Petroleum Refining & Petrochemicals

Welcome to
Petroleum Refining &

Petrochemicals
ECHM 404
Zin-Eddine Dadach
2013-2014
LISTEN...LEARN...THINK...GROW
L.Os of the course

Describe refinery products and feed stock qualities
Differentiate between atmospheric and vacuum crude oil distillation units
Explain the process and principles used for hydrotreating, catalytic
reforming, and isomerization.

Explain the process and principles for coking, catalytic cracking, and
hydrocracking units
Describe the petrochemical industry and discuss the properties and
manufacture of some typical end products

Highlight the common chemical reactions involved in the production of
petrochemicals.
Perform tasks using the internet to retrieve information about the markets for
crude oil, petroleum products, and petrochemical end products.
L.O #1:
Describe Refinery
products and feed stock
qualities
Crude oil is one of the most valuable commodities in the
world, but only after it has been refined into petroleum
products.
WHAT IS PETROLEUM OR
CRUDE OIL?
Petroleum (Latin Petroleum derived from Greek
(Latin petra) - rock + (Latin oleum) - oil)

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.
Crude oil may also be found in semi-solid form mixed
with sand, as in the Athabasca oil sands in Canada,
where it may be referred to as crude bitumen.
WHAT IS CRUDE OIL?

Crude oils are in liquid form containing complex
mixtures of many different hydrocarbon compounds.

Crude oils vary in appearance and composition from
one oil field to another.
Crude oils range in consistency from water to tar-like
solids, and in color from clear to black.
Crude oils are generally classified as paraffinic,
naphthenic, or aromatic, based on the predominant

proportion of similar hydrocarbon molecules.
MAIN COMPONENTS OF CRUDE OILS

Carbon - 84%
Hydrogen - 14%
Sulfur - 1 to 3% (hydrogen sulfide, sulfides, disulfides,
elemental sulfur)
Nitrogen - less than 1% (basic compounds with amine
groups)
Oxygen - less than 1% (found in organic compounds
such as carbon dioxide, phenols, ketones, carboxylic
acids)
Metals - less than 1% (nickel, iron, vanadium, copper,
arsenic)
Salts - less than 1% (sodium chloride, magnesium
chloride, calcium chloride)
MAJOR HYDROCARBONS IN
CRUDE OIL
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 part

of bitumen or asphalt.
Crude oil refining is a key transformation step in the

Midstream Sector of the oil and gas value chain
because it adds commercial value to the oil by
transforming it into many different marketable
products.
GLOBAL ECONOMY
DEPENDS ON ENERGY
The global economy receives almost 80% of its
energy subsidies from nonrenewable fossil sources:

crude oil, gas, and coal.
They are called "nonrenewable" because, for all
practical purposes, they're not being made any more.

Nonrenewable fossil sources are the major
contributors to global warming

DIFFERENT ENERGY
SOURCES
10
WORLD OIL RESERVES
11
ECONOMY AND CRUDE OIL IN

UAE?
Crude Oil production has been the mainstay of the
economy in the UAE and will remain a major

revenue earner long into the future, due to the vast
hydrocarbon reserves at the countrys disposal.
Proven recoverable oil reserves are currently put at
98.2 billion barrels or 9.5 percent of the global

crude oil proven reserves.
12
CRUDE OIL
REFINERIES
13
Refinery: From Crude to Useful

Products
14
WORLDS REFINERIES
Petroleum refineries are marvels of modern engineering.
Within them a maze of pipes, distillation columns, and
chemical reactors turn crude oil into valuable products.

Large refineries cost billions of dollars, employ several
thousand workers, operate around the clock, and occupy the

same area as several hundred football stadiums.
15
Useful Products from crude oil
16
Petroleum Refining Processes

Petroleum refining processes are the chemical engineering
processes and other facilities used in petroleum refineries

(also referred to as oil refineries) to transform crude oil into
useful products such as liquefied petroleum gas (LPG),
gasoline or petrol, jet fuel, diesel oil and fuel oils.
We will study the following processes:
Hydrodesulfuration as pretreatment
Isomerization
Reforming Catalytic
Thermal cracking
Cooking
17
ABU DHABI REFINERY
Following the discovery of oil in Abu

Dhabi in 1958, and the first export
shipments of Crude in 1962, plans were
drawn up for a grass root Refinery with a
capacity of 15,000 barrels per stream day
(BPSD) to meet a growing local need for
petroleum products
18
CRUDE OIL FOR ABU DHABI

REFINERY
The Refinery is a Hydro Skimming
Complex designed to process Bab

Crude as well as a mixture of AsabSahil, Shah and Thammama
Condensate.
19
REFINERY MAIN UNITS IN

ABU DHABI REFINERY
Crude Distillation Unit
Naphtha Hydrodesulphuriser Unit
Kerosene Merox Unit
Catalytic Reformer Unit
Gas Oil Hydrodesulphuriser Unit
LPG Treating and Recovery Unit
Naphtha Stabilizer Unit
Gas Sweetening Unit
Sulphur Recovery Unit
20
REFINERY FINAL PRODUCTS
21
STUDY THE MARKET

BEFORE YOU DECIDE
We need to study the market in order to adjust the production of each
refinery product to maximize profits

Various fractions are more important at different times of year. During the
summer driving months, the public consumes vast amounts of gasoline,

whereas during the winter more fuel oil is consumed.
These demands also vary depending upon whether you live in the frigid
north, or the humid south.

Modern refineries are able to alter the ratios of the different fractions to
meet demand, and maximize profit.
22
WORLD MARKETS
23
FROM THE WORLD MARKET

DISTILLATE AND GASOLINE ARE THE TWO MOST
IMPORTANT PRODUCTS
LIGHT CRUDE OILS CAN SATISFY THE MARKET BETTER
THAN HEAVY CRUDE OILS

FROM HEAVY CRUDE OILS , CRACKING PROCESSES ARE
NEEDED TO OBTAIN SMALLER CHAINS HYDROCARBONS

AS DISTILATE AND GASOLINE
24
Classification of Crude
Oils
WTI or Brent
Light or Heavy
Sweet or Sour
25
CLASSIFICATION OF CRUDE
OILS
The oil industry classifies "crude" by the location of its origin
(e.g., "West Texas Intermediate, WTI" or "Brent")

Often by its relative weight or viscosity ("light", "intermediate" or
"heavy");
Refiners may also refer to it as "sweet," which means it
contains relatively little sulfur, or as "sour," which means it

contains substantial amounts of sulfur and requires more
refining in order to meet current product specifications.
Each crude oil has unique molecular characteristics which are
understood by the use of crude oil assay analysis in petroleum
laboratories.
26
Brent Blend
Brent blend is a light crude oil (LCO), though not as
light as West Texas Intermediate (WTI). It contains

approximately 0.37% of sulphur, classifying it as
sweet crude, yet not as sweet as WTI.
Brent is suitable for production of petrol and middle
distillates. It is typically refined in Northwest Europe.
Brent Crude has an API gravity of around 38.06 and
a specific gravity of around 0.835.
27
WTI Crude Oil

WTI is a light crude oil, with an API gravity of around
39.6 and specific gravity of about 0.827, which is

lighter than Brent crude.
It contains about 0.24% sulfur thus is rated as a sweet
crude oil (having less than 0.5% sulfur), sweeter than
Brent which has 0.37% sulfur.
WTI is refined mostly in the Midwest and Gulf Coast
regions in the U.S.
28
HYDROCARBONS IN
CRUDE OILS
COMPOSITION OF PETROLEUM
(PAGES 62-64)
29
BASICS OF HYDROCARBON
CHEMISTRY
Crude oil is a mixture of hydrocarbon molecules, which
are organic compounds of carbon and hydrogen atoms

that may include from one to 60 carbon atoms.
The properties of hydrocarbons depend on the number
and arrangement of the carbon and hydrogen atoms in

the molecules.
Hydrocarbons containing up to four carbon atoms are
usually gases, those with 5 to 19 carbon atoms are

usually liquids, and those with 20 or more are solids.
30
THE MAIN HYDROCARBONS

OF CRUDE OILS
Paraffins
Aromatics
Naphtenes
Other hydrocarbons:
Alkenes
Dienes and Alkynes
31
PARAFFINS
The paraffinic series of hydrocarbon compounds found in

crude oil have the general formula CnH2n+2 and can be
either straight chains (normal) or branched chains
(isomers) of carbon atoms.
Examples of straight-chain molecules are methane,
ethane, propane, and butane (gases containing from one

to four carbon atoms), and pentane and hexane (liquids
with five to six carbon atoms).
32
THE SIMPLEST PARAFFIN

METHANE
33
BUTANE AND ISOBUTANE
C4H10
34
AROMATICS
Aromatics are unsaturated ring-type (cyclic) compounds which

react readily because they have carbon atoms that are deficient
in hydrogen.
All aromatics have at least one benzene ring (a single-ring
compound characterized by three double bonds alternating with

three single bonds between six carbon atoms) as part of their
molecular structure.
Naphthalenes are fused double-ring aromatic compounds.
The most complex aromatics, polynuclears (three or more fused
aromatic rings), are found in heavier fractions of crude oil.

35
AROMATIC COMPOUND
BENZENE (C6H6 )
36
DOUBLE-RING AROMATIC
COMPOUND
NAPTHALENE (C10 H8)
37
NAPHTHENES
(monocycloparaffins)
Naphthenes are saturated hydrocarbon groupings

with the general formula CnH2n , arranged in the form
of closed rings (cyclic) and found in all fractions of
crude oil except the very lightest.
Single-ring naphthenes (monocycloparaffins) with five
and six carbon atoms predominate, with two-ring

naphthenes (dicycloparaffins) found in the heavier
ends of naphtha.
38
CLASSIFICATION OF
CRUDE OILS
39
CHARACTERIZATION OF
CRUDE OILS ?
Attempts have been made to use
Distillation ranges in order to classify
crude oils as :
Paraffinic
Naphtenic
Aromatic
40
CRUDE OILS ARE DEFINED AS :

Paraffin base
Naphtene base
Asphalt base
Mixed based
Aromatic base ( up to 80% aromatics)
41
CRUDE OIL CLASSIFICATION

in order of decreasing value
1) PARAFFINIC CRUDE OILS
paraffins + naphthenes > 50%
paraffins > naphthenes
paraffins > 40%
2) NAPHTHENIC CRUDE OILS
2) paraffins + naphthenes > 50%
naphthenes > paraffins
naphthenes > 40%
42

3) PARAFFINIC- NAPHTENIC CRUDE OILS
Aromatics < 50%
paraffins < 40%
naphthenes < 40%
4) AROMATIC- NAPHTENIC CRUDE OILS:

Aromatics > 50%
naphthenes > 25%
paraffins < 10%
43

5)AROMATIC- INTERMEDIATE CRUDE OILS
Aromatics > 50%
paraffins > 10%
6)AROMATIC- ASPHALTIC CRUDE OILS
naphthenes > 25%
paraffins < 10%
44
PROBLEMS WITH HEAVY CRUDE

OILS
The heavier a crude oil is, the more difficult a challenge it
presents in extracting it from the ground and purifying it

into end products.
Crude oil's physical properties, such as viscosity, and its
chemical impurities affect the cost of recovery and
refining, and the amount of waste produced in
processing.
New air-pollution regulations have tightened the
restrictions on the amount of impurities, such as sulfur,
that can remain in petroleum products used as fuel.
45
HEAVY CRUDE OILS

SITUATION IN THE MARKET
So, oil companies have focused on bringing up the
lighter oil and leaving denser oil under ground.

Moreover, due to increased refining costs and high
sulfur content, heavy crude oils are often priced at a

discount to lighter ones.
46
LIGHT CRUDE OILS AND

GLOBAL MARKET
But industry predictions show that the supply of
light crude oils is dwindling, leaving an increasing

proportion of heavy grades for future use.
In fact, most of the Western Hemisphere's
remaining oil is heavy crude, creating a strong

strategic incentive to find new ways to extract and
use it.
47
COST INVOLVED FOR

HEAVY CRUDE OILS
The increased viscosity and density also makes
production more difficult.

Large quantities of heavy crude oils have been
discovered in the Americas including Canada,
Venezuela and Northern California.
The relatively shallow depth of heavy oil fields
(often less than 3000 feet) contributes to low
drilling costs.
48
PROPERTIES OF HEAVY
CRUDE OILS
Heavy crude oil is asphaltic. It is "heavy" (dense and
viscous).
heavy crude oils with a high content of naphthenic
compounds, such as asphaltenes.
Asphaltic crude oils are also known as naphthenebased crude oil when the paraffin wax content is low (
< 10%)
Heavy oil has over 60 carbon atoms and hence a high
boiling point and molecular weight.
49
ENVIRONMENTAL ISSUE OF
HEAVY CRUDE OILS
As a rule, heavy crude oils have a more severe
environmental impact than light ones.

Heavy crude oils also carry contaminants. For example,
Orinoco extra heavy oil contains 3.5% sulfur as well as
vanadium and nickel
Heavy crude oils contain more carbon in relation to
hydrogen, thus releasing more CO2 (believed to be

responsible for climate change) per amount of usable
energy when burned.
50
CHARACTERIZATION OF
CRUDE OIL
PROPERTIES/ASSAY
Pages 57-70
51
WHY CHARACTERIZE
CRUDE OILS ?
Crude grades vary considerably from each other - in yield
and properties.
Crude characterization is essential to estimate:
Feedstock properties for refinery units,

Produce an optimal amount of final products
Meet product quality specifications
Provide an economic assessment for crude oils.
52
CRUDE CHARACTERIZATION
IS UTILIZED BY:
UPSTREAM PLANNING
To determine the economic viability of new fields /

discoveries
SUPPLY ORGANIZATIONS
To assign crude value for individual grades
REFINERY OPERATIONS
To schedule crude receipts and determine product yields
MODEL ENGINEERS
To optimize refinery crude slates
RESEARCH & DEVELOPMENT
To design equipment and process planning
53
HOW TO CHARACTERIZE
CRUDE OILS
Because crude oils contain hundreds of
hydrocarbons and therefore exact composition of

crude oils is unknown
We need other methods to characterize crude oils
Properties of crude oils are then defined by
different assay.
54
WHAT IS A CRUDE OIL ASSAY?
An efficient assay is derived from a series of

test data is then used to give an accurate
description of crude oil quality.
These properties allow an indication of crude oil
behavior during the refining processes
55
THE IMPORTANCE OF CRUDE

OIL ASSAYS
Knowing what your crude is worth begins by
having good crude assay data.

The identification of chemical and physical
properties of crude oil provides the basis for

economic valuation, engineering design and
refinery processing.
56
THE MOST IMPORTANT ASSAY

Density or API Gravity
Distillation range
Characterization Factor
Pour point
Carbon residue
IMPURITIES :
Sulfur Content
Salt content
Nitrogen Content
57
SPECIFIC GRAVITY OF
CRUDE OIL
58
DEFINITION OF DENSITY
Density ( ASTM D-1298, IP 160) is an important property
used to determine the quality of crude oils

Petroleum and petroleum products are usually bought or sold
on the density basis

Definition: Density of a crude oil is the mass of oil by unit
volume at 150C
In laboratories, hydrometers, pycnometers or modern digital
density meter are used to measure specific gravity

59
CRUDE OILS API GRAVITY

Crude oils are defined in terms of API (American
Petroleum Institute) gravity.

The higher the API gravity, the lighter the crude.
Crude oils API gravity may range from less than
100API to over 500 API but most crude oils fall in

the 20 to 450 API
60
WHAT IS 0API?
61
API of different crude oils

Light crude oil is defined as having an API gravity higher than
31.1 API (less than 870 kg/m3)

Medium crude oil is defined as having an API gravity between
22.3 API and 31.1 API (870 to 920 kg/m3)

Heavy crude oil is defined as having an API gravity below 22.3
API (920 to 1000 kg/m3)

Extra heavy crude oil is defined with API gravity below 10.0
API (greater than 1000 kg/m3)

62
API DENSITY AND TYPE OF

HYDROCARBONS
Crude oils with low carbon, high hydrogen, and high
API gravity are usually rich in paraffins and tend to

yield greater proportions of gasoline and light
petroleum products VALUABLE CRUDE OIL
Those with high carbon, low hydrogen, and low API
gravities are usually rich in aromatics and more

impurities LESS VALUABLE CRUDE OIL
63
True Boiling Point or TBP

Curve
DISTILLATION TEST
64
TRUE BOILING POINT ( TBP)
A Distillation Curve
A plot of the boiling points (
temperatures) of crude oil versus %
volume of distilled fractions
TBP crude oil distillations by ASTM D
5236
65
TBP OF CRUDE OIL IS A KEY

ASSAY FOR REFINERIES
A full and comprehensive evaluation of the crude
starts with a True Boiling Point Distillation

The distillation test is a method used to give an
indication of the types of the products that can be

obtained by the crude oils
A boiling range of the crude oil gives an indication of

the quantities of the various products present
66
CRUDE OIL TBP ASSAY IN

OUR LAB
67
RESULT OF THE EXPERIMENT:

TRUE BOILING CURVE OF CRUDE OIL
68
ATMOSPHERIS AND VACUUM

DISTILLATION
ASTM D-86 ( Atmospheric distillation):
This test is carried out at atmospheric pressure and is

stopped at 3000C ( 5720F) to avoid thermal cracking
ASTM D-1160 (Vacuum distillation):
This test method covers the determination, at reduced

pressure, of the boiling temperature ranges of
petroleum products from the residue of the atmospheric
distillation.
69
DISTILLATION LABS
ATMOSPHERIC AND VACCUM

DISTILLATIONS
70
LAB for atmospheric distillation

ASTM D-86 ( Atmospheric Distillation):
71
LAB for Vacuum distillation

ASTM D-1160 (Vacuum distillation):
72
DISTILLATION RANGES FOR

REFINERY PRODUCTS
ATMOSPHERIC DISTILLATION PRODUCTS
Butanes and lighter

55-175 0F
Light Gasoline
175-300 0F
Light naphtha
300-400 0F
Heavy naphtha
400-500 0F
Kerosene
500-650 0F
Atmosphere Gas Oil

650-800 0F
VACUUM DISTILLATION PRODUCTS
Light Vacuum Gas Oil (LVGO)

800-1000 0F
Heavy. Vacuum Gas Oil (HVGO) 1000 0F
Vacuum Residue
> 1000 0F
73
Measuring the Density of

different fractions
74
0API
VERSUS % VOLUME
DISTILLED FRACTION
75
ASSAY TO DETERMINE
GASES IN CRUDE OILS
BY GAS CHROMATOGRAPHY
76
LIGHT HYDROCARBONS OR
GASES IN CRUDE OILS
The amount of the individual light
hydrocarbons in crude oils ( methane to butane)

is often included as part of a preliminary assay
The identification and quantification of each
light component is carried out by GC or gas

chromatography ( ASTM D-2427)
77
CLASS WORK #1
Study appendix C ( page 415)
about the specifications of

different crude oils
Group discussion
78
CLASS WORK #2
Study the data of the crude oil given in figure 3.5 page 66:
1)
Define its type knowing its density
Draw the TBP curve ( Temperature versus the percentage
distilled using figure 3.6 page 67 for the products of vacuum

distillation)
Draw the API curve ( 0 API versus the percentage distilled)
Perform an approximate material balances of the refinery using
this crude oil using the typical ranges of refinery products (given
above).
79
CHARACTERIZATION
OF CRUDE OILS
80
THE NEED FOR

CHARACTERIZATION FACTORS
Problems arise at ranges above 2000C, since
molecules can not be placed in one group (

naphthenic/ aromatic or cyclic/ paraffinic)
To overcome this situation, characterization
factors based on specific gravity and TBP

distillation were introduced to characterize the
different crude oils
81
CHARACTERIZATION OF
CRUDE OILS
The two mostly used correlations between yield
and aromaticity and paraffinicity of crude oils are:

UOP or Watson Characterization factor
( KW)
US bureau of Mines Correlation index
(CI)
82
WATSON CHARACTERIZATION
1/ 3
KW
TB
S .G
TB is the average boiling point in 0R
S.G is the specific gravity at 600F

KW ranges from less than 10 for highly aromatic crude
oils to almost 15 for highly paraffinic crude oils

KW ranges 10.5-12.5 for highly naphtenic (Cyclic)
crude oils and 12.5 -13 for highly paraffinic crude oils
83
CORRELATION INDEX (CI)
THE CORRELATION INDEX ( CI) IS BASED ON THE PLOT OF SPECIFIC

GRAVITY VS THE RECIPROCAL OF THE BOILING POINT IN
S.G is the specific gravity at 600F

the CI is useful for individual fractions ( PRODUCTS)
CI
87552
473 .7 xS .G 456 .8
TB
CI is based on straight paraffins having CI = 0 and benzene having
CI =100
Low CI ( 0-15) indicates great concentration of paraffins in the
fraction
Average CI ( 15-50) indicate a predominance of naphthenes or a
mixture of paraffins, naphthenes and aromatics
High CI ( above 50) indicates great concentration of aromatics
84
CLASS WORK
Solve problems 1, 2 and 3 page 68
85
KINEMATIC
VISCOSITY
86
DEFINITION
Viscosity is a measure of the resistance of a
fluid to deform under shear stress.

It is commonly perceived as "thickness", or
resistance to flow.
Viscosity describes a fluid's internal resistance to
flow and may be thought of as a measure of fluid

friction.
87
KINEMATIC VISCOSITY
In many situations, we are concerned with the ratio of the viscous
force to the inertial force, the latter characterized by the fluid density
.
This ratio is characterized by the kinematic viscosity (), defined as
follows:
=/
.
where is the dynamic viscosity, and is the density.
Kinematic viscosity (Greek symbol: ) has SI units (ms-1).
It is sometimes expressed in terms of centistokes (cS or cSt). In
U.S. usage, stoke is sometimes used as the singular form.

1 stokes = 100 centistokes = 1 cm2s1 = 0.0001 m2s1.
1 centistokes = 1 mm/s
88
KINEMATIC VISCOSITY OF
CRUDE OILS
Kinematic viscosity is usually

determined at 250C ( 770F) and 1000C
(2120F) by measuring the time for a
volume of liquid to flow under gravity
through a calibrated glass capillary
viscometer ( ASTM D-445)
89
WHY KINEMATIC VISCOSITY OF

CRUDE OILS IS IMPORTANT
Cost of exploitation and transportation of
crude oils depends on its kinematic

viscosity
Light crude oils have small kinematic
viscosity and then transportation cost are
low
90
HIGH VISCOSITY OF VENEZUELA

AND CANADIAN CRUDE OILS
For example, the viscosity of Venezuela's
Orinoco extra-heavy crude oil lies in the range

1000-5000 cP.
Canadian extra-heavy crude has a viscosity in
the range 5000-10,000 cP.
91
LAB #4 ( KINEMATIC
VISCOSITY)
92
POUR POINT
93
DEFINITION OF POUR
POINT
The pour point of a liquid is the lowest
temperature at which it will pour or flow under

prescribed conditions. It is a rough indication of
the lowest temperature at which oil is readily
pumpable.
Also, the pour point can be defined as the
minimum temperature of a liquid, particularly a

lubricant, after which, on decreasing the
temperature, the liquid ceases to flow.
94
CRUDE OILS BEHAVIOR AT

LOW TEMPERATURES
Viscosity and Pour point determinations are

performed to give us information about flow
characteristics of crude oils at low
temperatures
Some general information about the type of
crude oil can be derived from its pour point

data
95
POUR POINT OF CRUDE

OILS
The Pour point of crude oil is indicate the

lowest temperature at which the crude oil will
flow under specific conditions
The maximum and the minimum Pour points
temperatures provide the range of

temperatures in which the crude oil might
appear in liquid form as well as in solid form
96
POUR POINT OF CRUDE

OILS
Pour Point of crude oil is the temperature at which
the oil no longer flows when tilted in a test jar; the

liquid phase is trapped within the PARAFFIN
CRYSTAL STRUCTURE
The paraffins are the first components to crystallize
under low temperatures
97
PROBLEMS RELATED TO
POUR POINTS
The production and transportation of
crude oil and its fractions can be

significantly affected by deposition of
paraffin and asphaltenes in the reservoir
rock tubulars, pumps, vessels, and
pipelines.
98
ADDITIVES FOR
CRYSTALLIZATION PROBLEMS
The Pour point is also used to screen the effects of wax
interactions modifiers on the flow behavior of the crude oil

In a gas-oil NON-FLOW CONDITIONS happen at about
1% crystallization
whereas in a crude oil this happens at 2% crystallization.
The additives used to achieve this are usually referred to
as Pour Point Depressants or PPDs.

99
LAB # 6 ( POUR POINT)
100
CARBON RESIDUE
101
CARBON RESIDUE
The Carbon residue is roughly related to the
asphalt of the crude oil and to the quantity of the

lubricating oil fraction that can be converted
Determined by distillation to a coke residue in the
absence of air
The lower the Carbon Residue, the more
valuable is the crude

102
CARBON=POISON TO
CATALYSTS
Carbon residue cause rapid deactivation of
catalysts and high catalysts cost

For ARC feeds, we use catalytic processes
For VRC, we use non-catalytic processes
103
CRUDE OIL
IMPURITIES
104
INTRODUCTION
Crude oil is a dense, dark fluid
containing many varieties of complex

hydrocarbon molecules, along with
organic impurities containing sulfur,
nitrogen, and heavy metals.
105
SULFUR COMPOUNDS IN
HEAVY CRUDE OILS
Hydrogen sulfide (H2S),
Compounds (e.g. mercaptans, sulfides, disulfides,
thiophenes, aphthenes, etc.

Elemental sulfur
106
SULFUR REFINERY
PROBLEMS
Sulfur presence in crude oil is detrimental to the processing
because sulfur can act as catalyst poisons during processing

Compounds containing sulfur cause also equipment
corrosion and atmospheric pollution when products are

burned
The sulfur content in crude oil varies from 0.1% to 3% weight
and a sulfur content up to 8% was found in tar sand bitumen
107
SULFUR IN CRUDE OILS

Crude oils with less than 0.5% of sulfur are called sweet
crude oil and the crude oils with more than 0.5% are called
sour crude oils
Sour crude oils require special processing and are then
less expensive than the sweet crude oils

One of the most used technique to evaluate the percentage
of sulfur is the combustion of a sample in oxygen to convert

sulfur to sulfur dioxide which is titrated iodometrically or
detected by nondipersive infrared ( astm D-1552)
108
OXYGEN COMPOUNDS
Oxygen compounds such as phenols,
ketones, and carboxylic acids occur in crude

oils in varying amounts
Nitrogen is found in lighter fractions of crude
oil and more often in heavier fractions of crude

oil as non- basic compounds
109
NITROGEN CONTENT
A high nitrogen content is undesirable in crude
oils before organic nitrogen compounds cause

severe poisoning of catalysts and corrosion of
equipments
Crude oils containing nitrogen above 0.25% by
weight require special processing to remove

the nitrogen
110
METAL CONTENT ( PPM)

Metals found in crude oils come from the reservoir itself but
also during recovery, transportation and storage.

Even traces of metals can be deleterious to processes using
catalysts but can also cause corrosion and affect the quality of
products
Trace Metals. Metals, including nickel, iron, and vanadium are
often found in crude oils in small quantities

Test methods such as Atomic Absorption Spectrometry, X-ray
fluorescence spectroscopy are used to determine the amounts

of metals
111
SALTS IN CRUDE OILS

Salts. Crude oils often contain inorganic salts such as sodium
chloride, magnesium chloride, and calcium chloride in

suspension or dissolved in entrained water (brine).
Salts in crude oils come mostly from production practices used
in the field but at some extent from handling to tankers bringing

it to terminals
Most of the salts are dissolved with coexisting water and
removed in desalters but some can be dissolved in the crude oil

itself
112
SALTS CONTENT
Salts can accumulate in stills, heaters and
exchangers leading to fouling that requires expensive

clean up.
Salts content can be determined by potentiometric
titration
The amount of salts in crude oils is important to
decide whether and to what extent the crude oil needs

desalting
113
OTHER IMPURITIES WITH

SMALLER AMOUNTS
Carbon Dioxide
Naphthenic Acids: Some crude oils
contain naphthenic (organic) acids
114
CONCLUSION ON CRUDE
OILS PROPERTIES
API Gravity: oAPI defined as
oAPI=
(141.5/ sp.gr.) -131.5

Most crude oils fall in the 20-45 0API range ( the reference
temperature is 600F ( 15.60C)
TBP Curve
Sulfur Content ( wt%)
Sulfur content can be from 0.1% to 5%
More than 0.5%, crude are sour and need special
processing
115
INTERPRETATION OF
PROPERTIES
Pour point: Low pour point means lower paraffin and
the greater the content of aromatics

Carbon Residue ( wt%): Related to asphalt content
and to the quantity of the lubricating oil that could be

recovered
Salt Content ( lb/ 1000bbl): If the salt content , when
expressed as NaCl, is greater than 10 lb/ 1000bbl ( 30

ppm), it is necessary to desalt the crude in order to
avoid corrosion
116
MAJOR REFINERY PRODUCTS

DUE TO THE ACTUAL MARKET
LPG
Gasoline
Jet fuels
Diesel fuels
Home heating oils

117
SPECIFICATIONS OF
REFINERY FINAL
PRODUCTS
118
WHAT IS LPG?
Varieties of LPG bought and sold include mixes that are
primarily propane, mixes that are primarily butane, and the

more common, mixes including both propane (60%) and butane
(40%).
Depending on the seasonin winter more propane, in summer
more butane.
Propylene and butylenes are usually also present in small
concentration.
A powerful odorant, ethanethiol, is added so that leaks can be
detected easily
119
SECURITY FOR LPG

STORAGE IN REFINERIES
Large, spherical LPG containers may have up to a
15 cm steel wall thickness.

Ordinarily, they are equipped with an approved
pressure relief valve on the top, in the centre.
One of the main dangers is that accidental spills of
hydrocarbons may ignite and heat an LPG container,
which increases its temperature and pressure,
following the basic gas laws.
The relief valve on the top is designed to vent off
excess pressure in order to prevent the rupture of the
tank itself
120
STORAGE OF COMMERCIAL
PROPANE AND BUTANE FOR
HOMES
121
SECURITY FOR BOTTLES

In order to allow for thermal expansion of the contained
liquid, these bottles are not filled completely; typically, they

are filled to between 80% and 85% of their capacity.
Vapor pressure of LPG is approximately 220 kilopascals
(2.2 bar) for pure butane at 20 C (68 F), and

approximately 2.2 megapascals (22 bar) for pure propane
at 55 C (131 F).
LPG is heavier than air, and thus will flow along floors and
tend to settle in low spots, such as basements. This can

cause ignition or suffocation hazards if not dealt with.
122
MAIN USE OF LPG:

HEATING AND ENGINES
123
PROPERTIES OF
COMMERCIAL PROPANE
Vapor pressure ( PSIG)
700F
= 124
1300F
= 286
S.G liquid (60/600F) = 0.509
Limits of flammability (vol% gas in air)
Lower limit = 2.4
Upper limit = 9.6
Gross heating values:
Btu/ft3 gas
= 2,560
124
PROPERTIES OF
COMMERCIAL BUTANE
Vapor pressure ( PSIG)
700F
= 31
1300F
= 97
S.G liquid (60/600F) = 0.582
Limits of flammability (vol% gas in air)
Lower limit = 1.9
Upper limit = 8.6
Gross heating values:
Btu/ft3 gas
= 3,350
125
Motor gasoline characteristics:

The critical properties are:
* Ried vapor pressure ( RVP): Vapor pressure is a measure of

the surface pressure it takes to keep the liquid from vaporizing.
RVP is measured at 100oF
* RVP of gasoline must meet two conditions:
- On cold start , enough gasoline must vaporize to provide
ignitable mixture
- On hot restart, the gasoline should not expand in the
injection apparatus and must let air to come in
* Boiling range ( 100 -4000F)
* Antiknock characteristics: PON
* Desirable sulfur content is < 300 PPM
126
Octane number?
Definition: A value used to indicate the resistance of a motor fuel
to knock. Octane numbers are based on a scale on which
isooctane is 100 (minimal knock) and heptane is 0 (bad knock).
Example: A gasoline with an octane number of 92 has the
same knock as a mixture of 92% isooctane and 8% heptane.

We can measure antiknock by using the octane number :
PON: posted octane number
MON: motor octane number
RON : research octane number
Antiknock performance is the main difference between the
grades of gasoline
127
Posted Method Octane

number
Gasoline pumps typically post octane numbers as an average
of two different values. Often you may see the octane rating
quoted as PON=(RON+MON)/2.
One value is the research octane number (RON), which is
determined with a test engine running at a low speed of 600
rpm ( performance inside cities).
The other value is the motor octane number (MON), which is
determined with a test engine running at a higher speed of 900
rpm ( performance in high ways).
If, for example, a gasoline has an RON of 98 and a MON of 90,
then the posted octane number would be the average of the
two values or PON= 94.
128
CLASS WORK
WORK EXAMPLE 10.3.1 PAGE 216
129
DISTILLATE FUELS
Jet fuel
Diesel fuel
Heating fuels
WHAT IS JET FUEL?
The most expensive distillate fuel

Used for commercial aviation and military aircraft
Known also as turbine fuels
Primary fraction of jet fuel blending is the kerosene
fraction from Atmospheric distillation
Characteristics:
The most important characteristic: No freezing in the cold
temperatures of the skies ( -500C)
LAB ABOUT FREEZING POINT OF FUELS
Smoke point expressed in mm of flame height at which
smoke is detected ( environment)
Volume percent of total aromatics less than 20% and
naphthalene less than 3%
131
CLASS WORK
Study the different specifications of the jet fuels in
table 2-8 page 52
WHAT IS AUTOMOTIVE
DIESEL FUEL?
Used for high speed engines such as trucks and buses
Boiling range : 360-6000F (182-3160C)
Critical properties are : volatility, viscosity, ignition quality,
sulfur content, percent of aromatics and cloud point.

The cloud point of a fuel is the temperature at which the
fuel becomes hazy or cloudy because of the appearance of
wax crystals
Ignition properties are expressed as CETANE NUMBER
133
CETANE NUMBER?
Comparable to the octane number for gasoline.
A rating on a scale used to indicate the tendency of a fuel for
diesel engines to cause knock.

The rating is comparing the fuels performance in a standard
engine with that of a mixture of cetane ( HIGH IGNITION
QUALITYCN=100) and alpha-methyl-naphthalene ( LOW
IGNITION QUALITYCN=0).
The cetane number is the percentage by volume of cetane in
the mixture that has the same performance as the fuel being
tested.
134
WHAT IS A HEATING OIL?

Fuel oils No1 and No2:
Fuel oil No1 is similar to kerosene (Jet Fuel) but
generally has a:
* higher pour point ( Defined as 50F higher than
the temperature at which a liquid stops flowing)
*higher end point ( Defined as the lowest
temperature at which virtually 100% of a product will
boil off to vapor form)
135
WHAT IS FUEL OIL N02

Similar to diesel fuel
Blended from naphtha, kerosene, diesel, and
cracked gas oil

Critical properties are sulfur content, pour point,
distillation and flash point
136
WHAT IS RESIDUAL FUEL OIL ?

Composed of the heaviest part of crude oil and is
generally from bottoms of vacuum distillation

The critical properties are viscosity and sulfur content
Used in furnaces
137
CLASS WORK
tudy the different characteristics of the fuel oils in
table 2-9 page 54
REFINERY PROCESSES
Step I : Pretreatment
Step II Separations
Step III : Chemical transformation
139
CLASS WORK :
STUDY FIGURE 1.1 PAGE 3
140
CRUDE OIL
PRETREATMENT
DESALTING
141
INTRODUCTION
Historically, the main problems associated with salt in crude oil
were corrosion and fouling in the crude unit overheads.

As downstream treatment and conversion processes assume
an ever greater importance in refinery economics and

operations, sodium poisoning of catalysts and fouling in
downstream units become increasing concerns.
Many refiners are turning to desalter upgrades and expansions
to solve the problem at source
142
PROBLEMS CAUSED BY THE

PRESENCE OF SALTS
The salts that are most frequently present in crude oil
are calcium, sodium and magnesium chlorides.

Technical problems:
Sand, silts and salt cause deposits and foul heat
exchangers.
The high temperatures that occur downstream in the
process could cause water hydrolysis, which in turn
allows the formation of corrosive hydrochloric acid
Sodium, arsenic and other metals can poison catalysts
143
CRUDE OIL DESALTING

A desalter is a process unit in an oil refinery that removes salt from
the crude oil. The salt is dissolved in the water in the crude oil, not in
the crude oil itself.
The desalting is usually the first process in crude oil refining. The salt
content after the desalter is usually measured in PTB - pounds of salt
per thousand barrels of crude oil.
Usually desalting is necessary only when the salt content of a crude
oil is greater than 10 lb/ 1000bbl (expressed as NaCl)

But now almost all crude oils are desalted to increase the
efficiency of the refineries

144
Objectives of desalting
The basic principle is to wash the salt from crude oil
using water
Secondary but important function of desalting is to
remove solid particles from crude oil

These are usually fine sands, clays and soil particles
, iron oxides and iron sulfide particles from pipelines,

tanks and tankers
145
Electrostatic De-salter
146
Description of the process

The dehydration process of a desalter will reduce a
portion of the free brine as it exits the vessel. A certain

quantity of brine will continue to exit as an emulsion.
Depending on the product specifications, one, two, or
three stages of desalting may be required to satisfy

the process design requirements.
Recycling reduces dilution/wash water consumption
and disposal costs of the effluents.

147
THE DESALTING PROCESS

Washing the crude with 3 to 10% vol. of water
at 200-3000F then separating the water

AC or DC potentials from 12,000 to 35,000 V
are used
148
TECHNICAL PROBLEMS OF
THE PROCESS
The salt in crude oil is dissolved or in suspended salt crystals
in water emulsified with the crude oil.

Technical problems occur in
obtaining efficient water/ oil mixing
water-wetting of suspended particles
separation of the wash water from oil
the process is affected by :
pH, gravity and viscosity of crude oil
vol. of wash water by vol. of crude oil
149
TYPICAL DESALTING
CONDITIONS
0API
> 40
30 -40
< 30
Water ( %Vol.)
3-4
4-7
7-10
Temp (0F)
240-260
260-280
280-330
150
CLASS WORK
Study in group the desalting process
(Figure 4.6 PAGE 80)
151
PREHEATING AFTER
DESALTING
Following the desalter, the crude oil is further heated by exchanging heat
with some of the hot, distilled fractions and other streams. It is then heated in
a fuel-fired furnace (fired heater) to a temperature of about 398 C and
routed into the bottom of the first distillation unit.
152
STEP II: DISTILLATION AS

SEPARATION PROCESS
For any refinery, the first step is to separate the crude oil
into different fractions using distillation techniques.

two distillation columns are used ( atmospheric and
vacuum)
The amount of each fraction depends on the TBP curve of
the crude oil.
153
STEP III: CHEMICAL AND THERMAL

PROCESSES TO PRODUCE MORE
GASOLINE
154
STEP II : SEPARATION
OF CRUDE OIL INTO
FRACTIONS
DISTILLATIONS
(ATM AND VACCUM)
155
Step II: Crude distillation

The crude atmospheric and vacuum distillations are the rst major
processing units in any renery.
They are used to separate the crude oils into fractions according to
boiling point so that each of the processing units following will have
feedstock that meet their particular specications.
Higher efciencies and lower costs are achieved if the crude oil
separation is accomplished in two steps:

First
by fractionating
atmospheric pressure;
the
total
crude
oil
at
essentially
Then by feeding the high-boiling bottoms fraction (topped or
atmospheric reduced crude) from the atmospheric still to a

second fractionator operated at a high vacuum
OVERVIEW OF THE TWO

DISTILLATION UNITS
157
ATMOSPHERIC AND VACUUM

DISTILLATIONS
Atmospheric distillation operates under atmospheric
pressure and a gradient of temperatures from high

temperature in the bottom to low temperature at the
top
Vacuum distillation operates at very low pressure to
avoid thermal cracking of the heavy fractions
The fractions are separated according to their boiling
point
158
Vacuum Distillation
The vacuum still is employed to separate the
heavier portion of the crude oil into fractions

because the high temperatures necessary to
vaporize the topped crude at atmospheric
pressure cause thermal cracking to occur, with
the resulting loss to dry gas, discoloration of
the product, and equipment fouling due to coke
formation.
159
CRUDE DISTILLATION UNIT

PRODUCTS
Fuel gas: The fuel gas consists mainly of methane and ethane. In some
reneries, propane in excess of LPG requirements is also included in the

fuel gas stream. This stream is also referred to as Dry gas.
Wet gas: The wet gas stream contains propane and butanes as well as
methane and ethane. The propane and butanes are separated to be used
for LPG and, in the case of butanes, for gasoline blending and alkylation unit
feed.
LSR or Light Straight-Run Naphtha: The stabilized LSR naphtha (or LSR
gasoline) stream is desulfurized and used in gasoline blending or processed

in an isomerization unit to improve octane before blending into gasoline.
CRUDE DISTILLATION UNIT

PRODUCTS
HSR naphtha or HSR gasoline: The naphtha cuts are generally used as
catalytic reformer feed to produce high-octane reformate for gasoline

blending and aromatics.
Gas oils: The light, atmospheric, and vacuum gas oils arm processed in a
hydrocracker or catalytic cracker to produce gasoline, jet, and diesel fuels.

The heavier vacuum gas oils can also be used as feedstocks for lubricating
oil processing units.
Residuum: The vacuum still bottoms can be processed in a visbreaker,
coker, or deasphalting unit to produce heavy fuel oil or cracking and/or lube
base stocks. For asphalt crudes, the residuum can be processed further to
produce road and/or roong asphalts.
Typical Boiling Ranges of typical

products of the distillation
process
PROCESS DESCRIPTION OF
ADU (Atmospheric Distillation Unit)
ADU contains around 20 fractionation trays and is
equipped with one top pump around, an overhead reflux

system, and three side strippers (for naphtha, kerosene,
and gas oil products).
The ADU (Atmospheric Distillation Unit) separates most of
the lighter end products such as gas, gasoline, naphtha,

kerosene, and gas oil from the crude oil.
The bottoms of the ADU is then sent to the VDU (Vacuum
Distillation Unit).
163
OVERVIEW OF ADU
164
TOP OF ADU: LPG AND

GASOLINE PRODUCTS
The condensed gasoline and water are separated
by gravity in the reflux drum. Part of the gasoline is

pumped back to the tower as reflux, with the rest
going to storage.
The water is drained to disposal and the vapor
from the ADU overhead is passed to an untreated

fuel gas system.
165
OVERVIEW OF THE TOP OF

ADU
166
NAPHTHA PRODUCT
Naphtha draw is located at tray 5.
The naphtha product flows by gravity to the top of
the naphtha stripper.

Stripping steam is used to remove the light ends,
improving the flash point.
The stripped naphtha product is pumped to storage.
167
KEROSENE PRODUCT
Kerosene draw is located at tray 12.
The kerosene product flows by gravity to the top of
the kerosene stripper.

The stripped kerosene product is pumped to storage.
168
GAS OIL PRODUCT

At tray 19, a draw pan is located from which gas oil
product is drawn.
The gas oil product flows by gravity to the top of the
gas oil stripper.
The stripped gas oil product is pumped to storage.
169
NAPHTHA + KEROSENE +
GAS OIL PRODUCTS
170
ARC :BOTTOM PRODUCT

OF ADU
The liquid part of crude oil ARC is sent for further
processing to the VDU ( Vacuum Distillation Unit).

Steam is injected into the base of the tower to reduce
the hydrocarbon partial pressure by stripping some

light boiling components from the bottoms liquid.
171
BOTTOM OF ADU
172
ATMOSPHERIC
DISTILLATION PRODUCTS
FUEL GAS C1 AND C2)
LPG (C3 and C4),

Unstabilized light naphtha,
Heavy naphtha,
Kerosene,
Gas oil
TOP (reduced) crude (ARC)
173
WHAT DEFINES A GOOD

SEPARATION ?
The relationship between the ASTM distillation temperatures

at 95%vol and 5%vol of two adjacent fractions, light and
heavy, respectively.
ASTM 5%vol T (heavy) 95%vol T (light) = DT
(e.g., LGO)
(e.g., kerosene)
IF DT > 0, called ASTM gap
(good separation)
IF DT < 0, called ASTM overlap (bad separation)

174
FACTORS FOR A GOOD

SEPARATION
1) Number of plates
2) Reflux ratio
3) Steam injection - particularly for better separation
of heavy fractions
175
CLASS WORK: ADU DISTILLATION
Fractional distillation is useful for separating a mixture of
substances with narrow differences in boiling points, and is

the most important step in the refining process.
STUDY FIGURE 4.8 PAGE 83
176
SECOND DISTILLATION : VDU

OR VACUUM DISTILLATION
The VDU (Vacuum Distillation Unit)
takes the ARC from the Atmospheric

Distillation Unit bottom and separates it
into products such as vacuum gas oil,
vacuum distillate, slop wax, and residue.
177
OVERVIEW OF VDU
178
PREHEATING OF ARC
ARC is preheated by the bottoms feed
exchanger, further preheated and partially

vaporized in the feed furnace, and passed before
passing to the vacuum tower
179
VDU COMPONENTS
This tower contains a combination of 14 fractionation
trays.
It is equipped with three side draws and pump around
sections for
1) Vacuum Gas Oil,
2) Vacuum Distillate
3) Slop Wax products.
180
VDU OVERHEAD
181
PROCESS OF VDU
OVERHEAD
The overhead from the VDU is condensed and
combined with the vacuum steam.

The slop oil and water are separated by gravity in
the vacuum drum.
The water is drained to disposal, while the slop oil
is accumulated and occasionally drained to slop
collection.
182
VDU GAS OIL& DISTILLATE

&SLOP WAX PRODUCTS
183
VACUUM GAS OIL

PRODUCT
VGO draw is located at tray 4.
The vacuum gas oil draw tray is also a total draw
tray, where the reflux from the tray is pumped

under flow control to the tray below.
The product and pump around are cooled with the
vacuum gas oil product going to storage, while the

pump around is returned to the tower at tray 1.
184
VACUUM DISTILLATE
PRODUCT
The next product draw is located at tray 8, where the draw for
vacuum distillate product is located.

The vacuum distillate draw tray is a total draw tray, where the
reflux from the tray is pumped under flow control to the tray
below.
The product and pump around are cooled, with the vacuum
distillate product going to storage, while the pump around is
returned to the tower at tray 7.
185
VACUUM SLOP WAX

PRODUCT
At tray 14, a draw pan is located from which slop
wax product is drawn.

The slop wax product and pump around are
cooled, with the slop wax product going to

storage, while the pump around is returned to the
tower at tray 11.
186
VDU BOTTOM PRODUCT

The liquid from the feed furnace enters the tower
bottoms, where it is collected and sent for further

processing.
Steam is injected into the base of the tower to reduce
the hydrocarbon partial pressure by stripping some
light boiling components from the bottoms liquid.
The vapors from the feed heater enter the tower
below tray 14.
187
DISTILLATION
SPECIFICATIONS
AND CONTROL
CASE STUDY
188
EXAMPLE OF ADU
OPERATING CONDITIONS
The ADU feed is heated to 690 0F before entering
the tower which is maintained at 2.70 PSIG.

The top temperature is controlled at 280 0F which
maintains the Gasoline quality,
Draw temperatures of 355 0 F for the Naphtha, 529
0F for the Kerosene and 583 0F for the Gas Oil.
189
PROCESS CONTROL
SYSTEM OF ADU
DISTILLATION
190
CONTROL OF THE FEED

The ADU feed is pumped by P-100 (HS-100) and
controlled by FIC-100. \
It is preheated in the bottoms feed exchanger (E100) before entering the Feed Furnace (F-100).
TIC-100 controls the crude oil temperature
entering the ADU (T-100) by adjusting fuel gas
flow to the furnace.
191
CONTROL OF THE BOTTOM

OF ADU
Bottoms liquid is collected and sent to the VDU by
LIC-114 through the Bottoms Pump P-114 (HS-114).

This flow is indicated by FI-124.
Stripping steam is injected into the ADU bottoms by
FIC-134.
192
CONTROL OF GAS OIL

QUALITY
Hot gas oil flows by gravity to the Gas Oil Stripper (T-113)
through FIC-113.
The gas oil enters the stripper at the top and flows downward
over six trays.
Stripping steam is introduced into the bottom of the stripper
through FIC-133.
The gas oil product is pumped from the base of the stripper by
the Gas Oil Product Pump P-113 (HS-113) to storage.
The gas oil product flow is controlled by LIC-113 and the flow
rate is indicated by FI-123.
The gas oil product's 95% point is monitored by AI-123.
193
CONTROL OF KEROSENE
QUALITY
Hot kerosene flows by gravity to the Gas Oil Stripper (T-112)
through FIC-112.
The kerosene enters the stripper at the top and flows downward
over six trays.
through FIC-132.
The kerosene product is pumped from the base of the stripper
by the Gas Oil Product Pump P-112 (HS-112) to storage.
The gas oil product flow is controlled by LIC-112 and the flow
The kerosene product's 95% point is monitored by AI-122.
194
CONTROL OF NAPHTHA
QUALITY
Hot naphtha flows by gravity to the Naphtha Stripper (T-111)
through FIC-111.
The naphtha enters the stripper at the top and flows downward
over six trays.
through FIC-131.
The naphtha product is pumped from the base of the stripper
by the Naphtha Product Pump P-111 (HS-111) to storage.
The naphtha product flow is controlled by LIC-111 and the flow
The naphtha product's 95% point is monitored by AI-121
195
NAPHTHA PUMP AROUND

A naphtha pump around is drawn from tray 6,
pumped through P-115 (HS-115) and controlled

by FIC-115.
The pump around return temperature is controlled
by TIC-115 which modulates cooling water flow to

E-115.
196
CONTROL OF GASOLINE
QUALITY
The ADU overhead vapor flows through the overhead
condenser E-110 (HV-110), whose outlet temperature is

indicated by TI-120, into the Overhead Reflux Drum D-111.
The hydrocarbons are partially condensed and the two phases
(vapor and liquid) enter the overhead reflux drum where the
condensed water separates from the hydrocarbon liquid by
gravity.
The uncondensed gas (FI-130) is sent to fuel gas through PIC120, which maintains the ADU back pressure.
Analyzers are present to monitor the C3 composition of the off
gas (AI-130) and vapor pressure (AI-120) of the gasoline.
197
PROCESS
CONTROL OF A VDU
DISTILLATION
198
EXAMPLE OF VDU
OPERATING CONDITIONS
The VDU feed is heated to 750 0F before entering the
tower which is maintained at 2.00 in Hg.

The top draw temperature is controlled at 310 0F
which maintains the Vacuum Gas Oil quality

Draw temperatures of 607 0F for the Vacuum
Distillate, and 668 0F for the Slop Wax.

199
CONTROL OF THE VDU

FEED
The VDU feed is pumped by P-114 (HS-114)
controlled by LIC-114 and indicated by FI-124.
It is preheated by the bottoms feed exchanger E-200
before entering the Feed Furnace (F-200).

TIC-200 controls the temperature of the feed entering
the VDU (T-200) by adjusting fuel gas flow to the

furnace.
200
CONTROL OF VDU BOTTOM

PRODUCT QUALITY
Bottoms liquid is collected and sent to storage
through pump P-214 (HS-214), controlled by LIC214, and indicated by FI-224.

This residue's 95% point is monitored by AI-224.
Stripping steam is injected into the VDU bottoms by
FIC-234.
201
CONTROL OF SLOP WAX

QUALITY
Hot slop wax is pumped from the tower by pump P-
213 (HS-213).
The slop wax product flow to storage (FI-223) is
controlled by LIC-213, and it's 95% point is
monitored by AI-123.
Cooled pump around is controlled by FIC-213 and
returned to the tower above the slop wax draw tray.
202
CONTROL OF DISTILLATE
QUALITY
Hot vacuum distillate is pumped from the tower by pump P-
212 (HS-212).
The vacuum distillate product flow to storage (FI-222) is
controlled by LIC-212, and it's 95% point is monitored by AI122.

Cooled pump around is controlled by FIC-212 and returned
to the tower above the vacuum distillate draw tray.

Vacuum distillate reflux is controlled by FIC-232 and
returned to the tower below the vacuum distillate draw tray.

203
CONTROL OF VGO QUALITY

Hot vacuum gas oil is pumped from the tower by pump P-
211 (HS-211).
The vacuum gas oil product flow to storage (FI-221) is
controlled by LIC-211, and it's 95% point is monitored by AI121.

Cooled pump around is controlled by FIC-211 and returned
to the tower above the vacuum gas oil draw tray.

Vacuum gas oil reflux is controlled by FIC-231 and returned
to the tower below the vacuum gas oil draw tray.

204
CONTROL OF VDU
OVERHEAD
The VDU overhead vapor flows through the
overhead condenser E-210 (HV-212) into the

Overhead Vacuum Drum D-211.
The hydrocarbons are fully condensed and mixed
with the vacuum condensate flow from E-211.
205
CONTROL OF VACUUM IN
VDU TOP
The VDU vacuum pressure is maintained by the
steam to the vacuum ejector (HV-211), the cooling

water (HV-212) to the steam condenser E-211, and
the hydrocarbon condenser E-210.
The pressure is regulated by PIC-210, which
reduces the vacuum by circulating water to the

vacuum ejector.
206
CHEMICAL
TRANSFORMATION OF
HYDROCARBONS
207
L.O #3 :Explain the process and

principles used for hydrotreating,
catalytic reforming, and
isomerization.
208
OBJECTIVE OF THIS
SECTION
THE MAIN PURPOSE OF THIS
SECTION IS TO STUDY HOW A

REFINERY USE CHEMICAL
PROCESSES TO PRODUCE
GASOLINE FROM THE OTHER
FRACTIONS
209
CHEMICAL TRANSFORMATION
FOR ADU PRODUCTS
210
CHEMICAL TRANSFORMATION
FOR VDU PRODUCTS
211
THREE WAYS OF CHEMICAL

TRANSFORMATION
You can change one fraction into
another by one of three methods:

breaking large hydrocarbons into
smaller pieces (cracking)
combining smaller pieces to make
larger ones (unification)
rearranging various pieces to make
desired hydrocarbons (alteration)
212
THE NECESSITY OF THE

BREAKING PROCESSES
Very few of the components come out of
the fractional distillation columns ready

for market.
Many of them must be chemically
processed to make other fractions.
For example, only 40% of distilled crude
oil is gasoline; however, gasoline is one
of the major products made by oil
companies.
213
BREAKING PROCESSES
TRANSFORM HEAVIER
FRACTIONS GASOLINE
Rather than continually distilling large
quantities of crude oil, oil companies

chemically process some other
HEAVIER fractions from the distillation
column to make gasoline
This processing increases the yield of
gasoline from each barrel of crude oil.
214
CATALYTIC REFORMING
215
WHAT IS CATALYTIC REFORMING
THE MAIN PROPERTY OF GASOLINE IS
HIGH OCTANE NUMBER

LOW OCTANE NUMBER GASOLINE
DESTROY THE CAR ENGINE
Catalytic reforming is an important process
used to convert low-octane naphtha into

high-octane gasoline blending components
called reformates.
216
FEED TREATMENT SECTION

BEFORE REFORMING
Naphtha from heavy and sour crude oils
will contain some components like

hydrogen sulfide, ammonia, organic
nitrogen and sulfur compounds which
will deactivate the Reforming catalyst
More or less standard is a feed
preparation section in which, by
combination of hydrotreatment and
distillation, the feedstock is prepared to
specification.
217
HYDROTREATING OF SOUR
NAPHTHA
The hydrotreater uses Co/Mn Catalyst to
convert organic sulfur and nitrogen compounds

into H2S and NH3
These gases are removed with the unreacted
Hydrogen
The metals in the feed are retained by the
hydrotreater
The hydrogen needed come from the catalytic
reformer
LEAN NAPHTHA ENTERS THE CATALYTIC
REFORMING SECTION
218
HYDROTREATING CHAPTER 9 FROM
BOOK
219
THE OBJECTIVE OF
CATALYTIC REFORMING
Lean naphtha is used for the production of
very high concentrations of toluene, benzene,

xylene, and other aromatics needed in the
final product : GASOLINE
The properties of the naphtha feedstock (as
measured by the paraffin, olefin, naphthene,
and aromatic content) will be changed using
catalysts and appropriate operating
conditions.
A significant by-product, is separated from the
reformate ( gasoline) for recycling and use in
other processes.
220
PONA ANALYSIS BEFORE

AND AFTER REFORMING
Component
NAPHTHA
* Paraffins
30-70
* Olefins
0-2
* Naphtenes
20-60
* Aromatics
7-20
GASOLINE
30-50
0
0-3
45-60
221
THE CATALYTIC
REFORMING PROCESS
222
CATALYTIC REFORMING
PROCESS
catalytic reformer comprises a reactor section
and a product-recovery section.

Naphtha feed and recycle hydrogen are mixed,
heated and sent though successive reactor
beds.
Each reactor needs heat input to drive the
reactions
Final effluent is separated with the hydrogen
being recycled or purged for hydrotreating
The reformate can be used as for gasoline
blends or treated to separate aromatics
components for petrochemical industries.
223
CATALYST AND CONDITIONS

The catalyst
A typical catalyst is a mixture of

platinum and aluminum oxide.
With a platinum catalyst, the process is
sometimes described as "platforming".
Temperature and pressure
The temperature is about 500C, and the
pressure varies either side of 20 atm.
224
THE FOUR MAJOR REACTIONS

OF REFORMING
Dehydrogenation of naphtenes to
aromatics
Dehydrocyclization of paraffins to
aromatics
Isomerization
Hydrocraking
225
Dehydrogenation of naphtenes to
aromatics
Methylcyclohexane Toluene + 3H2
Methylcyclopentane Cyclohexane
Benzene +3H2
N-heptane Toluene + 4H2
226
Dehydrocyclization of paraffins
to aromatics
For example, cyclohexane, C6H14, loses
hydrogen and turns into benzene..
Heptane turns to methylbenzene or
toluene
227
ISOMERIZATION OF
OLEFINS AND PARAFFINS
Paraffins are isomerized and to some
extent converted to naphtenes and

naphtenes are converted to aromatics
Olefins are saturated to form Paraffins
which then react as the first step
Naphtenes are converted to aromatics
Aromatics are essentially unchanged
228
HYDROCRACKING
REACTIONS
Major hydrocracking reactions involve
the cracking and saturation of paraffins.

EXAMPLE: DECANE N-BUTANE
229
MAIN REACTIONS IN THE

FIRST REACTOR BED :
Dehydrogenation &
Dehydrocyclization Reactions:
* highly endothermic
* The temperature decreases in the
reactor
* Highest reaction rates
230
MAIN PROPERTY OF REACTOR

IS ITS SPACE VELOCITY (SV)
Space velocity represents the relation between
volumetric flow and reactor volume.

It is often denoted by SV and it is related to the
residence time in a chemical reactor, .
In the relationship, SV = 1/ = volumetric
flow/volume ( ex: m3/hr/m3)
The space velocity, in chemical reactor design,
indicates how many reactor volumes of feed
can be treated in a unit time.
For example, a reactor with a space velocity of
7 hr-1 is able to process feed equivalent to
seven times the reactor volume each hour
231
AROMATICS YIELDS IN FIRST

REACTOR INCREASED BY:
High temperature ( Increases rate of
reactions)
Low pressure ( Shift chemical reaction
to the production of aromatics)
Low space velocity ( promotes approach
at equilibrium)
Low hydrogen to Hydrocarbon ratio
232

SECOND REACTOR BED
Isomerization Reactions
Isomerization yield is increased by:

High temperature
Low space velocity
Low Pressure
Fairly rapid reactions
233

THIRD REACTOR BED
Hydrocracking Reactions
Exothermic reactions and produce lighter

liquid and gas products
Relatively slow reactions
Major reactions are cracking and saturation of
paraffins
Hydrocracking yields are increased by:
* High Temperature
* High Pressure
* Low space velocity
234
Undesirable reactions In
reforming
Dealkylation of side chains on naphtenes
and aromatics to produce butane and

lighter paraffins
Cracking of paraffins and naphtenes to
form butane and lighter paraffins
235
Catalytic Reforming Processes

Depending upon the frequency of catalyst
regeneration, Reforming Processes are
classified as:
continuous,
cyclic
semigenerative
236
Continuous catalytic reforming

( figure 10.2 page 218)
Recently built reformers are continuous catalyst

regeneration licensed by IFP and UOP
In this process, the catalyst flows by gravity from one
reactor to another
the catalyst is then sent pneumatically to a regenerator
and then sent to the first reactor
removal and replacement of catalyst during normal
operation.
expensive process
the catalyst is always maintained at his highest
activity.
237
Semiregenerative catalytic
reforming
Regeneration of catalyst occurs when:

the octane number of the gasoline becomes low
when the temperature in the reactor is close to the
maximum allowable
The unit should be shut down
high hydrogen recycle rates and high pressure are used
to minimize coke deposit on the catalyst
Depending on the severity of the process , the
regeneration takes place every 3 to 24 months
Low capital cost
238
Cyclic catalytic reforming

Its intermediate between the two
extremes
Only one reactor is shut and
regenerated when it is replaced by a
new reactor called a swing reactor
239
PRODUCT OF CATALYTIC
REFORMING: GASOLINE
THE MAIN PRODUCT OF ANY

REFINERY
240
Motor gasoline is a blend of

*
*
*
*
*
*
Light straight line

Catalytic Reformate
Catalytically cracked gasoline
Hydrocracked gasoline
Polymer gasoline
Additives
241
WHAT IS GASOLINE?
Source of energy for motors
Complex mixture of hydrocarbons with a
boiling point range:100-400oF (38205oC) by ASTM method

Grades of Gasoline: Unleaded, Regular,
Premium and superpremium
242
CHEMICAL TANSFORMATION OF
DIFFERENT HYDROCARBONS
MAKE MORE GASOLINE FROM THE
SAME CRUDE OIL FEED RATE
THREE WAYS OF CHEMICAL

TRANSFORMATION
You can change one fraction into another
by one of three methods:
Rearranging various pieces to make
desired hydrocarbons (alteration)
Combining smaller pieces to make
larger ones (unification)
Breaking large hydrocarbons into
smaller pieces (cracking)
244
REARANGING THE
MOLECULAR STRUCTURE
We have studied this transformation in
the Catalytic Reforming Process where

paraffins, olefins and naphtenes were
transformed into is-paraffins or aromatics
which have highest octane number
Combining smaller pieces to make

larger ones
This transformation will be studied in this
chapter where small molecules
Alkylation Process
Isomerization process
ALKYLATION PROCESS
DEFINITION
In petroleum terminology, the term
Alkylation is used for the reaction of low

molecular weight olefins with an isoparaffin to form higher molecular weigh
iso -paraffin
STUDY THE ALKYLATION REACTIONS
PAGE 232 AND 233
THE ALKYLATION PROCESS

FEED:
Alkylation combines low-molecular-weight olefins (primarily

a mixture of propylene and butylenes) with isobutene.
CATALYST:
Either sulfuric acid or hydrofluoric acid.
PRODUCT:
The product is called alkylate and is composed of a mixture
of high-octane, branched-chain paraffinic hydrocarbons.
PRODUCT SPECIFICATIONS:
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.
TYPICAL FEEDSTOCKS FOR

ALKYLATION PROCESS
Petroleum gas from Distillation or
cracking units
Olefins from Catalytic cracking or
hydrocracking units
Sulfuric Acid Alkylation

Process
FEED:
In cascade type sulfuric acid (H2SO4) alkylation units, the feedstock
(propylene, butylene, amylene, and fresh isobutane) enters the reactor
CATALYST
the concentrated sulfuric acid catalyst (in concentrations of 85% to 95% for
good operation and to minimize corrosion).
THE REACTOR
The reactor is divided into zones, with olefins fed through distributors to
each zone, and the sulfuric acid and isobutanes flowing over baffles
from zone to zone.
The reactor effluent is separated into hydrocarbon and acid phases in a
settler, and the acid is returned to the reactor. The hydrocarbon phase
is hot-water washed with caustic for pH control before being
successively depropanized, deisobutanized, and debutanized.
THE PRODUCT
The alkylate obtained from the deisobutanizer can then go directly to motorfuel blending or be rerun to produce aviation-grade blending stock. The
isobutane is recycled to the feed.
SCHEMA OF THE PROCESS
PROCESS VARIABLES
REACTION TEMPERATURE
ACIDITY
ISOBUTANE CONCENTRATION
OLEFIN SPACE VELOCITY
REACTON TEMPERATURE
Normal temperatures are from 5 to 100C
Lower temperatures will increase
significantly the acid solution viscosity

Bad mixing and separation of products
Higher temperatures ( >200C)
Polymerization of olefins
ACIDITY OF SOLUTION
Highest Octane number and highest
yields are obtained at:

93-95% weight acid
1-2% water
Hydrocarbons diluents
Higher concentration of water will lower
the activity of the catalytic solution
ISOBUTANE
CONCENTRATION
Higher isobutane/olefin ratio will increase
the octane number and the yield of the

alkylate
In industrial practice the ration from 5:1
to 15:1 is used
Reactors using internal circulation use
up to 100:a to 1000:1 ratio
OLEFIN SPACE VELOCITY

Lowering the olefin space velocity or
increasing the contact time, it will:

Reduce the production of high boiling
points hydrocarbons
Increase the alkylate octane number
Contact time varies from 5 to 25 min
CORRELATON FACTOR
Mrstik et al. developp a correlation factor
I E .( I / O) F
F
100 .(SV ) 0
IE= % OF ISOBUTANE VOLUME IN REACTOR

(I/O)F= VOLUMETRIC ISOBUTANE/OLEFIN RATIO IN FEED
(SV)0= OLEFIN SPACE VELOCITY (hr-1)
NORMAL VALUES OF F : 10 TO 40
HIGHER VALUES GIVE HIGHER ALKYLATE OCTANE NUMBER
SAFETY PRECAUTIONS:
HAZARDOUS SULFURIC ACID
Loss of coolant water, which is needed
to maintain process temperatures, could

result in an upset.
Precautions are necessary to ensure
that equipment and materials that have
been in contact with acid are handled
carefully and are thoroughly cleaned
before they leave the process area or
refinery.
..
Immersion wash vats are often provided
for neutralization of equipment that has

come into contact with hydrofluoric acid.
Hydrofluoric acid units should be
thoroughly drained and chemically
cleaned prior to turnarounds and entry to
remove all traces of iron fluoride and
hydro-fluoric acid
SAFETY PRECAUTIONS:
HAZARDUS SULFURIC ACID
Following shutdown, where water has
been used the unit should be thoroughly

dried before hydrofluoric acid is
introduced
Leaks, spills, or releases involving
hydrofluoric acid or hydrocarbons
containing hydrofluoric acid can be
extremely hazardous.
Care during delivery and unloading of
acid is essential.
Process unit containment by curbs, drainage,
and isolation so that effluent can be neutralized

before release to the sewer system is
considered.
Vents can be routed to soda-ash scrubbers to
neutralize hydrogen fluoride gas or hydrofluoric
acid vapors before release.
Pressure on the cooling water and steam side
of exchangers should be kept below the
minimum pressure on the acid service side to
prevent water contamination.
CORROSION PROBLEMS
Some corrosion and fouling in sulfuric
acid units may occur from the

breakdown of sulfuric acid esters or
where caustic is added for neutralization.
These esters can be removed by fresh
acid treating and hot-water washing.
To prevent corrosion from hydrofluoric
acid, the acid concentration inside the
process unit should be maintained above
65% and moisture below 4%.
NEW UOP ALKYLATION

PROCESS
UOP has developed a new approach to
produce a gasoline blending component similar

in quality to traditional motor alkylate.
The InAlk process uses commercial, solid
catalysts for reacting light olefins to produce a
high octane, paraffinic gasoline component
similar to traditional alkylate.
The InAlk process is based on proven
technology and light hydrocarbon chemistry.
The Alkylene process is a novel solid-catalyst

alkylation process with a product equal to that
produced by liquid HF alkylation.
ISOMERIZATION PROCESS
265
PROCESS OBJECTIVE
ABU DHABI REFINERY : LIGHT NAPHTA AND
HEAVY NAPHTA ARE SEPARATED AND :

LIGHT NAPHTA TO ISOMERIZATION
HEAVY NAPHTA TO CATALYTIC
REFORMING
CONVERT LOW OCTANE N-PARAFFINS OF
LIGHT NAPHTA ( C41800F and RON ~70) TO
HIGH OCTANE ISO PARAFFINS ( RON~92) IF
RECYCLING IS USED
PROCESS TECHNIQUE
Isomerization occurs in a chloride
promoted fixed bed reactor where nparaffins are converted into iso-paraffins
Catalyst very sensitive to incoming
contaminants ( water and sulfur)
PROCESS STEPS
Desulfurized feed and hydrogen are dried in
fixed beds of solid desiccants prior to mixing

together
The mixed feed is heated and passes through a
hydrogenation reactor to saturate olefins to
paraffins and saturate benzene
The hydrogenation effluent is cooled and
passes through a isomerization reactor
The final effluent is cooled and separated as
hydrogen and LPG which go as fuel gases and
isomerate product to gasoline blend.
FIGURE 10.9 PAGE 225
PROCESS VARIABLES
The yield of the process is increased by:
High temperature ( reaction rate )

Low space velocity ( reaction time )
Low pressure
High H2/HC Phc isomers yield
GASOLINE BY CRACKING
LONG CHAIN HYDROCARBONS
CRACKING CATALYTIC
HYDROCRACKING
THERMAL CRACKING
CRACKING UNIT
272
Catalytic cracking?
The most important and widely used refinery
process
Convert heavy oils into valuable gasoline and
lighter products
Originally cracking was accomplished thermally
Catalytic cracking produces more gasoline with
higher octane number
Comparison between thermal and catalytic
cracking is shown in Table 6.1 page 122
273
PRIMARY CRACKING
REACTIONS
The primary reactions can be
represented as follow:
PARAFFIN paraffin + olefin
ALKYL NAPHTENE naphtene + olefin
ALKYL AROMATIC aromatic + olefin
274
HEAT OF CRACKING
REACTIONS (REACTOR)
The cracking reaction is endothermic or
exothermic?
ENDOTHERMIC
WHY?
Because we need energy to get
small molecules from big molecules
275
HEAT OF REGENERATION
(REGENERATOR)
The regeneration reaction is
endothermic or exothermic?
Exothermic
Why ?
Because burning coke is an
oxidation and oxidation release heat
276
Temperatures of reactor and

regenerator
Reactor temperature are around 900 to
10000F ( 480-5400C)
The feed temperature is around 500 to
9000F ( 260-4250C)
regeneration exit temperature is around
1200 to 15000F ( 650-8150C)
277
Different types of processes

Two Classes:
Moving bed
Fluidized bed
These days, there are very few
Moving bed reactors
278
FLUIDIZED BED?
In a Fluidized Bed Reactor, the catalyst
is distributed in the fluid phase and

behaves as a fluid.
CATALYST STAYS INSIDE THE
REACTOR
Fluid catalytic cracker

The fluid catalytic cracker (FCC) is
representative of the fluidized bed units

The FCC can be classified as :
Bed FCC
Riser FCC
Depending where the major fraction of the
cracking reactions occur
280
THE REACTOR AND

REGENERATOR
REACTOR
REGENERATOR
281
PROCESS DESCRIPTION FOR

RISER FCC:
A) FEED AND RISER:
Pre-heated feed is sprayed into the base
of the riser via feed nozzles where it
contacts extremely hot fluidized catalyst
at 1230 to 1400 degrees F
The hot catalyst vaporizes the feed and
catalyzes the cracking reactions that
break down the high molecular weight oil
into lighter components including LPG,
gasoline, and diesel
282
PROCESS DESCRIPTION:
B) REACTOR AND CYCLONES:
The catalyst-hydrocarbon mixture flows upward
through the riser for just a few seconds and
then the mixture is separated via cyclones.
The catalyst-free hydrocarbons are routed to a
main fractionator for separation into fuel gas,
LPG, gasoline, light cycle oils used in diesel
and jet fuel, and heavy fuel oil.
283
C) STRIPPER: During the trip up the riser,
the cracking catalyst is "spent" by
reactions which deposit coke on the
catalyst and greatly reduce activity and
selectivity.
The "spent" catalyst is disengaged from
the cracked hydrocarbon vapors and
sent to a stripper where it is contacted
with steam to remove hydrocarbons
remaining in the catalyst pores
284
D) REGENERATOR:
The "spent" catalyst then flows into a fluidizedbed regenerator where air (or in some cases air
plus oxygen) is used to burn off the coke to
restore catalyst activity and also provide the
necessary heat for the next reaction cycle,
cracking being an endothermic reaction.
The "regenerated" catalyst then flows to the
base of the riser, repeating the cycle
Figures 6.1 a and 6.1 b
285
CATALYST IN FCC
The FCC uses very fine particles catalyst
( 70m) which behave as a fluid when

aerated with vapor
The fluidized catalyst is circulated
continuously between the reactor and
the regenerator
286
TYPES O CATALYST
Commercial cracking catalyst can be
divide into 3 classes:

1) acid treated natural aluminosilicates
2) amorphous synthetic silica-alumina
mixtures
3) crystalline synthetic silica-alumina
catalysts called zeolites
287
INDUSTRIALY USED
CATALYSTS
The most commonly used are classes 2
and 3 Tables 6.2 and 6.3 PAGE 137
288
Advantages of zeolites catalyst

Higher activity
Higher gasoline yield

Lower coke yield
289
CRACKING MAIN PROBLEM:

COKING
The cracking process produces carbon which
remains on the catalyst and lowers its activity

What should we do to maintain the activity of
catalyst high?
Regenerate the catalyst by burning off the
coke with air
As a result, the catalyst is continuously
moved from reactor to regenerator
( Figure 6.1a page 95)
290
Catalytic hydrocracking?
A process similar to catalytic cracking in
its industrial purpose but effected under

hydrogen pressure.
The catalyst of hydrocracking containing
two functions:
A cracking function
A hydrogenating function ( Figure 7.2
page 144 shows a two-stages system).
291
Hydrocracking Catalyst
Most of the hydrocracking catalyst
consist of a crystalline mixture of silica

alumina with a small uniformly
distributed amount of rare earths
containing within the crystal line lattice.
The silica-alumina provides cracking
Rare earth component provides
hydrogenation
292
Hydrocracking and catalytic

cracking
They work as a team:
The catalytic cracker takes the more easily

cracked paraffinic atmospheric and vacuum
gas oils as charge stocks
The hydrocraking uses more aromatic
cycle oils and cooker distillates as feed.
These streams resist to catalytic cracking but
high pressure and hydrogen atmosphere make
them easy to crack
293
Why catalytic hydrocracking?

NEW DEMAND: The demand for petroleum
products has shifted to high ratio of gasoline

and jet fuel compared with the usage of diesel
fuel and home heating fuels.
DISPONIBILTY OF HYDROGEN: by product
hydrogen at low cost and in large amounts has
become available from catalytic reforming
operations
ENVIRONMENTAL CONCERNS: limiting
sulfur and aromatic compounds concentrations
in motor fuels have increased
294
PRETREATMENT OF HEAVY
DISTILLATE FRACTIONS
REMOVING IMPURITIES TO AVOID
CATALYST POISENING AND
ENVIRONMENTAL PROBLEMS
CATALYTIC PROCESS MAIN

PROBLEMS
Catalysts of Reforming catalytic &
Cracking catalytic & Hydrocracking

can be poisoned by sulfur , nitrogen
and oxygen compounds and
metallic salts present in the their
respective feedstocks
FEEDSTOCKS PREPARATION
Feed impurities are removed by a
hydrotreatment process to:

Saturate the olefins
Remove sulfur, nitrogen and
oxygen compounds.
Molecules containing metals are
cracked and the metals are retained
by the catalyst
297
HYDROTREATING
OBJECTIVE:
Hydrotreating is used for removing the
undesired compounds and stabilizing

the heavy distillate fractions.
Hydrotreating uses:
A catalyst
A substantial quantities of hydrogen.
298
ENVIRONMENTAL ISSUES
The main impurities that could also harm
the environment are nitrogen and sulfur

compounds.
They are removed by conversion of
sulfur and nitrogen elements into
ammonia and hydrogen sulfide.
Because of the new environmental
regulations due to global warming, the

amount of sulfur and nitrogen in the refinery
products are around 50 ppm and less
MAIN HYDROTREATING
PROCESSES
The most used Hydrotreating
processes are:
Desulphurization (remove sulphur
compounds)
Denitrification (remove nitrogen
compounds)
Conversion of olefins to paraffins
HDS MAIN REACTIONS

Mercaptans: RSH + H2 RH + H2S
Sulfides
: R2S + 2H2 2RH + H2S
Disulfides : (RS)2 + 3H2 2RH + 2H2S
Thiophenes :
+4H2 C4H10 + H2S
S
The reactions: EXOTHERMIC
301
HDS CATALYST
The most economical catalyst for HDS
is: Cobalt- Molybdene oxides on alumina
THE OTHER REACTIONS OF

THE HDS PROCESS
In the HDS reactor, other reactions
take place like:

Denitrogenation
Deoxidation
Dehalogenation
Hydrogenation
Hydrocracking.
303
DENITROGENATION
Nitrogen is more difficult to remove
than sulfur
Reactions :
Pyrrole: C4H4NH + 4H2 C4H10 + NH3
Pyridine: C5H5N + 5H2 C5H10 + NH3
For middle distillate fractions having
high concentration of nitrogen, the
catalyst used is : 90% Ni- Mo oxides and
10% nickel-tungsten
Operating Conditions
270- 3400C
Pressure
690- 20,700 kPag
Hydrogen/ unit feed:
Recycling
360m3/m3
Consumption
36-142m3/m3
Space velocity
1.5 -8.0
Space velocity is defined as the rate of feed
per unit mass of catalyst ( mass of catalyst
because catalyst is very expensive)
Temperature
305
CLASS WORK #1
Study the process of HDS figure 9-1
page 196
CLASS WORK #2:

study figure 9-2 page 199
Discuss the effects of process variables on its
efficiency:
T Removal , H2 Consumption
and coke
PH2 Removal and H2 Consumption
P H2 Consumption and Coke

Space velocity Removal and H2
Consumption and Coke
307
ACID GAS REMOVAL
ACID GAS REMOVAL

Gases from various operations of sour
crude oil contain hydrogen sulfide

The hydrogen sulfide is produced in
units such as hydrotreating, cracking and
coking
Recent air pollution regulations require
that most of the sulfur to be removed
from gases and converted to element
sulfur
309
THREE DIFFERENT KINDS OF

PROCESSES TO REMOVE H2S
Chemical solvent processes
Physical solvent processes

Dry adsorbents processes
310
Chemical solvent processes

: FIGURE 13.5
*
*
*
*
*
Monoethanolamine (MEA)
Diethanolamine
(DEA)
Methyl- Diethanolamine (MDEA)
Diglycolamine (DGA)
Hot Potassium Carbonate
Physical solvent processes

Physical solvent processes:
*
*
*
*
Selexol
Propylene Carbonate
Sulfinol
Rectisol
Dry adsorbents processes:
*
*
*
*
Molecular sieve
Activated charcoal
Iron sponge
Zinc oxide
Class work #3
Discuss the figure 13.5

page 284 and explain all
the steps of the process
314
SULFUR RECOVERY PROCESS
THE MODIFIED CLAUSS PROCESS:
The most practical method for converting
hydrogen sulfide to elementary sulfur

Best suited for gases containing more
than 50% hydrogen sulfide is the
PARTIAL COMBUSTION PROCESS.
316
PARTIAL COMBUSTION
PROCESS (FIGURE 13.7 PAGE
287)
Hydrogen sulfide is burned with 1/3 the
stoichiometric quantity of air

2H2S + 3O2 2H2O + 2SO2
The hot gases are sent to a reactor with
alumina as catalyst to react sulfur
dioxide with unburned hydrogen sulfide
to produce free sulfur
2H2S + SO2 2H2O + 3S
317
TAIL GASES OF CLAUS

PLANT
Carbon sulfide (COS) and carbon disulfide CS2
have presented problems in many Claus plant

operations.
These compounds are formed in the
combustion step ( see reactions page 289)
Unconverted, these compounds represent a
loss of sulfur recovery.
They are in the tail gas of the Claus process
and sent to the Scot process
CLASS WORK #4
USING THE BOOK, DESCRIBE ALL
THE STEPS OF THE CLAUSS

PROCESS IN FIGURE 13.7 PAGE 287
PROCESS FLOW DIAGRAM
320
THE SCOT PROCESS

THE TAIL GAS OF THE CLAUS
PROCESS ARE SENT TO THE SCOT
PROCESS
DESCRIPTION OF THE SCOT

PROCESS ( fig 13.9 page 291)
The tail gas of the Claus unit contains small amounts of

CARBONYL SULFIDE and CARBON DISULFIDE as well as
SO2 and H2S
The gas is combined with hydrogen or a mixture of ( CO + H2)
The mixture is heated at 480 to 5700F,
Pass through a catalytic reactor where sulfur compounds are
converted to Hydrogen sulfide
The reactor effluent is cooled and H2S is absorbed with amine
solution
The H2S from the amine generation unit is sent back to the
Claus process
The H2S exiting the amine unit ( 50 to 400 ppm) is burned to
produce SO2
322
Class work: study the process

in figure 13.9 page 291
323
LUBRICATING OILS
INTRODUCTION
The lube oil sold in the market are a
mixture of:
Lubricating oil base stocks
Additives
Lubricating oils
The feeds for the production of
lubricating oils come from the vacuum

distillation
The feeds are treated to improve the
quality of the lubricating oils
Chemicals are added to improve the
properties
USES OF LUBRICATING
OILS
Motor oil is a lubricant in internal combustion engines,
typically found in automobiles and other vehicles, boats,

lawn mowers, trains, airplanes.
In engines there are parts which move very closely
against each other at high speeds, often for prolonged
periods of time.
Such motion causes friction, absorbing otherwise useful
power produced by the motor and converting the energy
to useless heat.
Friction also wears away the contacting surfaces of
those parts, which could lead to lower efficiency and
degradation of the motor.
This increases fuel consumption.
USES OF LUBRICATING
OILS
Lubricating oil makes a film between surfaces
of parts moving next to each other so as to

minimize direct contact between them
decreasing friction, wear, and production of
excessive heat, thus protecting the engine.
Motor oil also carries away heat from moving
parts, which is important because materials
tend to become softer and less abrasionresistant at high temperatures.
Some engines have an additional oil cooler.
MOST IMPORTANT
PROPERTY OF MOTOR OILS
One of the most important properties of
motor oil in maintaining a lubricating film

between moving parts is its viscosity
The viscosity must be high enough to
maintain a satisfactory lubricating film,
but low enough that the oil can flow
around the engine parts satisfactorily to
keep them well coated under all
conditions.
VISCOSITY INDEX
The viscosity index is a measure of how
much the oil's viscosity changes as

temperature changes.
A higher viscosity index indicates the
viscosity changes less with temperature
than a lower viscosity index
POUR POINT OF MOTOR

OILS
Motor oil must be able to flow at cold winter
temperatures to lubricate internal moving parts

upon starting up the engine.
Another important property of motor oil is its
pour point, which is indicative of the lowest
temperature at which the oil could still be
poured satisfactorily.
The lower the pour point temperature of the
oil, the more desirable the oil is when starting
up at cold temperature.
FLASH POINT OF MOTOR

OILS
Oil is largely composed of hydrocarbons which
can burn if ignited.

Still another important property of motor oil is its
flash point, the lowest temperature at which the
oil gives off vapors which can ignite.
It is dangerous for the oil in a motor to ignite
and burn, so a high flash point is desirable.
At a petroleum refinery, fractional distillation
separates a motor oil fraction from other crude
oil fractions, removing the volatile components
which ignite more easily, and therefore
increasing the oil's flash point.
TOTAL BASE/ACID NUMBER

Another test done on oil is to determine the
Total Base Number (TBN), which is a

measurement of the reserve alkalinity of an oil
to neutralize acids.
The resulting quantity is determined as mg
KOH/(gram of lubricant).
Analogously, Total Acid Number (TAN) is the
measure of a lubricant's acidity.
Other tests include zinc, phosphorus, or sulfur
content, and testing for excessive foaming.
LUBRICATING OIL
BLENDING STOCKS
The main properties of lubricating oils are:
* Viscosity
* Viscosity Index
* Pour Point
* Oxidation Resistance
* Flash Point
* Boiling Temperature
* Acidity
334
VISCOSITY
From a given crude oil; the higher the boiling point; the
greater is the viscosity
The viscosity of a lubricating oil can be selected by the
distillation boiling point of the cut
Measure of internal resistance to flow
The higher is the viscosity the ticker the film of oil that
clings to a surface
Depending upon the service:
* The oil should be thin and free flowing
* Or should be tick and resistant to flow
335
VISCOSITY INDEX (VI)

The rate of change of viscosity with
temperature
The higher is the VI, the smaller is the
change of viscosity with temperature
The VI of lubricating oils vary from negative
values for oils from naphtenic crude oils to
about 100 for oil from parrafinic crude oils.
Some specially processed oils with chemical
additives can have VI higher than 130
336
ADDITIVES TO IMPROVE VI
Polyisobutylenes or polymethacrylic acid esters
are used to improve the VI of lubricating oils

Motor oils must be thin enough at low
temperatures to permit easy starting
Viscous enough at engine operating
temperatures ( 80-1200C) to reduce friction by
providing enough oil thickness between metal
surfaces
337
POUR POINT
The lowest temperature at which oil will
flow under standards conditions

A Low pour point is important in cold
days to obtain easy starting of the
engine
They are two types of pour point:
* Viscosity pour point
* Wax pour point
338
Viscosity pour point

The Viscosity pour point is approached
gradually as the temperature is lowered

and the viscosity of the fluid increase
until it will not flow under the standards
conditions
339
Wax pour point

The wax pour point occurs abruptly as
the paraffin wax crystals precipitate from

oil and the solution solidifies
Additives can be used to lower the wax
pour point
340
Cloud point
The cloud point is also used to report
the temperature at which wax or other

solid material begins to separate from
solution
For parrafinic oils, this is the starting
point of crystallization of parrafinic waxes
341
Oxidation resistance
The high temperature of engines causes
the rapid oxidation of motor oils

Especially in piston heads where
temperature can attain 4000C.
Oxidation causes the formation of coke
Anti oxidation additives, such as
phenolic compounds , can be added to
suppress oxidation
342
Flash point
It is only an indication of the
hydrocarbons emissions
Low flash point indicate greater
hydrocarbon emissions during use
It also indicate if a mixture of high
viscosity and low viscosity cuts or is a
central cut with average viscosity
343
Boiling temperature
The higher is the boiling temperature means
the higher is the molecular weights of the

components and the greater is the viscosity
The boiling ranges and the viscosities of the
fractions are the major factors in selecting the
cut points for the lube oil blending stocks on the
vacuum distillation unit.
344
Acidity
The organic acids formed during the
oxidation of lubricating oil causes

corrosion because of their acidity
The alkaline materials are added to
lubricating to neutralize the acid
contaminants.
Lube oils blending from parrafinic crude
oils have higher oxidation stability and
exhibit lower acidity than the naphtenic
crude oils
345
LUBE OIL PROCESSINGS
LUBE OIL PROCESSING

The objective of lube oil processing is to
improve the properties of raw lube oil

fractions from most crude oils which
contain components which have
undesirable characteristics for finished
lubricating oils
The heavier lube oil raw stocks are included in
the vacuum fractionating tower bottoms with
asphaltenes, resins, and other undesirables
materials
347
The choice of the cut for lube

oils
The first step is the separation on the
crude oil distillation units of the individual

fractions according to viscosity and
therefore by boiling range
specifications
Heavy lube oils are produced by heavy
hydrocarbons who have high boiling
points
PROPERTIES TO BE
IMPROVED
The undesirable characteristics of these
impurities include:
High Pour Point
High Cloud Point
Low VI ( large change of viscosity with
Temperature)
Poor oxygen stability
Poor Color
High Organic acidity
High carbon and sludge-forming tendencies
349
CLASS WORK #1
STUDY AND DISCUSS WITH YOUR
FRIENDS THE MAIN PROPERTIES OF

LUBE OILS IN PAGE 309.
The processes used to change

these characteristics are:
Solvent deasphalting to reduce carbon and
sludge- forming tendencies

Solvent extraction and hydrocracking to
improve VI
Solvent dewaxing and selective hydrocracking
to lower cloud and pour point
Hydrotreating and clay treating to improve
color and oxygen stability and lower organic
acidity
351
PROPANE DEASPHALTING
The lighter distillate feedstocks for
producing lubricating oil base stocks can

be sent directly to the solvent extraction
unit, however the atmospheric and
vacuum still bottoms require deasphalting to remove the asphaltenes
and the resins before solvent extraction
352
QUALITIES OF PROPANE
Propane is usually used but can sometimes be
mixed with ethane or butane in order to obtain

desired solvent properties
Propane has unusual solvent properties:
From 40 to 600C, the paraffins are very
soluble in propane but this solubility when the
temperature increases until the critical
temperature of propane ( 96.80C)
The asphaltens and resins are largely
insoluble in propane
353
The Process
The feed is mixed with 4 to 8 volumes of liquid
propane at the desired temperature

The extract phase contains from 15 to 20% by
weight of oil with the remaining solvent
The heavier is the feed , the higher propane to
feed ratio
The raffinate phase contains 30 to 50%
propane by volume and is an emulsion of
precipitated asphaltic materials with propane
354
CLASS WORK :
STUDY AND DISCUSS WITH YOUR
FRIENDS FIGURE 15.1 PAGE 313
Viscosity Index improvement

and solvent extraction
Three solvent used for the extraction of aromatics from

lube oil feeds:
Furfural
Phenol
N-methyl-2-pyrrolidone ( NMP)
The purpose of solvent extraction is to improve VI,
oxidation resistance and color of the lube oil and to

reduce the carbon and sledges- forming tendencies of
the lubrificants by separating the aromatic portion from
the naphtenic and parrafinic portions of the feed
356
Furfural Extraction
Similar to the propane deasphalting unit

Except: The solvent recovery which is more complicated
The extraction column is a rasching ring packed column
or sometimes a rotating disc column RDC
The temperature gradient in the column is 300C to 500C
between the top and the bottom
The temperature of the top depends on the miscibility
temperature of furfural and oil Usually from 1050C to
1500C
357
VI OF LUBE OILS IMPROVED BY

HYDROCRACKING OF GAS
OILS
Table 15.1 ( page 317) shows that the VI of

mononaphtene and paraffins are high
Hydrocracking of vacuum gas oils increase the
concentration of parrafins and the VI of the lube oil
When the severity of the process increases
mononaphtalenes and isoparaffins increases
The good conditions of the process are :
* High conversion
* Low space velocity
* Low reaction temperature
358
DEWAXING
All lube oils , except those from very few
naphtenic crude oils, must be dewaxed

Dewaxing is the most important process
otherwise the lube oils will not flow at ambient
temperatures
Two types of processes:
Refrigeration to crystallize the wax and
solvent to dilute the oil fraction sufficiently to
permit rapid filtration
Selective hydrocracking to crack wax
molecules into light hydrocarbons
359
SOLVENT DEWAXING
Two principal solvents: Propane and
ketones
The ketone process uses :
* Methyl Ethyl Ketone (MEK) with
Methyl isobutyl ketone ( MIBK)
* MEK with Toluene
360
CLASS WORK #3
STUDY THE DEWAXING BY PROPANE
PAGE 319-320
DILCHILL DEWAXING
( Figure 15.3 PAGE 320)
Developed by EXXON
Describe Process in Figure
362
GRADES OF MOTOR OILS

SINGLE GRADE
MULTI GRADE
363
SINGLE GRADE
The Society of Automotive Engineers,
usually abbreviated as SAE, has

established a numerical code system for
grading motor oils according to their
kinematic viscosity.
For single-grade oils, the kinematic
viscosity is measured at a reference
temperature of 100 C (212 F) in units
of mm/s or the equivalent older non-SI
units, centistokes (abbreviated cSt).
SINGLE SAE GRADE

The higher the viscosity, the higher the
SAE grade number is.

These numbers are often referred to as
the weight of a motor oil.
Based on the range of viscosity the oil
falls in at that temperature, the oil is
graded as an SAE number 0, 5, 10, 20,
30, 40, 50, 60 or 70.
SINGLE GRADES IN WINTER

(W)
On single-grade oils, viscosity testing can be
done at cold, winter (W) temperature (as well

as checking minimum viscosity at 100 C or 212
F) to grade an oil as SAE number 0W, 5W,
10W, 15W, 20W, or 25W
A single-grade oil graded at the hot temperature
is expected to test into the corresponding grade
at the winter temperature; i.e. a 10 grade oil
should correspond to a 10W oil.
MOTOR OILS WITH

ADDITIVES
A specific oil will have high viscosity when cold
and a low viscosity at the engine's operating

temperature.
The difference in viscosities for any singlegrade oil is too large between the extremes of
temperature.
To bring the difference in viscosities closer
together, special polymer additives called
viscosity index improvers are added to the oil.
These additives make the oil a multi-grade
motor oil.
WHY MULTIGRADE LUBE

OILS
The idea is to cause the multi-grade oil to have
the viscosity of the base number when cold and

the viscosity of second number when hot.
The viscosity of a multi-grade oil still varies
logarithmically with temperature, but the slope
representing the change is lessened.
This slope representing the change with
temperature depends on the nature and amount
of the additives to the base oil.
API/SAE SCALE FOR

MLTIGRADE LUBE OILS
The API/SAE designation for multi-grade oils includes
two grade numbers.

For example, 20W-50 designates a common multi-grade
oil in UAE.
Historically, the first number associated with the W (again
'W' is for Winter, not Weight) is not rated at any single
temperature.
The 20W" means that this oil can be pumped by your
engine as well as a single-grade SAE 20 oil can be
pumped.
The second number, 50, means that the viscosity of this
multi-grade oil at 100 C (212 F) operating temperature
corresponds to the viscosity of a single-grade 50 oil at
same temperature
370
371
Hydrogen production &

purification
Many refineries produce enough hydrogen
for hydrotreating from the catalytic reforming
unit.
Some modern plants with extensive
hydrotreating and hydrocracking operations
require more hydrogen than they produce
This hydrogen can be produced:
-- By partial oxidation of heavy

hydrocarbons such as fuels
-- By steam reforming of methane( natural
gas) , ethane
or propane ( FIGURE 13.1)
372
Steam Reforming of natural gas in

four steps
STEP ONE: REFORMER :
CH4 + H2O CO + 3H2
Catalytic reaction
temperature range : 1400-15000F
Endothermic reaction
gas pass through a filled catalyst furnace
Catalyst: hallow cylindrical rings of in in
diameter . 25 to 40% nickel oxide deposited on
silica refractory base.
373
STEP 2 :SHIFT CONVERTER

In the shift converter, more steam is added to convert the
CO produced by the REFORMER to an equivalent amount

of hydrogen.
SHIFT CONVERTER: CO + H2O CO2 + H2
The shift reaction is:
*
*
*
*
Exothermic reaction
In fixed bed catalytic reactor
Temperature: 6500F
Catalyst : Mixture of chromium and iron
oxide
374
STEP 3 : GAS PURIFICATION

The third step is the removal of CO2 in
circulating amine or hot potassium

carbonate solution. CO2 being acid is
absorbed by a basic solution like amine
Absorption column with 24 trays
375
STEP 4 : METHANATION
in this last step of steam reforming, the
remaining quantities of CO and CO2 are

converted to methane :
* Exothermic Reactions:
CO + 3H2 CH4 + H2O
CO2 + 4H2 CH4 + 2H2O
* Fixed bed catalytic reactor
* Temperature range : 700-8000F
* Catalyst : 10 to 20% Ni on a refractory base
376
Future Trends in Petroleum

Refining
There are four major forces which affect the development of petroleum refining processes:
Demand for products (i.e. gasoline or diesel, fuel oil or jet fuel ) to be cleaner and higher-performance
Feedstock supply increasing heavier and more sour crude supply alternative feed supplies include oil
sand, and coal.
Environmental regulations
Technology development (i.e. new catalysts and processes) the development of fuel cells would drive
refineries to become H2 producers
Current Government Regulations on sulfur content in diesel fuel US EPA has reduced from 5000 ppm to 500
ppm in 1993
EEC has limited to 500 ppm since 1996,
Japan has limited to 500 ppm since 1997,
Canada has limited to 500 ppm since 1998.
New US EPA Tier 2 Regualtions on sulfur content in diesel and gasoline
Most refiners must meet a 30 ppm sulfur average with a 80 ppm cap for both conventional and reformulated
gasoline by January 1, 2006
New on-road diesel regulations = 15 ppm sulfur cap by January 1, 2006
New Processes for Low-Sulfur Fuels
More active and selective catalysts for existing HDS processes
Novel processing schemes that dont depend on HDS technology
Reactive adsorption of sulfur without high-pressure H2 (Phillips Petroleum)
Selective adsorption of sulfur compounds without H2 (PSU)
Liquid-phase oxidation followed by extraction
Bio-desulfurization that is not limited by steric restriction of 4,6-DMBT (Energy Biosystems)
377
GAS PROCESSING UNIT

Main objectives:
Recovery of valuable C3,C4,C5 and C6

compounds from various gas streams
generated by crude distillation, cokers, cat
crackers, reformers and hydrocrackers
Production of desulfurized dry gas
consisting mostly of methane and ethane for
use as fuel gas or feedstock for hydrogen
production
378
THE PROCESS (FIGURE

13.3)
Compressing the gas
Feed an absorber- deethanizer unit where naphta is used to absorb 90%
of the C3 and all the C4+

The vaporized heavy hydrocarbons leave the top of the absorber with
the light gases and are recovered in a sponge absorber
The non volatile kerosene can be used as sponge oil
The deethaniser rich oil will feed the debutanizer where all the
propane and butane are recovered and then desulfurized and separated
in a depropanizer
Natural gasoline from the bottom of the debutanizer is the feed of the
naphta splitter where Light Straight Run ( C5 and C6) is produced at the
top sweetened and used as gasoline blend. The lean absorbing oil is
obtained at the bottom
379
TWO STAGES PROCESS

( Page 144)
The fresh feed is mixed with Make up and
recycled Hydrogen
then pass through a heater and the first reactor
( If the feed is not treated, It should pass
through a guard reactor before hydro cracking
to eliminate the impurities such as organic
sulfur and nitrogen compounds)
The hydrocracking reactor is operated as high
temperature to convert 40 to 50% vol of the
reactor effluent to material boiling below 4000F.
380
The reactor effluent goes through heat
exchangers and a high pressure

separator where the gas rich in hydrogen
is recycled . The liquid go to the
distillation column where light gases,
naphta and diesel are produced
The fractionator bottom is used as a
feed to the second hydrocracker
381
Typical hydrocracker
feedstocks
Feed
Products
Kerosine
Naphta
SR- Diesel Naphta , jet fuel
Atmospheric G.oil Naphta, jet fuel, diesel
Vacc. G.oil
Naph, J,Fuel, Diesel, Lube oil
Light FCC cycle gas oil Naphta
Heavy FCC cycle gas oil Naphta / distillates
Light Cooker Gas oil
Naphta / distillates
Heavy Cooker Gas oil Naphta / distillates
382
Hydrocracking Reactions
Cracking is the scission of carbon-carbon single bond
hydrogenation is the addition of hydrogen to a
carbon-carbon double bond

Cracking provide double bonds for hydrogenation
(page 139 and 140)
Isomerization is another reaction in hydrocracking
The olefinic products formed are rapidly
hydrogenated maintaining a high concentration of high
octane isoparaffins and preventing the back reactions
to straight chain molecules
383
Hydrotreater
Number of reactions take place:
Olefin saturation
aromatic ring saturation
cracking is almost insignificant
The exothermic heats of
desulphurization and denitrogenation are

high ( 2800 kJ/std m3)
384
The saturation of olefins contribute also
in the exothermicity of the reaction,

However for virgin stocks, this is
negligible reaction
Reduce the water content to 25 ppm
In average, this process consume 27 to
54 m3 of hydrogen by m3 of feed)
385
Hydrocracking Process
Figure 7.2
Freed is mixed with recycled hydrogen
Pass trough a heater and a first reactor
If the feed was not treated , the first reactor is a
guard reactor with catalyst Co-Mo on silica alumina to
convert organic sulfur and nitrogen compounds to
protect the hydrocracking catalyst
The hydrocracking reactor is at 660-7850F and 10002000 psig
The reactor effluent goes trough heat exchanger and
a high pressure separator
The hydrogen is recycled and the liquid sent to
386
distillation
Process variables
Reactor temperature is the primary means of conversion
control..200C increase in temperature almost double the

conversion rate
Reaction Pressure: The primary effects of pressure on
conversion is in its effects on the partial pressure of
hydrogen which increases conversionthe effects of
partial pressure of ammonia is to decrease conversion but
this effect is smaller than the increase of partial pressure of
hydrogen
387
Space velocity: The volumetric space velocity is
the ratio of liquid flowrate in barrels per hour on the

catalyst volume in barrels.
The catalyst volume is constant, therefore , space
velocity varies directly with feed rate. As feed rate
increases, the contact time with catalyst decreases
and therefore the conversion decreases
388
Nitrogen Content: The increase of nitrogen content will
deactivate more the catalyst and therefore conversion

decreases
Hydrogen sulfide: A small concentration of H2S acts as
catalyst to inhibit the saturation of aromatic rings which
have higher octane number than the naphtenic. However,
small amount of H2S produces very low smoke point jet fuel
( Bad burning quality jet fuel)
389
Hydrogen sulfide: A large amount of H2S increases
corrosion and inhibit the cracking activity of the catalyst

Heavy Polynuclear Aromatics: HPNA
HPNA are formed in small amounts from hydrocracking

reactions.these amounts can build up when the
fractionator's bottoms is recycled and causes fouling of
heat exchangers
390
ETHYLENE
Lightest olefinic hydrocarbon
Does not occur freely in nature

Largest building block for a variety of
petrochemicals such as plastics, resins, fibers,

solvents,
Produced primarily from the thermal cracking of
hydrocarbons feedstocks derived from natural gas
and crude oil
391
PRODUCTION OF
ETHYLENE
Thermal Pyrolysis of hydrocarbons
Conventional feedstocks include ethane, propane, butane
and naphta
Reaction of cracking occurs in tubular coils located in the
radiant zone of furnaces
Steam is added to reduce the partial pressure of
hydrocarbons in the coils
Transformation of saturated hydrocarbons to olefins is
endothermic reaction and require temperature around 750
to 9000C
392
Reactions of thermal cracking

Rice and Herzfeld proposed the concept of free radical
mechanism
Chain Initiation: Initiation of Radicals
CnH2n+2 CmH2m+1. + C(n-m)H2(n-m)+1.
Chain propagation: Reaction of Radicals with
molecules
CnH2n+2 + CmH2m+1. CnH2n+1. + CmH2m+2
CnH2n+1. CmH2m + C(n-m)H2(n-m)+1.
Chain Termination: Disappearance of radicals
CnH2n+1. + CmH2m+1. CnH2n + CmH2m+2
393
PROCESS
First Stage: Pyrolysis or cracking of feed
Second Stage: Gasoline fractionator to remove heavier
fuel components if the feed is naphta. Bottom temperature

190 to 2300C and Top temperature 95 to 1200C
Third Stage : Fuel Oil Stripper where fuel oil are stripped
and sent to fuel handling facilities
Fourth Stage: Water Quench tower where the cracked gas
is cooled to 400C with circulating water
394
PROCESS
Fifth Stage: Compression: The cracked gas leaving the
quench tower is compressed to 32 to 37 bars in four or five

centrifugal compressor
Sixth Stage: Acid gas removal and drying:
between the third and fourth stage of compression, CO2
and H2S are removed with dilute caustic soda
Seventh Stage: Chilling train and Demethanizer
to separate H2, ethane from C2+
395
PROCESS
Eighth stage: Deethanizer and Ethylene
production
396
High Density Polyethylene

HDPE
The Hastalen process is designed to
produce HDPE from ethylene monomer

The Process consists on 2
polymerization reactors that can be
operated in parallel ( unimodal product)
or in series ( bimodal product)
Catalyst is injected in the stirred slurry
reactor where the liquid phase is hexane
as suspending agent
397
HDPE
After the reaction, the polymer is
separated from the slurry mixture and

dried
The polymer is send to the extrusion
unit
398
PROCESS
Catalyst preparation and feeding
Polymerization
Powder drying
Extrusion and pellets handling
Hexane recycling
Butene recycling
399
Catalyst preparation
Production of Catalyst THT/THE/ THB is
performed batchwise from four

commercially available components in
one catalyst preparation vessel under
precisely defined conditions
Finished catalyst batches are
transferred into catalyst dilution vessels
and further diluted to the correct
concentration
400
POLYMERIZATION
The reactors are CSTRs. They are
operated at different conditions and

residence times
The reactor is fed continuously with
monomers, catalyst and co catalyst,
hydrogen and hexane recycled from the
process
The reaction is extremely exothermic;
the pressure is around 5 to 10 bars and
the temperature around 75 to 850C.
401
The heat of reaction is removed by
cooling water
402
HDPE Powder Drying /

Diluent's separation
Suspensions leaving the receiver ( Figure) are
separated in a decanter centrifuge into a liquid

and a solid fraction
The solid part will feed a fluidized bed dryer
operated with nitrogen and the liquid part (
hexane) goes back to reactors
Dried HDPE powder passes through a sieve
and is pneumatically conveyed by nitrogen to
the extrusion unit
403
Reaction Mechanisms
The Hostalen process is based on a
Ziegler reaction mechanism with the so

called ziegler catalyst.
These catalyst are produced with TiCl4
and Al(C2H5)3 according the the formula
given in Figure
404
POLYPROPYLENE
The polymerization of propylene to
polypropylene was performed in 1954 by

Giulio Natta ( 1963 Nobel prize in
Chemistry)
Propylene can polymerize into three
distinct structural chains ( Figure 16.1.1)
* Isotactic
* syndiotactic
* atactic
405
Isotactic PP occurs when all the methyl
groups are located on the same side

Syndiotactic PP occurs when the methyl
groups are located on alternating sides
of the chain
Atactic PP occurs when the methyl
groups are randomly dispersed around
the chain
406
The catalyst System

The catalyst system is composed of:
* Solid catalyst, generally TiCl4

supported by MgCl2
* an internal or external Lewis Base
* an Aluminium Alkyl
407
Catalyst Function
The catalyst is composed of two main
elements: a transitional salt and an inert

support structure
The MgCl2 support has the following function:
* It creates a highly disorganized crystalline
structure the reaction sites are greater in
number and therefore higher activity
The active part of the catalyst ( TiCl4) should
be activated by an Aluminum Alkyl and Lewis
base
408
Catalyst Evolution ( Table 16.1.1)

The rapid & successful
commercialization of PP is due to the

continuous development of new
improved catalysts
the yield of catalyst has increased from
1 to 120 kg/ g catalyst
409
Polymer Chain Control

The length of the polymer chain has a
significant impact on its performances and

mechanical properties.
Direct measurement of the chain length is
difficult For many years the intrinsic Viscosity
IV was used
IV results were directly related to the polymer
chain
The higher the IV the longer is the chain
410
Recently, The melt-flow rate (MFR)
technique is used
MFR is the weight of melted polymer that
can flow through a specific orifice under
standard conditions
Standard Load = 2.16 kg
Standard temperature = 230 0C
Standard Time = 10 min
411
Molecular Weight Distribution

(MWD)
In the polymer, the chains have different length
and one way to know the length distribution is

the MWD
A fundamental measurement of MWD is gel
permeation also known as size-exclusion
chromatography
In this technique, the polymer is dissolved in a
solution and the chains elute at different times
through a porous media
412
MWD
We can distinct Mn and Mw
Mn is the number average molecular weight
Mn
nM
n
i
Mw is the weight average molecular weight
M w ni M i2 / ni M i
413
Polydispersity
Polydispersity is the ration of Mw/Mn
Polydispersity is used to describe the
MWD
414
PP Polymerization Processes
In the 1960s, PP process used first
generation low-yields catalyst ( <
1000kgPP/ kg of catalyst) in mechanically
stirred reactors filled with an inert hydrocarbon
diluent
PP produced had unacceptable high residual
metals and contained 10% atactic PP which
needed separation
415
Second Generation catalyst

An intermediate step was reached with
a second generation catalyst increasing

yield to 6000/15000Kg PP by kg of
catalyst
But isotacticity not yet at level that allow
simplification of the process
416
Third Generation Catalysts

In the 1970s, the discovery of the third
generation catalyst ( 15000 to 30000kg

PP by kg catalyst) eliminated the need
for catalyst residue removal but atacticity
was still high and the atactic recovery
step was not eliminated
417
The Fourth Generation

Catalyst
In the 1980s, the fourth-generation high
yield , high selectivity ( HY/HS) catalyst

was discovered ( 30000kg of PP by kg of
catalyst)
this eliminated the need of catalyst and
atactic removal
In 1982, the Spheripol process was
developped
418
Spheripol Process
It has the unique ability to produce
polymer spheres directly in the reactor

Spherical PP differs considerably from
the small, irregularly shaped, granular
particles produced by other technologies
419
Process Description
The Polymerization Unit involves the following
sections:
* Catalyst Feeding
* Polymerization:
- Prepolymerization
- Bulk Polymerization
- Gas phase Polymerization
- Finishing
420
The catalyst
The catalytic system has three
components:
- Solid catalyst
- Aluminium Alkyl used to activate the
catalyst
- Lewis Base used to control the
cristallinity and the homopolymer grade
421
Bulk polymerization
Bulk Polymerization employs jacketed
tubular reactor completely filled with

liquid propylene to produce
homopolymer, random copolymer and
terpolymer
The catalyst, liquid propylene and the
hydrogen are fed continuously into the
loop reactor
The Polymerization reaction is
exothermic
422
Commercial uses of PP
Table 16.3.1
423
Synthetic Polymers
The synthetic polymer industry is the major
use of many petrochemical monomers such as

ethylene, propylene, styrene and vinyl chloride
Many articles previously produced from natural
material such as wood, cotton, wool, iron ,
aluminum and glass are now replaced or
partially substituted by synthetic polymers
Polymerization can now be tailored to produce
polymers stronger than steel
424
Thermoplastics
Polyethylene ( LDPE and HDPE)
Polypropylene
Polyvinyl Chloride (PVC)
Polystyrene
Nylon resins
425
POLYETHYLENE
The most extensively used thermoplastic

Because of the abundance of the monomer from the
abundant raw materials ( FG, LPG, naphta)
Other factors include
* Low cost, ease processing the polymer, resistance to
chemicals,
World production of PE was 100 billions pounds in 1997
and predicted 300 billions pounds in 2015
The two grades of PE include LDPE and HDPE
426
LDPE
Produced under High pressure in the
presence of free radical initiator

Temperature of reaction: 100-2000C
Pressure of reaction: 100-135 atm
Polymer highly branched (?)
Low crystallinity (?)
By adding copolymers , we obtain
copolymers with lower crystallinity,
higher impact stenght
427
HDPE
Low pressure process
High cristallinity
high melting point ( compared to LDPE)
due to absence of branching
428
Properties and uses of PE
Inexpensive thermoplastic
can be modeled to almost any shape, extruded into fibers or filaments
and blown or precipitated into films or foils
LDPE is flexible and transparent can be used for the production of films
and sheets and for film production
HDPE can be used to produce bottles and hollow objects by blow
molding ( about 64% of bottles are made by HDPE)
Injection molding is used to produce solid objects
Pipes produced from HDPE are flexible, tough and corrosion resistant
429
POLYPROPYLENE (PP)
Major thermoplastic polymer
The delay in PP production is attributed to its
polymerization
PP produced by free radical is mainly atactic form having
low cristallinity which is not suitable for thermoplastic or
fiber use
The turning point in PP production is the development of
a Ziegler-type catalyst developed by Natta to produce
isotactic PP
430
Properties and Uses of PP

Good chemical and electrical resistance
Low water absorption

Light weight ( lowest thermoplastic
polymer density)
High abrasion resistance
high impact strength
no toxicity
431
PP can be extruded into sheets
Due to its light weight and toughness,
PP is widely used in automobile parts
432
PVC
widely used thermoplastic
blow modeled into bottles, used in common
items such as garden hoses, shower curtains,

irrigation pipes, paint formulation
Excellent chemical and abrasion resistance
self extinguishing due to the presence of
chlorine atom
Can be used as tablecloth, cable insulation
433
POLYSTYRENE (PS)
Polymerized by free radical or using
coordination catalysts
Copolymers Styrene- acrylonoitrile
(SAN)
have higher tensile strength than PS
A copolymer of acrylonitrile, butadiene
and styrene (ABS) is an engineering
plastic due to its better mechanical
properties
434
Properties and Uses of PS

Highly amorphous if produced by free radical
polymerization
SBR ( a block copolymer with 75% Butadiene
) is produced by anionic polymerization
PS is used mostly in packaging
Molded PS is also used in automobile interior
parts, furniture and home appliances
435
Project by Internet
Uses of PE
Uses of PP
What is PVC ( polyvinyl Chloride)
What is PS ( Polystyrene)
436

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Welcome to

Petroleum Refining &

L.Os of the course

reforming, and isomerization.

manufacture of some typical end products

(Latin petra) - rock + (Latin oleum) - oil)

WHAT IS CRUDE OIL?

mixtures of many different hydrocarbon compounds.

solids, and in color from clear to black.

Crude oils are generally classified as paraffinic,

naphthenic, or aromatic, based on the predominant

MAIN COMPONENTS OF CRUDE OILS

viscous, and the longest chains are part

Crude oil refining is a key transformation step in the

energy subsidies from nonrenewable fossil sources:

They are called "nonrenewable" because, for all

practical purposes, they're not being made any more.

contributors to global warming

WORLD OIL RESERVES

ECONOMY AND CRUDE OIL IN

economy in the UAE and will remain a major

98.2 billion barrels or 9.5 percent of the global

Refinery: From Crude to Useful

chemical reactors turn crude oil into valuable products.

thousand workers, operate around the clock, and occupy the

Useful Products from crude oil

Petroleum Refining Processes

processes and other facilities used in petroleum refineries

ABU DHABI REFINERY

Following the discovery of oil in Abu

CRUDE OIL FOR ABU DHABI

Complex designed to process Bab

REFINERY MAIN UNITS IN

REFINERY FINAL PRODUCTS

STUDY THE MARKET

refinery product to maximize profits

summer driving months, the public consumes vast amounts of gasoline,

north, or the humid south.

FROM THE WORLD MARKET

THAN HEAVY CRUDE OILS

NEEDED TO OBTAIN SMALLER CHAINS HYDROCARBONS

(e.g., "West Texas Intermediate, WTI" or "Brent")

contains relatively little sulfur, or as "sour," which means it

light as West Texas Intermediate (WTI). It contains

WTI Crude Oil

39.6 and specific gravity of about 0.827, which is

are organic compounds of carbon and hydrogen atoms

and arrangement of the carbon and hydrogen atoms in

usually gases, those with 5 to 19 carbon atoms are

THE MAIN HYDROCARBONS

The paraffinic series of hydrocarbon compounds found in

Examples of straight-chain molecules are methane,

ethane, propane, and butane (gases containing from one

THE SIMPLEST PARAFFIN

BUTANE AND ISOBUTANE

Aromatics are unsaturated ring-type (cyclic) compounds which

All aromatics have at least one benzene ring (a single-ring

compound characterized by three double bonds alternating with

The most complex aromatics, polynuclears (three or more fused

aromatic rings), are found in heavier fractions of crude oil.

Naphthenes are saturated hydrocarbon groupings

Single-ring naphthenes (monocycloparaffins) with five

and six carbon atoms predominate, with two-ring

Petroleum Refining & Petrochemicals

Petroleum Refining & Petrochemicals