 8
weight percent ), but as a rule the proportion, stability, and complexity
of the compounds are greater in heavier crude-oil fractions.
 Hydrogen sulfide is a primary contributor to corrosion in refinery
processing units. Other corrosive substances are elemental sulfur
and mercaptans.
Moreover, the corrosive sulfur compounds have an obnoxious
odor.
The combustion of petroleum products containing sulfur compounds
produces undesirables such as sulfuric acid and sulfur dioxide.
 Catalytic hydrotreating processes such as hydrodesulfurization
remove sulfur compounds from refinery product streams.
 Sweetening processes either remove the obnoxious sulfur
compounds or convert them to odorless disulfides, as in the case of
mercaptans.
Oxygen Compounds
 less than 1% (found in organic compounds
such as carbon dioxide, phenols, ketones,
carboxylic acids)
Carboxylic (OH-C=O bonded to a benzene ring)
Phenolic (OH bonded to a benzene ring)
 Oxygen compounds are responsible for petroleum
acidity
Nitrogen Compounds
 less than 1% (basic compounds with amine groups)
 carbazole (2 benzene rings separated by 1 N atom) – neutral
Quinoline (2 benzene rings with 1 N atom on 1 ring) – basic
 Nitrogen oxides can form in process furnaces. The
decomposition of nitrogen compounds in catalytic cracking
and hydrocracking processes forms ammonia and cyanides
that can cause corrosion.
Metals
 less than 1% (nickel, iron, vanadium, copper,
arsenic)
 Often found in crude oils in small quantities and are
removed during the refining process.
 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.
Salts
 less than 1% (sodium chloride, magnesium chloride, calcium
chloride.
 Crude oils often contain inorganic salts such as sodium
chloride, magnesium chloride, and calcium chloride in
suspension or dissolved in entrained water (brine).
 These salts must be removed or neutralized before
processing to prevent catalyst poisoning, equipment
corrosion, and fouling.
 Salt corrosion is caused by the hydrolysis of some metal
chlorides to hydrogen chloride (HCl) and the subsequent
formation of hydrochloric acid when crude is heated.
 Hydrogen chloride may also combine with ammonia to form
ammonium chloride (NH4Cl), which causes fouling and
corrosion.
Naphthenic Acids
 Some crude oils contain naphthenic (organic)
acids, which may become corrosive at
temperatures above 450° F when the acid value of
the crude is above a certain level.
Basic products:
Petroleum refineries are large, capital-intensive manufacturing facilities with
extremely complex processing schemes. They convert crude oils and other
input streams into dozens of refined (co-)products, including: The basic
products from fractional distillation are:
 Liquid 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 (liquified petroleum gas)
Gasoline - motor fuel:
 Its main use is as fuel for internal
combustion engines.
 Liquid
 Mix of alkanes and cycloalkanes (5 to 7
carbon atoms)
 Boiling range = 90-220 degrees Fahrenheit
/ 27-93 degrees Celsius
 Naphtha :
 Intermediate that will be further processed
to make gasoline
Mix of 6 to 10 carbon atom alkanes
Boiling range = 220-315 degrees Fahrenheit
/ 93-177 degrees Celsius
 Kerosene :
 Used for heating, 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
Gas oil or Diesel distillate:
 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
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
Heavy gas or 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
Residuals :
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
Fourth Year - Chemical Process Eng. Branch
By
Thermo-physical Properties of Petroleum
Fractions and Crude Oils
Classification of Petroleum
 Objective of Crude Oil Characterisation / Crude
Assay
 Marketing / Pricing of Crude Oil

 Transportation of Crude Oil
 Design of Grass Root Refinery
 Processing of a new crude oil in an operating
Refinery
 Expansion / Modification of an operating Refinery –
Primary / Secondary operations
 Optimization of the product yields
 Value Addition
The petroleum industry generally classifies crude oil
By the geographic location it is

produced in (e.g. West Texas,
Brent, or Oman),
Its API gravity (an oil industry
measure of density), and
By its sulfur content.
According to Location
 West Texas Intermediate (WTI), a very high-quality, sweet,
light
oil delivered at Cushing, Oklahoma for North American oil
 Brent Blend, comprising 15 oils from fields in the Brent and
Ninian systems in the East Shetland Basin of the North Sea.
The oil is landed at Sullom Voe terminal in the Shetlands. Oil
production
from Europe, Africa and Middle Eastern oil flowing West tends
to
be priced off the price of this oil, which forms a benchmark
 Dubai-Oman, used as benchmark for Middle East sour crude
oil
flowing to the Asia-Pacific region
 Tapis (from Malaysia, used as a reference for light Far East
oil)
 Minas (from Indonesia, used as a reference for heavy Far
East oil)
 The OPEC Reference Basket, a weighted average of oil
blends
According “ API” Gravity
Specific gravity and API (American Petroleum Institute) gravity
are expressions of the density or weight of a unit volume of
material.
The specific gravity is the ratio of the weight of a unit volume of
oil to the weight of the same volume of water at a standard; both
specific gravity and API gravity refer to these constants at 60
⁰F(16 ⁰ C).
141.5
API = − 131.5 Sp . gr . =
141.5
Sp.gr.
API . + 131.5
• Light Crude Oil >31

• Mixed Based 22-31
• Heavy crude<22
API is a major factor for Crude pricing
According to Sulfur Content
 Crude oil naturally contains sulfur compounds.
 Crudes are classed as sweet or sour depending
on their sulfur content.
 If a crude has less than 0.5% sulfur in it, it is
considered to be "sweet".
 If has greater than 2.5% sulfur, it is "sour".
 A crude with a sulfur content between these two
endpoints is called "intermediate".
Light crude oil is more desirable than heavy oil
since it produces a higher yield of gasoline,
While sweet oil commands a higher price than
sour oil because it has fewer environmental
problems
and requires less refining to meet sulfur standards
imposed on fuels in consuming countries.
According to types of hydrocarbons ( parafffins , naphthenes ,
and aromatics).
This rating is important to the refinery since the value of the crude
oil decreases from classification 1 to 6
Crude Classifications (in order of decreasing value):
1) Paraffinic Crudes
• paraffins + naphthenes > 50%
• paraffins > naphthenes
• paraffins > 40%
2) Naphthenic Crudes
• paraffins + naphthenes >50%
• naphthenes > paraffins
• naphthenes >40%
3) Paraffinic – Naphthinic Crudes
• aromatics < 50%
• paraffins < 40%
• naphthenes < 40%
4) Aromatic – Naphthenic Crudes
• aromatics > 50%
5) Aromatic - Intermediate Crudes
• aromatics > 50%
• paraffins >10%
6) Aromatic – Asphaltic Crudes
• naphthenes > 25%
• paraffins < 10%
Quantitative Basis
Approach based on determining the base of a crude oil by one of the
following methods :
i) US Bureau of Mines Classification based on degree API:
Key Fraction Boiling point Pressure API Note
No. 1 482-527 atm. > 40 (Paraffinic Base)

33<API >40 (Intermediate
Base)
API < 33 (Napthene Base)
No. 2 527-572 (40-mm)Hg > 30 (Paraffinic Base) The presence of

733-779 1 atm API < 22 (Napthene Base) wax is noted by
22<API<30 (Intermediate cloud point (if
Base) below 5) it
indicates little wax
(Wax-free)
Characterization Factor: (C.F), (K)
The most widely used index is characterization factor (Watson,

Nelson and Murphy).
It was originally defined as:
3 TMABP
K =
sp.gr
In which:
TMABP is the molal average boiling point ( R)
Sp. gr. : is the specific gravity at 60 0F
It has since related to viscosity, aniline, temperature, molecular
weight, critical temperature, percentage of hydrocarbon etc.
K≥ 12.15 (Paraffinic Base)

K< 11.5 (Napthene Base)
K between 11.5-12.15 (Intermediate Base)
ii) Bureau of Mines Correlation Index (BMCI):
Like (C.F) related to boiling point and gravity
48640
C .I = + 473.7 sp.gr − 456.8
TMABP
The correlation index is useful in evaluating individual fractions from

crude oils.
 The CI scale is based upon straight-chain paraffins having a CI value
of 0 and benzene having a CI value of 100.
 The CI values are not quantitative, but the lower the CI value, the
greater the concentrations of paraffin hydrocarbons in the fraction;
 and the higher the CI value, the greater the concentrations of
naphthenes and aromatics.
Analysis of Crude Petroleum
When a refining company evaluate its own crude
oils to determine the most desirable processing
sequence to obtain the required products,
 Its own laboratories will provide data concerning
the distillation and processing of the oil and its
fractions.
The first step in refinery is distillation in which the
crude oil separated into fractions according to its
boiling point.
There are at least three types of distillation curves
or ways of relating vapor temperature and
percentage vaporized.
1. True-boiling-point (T.B.P)
2. Equilibrium or Flash Vaporization (EFV)
3. ASTM or no fractionating distillation
1. True-boiling-point (T.B.P)
 Fractional, run only on crude oil, batch . Fig (4.7)

 This test enlightens the refiners with
1. All possible information regarding the percentage quantum of
fractions,
2. Base of crude oil and
3. The possible difficulties beset during treatment operation etc.
 Distillation characteristics of a crude are assessed performing a
preliminary distillation called "True Boiling Point" analysis (TBP).
 True boiling point (TBP) and gravity-mid percent curves can be
developed:
 The first is the portion of the distillation at atmospheric pressure and
up to 527 0F (275 0C) end point, the second at 40 mm Hg total
pressure to 572 0F (300 0C) end point. Table (1)
 The distillation temperatures reported in the analysis be corrected to
760 mm Hg pressure , by use of chart Fig. (1)
 The gravity mid- percent curve is plotted on the same chart with
TBP. Fig .(3)
Table (1) U.S Bureau of Mines crude petroleum analysis (From Gary and Handwerk, 2001)
Figure (1) Boling point at 760 mmHg versus boiling point at 40mmHg (From Gary and Handwerk,
2001)
2. Equilibrium or Flash Vaporization (EFV).
The feed material is heated as it flows continuously through a heating
coil.
As vapor is formed it kept cohesively with liquid at some temperature and
a sudden release of pressure quickly flashes or separates the vapor from
the mixture without any rectification.
By successive flash evaporation like this the stock can be progressively
distilled at different increasing temperatures. a curve of percentage
vaporized vs. temperature may be plotted.
Travels along in the tube with remaining liquid until separation is
permitted in a vapor separator or vaporizer.
 By conducting the operation at a series of outlet temperature, a curve of
percentage vaporized vs. temperature may be plotted.
3. ASTM or no fractionating distillation:
(no fractional , run on fractions) .
It is supposed to be like EFV, a non fractionating distillation system.
It is a simple distillation carried out with standard ASTM flasks
100,200,500 ml flasks.
The data obtained is similar to TBP data
Fractionation column like (IP24 or D86).

TBP, EFV and ASTM curves for a 39.7 degree API
distillate
Calculation of (K) (Characterization Factor) for The Whole Crude
1. Calculate the TVABP using 20, 50, and 80 volume % TBP temperature.
2. Calculate the 10 to 70% slope of the whole curve.
3. Using a proper correction factor, convert TVABP to TMABP. (or some
time given ):
(TMABP=TVABP-ΔT)
4. Constract a spg mid percent curve and evaluate the spg for the whole
crude.
5. K is found as a function of TMABP and sp. gr.
Conversion between ASTM and TBP Distillation
The following equation suggested by Riazi and Daubert
where a and b are constants varying with percent of liquid sample distilled as
given in Table 3
TBP is true boiling point temperatures at 0, 10, 30, 50, 70, 90, and 95 volume
percent distilled, in degrees Rankin.
ASTM D86 isthe observed ASTM D86 temperatures at corresponding volume
percent
distilled, in degrees Rankin.
Table 3
Exampl
e
Solution
Application of the API method is straightforward using equation (3) and the
constants in Table 3
As can be seen from Figure E3.1, the
TBP distillation curve is below the ASTM
curve at volume distilled below 50% and
above it for volume distilled above 50%.
Distillation Fractions: All the components that boil between the two
specified temperature which called the cut point
Cut Point
Each fraction has an IBP and EP on ASTM curve because of un efficient
fractionation the IBP of heavier fraction is interrelated with the EP of lighter
fraction.
Figure 4: Cut points and end points.
H.W (1): 4000 BPD of (35 0 API) crude oil having the given TBP
data is available.
TBP ⁰F % vol. Distilled 0API % Sulfur
۸٥ ۱ ۱۱۰ -
۱۸۰ ۱۳ ٦۳ -
۳۸٥ ۳۰ ٤۹ 0.1
٥۱۰ ٥۰ ۳۸ 0.3
٦۲۰ ٦۳ ۲۳ 0.5
۷٥۰ ۷۳ ۲۰ 0.8
۱۰۰۰ ۸٤ ۱۷ 1.5
۱۰۰۰+ ۱۰۰ ۱۱ 2.3
a) Draw an assay curve.

b) Evaluate the given crude ; TMABP=TVABP- 120 ( 0 F )
c) Select TBP cut temperature for the products to be obtained from
distilling this crude and estimate their yields.
H.W (2) : For the given crude oil (35.5 0 API) ;
a) Evaluate the given oil.
b) Select TBP cut points for the products to be obtained from
processing this crude in an atmospheric distillation unit and
estimate the %yield for each cut.
% vol. Distilled TBP (⁰F ) API %S

0 40 --- ---
20 200 40 0.1
40 280 35 0.18
60 330 30 0.25
80 410 26 0.42
90 500 25 0.68
95 520 20 0.8
H.W (3) : For the given crude oil (31.7 0 API ),sulfur percent 0.15 ;
a) Evaluate the given oil.
b) Select TBP cut points for the products to be obtained from processing
this crude in an atmospheric distillation unit and estimate the %yield for
each cut.Stage 1- Distillation at atmospheric pressure 751 mm
Hg Cut Temp. Percent
Fraction Sum. Sp. gr. 0 API 60 ⁰F
No. ⁰F Distilled Percent 60/60 ⁰F

1 122 0.8 0.8 0.673 78.8
2 167 1.0 1.8 0.685 75.1
3 212 3 4.8 0.725 63.7
4 257 3.4 8.2 0.755 55.9
5 302 3.1 11.3 0.777 50.6
6 347 3.9 15.2 0.798 45.8
7 392 4.9 20.1 0.817 41.7
8 437 6.8 26.9 0.833 38.4
9 482 8.0 34.9 0.848 35.4
10 527 10.9 45.8 0.864 32.3
Stage 2- Distillation at atmospheric pressure 40 mm Hg
Fraction Cut Temp. Percent Sum. Sp. gr. 0 API 60 ⁰F

No. ⁰F Distilled Percent 60/60 ⁰F
11 392 7.3 53.1 0.873 30.6
12 437 7.8 60.9 0.879 29.5
13 482 6.2 67.1 0.889 27.7
14 527 5.7 72.8 0.901 25.6
15 572 6.9 79.7 0.916 22.94
16 ------- 20.3 100.0 0.945 18.2
Lect./4a Petroleum refinery
Degassing and Dehydration
In a producing oilfield the fluid obtained at the
wellhead is submitted to :
1- Dehydration 2- Degassing
operation operation
1- Degassing: -
At the high pressure existing at the bottom of the
producing well, crude oil contains great quantities of
dissolved gases. When crude oil is brought to the surface,
it is at a much lower pressure. Consequently, the gases
that were dissolved in it at the higher pressure tend to
come out from the liquid.
Two-Phase Gas–Oil Separation

High-pressure crude oils containing large amount of free
and dissolved gas flow from the wellhead into the flow line,
which routes the mixture to the GOSP. (This is usually done
by admitting the well fluid into a gas–oil separator plant
(GOSP) through which the pressure of the gas–oil mixture
is successively reduced to atmospheric pressure in a few
stages). In the separator, crude oil separates out, settles, and
collects in the lower part of the vessel.
Gas goes out the top of the separators to a gas collection

system, a vapor recovery unit (VRU), or a gas flow line.
Crude oil, on the other hand, goes out the bottom and is
routed to other stages of separation, if necessary, and then
to the stock tank (Fig. 1).
Figure 2 : Pressure-drop profile for a typical GOSP in the Middle East.
- Volatile components either sent to consumer centers as

natur al gas or used to repressur ize the oilfield.
- The stripped liquid components are marketed as stabilized
natur al gasoline.
CRUDE OIL (DESALTING)
* The fluid produced at the wellhead consists usually gas, oil, free
water, and emulsified water (water–oil emulsion).
* The gas remove by degassing process
* First step in the refining process is to remove salt and solids to
reduce corrosion, plugging, and fouling of equipment and to
prevent poisoning of the catalysts in processing units.
* contaminants must be removed by desalting (dehydration).
* If the salt content of the crude is greater than 10 lb/1000 bbl
(expressed as NaCl), the crude requires desalting to minimize
fouling and corrosion caused by salt deposition on heat transfer
surfaces and acids formed by decomposition of chloride
salts.(<1000 lb/bbl).
Typical Configuration Atmospheric Column w/o Preflash
The basic principles for the treating process are as

follows:
2. Resolution of
1. Removal of free water.
Emulsified Oil.
Free water is simply defined as that water produced with

crude oil and will settle out of the oil phase if given little
time.
There are several good reasons for
separating the free water first:
3. Minimization of 2. Reduction of heat 1. Reduction of

corrosion because free input when heating the size of flow
water comes into direct the emulsion (water pipes and treating
contact with the metal takes about twice as equipment.
surface, whereas much heat as oil).
emulsified water does
not.
Oil emulsions are mixtures of oil and water. In general, an

emulsion can be defined as a mixture of two immiscible
liquids, one of which is dispersed as droplets in the other (the
continuous phase), and is stabilized by an emulsifying agent.
In the oil field, crude oil and water are encountered as the two
immiscible phases together. They normally form water-in-oil
emulsion (W/O emulsion), in which water is dispersed as fine
droplets in the bulk of oil. This is identified as type C in
Figure 2.
For two liquids to form a stable

emulsion, three conditions must exist:
1. The two liquids 2. There must be

must be 3. There must be
sufficient energy of the presence of an
immiscible. agitation to disperse emulsifying agent.
one phase into the
other.
Some of the common emulsifiers are as

follows:
1. Asphaltic materials
2. Resinous substances
3. Oil-soluble organic acids

4. Finely dispersed solid materials such as sand,
carbon, calcium, silica, iron, zinc, aluminum sulfate,
iron sulfide, and so on.
Crude possessing emulsifying
To increase the coalescence of water drops. (Soda ash,
sodium hydroxide, salt of fatty acids petroleum sulfonates
which assist coalescence of water droplets).
Resolution of Emulsified Oil consists of three consecutive steps:
A. Breaking the emulsion:

 Using chemicals followed by settling can break some emulsions.
 Other emulsions require heating and allowing the water to settle out of the bulk
of oil.
 More difficult (tight) emulsions require, however, both chemicals and heat,
followed by coalescence and gravitational settling.
 Basically, a dehydration process that utilizes any or a combination of two or more
of the treatment aids mentioned earlier (heating, adding chemicals) is used to
resolve water-oil emulsions.
B. Coalescence: This involves the combination of water
particles that became free after breaking the emulsion, forming
larger drops.
C. Gravitational settling and separation of water
drops:
The larger water droplets resulting from the coalescence step will
settle out of the oil by gravity and be collected and removed.
Lect./4b Petroleum refinery
1.Introduction:
 Furnaces are used throughout the industry to
provide the heat, using the combustion of fuels.
 These fuels are solid, liquid or gaseous.
 Furnaces consist essentially of an insulated,
refractory lined chamber containing tubes.
 Tubes carry the process fluid to be heated, and
sizes are device for burning the fuel in air to
generate hot gases. A great variety of geometries
and sizes are used.
However, all furnaces have in common the
general feature of heat transfer from hot gas
source to a cold sink.
* 2.Types of furnaces used in process plant
* An industrial furnace or direct fired heater,Fig.(1), is an
equipment used to provide heat for a process or can serve as
reactor which provides heats of reaction.
* Furnace designs vary as to its function, heating duty, type of
fuel and method of introducing combustion air. However, most
process furnaces have some common features.
* Fuel flows into the burner and is burnt with air provided from
an air blower.
* There can be more than one burner in a particular furnace
which can be arranged in cells which heat a particular set of
tubes.
* The flames heat up the tubes, which in turn heat the fluid
inside in the first part of the furnace known as the radiant
section or firebox.
* Inthis chamber where combustion takes place, the heat is
transferred mainly by radiation to tubes around the fire in the
chamber.
* The heating fluid passes through the tubes and is thus heated
to the desired temperature.
* The gases from the combustion are known as flue gas.
* After theflue gas leaves the firebox, most furnace designs
include a convection section where more heat is recovered
before venting to the atmosphere through the flue gas stack.
Middle of radiant section Convection section
Furnace burner
Heating of Crude Oil
Pipe Still Heater
Pipe heaters can be categorized into three types:
1) Box/ Rectangular.
2) Cylindrical.
3) Radiant Wall
All these furnaces have got separate radiation section and

convection section. The most universal classification is based
on direction of tubes as well as shape of furnace and mode of
application of heat.
In most of the furnaces, the direction of tubes is horizontal as

in all box type heaters and vertical in cylindrical stills. Radiant
walls also use horizontal tubes; however tubes can be placed
vertically also.
The radiant section design is based on Stefan's law of
r adiation :
Qr = bAT = bA(TG − TB )
4 4 4
A: area of radiating surface, ft2

b : 1.72x109 Btu/ oF ft2 hr. at black bod conditions.
T: absolute temperature of the surface,oF
For a satisfactory design, the following schedule of heat

distribution may be employed:
Type of heat Percent

Convection heat transfer 30-50%
Radiant heat transfer 45-60%
Losses (Furnace) 5%
Stack losses 12%
Design of a furnace radiation section is based on

Hottle, Wilson method and radiant heat absorption is given
as:-
1
R= x100
G Q / αAcp
1+
S
R= % heat absorbed in radiant section.
Q = Total heat developed by flame
G= Air /fuel ratio (wt. basis).
α = Factor to convert actual exposed surface to cold surface:
0.986 for two rows at spacing 2 OD.
0.88 for one rows at spacing 2 OD.
If
Q in Kj / hr S=14200 Area in m2
Q in Btu/hr S=4200 Area in ft2
Q in Kcal/hr S=6930 Area in m2
C Acp = area of furnace wall that has tube mounted on it (ft2).

Acp = LN α Acp= equivalent cold plane surface (ft2)
12
L= length.
C= Center to center spacing.
N= Number of tube per row.
D
A = LnN
12
A= Projected area
D= Tube diameter ( in )
n= no. of rows
D
A = nAcp
C
A C
Acp =
n D
RQ = Aq
q= rate of heat absorption per square foot of projected tube area
Aq nAcp ( D / C )q
Q= =
R R
1
R= x100
q n D
G
1+ R α C
S
D n (1 − R ) 2 S 2
q( )= ( )
Cα R G
For a most commercial case D/C= 0.5 , n=2
(1 − R ) 2
S 2
1.014 xq =
'
( )
R G
C a '
q = 1.014 x x q
D n
Example:-
A petroleum stock at a rate of 1200 bbl/hr. of sp. gr. 0.8524 is
passed through a train of heat exchangers and is allowed to
enter directly the radiant section of box type heater at 220 o C .
The heater is designed to burn 3500 kgs per hour of refinery off
gases as fuel.
The net heating value of fuel is 47.46x103 Kj per kg.
The radiant section contains 150 sq. meters of projected area of
one row of tubes (10.5 cm, 12 m long and spaced at 2 OD).
>> Find the outlet temperature of the petroleum stock?
Where,
α=0.88
Air fuel ratio= 25
Average Specific heat of stock=2.268 Kj/Kg o C.
Solution
Total heat liberated (Q) = m fuel * NHV
= 47.46*103 * 3500 = 1.66*108 Kj/hr.
Projected area of one tube (L * D) = 12 * 0.105
No. of tubes = 150 / ( 12 * 0.105 ) = 120 tubes
α A cp= 0.88 * 120 * 0.105 * 2 * 12 = 266 Sq. m.
1
Heat absorption %(R) = x100
G Q / αAcp
1+
S
1
= = 44%
1.66 * 10 8
25 *
266
1+
14200
Outlet temperature of the stock:-

Q = m Cp Δt
0.44*1.66*108 = 1200 * 200 * 0.8524* 2.268 * Δt
‫ ؞‬Δt =157 o C
So the outlet temperature is equal to 157 + 220 = 377 o C
Example
A pipe still uses 7110 lb/hr of a cracked gas (Net Heating Value
(NHV) 20560 Btu/lb). The radiant section contains 1500 sq ft of
projected area, and the tube (5 in. outside diameter) are spaced at
a center-to-center distance of 10 in. there is only one row of
radiant tubes, and they are 40 ft long. The ratio of air to fuel is
(21 - 30 percent excess air).
a) What percentage of the heat liberation is absorbed in the
radiant section?
b) How many Btu are absorbed per hour through each square foot
of projected area?
Solution
Total heat liberated(Q)= m fuel * NHV
= 7110 * 20560
=146000000 Btu/hr
D
A = LnN
12
A = 1500
1500
N = number of tubes = = 90
40 * 5 / 12
C
Acp = LN = 40 * 90 *10 / 12 = 3000
12
α A cp= 0.88 * 3000 = 2640 sq ft
1
Heat absorption %(R) = x100
G * Q / αAcp
1+
S
1
= = 45.8%
6
1.46 x10
21 *
2640
1+
4200
Heat absorption in radiant section = 0.458 *146 *106

= 66900000 Btu/hr
Heat absorbed / sq ft projected area = q = 66900000/1500

= 44500 Btu/hr.ft2
H.W (1)
A furnace is to be designed for a heat duty of 30 x 106 Btu/hr
and efficiency of 75%.
The furnace is fired with gaseous fuel at a rate of 17 lb air/lb
fuel (NHV = 17000 Btu/lb).
The tube are arranged in two rows and are of 5 in OD., 40 ft
length and 2x OD.
Spacing, heat rate of 35000 Btu/hr of projected area is
recommended.
calculate:
1) % heat absorbed in radiation section (R %).
2) Heat absorbed in the convection section.
(State any assumptions used).
3) The number of tubes in the radiation section.
Solution
a)
D n (1 − R ) 2 S 2
q( )= ( )
Cα R G
5 2 (1 − R) 2 4200 2
35000( )= ( )
10 0.986 R 17
0.581= (1-R)2
R= 47.55%
Heat absorbed in radiation zone = R x Q= 0.4755X 40x106 = 19020000 Btu
b)
qxA=RxQ
35000 x A= 19020000
A= 543.42 ft 2
A= L n N D/12
N= 543.42 x12/( 40x2x5)
N= 16
C)
% Heat absorbed in the convection section= 100%- (Heat absorbed in radiation zone+ Losses (Furnace)+ Stack
losses)
% Heat absorbed in the convection section= 100%- (47.55+ 5+12)%
%Heat absorbed in the convection section =32.45%
Heat absorbed in the convection section=0 .3275 X 40x106 = 13.1x106 Btu
H.W (2)
7000 lb/hr of cracked gas of 20560 Btu/lb NHV is used as a
fuel in a furnace.
The radiant section absorbed 44500 Btu/hr ft2 of projected
area. The tubes are 5 in. OD. , 10 in. spacing, and 20 ft long.
They arranged in two rows. The air to fuel ratio is 21- 0.
Calculate :
1) the number of tubes in the radiation section.
2) the amount of heat absorbed in this section.
Lect./4c Petroleum refinery
Atmospheric Topping Unit
After desalting, the crude oil is pumped through a series of heat

exchanger and its temperature raised to about 550o F (288o C ) by
heat exchange with product and reflux streams.
It is then further heated to about 750o F (399o C ) in a furnace
(i.e. direct fired heater or "pipe still" ) and charged to flash zone
of atmospheric fractionators.
The furnace discharge temperature is sufficiently high to cause

vaporization of all products with drawn above the flash zone
+ about 20% of the bottom product.
The 20% "over flash" allows some fractionation to occur on the

trays just above the flashing zone by providing internal reflux in
excess of side stream withdrawals.
In many petroleum distillations, steam is admitted to the space

in which vaporization occurs, the steam reduce the partial
pressure in the vapor by Dalton's law, the boiling point of a
material may be reduced in only two ways:
1) the pressure may be reduced.
2) or some inert gas such as steam may be introduced.
The distillation causes the fractions to separate in increasing
order of boiling point. The top product being highly volatile has
to be condensed in a reflux condenser. Some portion of the
condensed fraction goes back as reflux.
All other fractions form the side draw products of distillation
column. There fractions are usually classified as heavy naphtha,
kerosene, gas oil.
Bottom product of atmospheric column is now again routed

through a furnace to reach a temperature of 350 to 400oC and is
allowed to flash in a vacuum column, vacuum gas oil, heavy
diesel, lubrications oil cuts / pressure distillates shall be the side
cuts.
Heat and Material Balances
1) The vapor liquid feed enters the tower at a high temperature,
and the product are withdrawn at lower temperature , hence heat
must be removed, and it is referred as
" reflux heat ".
2) The most satisfactory temperature datum is the vaporizer
temperature because this temperature can be accurately
estimated and is the temperature about which the entire design
of tower, and pipe still hinges.
3) By using this datum plane , the heat balance consists simply
of the sensible heat required to:
a) Cool each product from vaporizer temperature to its
withdrawal temperature.
b) Condense the products that are withdrawal as liquid.
Example (1) :
Heat Balance of a Fractionating Tower
A heat balance of the simple tower system shown in Fig. below will
be computed to determine the amount of heat that must be removed
to keep the tower in thermal balance.
The capacity is 1200bbl per day (2100 gal per hour of a 12.1 to 12.2
Characterization Factor crude oil.
At 576 o F the gasoline, naphtha, kerosene, and gas oil are vapor
and the reduced crude oil is a liquid.
A sufficient quantity of heat must removed from the vapors to cool
them as vapors to the temperature at which they are withdrawn from
the tower and to condense the naphtha, kerosene, and gas oil at their
withdrawal temperature.
Volume 50 % Mol. Latent

API Lb/gal Gal/hr Lb/hr
% bp wt heat
Gasoline 26.8 62.8 6.06 563 3415 260 110 120
Naphtha 5.63 52.8 6.39 118 754 370 155 113
Kerosene 19.8 45.6 6.65 416 2765 460 185 100
Gas oil 10.6 39.4 6.89 222 1530 585 240 90
Reduced
36.97 31.2 7.24 776 5610
crude
Loss 0.2 96
Crude 100.00 43.0 6.75 2100 14170
Solution : Energy Balance Basis =1hr
Sensible heat Btu
Gasoline (vapor) 3415 * (576 - 286) * 0.56 = 589000
Naphtha (vapor) 754 * (576 - 335) * 0.55 = 106000
Kerosene(vapor) 2765 * (576 - 420) * 0.57 = 261000
Gas oil (vapor) 1530 * (576 - 510) * 0.59 = 63000
Reduced crude (liquid) 5610 * (576 - 510) * 0.72 = 276000
---------------
1295000
Steam (vapor) 567 * (535 - 286) * 0.5 = 70600
---------------
1365600
Latent heat Btu

Gasoline ( withdraw as vapor )
Naphtha 754x113 = 85100
Kerosene 2765x100= 276500
Gas oil 1530x90= 138000
----------------
Total heat to be removed 1865200
1) Cold Reflux
Kinds of 2) Hot Reflux

Reflux :
2) Circulating
Reflux
1) Cold Reflux :
Is defined as reflux that is supplied at some temperature below
the temperature at the top of the tower. Each pound of this
reflux removes a quantity of heat equal to the its latent heat and
the sensible heat required to raise it temperature from the
storage tank temperature to the temperature at the top of the
Q = mλ + mC pL ∆T
tower
2) Hot Reflux:-
Admitted to the tower at the same temperature . Reflux or over
flow from plate to plate in the tower is essentially hot reflux
because it is always substantially at its boiling point. Hot reflux
capable of removing only the latent heat because no difference
in temperature is involved
Q = mλ
3) Circulating Reflux : It is not vaporized. It is only able to
remove the sensible heat that is represented by its change in
temperature as it circulate. This reflux is withdrawn from the
tower as a liquid at a high temperature as a liquid and is
returned to the tower after having been cooled.
Q = mC pL ∆T
Example (2) : (Quantity of Reflux)

A tower fractionating system is such that 1865200 Btu/hr of reflux
heat must be removed.
Example (1) illustrates the method of determining the reflux heat.
How many pounds of (1) hot (2) cold, and (3) circulating reflux
are required?
Solution
Hot reflux:
λ ( Gasoline ) =123 Btu/lb
lb of hot reflux = 1865200/120 = 15500 lb/hr
mole hot reflux = 15500/110 = 141
mole gasoline = 3415/110 = 31
moles vapor = 141 + 31 = 172
moles steam = 567/18 = 31.5
total moles at the top of the tower = 172 + 31.5 = 203.5
total pressure at the top of the tower = 780 mm Hg

the partial pressure in the gas phase is (172/203.5) * 780
= 660 mmHg ( according to Daltons law Pi = yi PT )
The dew point of 100% gasoline on EFV curve = 296 o F
(at 760 mm Hg)
>> At 660 mm Hg the temperature is calculated according to
Claussius – Clapeyron Eq.
p λ 1 1
ln = ( − )
po R To T
R= 1.987 Btu/lbmole.oR
660 120 x110 1 1

ln = ( − )
760 1.987 296 + 460 T
T=284 o F
The actual top temperature when using hot reflux = 286 o F
Cold reflux :
Assume storage tank at 80oF
1865200
Lb cold reflux = = 7950
120 + (286 − 80) * 0.58
Moles cold reflux = 7950/110 = 72.3
Mole gasoline 31
Moles vapor 103.3
Moles steam 31.5
Total moles 134.8
103.3
p= * 780 = 600 mm Hg
134.8
The equilibrium temperature of 296oF corrected to 600 mmHg= 275 oF
Circulating reflux :
Assuming the reflux is cooled from 286 to 200 o F.
Mole gasoline 31
Mole steam 31.5
Total moles 62.5
31
Partial pressure = * 780 = 387 mmHg
62.5
Correction 296 to 387 mm pressure gives 253 o F
1865200
Lb circulating reflux = = 35849
(286 − 200) * 0.605
Moles reflux = 10403/110 = 94.6

Side-Draw Temperature:
1) The method of calculating side-draw temperature is much the
same as the calculation of the top temperature except that
complications arise because of the presence of the low boiling
materials that pass the draw plate.
2) Making heat balance upon the drawn plate.
3) In practice, steam and vapor of lighter products are usually
present, and hence the effect of these vapors on the final
condensation temperature must be estimated. The lighter vapors
extended from materials boiling at almost the same temperature
as the side-draw product to materials that are substantially fixed
gases.
4) Those vapor materials which are far above their boiling point
behave as fixed gases and lower condensation point by Dalton's
law of partial pressures, just as steam does, but those vapor
materials which are at or near their boiling point are not
effective in reducing the partial pressure.
5) Arbitrarily, the vapors materials that will be condensed at the
second or higher draw plate above the plate under
consideration may be considered to act as fixed gases.
6) Also, the vapor constituting the materials that is withdrawn
from the draw plate above the one under consideration are
assumed to have no effect at all on the partial pressure.
7) thus in a tower producing, gasoline, naphtha, kerosene, and
gas oil , at the kerosene draw plate the gasoline vapor would
be considered as a fixed gas , whereas naphtha vapor would
assumed to have no effect on the condensation point.
Example (3) : (Calculation of Side Temperature)
This example is a continuation of examples (1) and (2). The temperature of
the kerosene plate will be computed.(actual temperature = 420oF)
Solution :
Heat balance on kerosene plate, quantity of reflux and reflux
(or vapor reflux) must be determined.
Cool gasoline (vapor) = 3415 * ( 576 – 420 ) * 0.58 = 327000
Cool naphtha (vapor) = 754 * ( 576 – 420 ) * 0.57 = 71000
Cool kerosene(vapor) = 2765 * ( 576 – 420 ) * 0.57 = 260000
Cool gas oil (vapor) = 1530 * ( 576 – 510 ) * 0.58 = 62000
Reduced crude (liquid) = 5610 * ( 576 – 510 ) * 0.72 = 276000
--------------
996000
Cool steam = 567 * ( 535 – 420 ) * 0.5 = 44000
Condense kerosene = 2765 * 100 = 276500
Condense gas oil = 1530 * 90 = 138000
---------------
Reflux heat at kerosene plate 1454000
QT 1454500
Moles internal reflux = = = 78.6
(λxM W ) K 185 x100
Moles fixed gases
Steam 31.5
Gasoline 31
Naphtha no effect ------
62.5
Total moles vapor = 62.5 + 78.6 = 141.1
Assume tower pressure at kerosene plate = 950 mmHg
P i = PT * y I
Partial pressure = 78.6 * 950 = 530 mmHg
141.1
p λ 1 1
ln = ( − )
po R To T
530 100 * 185 1 1

ln = ( − )
760 1.987 445 + 460 T
T= 414oF
T actual = 420oF
H.W:
Repeat the example above, recalculate the temperature of the naphtha
plate, assume a tower pressure of 810 mmHg?
H.W :
A) Calculate the amount of Hot, Cold and circulating reflux if the
storage temperature is 100oF and Cpv= 0.6 and Cpl = 0.7
Btu/lb.oF
B) Check the top tower temperature if hot reflux is used. The dew
point of gasoline is 296 o F and the pressure at the top plate is
780 mm Hg.
Fraction Lb\hr M.w. λ Temperature o F
Gasoline 33500 101 120 310

Kerosene 11800 185 108 410
Gas oil 32200 270 95 510
R.C 43500 - - 510
Steam 600 18 - 530
C.O. 121000 - - 576
Calculation of The Diameter of Distillation Column.
Example (4): See examples 1, 2 and 3 the quantities and conditions
will be taken from these examples.
Solution:
Density of vapor at top of column (the reflux in the column is
always hot reflux)
Mole gasoline 31
Mole hot reflux 141
Mole steam 31.5
------------
Total moles 203.5
P=780 mm Hg
T=286 o F
nRT 203.5 * 379 * (286 + 460) x760
Volume of vapors = = = 107600 ft 3
P 780 * 520
Mass of vapor =
mass of gasoline + mass of hot reflux + mass of steam
= 3415 + 15500 + 567 = 19482 lb/hr
ρV =19482 / 107600 = 0.181 lb/ft3
Assume density of liquid ρl = 42.7 lb/ft3
w
= K ρv (ρl − ρv )
a
Assume K= 735, K is constant dependent primarily on the tray spacing.
w lb
= 2040
a hrxft 2
mass 19482
A= = = 9.55 ft 2
massvelocity 2040
4A 4 x9.55
D= = = 3.5 ft 3
π π
To check the vapor velocity at top (3.5 ft/sec)
v 107600
u= = = 3.13 ft / sec , u is ok
A 9.55 * 3600
H.W:
120000 Lb/hr of 34oAPI crude oil at 650oF is fed to an atmospheric
distillation unit. Steam at a rate of 600 lb/hr and 850oF is used.
The fraction obtained were 34000 lb/hr gasoline (MW=110,
λ=120 ) at 310 oF; 12000 lb/hr kerosene ( MW=185, λ=108 ) at 420
o F; 30000 lb/hr gas oil ( MW=270, λ=95 ) at 510 oF .
The residue is withdrawn at 510oF. Assume CPL= 0.7 ,CPV= 0.6

Btu/lb.oF.
a) Check the top tower temperature if the dew point of gasoline is
296 o F and the pressure at the top plate is 780 mm Hg.
b) Calculate the diameter of the tower if K=735 and ρl= 42.7 lb/ft3.
H.W
1000 BPD of 32 o API crude oil at 650 o F is fed to an
atmospheric distillation unit. Steam at a rate of 600 lb/hr and
530 o F is used. The fractions obtained were 3500 lb/hr
gasoline (MW=110, λ=120) at 310 o F; 3000 lb/hr kerosene
(MW=185, λ=100) at 420 o F; 1500 lb/hr gas oil (MW=240,
λ=90) at 510 o F. The residue is withdrawn at 510 o F. Assume
CPL=0.7, CPV=0.6 Btu/lb o F. and the vaporizion
temperature=5760F .
Given: 1 BPD = 42gal , ρwater= 8.324 lb/gal
Check the gas oil plate temperature if the dew point and
bubble point of gas oil are 600 o F and 580 o F respectively
and the pressure at the withdrawn plate is 990 mm Hg.
Lect./5
Conversion Processes
Thermal cracking:
Is defined as the thermal decomposition, under pressure,
of large HC molecules to form smaller molecules. Lighter,
more valuable HC may be obtained from such relatively low
value stocks as heavy gas oils (boiling up to 540 oC (1005
oF)) and residues.
These processes are considered as upgrading processes

for vacuum residue.
Requirements of Thermal cracking:
Residual fractions (bottom of barrel) are the least valuable
streams of a refinery.
Nearly 30-40 % of the typical C.O in Iraq contains 370 + 0C
fractions.
Worldwide limited reserve of sweet crude oil.
Disposal problems due to stringent environmental
regulations.
Decreasing demand of fuel oil.
Gradually increasing demand of middle distillates.
Advantages of Thermal cracking:
It is simple and cost effective process. However rapid
uncontrolled thermal cracking produces undesirable
products like gas and coke.
Limitation of catalytic cracking for resid processing :
1. In resid feed stock presence of high molecular weight
compounds like resins, asphaltenes and metals it
unsuitable for catalytic cracking, FCC can process resid
feed only to certain limit.
2. Metal and sulfur compounds in resid feedstock as
catalyst poison.
Coking:
Coking are severe thermal cracking operations, most
commonly used carbon rejection process that upgrades
residues to a wide range of lighter H.C gases and distillates
through thermal cracking.
The byproduct of coking process is petroleum coke.
The goal of coker operation is to maximize the yield of
clean distillates and minimize the yield of coke.
Feed stock of coking process:
 Wide variety of feed stocks ( can have considerable
metals (nickel &vanadium) , sulfur, resin and asphaltens.
Most contaminants exit with coke.
Typical feed is vacuum resid.
The main produts:
 Off-gas from which LPG is recovered.
 Naphtha may be used as gasoline blending
agent although its O.N = 65-80 RON.
 Gasoil may be catalytic cracking
 Coke the main uses of petroleum coke:
1. Fuel
2. Manufacture of anode for electrolytic cell reduction of alumina
3. Direct use as chemical carbon source for manufacture of elemental
phosphorus, calcium carbide, and silicon carbide.
4. Manufacture of electrodes for use in electric furnace production of
elemental phosphorus, titanium dioxide, calacium carbide, and
silicon carbide.
5. Manufacture of graphite.
The major coking processes:
1) Delayed Coking
 Semi-continuous process.
 Feed :atm. Residue, cracked tar, and heavy cycle oil
 Feed heated and transferred to large soaking (or
coking drum).
 Long residence time need to allow the cracking
reactions to complete.
1. Moderate heating : 482-516 oC (900-960) o F
2. Soak drum : 452-482 oC (845-900) o F
3. Residence time : until they are fill of coke.
4. Coke is removed hydraulically
5. Coke yield= 30 %
Fig 1: Delayed coking unit
2) Fluid Coking or flexicoking
 A continuous process which uses the fluidized- solids
technique to convert residues to more valuable
products.
 The residue is coked by being sprayed into a fluidized
bed of hot, fine coke particles.
 The use of a fluid bed permits the coking reaction to
be conducted at higher temperature and shorter
contact times than those in delayed coking: Fluidized
bed with steam.
 Severe heating 482- 566 oC (900-1050) o F at 10 psig.
 Higher yields of light ends.
 Less coke yields ( 20 % for fluid coking and 2 % for
flexicoking)
Coke & liquid yields may be estimated by simple equations:
Example ( 1 ) : Develop preliminary estimate of product yields on the
processing of 1000+ Rc of 23760 BPD capacity. Conrad son carbon =
19%, 2.3% S, API = 10.7.
Solution :
(lb/bbl)
Feed BPD API lb/ hr lb/ hr wt% S lb/hr
(348.56)
1000+ RC 23700 10.7 14.52 345080 2.3 7940
Products wt% lb/ hr lb/ hr S
Coke wt % 30.4 104900 2382
Gas (C4 - ) wt% 10.5 36230 2382
Gasoline wt% 17.8 61450 397
Gas oil wt% 41.3 142500 2779
----- -------- -------
100 345080 7940
Visbreaking:
Visbreaking is a relatively mild thermal cracking operation
mainly used to reduce the viscosities and pour points of
vacuum tower bottoms to meet the requirements of fuel oil
reduce the amount of cutting stock required to dilute the
residue to meet the specifications.
 It is also used to increase catalyst cracker feed stocks and
gasoline yields.
Visbreaking:
The principal reactions which occur during the visbreaking operation
are :
1) Cracking of the side- chains attached to cyclo-paraffin
and aromatic rings.
2) Cracking of resins to light HC (primarily olefins) and
compounds which convert to asphaltenes.
3) At temperature above 900 oF some cracking of
naphthene rings.
Visbreaking:
There are two types of visbreaker operation
1) Coil or furnace cracker
Uses high furnace outlet temperature (885-930 oF), and
reaction time from 1-3 minutes. The feed is heated in a
furnace or coil and quenched as it exits the furnace with
gas oil or tower bottoms to slop the cracking reaction.
2) Soaker
The feed leaves the furnace at (800- 820) oF and pass
through a soaking drum which provides an additional
reaction time, before it is quenched.
 Catalytic cracking is the most important and widely used refinery
process for converting heavy oils into more valuable gasoline and
lighter products.
 Catalytic cracking breaks complex hydrocarbons into simpler
molecules in order to increase the quality and quantity of lighter, more
desirable products and decrease the amount of residuals.
 This process rearranges the molecular structure of hydrocarbon
compounds to convert heavy hydrocarbon feedstock into lighter
fractions such as kerosene, gasoline, LPG, heating oil, and
petrochemical feedstock.
Catalytic cracking is similar to thermal cracking except that catalysts
facilitate the conversion of the heavier molecules into lighter products.
Use of a catalyst (a material that assists a chemical reaction but does
not take part in it) in the cracking reaction increases the yield of
improved-quality products under much less severe operating conditions
than in thermal cracking.
There are three basic functions in the catalytic
cracking process:
1. Reaction: Feedstock reacts with catalyst
and cracks into different hydrocarbons;
2. Regeneration: Catalyst is reactivated by
burning off coke; and
3. Fractionation: Cracked hydrocarbon
stream is separated into various products.
Catalytic Cracking
Fluid Catalytic Cracking (FCC)
• The most common process is FCC, in which the oil is cracked in the
presence of a finely divided catalyst which is maintained in an aerated
or fluidized state by the oil vapors.
• The fluid cracker consists of a catalyst section and a fractionating
section that operate together as an integrated processing unit.
• The catalyst section contains the reactor and regenerator, which, with
the standpipe and riser, forms the catalyst circulation unit.
• The fluid catalyst is continuously circulated between the reactor and
the regenerator using air, oil vapors, and steam as the conveying media.
• A typical FCC process involves mixing a preheated hydrocarbon
charge with hot, regenerated catalyst as it enters the riser leading to the
reactor.
•The charge is combined with a recycle stream within the riser,
vaporized, and raised to reactor temperature (900°-1,000° F) by the hot catalyst.
• As the mixture travels up the riser, the charge is cracked at 10-30 psi. In the
more modern FCC units, all cracking takes place in the riser.
• The "reactor" no longer functions as a reactor; it merely serves as a holding
vessel for the cyclones.
• This cracking continues until the oil vapors are separated from the catalyst in
the reactor cyclones.
• The resultant product stream (cracked product) is then charged to a
fractionating column where it is separated into fractions, and some of the heavy
oil is recycled to the riser.
• Spent catalyst is regenerated to get rid of coke that collects on the catalyst
during the process.
• Spent catalyst flows through the catalyst stripper to the regenerator, where
most of the coke deposits burn off at the bottom where preheated air and spent
catalyst are mixed.
• Fresh catalyst is added and worn-out catalyst removed to optimize the
cracking process.
Fluid Catalytic Cracking
Moving-Bed Catalytic Cracking
• The moving-bed catalytic cracking process is similar to
the FCC process.
• The catalyst is in the form of pellets that are moved
continuously to the top of the unit by conveyor or
pneumatic lift tubes to a storage hopper, then flow
downward by gravity through the reactor, and finally to a
regenerator.
• The regenerator and hopper are isolated from the reactor
by steam seals.
• The cracked product is separated into recycle gas, oil,
clarified oil , distillate, naphtha, and wet gas.
Catalyst
 Both systems use basically similar catalysts but produced in a
different form, in the shape of beds for moving bed and fine powder for
fluidized bed.
1. Acid treated clays ground to a powder
2. Synthetic silica- alumina catalysts of higher activity (amorphous)
3. Crystalline synthetic silica – alumina catalyst called zealots or
molecular sieves.
The advantages of zealots over the natural and synthesis amorphous
catalyst are
1) Higher activity.
2) Higher gasoline yields at a given conversion.
3) Production of gasoline containing a larger % of paraffinic and aromatic HC.
4) Lower coke yield.
5) Increased iso-butane production.
6) Ability to go for higher conversion per pass without over cracking.
PROCESS VARIABLES
Catalytic cracking is differences with respect Thermal Cracking
 uses a catalyst
 lower temperature
 lower pressure
 more flexible
 different reaction mechanisms : ionic vs. free radical
 High thermal efficiency
 Good integration of cracking and regeneration
 High yields of gasoline and other distillates

 Low gas yields
 High product selectivity
 Low n-alkane yields
 High octane number
 Chain-branching and high yield of C4 olefins
 High yields of aromatics
Lect./6
Upgrading Naphtha
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.
Depending on the properties of the naphtha feedstock (as
measured by the paraffin, olefin, naphthene, and aromatic
content) and catalysts used, reformates can be produced
with very high concentrations of toluene, benzene, xylene,
and other aromatics useful in gasoline blending and
petrochemical processing.
Hydrogen, a significant by-product, is separated from the
reformate for recycling and use in other processes.
A catalytic reformer comprises a reactor section and a
product recovery section.
Role of Reformer in the Refinery and Feed Preparation
The catalytic reformer is one of the major units for gasoline production in
refineries. It an 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.
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.
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
5.2.
 Hydrogen, produced in the reformer can be recycled to the naphtha
hydrotreater, and the rest is sent to other units demanding hydrogen.
Reforming Reactions
(PONA) {Paraffin, Olefin, Naphthene, Aromatic}
1) P → isomerizes to some extent converted to N, and N
subsequently converted to aromatics.
2) O → saturated to form P which then react as in (1)
{hydro-cracking}.
3) N → converted to aromatics. {dehydrogenation}.
4) A→ unchanged.
Process Technology
There are several commercial processes available for reforming.
1. Semi-regenerative Fixed Bed Process :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. (Low capital cost).
2. Continuous Regenerative (moving bed) CCR Platforming :Catalyst
can be regenerated continuously and maintained at a high activity .
(Higher capital cost).
3. Cyclic :compromise between the two extremes having a swing
reactor for regeneration.
Catalyst
All of the reforming catalyst contains platinum suppor ted on
a silica alumina base.
In most cases r henium is combined with platinum to form a
more stable catalyst which permits operation at lower
pressure.
Platinum ser ve as a catalytic site for hydrogenation and
dehydrogenation reactions.
Chlor inated alumina provides an acids site for
isomer ization and hydro- cr acking reactions and
cyclization .
Example (2)
Example (3)
On processing 1200 ton / day of 27 API catalyst crackers feed stock at a
temperature of 450 oC, pressure =1050 mm Hg the following products were
obtained:
Products wt % API Mw
Gases 15 -- 32
C5+ gasoline 55 63 110
TCGO 26 5 260
Coke 4 -- 12
Given that: WHSV = 0.7 hr -1, Linear velocity of vapor (U) = 0.3 m/s,
ρ catalyst = 420 Kg /m3
Calculate: a) diameter of the cracker, b) weight of catalyst needed, c)
conversion, and d) efficiency.
Solution :
1200 ton/day * 1000 Kg/ton
m feed = -------------------------- = 50000 Kg /hr
24 hr/day
m gases = 0.15 * 50000 / 3600 =2.08 Kg/s
m C5+ gasoline = 0.55 * 50000/ 3600 =7.64 Kg/s
m TCGO = 0.26 * 50000/ 3600 = 3.61 Kg/s
Total moles of vapor = (2.08/ 32) + (7.64/ 110) + (3.61/ 260 )
n = 0.1479 Kg mole / s
22.4 (m3/ kg mole) * 760 mm Hg
R = --------------------------------- = 62.359
1 Kg mole * 273
nRT 0.1479* 62.359 *(450+273)

V= -------- = ------------------------= 6.35 m3/s
P 1050
П V 6.35 m3/s
A =----- D2 = ----- = ------- = 21.17 m2
4 U 0.3 m/s
m catalyst = 50000/0.7 = 71428 Kg

V catalyst = m/ ρ = 170 m3
4* 170
H= ---------------- = 8 m
3.14 * (5.19)2
Alkylation combines low-molecular-weight olefins (primarily a mixture of
propylene and butylene) with isobutane in the presence of a catalyst, either
sulfuric acid or hydrofluoric acid.
The product is called alkylate and is composed of a mixture of high octane,

branched-chain paraffinic hydrocarbons.
Alkylate is a premium blending stock because it has exceptional antiknock
properties and is clean burning.
The octane number of the alkylate depends mainly upon the kind of olefins
used and upon operating conditions.
 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.
Isomerization Reactions:
Isomerization is a reversible and slightly exothermic reaction:
n-paraffin i-paraffin
The isomerization reactions are slightly exothermic and the reactor works in
the equilibrium mode. There is no change in the number of moles and thus
the reaction is not affected by pressure change. Better conversions are achieved
at lower temperature
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.
Isomerization Catalysts
There are two types of isomerization catalysts:
1. The standard Pt/chlorinated alumina with high chlorine
content, which is considered quite active,
2. and the Pt/zeolite catalyst.
Lect./7
Product Blending
Product Blending
 Blending purpose is to allocate the available blending components in such a
way to meet product demands and specification at the least cost. We now
review how the properties of mixtures are estimated based on the properties of
the components.
Octane Blending:
True octane numbers do not blend linearly. It is therefore necessary to use
especial “blending” octane numbers to obtain linear expressions. The blending
is performed on a volumetric average basis.
The formula used for calculation is:
n
Bt ONt = ∑ ( BiONi ) ……………………………….. 1
i =1
where
Bt = total amount of blended gasoline , bbl
ONt = desired octane of blend
Bi = bbl of component i
ONi = blending octane number of component i.
contributing to product t and blending octane numbers, respectively. The
practice has been to use the following expression for the “blending” octane
number:
ON = ( MON + RON ) / 2 ……………………………….. 2
i i i
where MON and RON are the motor and research octane numbers, respectively.
Note that the true octane number is the one obtained using a CFR test engine.
For example, consider a 30% isomerate and 70% reformate blend. Isomerate has
the following octane values: MON=81.1, RON=83.0, whereas reformat has the
following octane numbers: MON=86.9 and RON=98.5. When blended in the
proportion given above, the blended pool has ON=89.505.
Pool Octane : is the average octane of the total gasoline production of the
refinery, if the regular, mid- premium, and super- premium gasolines are
blended together.
Posted Octane numbers (PON): are the arithmetic average of the motor octane
number (MON) and research octane number (RON).
Reid vapor pressure:
The desired RVP of a gasoline is obtained by blending n-butane with C5 (380 oF)
with C5 (193 oF) naphtha. The amount of n-butane required to give the needed
RVP is calculated by:
n
M t ( RVP) t = ∑ M i ( RVP) i ……………………………….. 3
i =1
Where:
M t = total moles blended product
(RVP) t = specification RVP for product, psi
M i = moles of component i
(RVP) i = RVP of component i, psi or kPa
The desired RVP for a blended gasoline is obtained by adding n-butane to reach
the desired value.
Example (1): calculate the amount of n-butane to be added to following base
stock to achieve an RVP of 10 psi( n- butane: MW=58, RVP=52).
Base
BPD Lb/hr MW RVP (psi)
stock
LSR
4000 39320 86 11.1
gasoline
Reformate 6000 69900 115 2.8
Alkylate 3000 30690 104 4.6

FCC
8000 87520 108 4.4
gasoline
Total 21000 5.38
Solution:
Base
BPD Lb/hr MW mol/hr mol% RVP PVP
stock
LSR
4000 39320 86 457 21 11.1 2.32
gasoline
Reformate 6000 69900 115 617 28.4 2.8 0.80
Alkylate 3000 30690 104 295 13.4 4.6 0.62
FCC
8000 87520 108 810 37.2 4.4 1.64
gasoline
Total 21000 2179 100

Butane requirement : (use Eq. (3) )
(2179) (5.38) + M (52) = (2179+ M) (10)
11732+52 M=21790 +10 M
M= 240 moles n-butane required.
The above method requires obtaining the molecular weight of each of the
streams involved, which could be a problem sometimes, although there are good
ways of estimating such molecular weights. To makes matter simpler, one can use
the method developed at Chevron. In this method “Vapor blending indices”
(VPBI), which work well. The RVP of a blend is then calculated using the following
volume averaging formula:
( RVP) = ∑Vi ( RVP)i ……………………………….. 4
blend
In the case where the volume of the butane to be blended for a given RVP is
desired :
A(VPBI)a + B(VPBI)b+ C(VPBI)c+ - - - - + W(VPBI)w= (Y+W) (VPBI)m …………... 5
where
A= bbl of component a, etc
W= bbl of n- butane (w)
Y= A+B+C+ ----------- ( all component except n- butane )
(VPBI)m = VPBI corresponding to the desired RVP of the mixture
w= subscript indicating n- butane.
Table 11-1 and 11-2 show the blending component values for different blending
streams and the blending indexes as a function of RVP values.
Table 11-1: Blending Component values (Gary and Handwerk, 2001)
Table 11-2: Blending Component values (Gary and Handwerk, 2001)
Example (2): Repeat Example (1) use vapor blending indices (VPBI) method.
Component BPCD RVP VPBI Vol x VPBI
n-Butane W 51.6 138 138 W
LSR gasoline 4000 11.1 20.3 81200
Reformat 6000 2.8 3.62 21720
Alkylate 3000 4.6 6.73 20190
FCC gasoline 8000 4.4 6.37 50960
Total 21000 + W 174070 + 138 W
Given : VPBI of n- butane =138

For 10 psi RVP, (VPBI)m = 17.8
Solution
17.8 (21000 + W) =174070 +138 W
(138-17.8) W =373800-174070
W= 1660 bbl n-butane required
Total 10 psi RVP gasoline =21000 + 1660 = 22660 BPCD
Although this differs slightly from the result in Example (1)
Example (3): Consider the following gasoline blending streams are available from
the various units. It is desired to produce a 50-50 split of premium and regular
gasoline having 91 and 87 posted octane numbers respectively, with both having an
RVP= to 10.2 psi . calculate the quantity of n- butane required to give the desired
vapor pressure.
Component Volume MON RON VPBI
Isomerate 5735 81.1 83 25.9
Reformat 14749 86.9 98.5 2.7
FCC gasoline 20117 76.8 92.3 6.4

Light
814 82.4 82.8 24.4
hydrocrackate
Alkylate 4117 95.9 97.3 6.7
Polymer 2071 84 96.9 14.9
Total 47603

For 10.2 psi RVP, (VPBI)m = 18.2
Solution
Starting with the given flow for all of the above streams and calculating the amount
of n-butane to add to fix the RVP.
Component Vol. RVP VPBI Vol (VPBI)
n- butane W 51.6 138 138 W
Isomerate 5735 13.5 25.9 148395
Reformate 14749 2.2 2.7 39517
FCC gasoline 20117 4.4 6.4 128199
Light
814 12.9 24.4 19895
hydrocrackate
Alkylate 4117 4.6 6.7 27732
Polymer 2071 8.7 14.9 30950
Total 47603 +W 394688+138W
18.2 (47603 + W )= 394688 + 138 W

W = 3937 bbl n- butane
The total volume of 10.2 psi RVP premium gasoline = 47603 + 3937 = 51540 BPCD
Octane calculations for pool Gasoline
Component Volume Vol. fract. MON ∑ MON RON ∑ RON
n- butane 3937 0.077 92.0 7.05 93.0 7.12
Isomerate 5735 0.111 81.1 9.02 83.0 9.23
Reformate 14749 0.286 86.9 24.85 98.5 28.18
FCC gasoline 20117 0.390 76.8 29.97 92.3 36.02

Light
814 0.016 82.4 1.30 82.8 1.31
hydrocrackate
Alkylate 4117 0.080 95.9 7.66 97.3 7.77
Polymer 2071 0.040 84.0 3.38 96.9 3.89
Total 51540 1.000 83.23 95.53
Pool octane [ (∑ MON + ∑ RON ) / 2 )] = 88.38 PON

This is not acceptable, as the octane requirement for pool gasoline is 89 PON.
There are several ways of correcting this. Among the possibilities are :
Increase severity of reforming to produce a 98.8 to 100 RON clear reformate.
Use an octane blending agent, such as MTBE ( methyl tertiary butyl ether ) and
ETBE ( ethyl tertiary butyl ether ).
Recalculating pool gasoline RVP and PON after adding sufficient MTBE to increase
the PON to 89.0 gives the following .
Component Vol. RVP VPBI Vol (VPBI)
n- butane W 51.6 138 138 W
Isomerate 5735 13.5 25.9 148395
Reformate 14749 2.2 2.7 39517
FCC gasoline 20117 4.4 6.4 128199
Light
814 12.9 24.4 19895
hydrocrackate
Alkylate 4117 4.6 6.7 27732
Polymer 2071 8.7 14.9 30950
MTBE 1593 9.0 15.6 24832
Total 49195 +W 419520+138W
49195 +W=18.2 (419520+138W)

119.8W=895349-419520=475829
W=3984 bbl
Total pool 10.2 RVP, 89.0 PON gasoline= 53179 BPCD
Other properties:
Several other properties of blend pools (viscosities, aniline point, pour points,
flash points) can be estimated using a technique similar to that of the Chevron
Method for RVP, that is:
n
Pt = ∑ (vi Pi ) ……………………………….. 6
i =1
where vi is the volume fraction of blending stream i as above, and Pt as well as Pi

are the “blending” properties of the product and the blending streams,
respectively. The blending properties are, of course, compiled in tables much in
the same way as in the case of RVP. These additional properties are important for
Diesel blending. Finally, properties like sulfur or nitrogen content are monitored
and blended linearly with percentages.
Home work (1) :
Using the value from the following table, calculate the number of barrels of n-
butane that have to be added to a mixture of 1250 barrels of HSR gasoline, 750
barrels of LSR gasoline, and 620 barrels of C5 FCC gasoline to produce a 9.0 psi
Reid vapor pressure . What are the research and motor octane number of the
blend?
Component Volume MON RON RVP VPBI
HSR
1250 58.7 62.3 1.0 1.0
gasoline
LSR
750 61.6 66.40 11.1 20.3
gasoline
C5 FCC
620 77.1 92.1 4.4 6.4
gasoline
Given : VPBI of n- butane =138 , MON=92.0 , RON=93

For 8 psi RVP, (VPBI)m = 13.4
Home work (2) :
Calculate the octane number of the final blend and amount of n- butane needed
for producing a 9.5 psi RVP gasoline from 5100 BPSD of LSR gasoline, 3000 BPSD
light hydrocrackate,4250 BPSD alkylate, 10280 BPSD heavy hydrocrackate, 14500
BPSD C5 FCC gasoline,14200 BPSD of 96 RON reformat, and 2500 BPSD of polymer
gasoline.
Component Volume MON RON RVP VPBI
LSR gasoline 5100 61.6 66.4 11.1 20.3
light
3000 82.4 82.8 12.9 24.4
hydrocrackate
alkylate 4250 95.9 97.3 4.6 6.7
heavy
10280 67.3 67.6 1.1 1.24
hydrocrackate
C5 FCC
14500 77.1 92.1 4.4 6.4
gasoline
Reformate
14500 86.5 98.0 2.2 2.7
RON 96
Polymer 2500 84 96.9 8.7 14.9

For 9.5 psi RVP, (VPBI)m = 17.6
Home work (3) : A regular gasoline is to be blended using the components listed in the
table below. The target (ON) specification is 90. Using the information provided,
determine the volume of Reformate required meeting the blending specification.
Component Volume (barrels) RON MON

Hydrocracate 3000 82.8 82.4
Alkylate 1000 89.7 89
Reformate ------- 98 91
Straight run 1000 79 78
naphtha
Lect./8
Supporting Processes
Supporting Processes
Not directly involved in the processing of petroleum
based fuels Processes
» Hydrogen production & purification
» Acid gas treating
» Sulfur recovery
» Gas processing units
» Water treatment
Hydrogen Production & Purification
 Many refineries produce sufficient quantities of hydrogen
for hydro treating from their naphtha-fed platinum catalyst
reforming operations.
 however, require more hydrogen than is produced by
their catalytic reforming units
 This supplemental hydrogen requirement can be
Provided by one of two processes:
1.Steam reforming of light ends such as methane (natural
gas), ethane, or propane
2.Partial oxidation of heavy hydrocarbons such as fuel oil
Steam reforming
Steam reforming for hydrogen production is accomplished in four
steps:
1. Reforming. This involves the catalytic reaction of methane with steam at
temperatures in the range of 1400 to 1500°F (760–816°C), according to the
following equation:
CH4 + H2O → CO + 3H2 (1)
This reaction is endothermic and is carried out by passing the gas through
catalyst-filled tubes in a furnace. The catalyst usually is in the form of
hollow cylindrical rings ranging up to 3/4 inch in diameter. It consists of 25
to 40% nickel oxide deposited on a low-silica refractory base.
2. Shift conversion. More steam is added to convert the CO from step 1 to
an equivalent amount of hydrogen by the following reaction:
CO + H2O → CO 2 + H2 (2)
This is an exothermic reaction and is conducted in a fixed-bed catalytic
reactor at about 650°F (343°C). Multiple catalyst beds in one reactor with
external cooling between beds are commonly employed to prevent the
temperature from getting too high. The catalyst used is a mixture of
chromium and iron oxide.
3. Gas purification. The third step is removal of carbon dioxide by absorption in
a circulating amine or hot potassium carbonate solution. Several other
treating solutions are in use. The treating solution contacts the hydrogen and
carbon dioxide gas in an absorber containing about 24 trays, or the equivalent
amount of packing. Carbon dioxide is absorbed in the solution, which is then
sent to a still for regeneration.
4. Methanation. In this step, the remaining small quantities of carbon
monoxide and carbon dioxide are converted to methane by the following
reactions:
CO + 3H 2 → CH4 + H2O
CO 2 + 4H 2 → CH4 + 2H 2O (3)
This step is also conducted in a fixed-bed catalytic reactor at temperatures of
about 700 to 800°F (427°C). Both reactions are exothermic and, if the feed
concentration of CO and CO 2 is more than 3%, it is necessary to recycle
some of the cooled exit gas to dissipate the heat of reaction. The catalyst
contains 10 to 20% nickel on a refractory base.
Partial oxidation of fuel oils
 Partial oxidation of fuel oils is accomplished by burning
the fuel at high pressures (800 to 1300 psig) with an
amount of pure oxygen which is limited to that required to
convert the fuel oil to carbon monoxide and hydrogen.
Enough water (steam) is added to shift the carbon
monoxide to hydrogen in a catalytic shift conversion step.
The resulting carbon dioxide is removed by absorption
in
hot potassium carbonate or other solvents.
Ideally the partial oxidation reactions are as follows:
2CnHm + nO 2 → 2nCO + mH2

2nCO + 2nH 2O → 2nCO 2 + 2nH2
ACID GAS REMOVAL
 Gases from various operations in a refinery processing sour crudes

contain hydrogen sulfide and occasionally carbonyl sulfide.
 Some hydrogen sulfide in refinery gases is formed as a result of
conversion of sulfur compounds in processes such as hydrotreating,
cracking, and coking. Recent air pollution regulations, however, require
that most of the hydrogen sulfide be removed from refinery fuel gas and
converted to elemental sulfur.
 In addition to hydrogen sulfide many crudes contain some dissolved
carbon
dioxide which through distillation finds its way into the refinery fuel gas.
 These components—hydrogen sulfide and carbon dioxide—are
generally termed acid gases.
 They are removed simultaneously from the fuel gas by a number of
different processes, some of which are:
Amine Treating Unit
 Hydrogen sulphide and carbon dioxide readily combine with aqueous
solutions of certain alkanol amines at temperatures usually close to ambient ,
 and may be driven off from the fat solutions by heating to about 100 oC .
 The reaction with hydrogen sulphide is :
2 RNH2+ H2S (RNH3)2S

 Amine (mono- di and tri ethanol amines and
methyl di ethanol amine)
 The conventional equipment , comprising a bubble- cup
tower together with a bubble cup tower for regeneration.
 The treating temperature is 5 to 10 oC above the dew
point of the gas to ensure that no hydrocarbons liquid
condenses out of the plant.
 This process is the most widely used method for the
regenerative removal of H2S from both gases and liquids.
 Its use is not only in refineries but also for oilfield
treatment of natural gases and LPG.
 The choice of the proper amine and solution depends on
the composition of the gas to be treated and the final
purity desired.
Sulphur Recovery
 Acid gas streams from hydrodesulphurization containing
H2S are sent to sulphur recovery unit (Claus unit).
 Furthermore, sulphur removal is carried out by tail gas clean
up schemes.
 The purpose of removing the sulphur is to reduce the sulphur
dioxide (SO2) emissions in order to meet environmental
guidelines.
Claus Process
 The Claus process is the most significant elemental sulphur recovery process
from gaseous hydrogen sulphide.
 Gases with an H2S content of over 25% are suitable for the recovery of sulphur in
the Claus process.
 Hydrogen sulphide produced, for example, in the hydrodesulphurization of refinery
products is converted to sulphur in Claus plants .
 The main reaction is
2H2S + O2 2S + 2H2O
The Claus technology can be divided into two process stages :
thermal and catalytic.
In the thermal stage, hydrogen sulphide partially oxidized at temperatures
above 850 0C (1562 F) in the combustion chamber.
This causes elemental sulphur to precipitate in the downstream process gas
cooler.
If more oxygen is added, the following reaction occurs:
2H2S + 3O2 2SO2 + 2H2O
This gas contains 20–30% of the sulphur content in the feed stream.
Activated
alumina or titanium dioxide is used. The H2S reacts with the SO2 and
results in gaseous, elemental sulphur. This is called the Claus reaction:
2H2S + SO2 3S + 2H2O
GAS PROCESSING UNIT
Gaseous Fuels
The Importance of Gaseous Fuel
- Generally very clean burning. Little soot.
- Easy to burn - No grinding or atomisation.
Excellent mixing
- No problems with erosion or corrosion
- No ash
- The gas is easy to clean. E.g. if sulphur is
present, it may be easily removed prior to
combustion.
- Simplest combustion plant of all - Burners
- Problems with distribution and storage
- Explosion risk - very volatile.
- Relatively costly. Offset by cheaper and more
efficient plant.
Classification of Gaseous Fuels
(A) Fuels naturally found in nature:
Natural gas
Methane from coal mines
(B) Fuel gases made from solid fuel
Gases derived from Coal
Gases derived from waste and Biomass
From other industrial processes (Blast furnace gas)
(C) Gases made from petroleum
Liquefied Petroleum gas (LPG) Refinery
gases
Gases from oil gasification
(D) Gases from some fermentation process
Natural Gas
Natural gas is a gaseous fossil fuel consisting primarily of methane but
including significant quantities of ethane, butane, propane, carbon
dioxide, nitrogen, helium and hydrogen sulfide.
It is found in oil fields and natural gas fields, and in coal beds. When
methane-rich gases are produced by the anaerobic decay of non-fossil
organic material, these are referred to as biogas.
Natural gas is often informally referred to as simply gas, especially when
compared to other energy sources such as electricity.
Before natural gas can be used as a fuel, it must undergo extensive
processing to remove almost all materials other than methane.
The by-products of that processing include ethane, propane, butanes,
pentanes and higher molecular weight hydrocarbons, elemental sulfur,
and sometimes helium and nitrogen.
Chemical composition
 The primary component of natural gas is methane (CH4), the shortest and
lightest hydrocarbon molecule.
It also contains heavier gaseous hydrocarbons such as ethane (C2H6),
propane (C3H8) and butane (C4H10). as well as other sulphur containing
gases, in varying amounts.
Nitrogen, helium, carbon dioxide and trace amounts of hydrogen sulfide,
water and odorants can also be present.
 Mercury is also present in small amounts in natural gas extracted from some
fields.
 The exact composition of natural gas varies between gas fields.
Organosulfur compounds and hydrogen sulfide are common contaminants
which must be removed prior to most uses.
Gas with a significant amount of sulfur impurities, such as hydrogen sulfide, is
termed sour gas; gas with sulfur or carbon dioxide impurities is acid gas.
Natural gas processing plant
There are a great many ways in which to configure the various unit processes
used in the processing of raw natural gas.
The block flow diagram , Fig. (3), is a generalized, typical configuration for the
processing of raw natural gas from non-associated gas wells.
Figure 3: Natural gas processing plant

It shows how raw natural gas is processed into sales gas pipelined to the end
user markets.
It also shows how processing of the raw natural gas yields these byproducts:
• Natural gas condensate
• Sulfur
• Ethane
• Natural gas liquids (NGL): propane, butanes and C5+ (which is the
commonly used term for pentanes plus higher molecular weight
hydrocarbons) .
1- Raw natural gas is commonly collected from a group of adjacent wells and
is first processed at that collection point for removal of free liquid water and
natural gas condensate. The condensate is usually then transported to an oil
refinery and the water is disposed of as wastewater.
2- The raw gas is then pipelined to a gas processing plant where the initial
purification is usually the removal of acid gases (hydrogen sulfide and carbon
dioxide). There a many processes that are available for that purpose as
shown in the flow diagram, but amine treating is the most widely used
process.
3- The acid gases removed by amine treating are then routed into a sulfur
recovery unit which converts the hydrogen sulfide in the acid gas into
elemental sulfur. There are a number of processes available for that
conversion, but the Claus process is by far the one usually selected. The
residual gas from the Claus process is commonly called tail gas and that gas
is then processed in a tail gas treating unit (TGTU) to recover and recycle
residual sulfur-containing compounds back into the Claus unit.
4- The next step in the gas processing plant is to remove water vapor from the
gas using the either regenerable absorption in liquid triethylene glycol (TEG)
or a Pressure Swing Adsorption (PSA) unit which is regenerable adsorption
using a solid adsorbent. Another newer process using membranes may also
be considered.
5- Mercury is then removed by using adsorption processes (as shown in the
flow diagram) such as activated carbon or regenerable molecular sieves.
6- Nitrogen is next removed and rejected using one of the three processes
indicated on the flow diagram:
7- The next step is to recover of the natural gas liquids (NGL) for which most
large, modern gas processing plants use another cryogenic low temperature
distillation process involving expansion of the gas through aturbo-expander
followed by distillation in a demethanizing fractionating column. Some gas
processing plants use lean oil absorption process rather than the cryogenic
turbo-expander process.
8- The residue gas from the NGL recovery section is the final, purified sales
gas which is pipelined to the end-user markets.
9- The recovered NGL stream is processes through a fractionation train
consisting of three distillation towers in series: a dethanizer, adepropanizer
and and a debutanizer. The overhead product from the deethanizer is ethane
and the bottoms are fed to the depropanizer. The overhead product from the
depropanizer is propane and the bottoms are fed to the debutanizer. The
overhead product from the debutanizer is a
mixture of normal and iso-butane, and the bottoms product is a C5+ mixture.

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Fourth Year - Chemical Process Eng.

• What is natural gas?

•Biogenic : from organics, by bacterial transformation :

• Where have crude oil and natural gas come from?

The proportion of hydrocarbons in the mixture is highly variable and

Figure( 1 ) Paraffins in crude oil.

Figure 2: Naphthene compounds

Figure 3: Aromatic compounds

Figure 4: Olefin compounds

Figure 5: Di-olefin compounds

 Marketing / Pricing of Crude Oil

By the geographic location it is

• Light Crude Oil >31

No. 1 482-527 atm. > 40 (Paraffinic Base)

No. 2 527-572 (40-mm)Hg > 30 (Paraffinic Base) The presence of

The most widely used index is characterization factor (Watson,

K≥ 12.15 (Paraffinic Base)

The correlation index is useful in evaluating individual fractions from

 Fractional, run only on crude oil, batch . Fig (4.7)

Fractionation column like (IP24 or D86).

a) Draw an assay curve.

% vol. Distilled TBP (⁰F ) API %S

No. ⁰F Distilled Percent 60/60 ⁰F

Fraction Cut Temp. Percent Sum. Sp. gr. 0 API 60 ⁰F

Two-Phase Gas–Oil Separation

Gas goes out the top of the separators to a gas collection

Figure 2 : Pressure-drop profile for a typical GOSP in the Middle East.

- Volatile components either sent to consumer centers as

The basic principles for the treating process are as

Free water is simply defined as that water produced with

3. Minimization of 2. Reduction of heat 1. Reduction of

Oil emulsions are mixtures of oil and water. In general, an

For two liquids to form a stable

1. The two liquids 2. There must be

Some of the common emulsifiers are as

3. Oil-soluble organic acids

A. Breaking the emulsion:

All these furnaces have got separate radiation section and

In most of the furnaces, the direction of tubes is horizontal as

A: area of radiating surface, ft2

For a satisfactory design, the following schedule of heat

Type of heat Percent

Design of a furnace radiation section is based on

C Acp = area of furnace wall that has tube mounted on it (ft2).

Outlet temperature of the stock:-

Heat absorption in radiant section = 0.458 *146 *106

Heat absorbed / sq ft projected area = q = 66900000/1500

Heat absorbed in radiation zone = R x Q= 0.4755X 40x106 = 19020000 Btu

After desalting, the crude oil is pumped through a series of heat

The furnace discharge temperature is sufficiently high to cause

The 20% "over flash" allows some fractionation to occur on the

In many petroleum distillations, steam is admitted to the space

Bottom product of atmospheric column is now again routed

Volume 50 % Mol. Latent

Steam (vapor) 567 * (535 - 286) * 0.5 = 70600

Latent heat Btu

Kinds of 2) Hot Reflux

Example (2) : (Quantity of Reflux)

total pressure at the top of the tower = 780 mm Hg

660 120 x110 1 1

Moles reflux = 10403/110 = 94.6

530 100 * 185 1 1

Fraction Lb\hr M.w. λ Temperature o F

Heat absorption in radiant section = 0.458 146 106