NNPC MODIFIED FOUNDATION SKILLS TRAINING

PROGRAM

LECTURE NOTES

ON

FUNDAMENTALS OF REFINING AND

PETROCHEMICALS PROCESSES

1
GENERAL OVERVIEW OF REFINING
AND PETROCHEMICALS COMPLEX

2
 CONTENT
INTRODUCTION
REFINING PROCESSES - FUELS
COMMON PROCESS UNITS IN THE REFINERY
SITING OF REFINING PLANTS
SAFETY AND ENVIRONMENTAL CONCERNS
EVOLUTION OF REFINING PROCESSES
DEVELOPMENT OF REFINING IN NIGERIA
REFINING OPERATIONS :
TYPES OF REFINING PROCESSES ( 4 STEPS ) :

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INTRODUCTION
Crude oil processing is mainly aimed towards the
production of fuels and so only a small fraction of its
products is used for specialty chemicals and
petrochemicals production. Consequently refineries are
set up primarily to produce transportation fuels;
Aviation fuels, Gasoline(Petrol) and Automotive Gas oil
(Diesel Oil). It is the need to produce more and more of
these products from the a barrel of crude oil that has
been the force driving refining process design and
catalyst technology. Production of speciality products
( solvents, lubricants, petrochemical feedstocks, etc. ) is
ancillary to transportation fuels production.
Indeed modern conversion refinery output is
unleaded gasoline (PMS) and the balance of is
distributed between LPG, Jet fuels, Diesel fuel, coke,
Solvent Extraction for lubricants manufacture and
Petrochemicals units to recover Propene, Butenes,
Benzene, Toluene and Xylenes for further processing
into Polymers.

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REFINING PROCESSES - FUELS
Crude oil is a very complex mixture of materials, several
thousands of them; a lot of some, a little of the others,
but thousand of kinds in any case. Crude oils chemical
constituents vary with location, age and the depth of the
individual well.
As a mixture, Crude Oil is off little practical use but we
are able to obtain more than 3000 useful and saleable
products from it.
Petroleum Refininig Plants are large sprawling industrial
complexes typically with extensive network of pipings
carrying streams of fluids between large chemical
processing units where Crude Oil is processed into useful
petroleum products (LPG, Gasoline / Petrol, Kerosene,
Diesel Oil, Heating Oils, Lubricants and Byproducts). In
other words, a refinery comprises group of
manufacturing plants (units) which vary in number with
the variety of products produced.
Refinery Byproducts are processed to products such as
Solvents, Detergents, Plastics, Elastomers (Synthetic
Rubbers) and Fibres (Nylon and Polyesters).
Refining processes have evolved continuously since the
advent of crude distillation in response to changing
consumer demand for various premium products and
environment protection.
There are three types of Refinery :

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1. Topping Refinery a simple refinery made up of
CDU, Gas plant and Light hydrocarbon recovery
and the necessary Utility system. It produces
large amounts of unfinished oils, Residuals.
2. Hydro-skimming Refinery Topping Refinery into
which Hydro-treating and Catalytic Reforming
Units have been incorporated. Usually about half
of its output is residual fuel oil ( Old PHC
Refinery). Operations can be seriously
jeopardized in an era of low sulfur fuel oil
demand.
3. Conversion Refinery Hydro-skimming Refinery
plus Cat Cracking, Hydro-cracking, Coking, etc.,
to sharply reduce or eliminate residual fuels

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COMMON PROCESS UNITS IN THE REFINERY
The number and nature of process units determine
Complexity Index of a Refinery. But the Refinery
Configuration is the number of the types of processes
employed to produce the desired product slate.
The following items are what one may expect to find in a
modern day refinery :
The Desalter reduces salts and other contaminants from
Crude Oil before distillation.
Atmospheric Distillation for Crude Oil processing into the
different cuts and Vacuum Distillation for Residues.
Naphtha Hydrotreater which substantially reduces S, N
and metallic impurities from Intermediate stocks.
Catalytic Reforming produces high octane Reformate.
Distillate Hydrotreater desulphurises, denitrogenates
and demetallises Middle and Heavy distillates.
Fluid Catalytic Cracker upgrades heavy fractions into
lighter and more valuble products.
Hydrocracker is catalytic cracking of heavy fractions but
with hydrogenation superimposed.
Visbreaker upgrades heavy residual Oils by thermal
cracking into lighter, more valuable products with
reduced viscosity.
Coker (Delayed, Fluid- and Flexi-) unit processes very
heavy residual Oils into Gasoline, Diesel Oil and
Petroleum Coke.

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Merox unit removes bad odour from LPG, Kerosene and
Jet Fuels.
Alkylation unit produces high octane Gasoline blend
components.
Dimerisation unit converts Olefins to high octane
Gasoline blend components : Butene to Isooctene then
Isooctane.
Isomerisation unit converts linear molecules to high
octane branched molecules for Gasoline blend.
Steam Reforming for Hydrogen production and Light
Olefins.
Amine Gas Treater removes acid gases, e.g. Hydrogen
Sulphide from gas streams.
Claus unit converts Hydrogen Sulphide in Tail Gases to
Sulphur.
LPG storage Spheres or Bullets.
Storage tanks for Crude Oil, Intermediate and Finished
products, usually cylindrical with vapour emission
control surrounded by Bound Wall to contain spills.
Utility units such as :
Cooling Towers for circulating cooling water.
Boilers for steam generation.
Compressed Air unit for instrument air and
Nitrogen production.

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 Power generation unit and Electrical Sub-
Stations.
Waste water collection and treatment facilities to make
foul water suitable for reuse or disposal.
Solvent Refining unit to remove unwanted asphaltenic
materials and polynuclear aromatics from lube base
stocks.
Solvent Dewaxing to remove heavy waxy components
from High Vacuum distillates for pour point control.
Solvent Deoiling of Slack waxes to produce Hard Waxes.

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SITING OF REFINERY AND PETROCHEMICALS PLANT.
The principles are similar to those for other chemical
plants:
Reasonable distance from residential areas.
Easy access to raw materials.
Easy access of products delivery to market.
Adequate avalibity of processing energy
requirements.
No difficuties in waste (liquid and solids )
disposal.
For plants which use large amounts of process
steam and cooling water, an abundant source
of water is important. Hence location near
navigable rivers or on a sea shore associated to
a port.
This also makes cheap transport by river or sea available
although transport by pipeline is most economical.
Choice of Areas where abundant space is available so
the same company or others can construct
Petrochemicals Plants, Solvent manufacturing or similar
Plants which will then have easy access to large output
of Refinery products and Byproducts.

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SAFETY / ENVIRONMENTAL CONCERNS
Petroleum Refinery and Petrochemicals Plants release
numerous different chemicals into the atmosphere
( fugitive emissions ) : there is substantial air pollution
and notable odour accompany their presence.
Other concerns are :
Waste water concerns.
Solid and Sludge disposal
Noise health hazards due to industrial noises.
Risk of accidents such as fire and explosion.
Therefore many government agencies place restrictions
on these contaminants, pollution and risks.
Hence most Plants have installed equipment needed to
comply with the requirements of the pertinent
Environmental Protection Regulatory Agency.
Compliance with these requirements makes it difficult to
construct new Plants in some countries (Marathons
Garyville Louissiana since 1976).

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 EVOLUTION OF REFINING PROCESSES
(FIRST COMMERCIAL OIL WELL, 1859)

YEAR PROCESS NAME PURPOSE BY-PRODUCT

1862 Atmospheric Distillation Produced kerosene initially Naphtha, tar, etc

1870 Vacuum Distillation Lubricants (originally) Cracker feedstocks Asphalt, residual Coker feed
(1930's) stocks
1913 Thermal Cracking Increased gasoline production Bunker fuel
1916 Sweetening Reduces sulfur& odor Sulfur
1930 Thermal Reforming Improves octane number Residual
1932 Hydrogenation Remove sulfur and Nitrogen Sulfur
1932 Coking Produces more gasoline Coke
1933 Solvent extraction Lubricant Base oils, Improves viscosity index Aromatics

Improves pour point

1935 Solvent Dewaxing Waxes
Improve gasoline yield
1935 Cat. Oligomerization & octane number Petrochemical feedstocks

YEAR PROCESS NAME PURPOSE BY-PRODUCT,

1937 Catalytic Cracking Higher octane gasoline product Petrochem. feed stocks
1939 Visbreaking Reduces viscosity Increased distillate, tar
1940 Alkylation Increases gasoline octane & yield High-octane aviation
1940 Isomerization Produces alkylation feedstock gasoline
1942 Fluid Catalytic Hydrocracker Increases gasoline yield/octane Naphtha
1950 Deasphalting Upgrades heavy fractions Petrochem. feed stocks
1952 Catalytic Reforming Increases cracker feedstock Asphalt
1954 Hydrodesulfurization Treats low-quality naphtha Aromatics
1956 Inhibitor sweetening Removes sulfur & Nitrogen Sulfur
1957 Catalytic Isomerization Removes mercaptans Disulfides
1960 Hydrocracking Converts to high octane number Alkylation feedstocks
1974 Catalytic dewaxing Improves quality/ reduces sulfur Alkylation feedstocks
1975 Residual Hydrocracking Improves pour point Wax
Increases gasoline yield from residual Oils Distillates

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DEVELOPMENT OF PETROLEUM REFINING IN NIGERIA
OLD PORT HARCOURT REFINERY
Commissioned In 1965, Initial Capacity = 35,000
BPSD.
Debottle-necked In 1972 To 60,000 BPSD.
Built To Produce Fuels (PMS Kero, AGO). Hitherto
Imported From Europe.
WARRI REFINERY
Commissioned In 1978, Initial Capacity: - 100,000
BPSD.
Debottle Necked In 1986 To A Capacity Of 125,000
BPSD.
KADUNA REFINERY
Commissioned In 1980, Initial Capacity: - 100,000
BPSD.
Debottle Necked In 1986 To A Capacity Of 110,000
BPSD.
NEW PORT HARCOURT REFINERY
COMMISSIONED IN 1989, CAPACITY: - 150,000
BPSD.

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TYPES OF REFINING PROCESSES
Refining processes can be conveniently grouped into 3
major types:
Separation Processes involving Physical Changes
that separate crude into the various fractions
depending on the nature of the crude
Conversion Processes involving Chemical Changes /
Reactions resulting in the production of marketable
materials from crude by skeletal alteration or even
alteration fo the chemical type of crude
components and may involve Decrease / Increase in
Average Molecular Weights or neither.
Catalytic Reforming, Catalytic Cracking,
Hydrocracking, Hydrodealkylation, Alkylation,
Isomerisation and Polymerisation all involve
reactions initiated by acid-type catalyst that
promotes carbenium in formation. The other
processes are heterogeneous Hydrogenation.
Finishing Processes : Quality Improvement :
removal of contaminants and blending various
stocks, adding appropriate additives and provide
short term storage before products are sold out.

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REFINING PROCESS - FUELS SCHEMES
REFINING PROCESS SCHEMES
DIFFERENT TYPES AND COMPONENTS
Pages 11 to 13 list different types of Process
Units that may be seen in a Refinery and the
last page of this note shows KRPC Fuels Plant
Flow Scheme.
Components will invariably include Columns,
Drums, Coolers, Heat exchangers, Fired
heaters, Reactors, Fans, Turbines, Electric
Motors, Pumps, Compressors and Net works of
pipe line and Instrumentation items.
FACTORS INFLUENCING CHOICE OF SCHEME:
All crude oils are assayed and valued depending on
their processibility and potential yields. Crude oils
with low assay numbers, called Opportunity Crudes,
are difficult to process due to higher levels of
contaminants and water and are cheap.

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RAW MATERIAL (FEED STOCK)

CRUDE OILS

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RAW MATERIAL (FEED STOCKS) CRUDE OILS
INTRODUCTION: WHAT IS CRUDE OIL
Crude Oil or Petroleum (GK: Petra Rock; Oleum Oil or
Rock Oil) because found only under Sedimentary Rocks .
Usually greenish brown or blackish gelatinous and free
flowing liquid with Boiling Point range: 37.8 oC to 760oC
(100oF to 1,400oF) and easily transported through pipe
lines, barges and ocean liners.
The term crude oil is the name applied to the degassed
raw petroleum that has been removed from the ground.
Petroleum on the other hand, is the general name
applied to an oily, usually dark-colored liquid that occur
naturally in many parts of the world. Physically,
petroleum is a liquid containing gaseous, liquid, and
solid element and its consistency can vary from a liquid
as thin as kerosene to a liquid so thick that it can barely
flow. Petroleum is believed to be the product of
decomposition of certain types of plants or animals.
Over a period of hundreds of years these decomposed
of organic substances were buried by the decomposed
of sand or other inorganic substances and chemical
altered by the action of heat and pressure deep within
the earth to form petroleum. Petroleum is usually
associated with salt water and with natural gas, forming
three layers, with the gas above and the salt water
below the petroleum. When a well is sunk into the
petroleum layer, the petroleum is forced to the surface
by the pressure of the natural gas.

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From the wellhead, the petroleum is run to a high-
pressure vessel for flashing off the dissolved natural gas
before being run to crude oil storage tanks.
At one time, petroleum was only burned for its fuel
content but today it is refined to manufacture fuels such
as gasoline, diesel oil, and coke plus specialty products
such as benzene and styrene.
Another definition for petroleum is a non-homogeneous
mixture of substances of which the main constituents
are hydrocarbons along with various quantities of sulfur,
oxygen and nitrogen derivatives of hydrocarbons.
Petroleum may also contain dissolved gases in varying
amounts and small amounts of metallic compounds.
Petroleum differs widely among themselves in their
physical properties.
This is the ratios of hydrocarbon types present. Non-
dissolved water is commonly associated with petroleum.
The ratios of the different types of hydrocarbons in a
specific crude oil are important in determining the
refining process to be used.

ORIGIN OF CRUDE OIL

Crude oils are confirmed to have been formed from
Marine Organisms (both Plants and Animals) that lived
and died Millions of Years ago. And evidence of its
Biological origin stems from presence in it, some of
these chemical constituents :

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 Isoprenoids : Natural rubber monomer.
Steriods : Hormones.
Porphyrins : Usually associated with the metallic ( V,
Ni or Fe ) contaminants ; Haemoglobin and
Chlorophyll.
Many of its compounds have even number of
carbon atoms (De-carboxylation).
An American, Edwin L. Drake discovered the first
commercial Crude Oil well onshore in Pennsylvania
1859. Wells are now drilled both on- and off-shore.

COMPOSITION OF CRUDE OIL

Crude oil is a complex mixture with highly individual
composition not exactly matched by any other crude
and consists mainly of hydrocarbons (HC compounds
of Carbon & Hydrogen only).
COMPOSITION BY ELEMENTS
Carbon; 83 87%.
Hydrogen; 10 14%.
Sulfur; 0.1 3% rarely up to 7%.
Nitrogen; less than 0.1% occassionally as high as 2%
Oxygen; 0.2 up to 1.5% .
Others (Traces) : Vanadium, Nickel, Sodium, Iron,
Chlorine, Arsenic, Copper, Ca, Ag, Hg and Lead.

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 Virtually all metal impurites are at the bottom end.
COMPOSITION BY COMPOUND GROUPS
HYDROCARBONS AND HC TYPES :

Paraffins (Alkanes): normal and iso .

Naphthenes (Cylo alkanes) : Mono, bi and
Tricyclo parafffins
Aromatics : Benzene, Naphthalene,
Anthracene, Phenanthrene, Fluorene, Pyrene,
etc.
Hybrid Molecules with alkyl groups attached to
Naphthene or Aromatic ring or
Naphthenoaromatics.
NON HC COMPONENTS
Sulfur ( organic and inorganic ) compounds: H 2S,
Alkylmercaptans, Linear and cyclic sulfides and
Disulfides; Thiols, Thiophenol, Thiophene and
Diphenyl Disulfide.
Nitrogen compounds: include Pyrrole, Indole,
Pyridine, Hydroxipyridine, Quinolines,
Hydroxiquinoline, Carbazole, Acridine and
Phenanthridine.
Oxygen compounds: Phenols, Aryl Fatty Acids,
Naphthenic Acids etc are responsible for crude
oil acidity.
Metal ( V, Ni, Fe, etc ) precursors.

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NB: Olefinic and Acetylenic compounds are not usually
present in the crude oil but are products of its
processing.

CRUDE OIL ANALYSIS

The tests that are applied to crude and its fractions for
effective utilisation and potential market value are:
Physical Properties Measurements (SG, Viscosity
etc).
ASTM Distillation for TBP curves.
Chemical Analysis for Sulfur, Nitrogen, Chlorides
and Trace metals.
Compounds Data :
Individual Saturates up C8.
Paraffins up to C30 and above.
Naphthenes.
Aromatics.
Hybrid Molecules : Alkyl naphthenes and Alkyl
aromatics.
Semi-empirical tests Pour Point, Cloud point,
Octane Rating etc.
The data so generated provide information for Planning,
Plant Construction and assessing Suitability for Speciality
Products manufacture .

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CLASIFICATION OF CRUDE OILS
Knowledge of the constituents of crude oil to be
processed is important to a refiner if the purpose is to
produce chemicals or to modify process variables. In
most refineries where atmospheric distillation is one
of the processes used to produce conventional fuels,
detailed knowledge of the crude oil is not necessary.
For this reason, plus the economy of a simple process
to determine the characteristics of crude, a broad
classification of crudes has been developed based on
some physical and chemical properties.
Crude oils are generally characterized as belonging to
one of four types depending upon the relative
amounts of waxes and asphalts present. The wax
content shows the degree to which the crude is
1. Paraffinic- crude oils with a relatively low wax
content.
2. Highly Paraffinic- crude with high wax content and
relatively low asphalt content in residue.
3. Naphthenic- crude oils with trace amounts of
waxes and high asphalt content in the residue.
4. Aromatic- crude with high aromatic content in the
residue.
The term mixed crude is used when the crude has
average properties between paraffinic and
naphthenic.
Some types of crude oils have economic advantages
as sources of fuels and or lubricants, with highly

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 restrictive characteristics, because they require less
specialised processes than that needed for the
production of the same products from many cude oil
types. Others may contain unusually low
concentrations of components that are desirable for
fuels or lubicants constituents and production of
these items from such crudes may not be
economically feasible or viable.
Crudes with high API gravity are generally rich in
paraffins and tend to yield greater proportions of
gasoline and light petroleum products.
Crude Type : eg. Light, Heavy.
Product yield : Light vs Middle Distillates.
Product Quality.
In general crude oil characteristics are very important
in meeting product demand and in determining what
further processes the initial fractions may require.
Sulfur content is usually considered in determining
crude oil commercial values. And because Light crudes
yield more valuable Light and Middle Distillates they
are usually sold at higher prices.
Crudes can also be classified based on Density as Light,
Medium and Heavy.
Specific Gravity (SG): Upper Limit of 1.0000 and
Lower Limit of 0.8000 or oAPI of 10 45.
oAPI = 141.5 / SG - 131.5.

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 Therefore oAPI varies inversely as the SG. High oAPI
for Light Crudes and Low oAPI for Heavy Crudes.
For Light Crudes degree API is 38 degrees and above.
For Intermediate Crudes degree API is 22 to 38 degrees.
For Heavy Crudes degree API is 22 degrees and below.
SG is usually high for Aromatic / Naphthenic Crudes
(lower gasoline yields ) and low for Paraffinic Crudes
( higher gasoline yields ).
Classification can also be based on Sulphur Content :
Sweet / Sour.
A Low Sulphur Crude has S of content <1%.
Medium Sulphur Crudes have S content of 1 3% and
High Sulphur Crudes have S content >3%.
Sweet Crudes have premium prices.

PHYSICAL SEPARATION
The crude in the ground is usually sandwiched between
a water layer below it and Asssociated Natural gas layer
above. The dissolved gas pressure propels the crude to
the surface where it is subjected to dewatering, solid
removal and gas recovery before being made ready for
sale. The Base Sediment and Water ( BS&W ), usually 1
3%, is one of the major market specifications. Others are
the SG, API Gravity, Viscosity, Asphaltene and Wax
contents ( tranportation consideration ), Hydrocarbon

24
types , Organic acids, Sulfur content ( Process
considerations ), etc.

TRANSPORTATION
Crude oil is normally transported from the field storage
tanks through pipeline to the loading terminal then to
barges or ocean liners to the importer destination and
from a receiving Jetty and another pipeline to storage
tanks from where it is pumped again through pipeline to
the Refinery and finally to the Process Units.
There is usually a designated custody transfer point
where quality and quantity are agreed on apart from
other shipping documentations for financial purposes.

INITIAL AND FURTHER USES

The primary use of crude oil, before the advent of motor
car, was mainly for kerosene product to illuminate
lamps. With Industrial Revolution came mechanization
and wider uses for crude oil thereby accelerating the
development of complex Petroleum Refining and
Petrochemicals Process Technology.
Now increasing demand for energy and environmental
concerns are the forces driving Technology.
Main driving force: relatively cheap source of Energy.
The world is 87% dependent on Fossil Fuels: Oil, Gas and
Coal as primary energy sources.
Oil - 37%; Gas - 24%; Coal - 16%;

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 Non Fossil Fuels - 14%.
Nuclear Energy - 6.15%
Hydro Energy - 6.11%
Others (Wind, Solar, Biofuel) - 1.51%
To Date Petroleum energy is the most economical and
efficient energy reserve for transportation fuels.

REFINERY CRUDE PLUS CAT PLUS

DISTILLATION CRACKER ALKYLATION
PLUS REFORMING
Product %Wt
Gas 1.0 7.0 2.4
Gasolines 23.5 33.4 38.0
Middle 13.5 11.8 11.8
Distillates
Fuel Oil 62.0 46.1 46.1
Loss - 1.7 1.7
TOTAL 100.0 100.0 100.0

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FUNDAMENTALS OF PROCESS ENGINEERING

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CONTENTS
PROCESS
PROCESS VARIABLES
DENSITY, SPECIFIC GRAVITY AND API GRAVITY
FLOWRATES
MASS, MOLE, MASS FRACTION AND MOLE FRACTION
AVERAGE ( MEAN ) MOLECULAR WEIGHT
CONCENTRATION
PRESSURE
TEMPERATURE
TABLE OF EQUIVALENTS ( CONVERSION FACTORS )
VAPOR PRESSURE AND PARTIAL VAPOR PRESSURE
DALTONS LAW OF PARTIAL PRESSURES AND RAOULTS
LAW
THEIR APPLICATION TO BINARY MIXTURES
CONCEPT OF MATERIAL BALANCE
FLOW SHEETS( CHARTS ) AND THEIR FEATURES

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PROCESS
A Process is any change or a series of changes effected
to achieve a given goal.
The change may be chemical or physical and generally
there are two sides to a process : Input ( Feed ) and
Output (Product ).
A process can also have many stages, each being carried
out in a Unit which has its own input and output.
A process can also be a Batch process in which inputs
are rapidly feed to a tank and outputs (products) and
unused feeds removed sometime later when the system
has come to an equilibrium.
A continuous process involves movement of input
species and outputs species continuously throughout
the duration of the process like in continuous distillation.
A semibatch process is neither batch nor continuous. An
example is slow blend of several liquids into a tank from
which nothing is being removed at least temporarily.
Process Design involves developing a process flow
diagram which indicates the amount, compostion and
conditions of both the input stream(s) and output
stream(s).
Process Operations is the daily routine monitoring of the
processes to ensure that input and output rates are as
designed and output has the specified properties, that
is, is on-spec or meets specifications.

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Important variables in design and operations are :

Density() which relates the mass and volume of a

given quantity of a substance.

Specific gravity ( SG ) relates the density of a

substance to that of a reference substance, usually
water, at a given condition and since it is a ratio it has
no dimension.

Density of water at 4oC = 1.000gm/cm3

= 1000kg/m 3
= 62.43lb(m)/f3
The density of any liquid or solid in g/cm 3 is numerically
equal to its specific gravity.
FLOW RATES : This is usually applied to fluids ( liquids
and gases ) and can be mass flow rate ( kg of fluid/sec )
or volumetric or cubic flow rate ( m 3/sec ). The fluid
density is used to convert one to the other. Flow rates
are normally measured with a Rotameter or an Orifice
meter using the difference in pressure between the
upstream and downstream of an orifice plate.
MOLECULAR WEIGHT AND MOLE : The molecular
weight of any substance is the summation of the atomic
weights of the constituent elements.
The mole is a given mass divided by the molecular
weight. Hence 1gm-mole or simply mole of a substance
is the mass, in gm, that is equal to its molecular weight.
Other ways of expression are kg-mole(kmole), lb-mole,
ton-mole etc.

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In general if the molecular weight is M, then there is
Mkg/kgmole, Mgm/mole or Mlb(m)/lbmole.
NB : 1gm-mole of any substance contains 6.02x1023
( Avogadro Number ) molecules of the substance.
454gm = 1lb(m)
1mole of gas occupies 22.4litres @ STP
Mass flow rate can readily be converted to
Molar flow rate by dividing the mass flow
by the molecular weight.
MASS FRACTION, MOLE FRACTION AND AVERAGE
MOLECULAR WEIGHT :
These terms are used to define the composition of
mixture of substances.
The mass fraction of component A (aA) = Mass of A /
Total Mass of all components.
The mole fraction of component A ( xA ) = Moles of A /
Total Moles of all components.
It is possible to convert one to the other .
Consider a gas mixture with the composition( mass
fraction) :
O = 20%, Steam = 63%, CO2 = 17%.
Assumig a total mass of 100kg gives
O = 0.2x100kg = 20kg, mole = 20/32 = 0.63

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H2O(v) = 0.63x100kg = 63kg, mole = 63/18 = 3.5
CO = 0.17x100kg = 17kg, mole = 17/28 = 0.61
Total moles = 0.63 + 3.5 + 0.61 = 4.74
Mole fraction for O = 0.63/4.74 = 0.133
Mole fraction for steam = 3.5/4.74 = 0.738
Mole fraction CO = 0.61/4.74 = 0.129
The Average / Mean Molecular Weight ( Ma ) of a
mixture is given by the equation :
If x1 is the mole fraction of one component with
molecular weight M1 then
Ma = x1M1 + x2M2 + x3M3+ -------------- + xiMi
And if a1 is the mass fraction then
1/Ma = a1/M1 + a2/M2 + a3/M3 + --------- ai/Mi
CONCENTRATION
Concentration can be expressed as mass concentration
or molar concentration
The mass concentration of component in a mixture or
solution is its mass per unit volume of the mixture or
solution , that is, gm/cm3, lb(m)/f3 or kg/m3.
The molar concentration is the number of moles / unit
volume; gmole/cm3, kmol/m3 or lbmol/f3.
The Molarity of a solution is the number of moles of the
solute / litre of solution.

32
Mass or molar concentration can be used to determine
sample volume and mass or molar flow rates and total
flow rate.
PARTS PER MILLION (ppm) AND PARTS PER BILLION
(ppb) are used to express concentrations of substances
present in minute amounts in a mixture of fluids. They
can be mass ratio for liquids and molar ratio for gases
and indicate parts (grams or moles) of the substance
present / million or billion (grams or moles) of the
mixture.Parts per thousand barrel(ptb) is used to
express salt concentration in crude.
If yi is the fraction of component y in solution or the
mixture then,
ppmi = 10-6yi and ppbi = 10-9yi
FLUID ( LIQUID OR GAS ) PRESSURE AND STATIC HEAD
Pressure is defined by the quotient of Force and the
Area on which the force is exerted, that is , P = F/A. The
common units are lb/in2 (psi), dynes/cm2 or N/m2 =
1Pascal(Pa).
The pressure exerted by a column of a liquid at the
bottom of the container is given by :
P = Ptop + gh where g = gravitation acceleration and h =
column height.
If Ptop = 0, then P = gh and since and g are constant,
then P h.

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The pressure exerted by a height of a fluid is called the
Head of the fluid, which for water is 0.433psi since the
density for water is 62.4lb/f3(62.4/12 x 12).
Pressure is usually measured with Bourdon tubes,
bellows, diaphgram or more commonly with a
Manometer.
Pabsolute = Patmos + Pgauge.
TEMPERATURE
Temperature is a measure of the average energy of
motion(kinetic energy) of the atoms or molecules of a
substance which can be measured indirectly using some
physical property which is temperature dependent in a
known and precise way. For example expansion or
volume change of a given mass of fluid in the
Thermometer, electrical resistance of a conductor in a
Resistance thermometer, voltage developed at the
junction of two dissimilar metals in the Thermocouple or
the radiation spectrum in the Pyrometer.
Temperature scale is developed in an arbitrary way by
giving values to two measurable temperatures that are
readily reproducible, e.g., 0 value for the freezing point
and BP at 1bar, 100 value thereby giving value to the
length of a unit temperature interval called a degree as
1/100 as the distance between the two specified points
on the scale. A degree is therefore both a temperature
and a temperature interval.
As a consequence we have the following temperature
scales :

34
Celsius or Centigrade scale has 0o and 100o as the
reference points.
Fahrenheit has 32o and 212o as the reference points.
Absolute Zero (the minimum temp that can be
theoretically attained) is -273.15oC on the Celsius scale
and -459.67oF on the Fahrenheit scale.
The Kelvin(K) and the Rankine(R) Scales have absolute
Zero with 0o value and the value of a degree is the same
as on the Celsius scale for K and Farenheit for R scales
respectively.
The conversion of one to the other are as follow ;
K = oC + 273, R = oF + 460, o
F = 1.8oC + 32.

VAPOR PRESSURE AND PARTIAL VAPOR PRESSURES

If a liquid like water is kept in a sealed container, a
certain amount of it will evaporate to form vapor which
will exert a pressure like any gas does and as long as the
temperature remains the same an equilibrium (Evap =
Cond) is soon established between the liquid phase and
the vapor phase. The vapor pressure thus established
depends on the nature of the fluid and is a constant at
any given temperature and is called the saturated vapor
pressure (simply VP) of the fluid. For example the VP of
water @ 25oC is 23.76mmHg (0.46psi) and 760mmHg
(14.7psi) @ 100oC. It is obvious from these values that
VP is temperature dependent(See Attachment Graph
of VP vs Temp for some HCs).

35
As the container above is heated, more and more liquid
evaporates and the VP rises. However as long as the VP
is maintained, the liquid exhibits no further tendency to
evaporate into the gas phase.
At a lower pressure, liquid will evaporate while at higher
pressure vapor will condense till another equilibrium is
established.
VP is therefore a measure of the tendency of atoms or
molecules to escape from the liquid or solid body.
The atmospheric Boiling Point of a liquid is the
temperature at which its VP equals the surrounding
atmospheric pressure and is called its Normal Boiling
Point. The higher the VP at a given temperature, the
lower the BP of the liquid.
NB : Evaporation is accompanied by Heat absorption and
Condensation by Heat release and for a pure substance,
Heat absorbed at evaporation is numerically equal to the
Heat released at condensation at a constant temp.
DALTONS LAW OF PARTIAL PRESSURES
Different gases or vapors inside one container diffuse or
mix rapidly and each exerts a pressure as if it alone
occupies the total space in the container. The pressure
thus exerted is called the partial pressure of the
component and is a measure of the thermodynamic
activities of its molecules.
Gases will always flow from a higher P to a lower P and
the larger the P, the faster the flow. Hence gases
dissolve, diffuse and react according to their partial

36
pressures and not necessarily according to their
concentration in a gas mixture.
John Dalton(1801) propounded his law of partial
pressures which states that at constant temp., the total
pressure (PT) exerted by a mixture of gases in a definite
volume is equal to the sum of the individual pressures
each gas would exert if it alone occupies the same total
volume : PT = p1 + p2 + p3 + ------------- + pi (1).
It has been proved in Physical Chemistry that for Ideal
gas mixtures and for any component i that :
Pi = y i PT (2) where
pi = partial presure and yi = mole fraction of the
component. In other words, the PP of any component in
gas mixture is equal to the product of its mole fraction
and the total pressure( PT ) exerted by the mixture.
Equation (2) above is very important in Chemical and
Chemical Engineering calculations since it relates the PP
of a gas to the total pressure, which is easily measured,
of the gas mixture and the mole fraction relates the
moles of a given component to the total number of
moles of the gases present.
It is easily proved that the summation of mole fraction is
equal to 1 (one) in liquid and gas mixtures and solutions.
RAOULTS LAW
This law deals with the behavior of liquid mixture.
The VP of an Ideal liquid solution is dependent on the VP
of each component and the mole fraction of the
component in the solution. Once the components in

37
solution are at equilibrium and if they are volatile and
completely miscible and non-reactive, then the PP of a
component equals the product of its mole fraction in the
mixture and the VP of the pure component :
p i = x i Pi o (3)
Hence as the number of the components increases, the
individual VP decreases since mole fraction of each
component decreases with each additional component.
Consider two volatile and completely miscible liquids A
and B in a sealed container.
By Raoults law :
pa =xaPao and pb = xbPbo ( 4- 1 & 4-2)
And by Dalton;s law, the total VP exerted above the
solution will be
PT = pa + pb (5)
= xaPao + xbPbo (6)
But xa + xb = 1 or xa = 1 - xb or xb = 1- xa (7)
Hence PT = Pao(1-xb) + xbPbo
= xb(Pbo Pao) + Pao (8)
Similarly,
PT = xa(Pao Pbo) + Pbo (9)
For any system at a given temperature; P ao and Pbo are
constant, hence a plot of PT vs xb in (8) gives a straight
line with PT = Pao at xb = 0 and PT = Pbo at xb = 1.

38
The dotted lines in the Attachment( Fig 8.3) are plots
of pa = xaPao and pb = xbPbo of each component and these
vary linearly from pa = Pao for xa = 1 and Pbo = 0 for xb = 0
to Pao = 0 and pb = Pbo at xb = 1.
The PT for each concentration, say x, lies on the straight
line joining Pao and Pbo and is also the sum of the PP
ordinates.
LIQUID - VAPOR COMPOSITION
If yb is the mole fraction of B in the vapor phase above
the solution with composition xb then, yb = pb/PT by
Daltons law and pb = xbPbo by Raoults law.
Therefore yb = xbPbo / xb(Pbo Pao) + Pao from eqn 8.
The above relation shows that a definite vapor
composition corresponds to a definite liquid
composition and that yb can not be equal to xb except Pao
= Pbo and then there is no longer a mixture but one
component .
Using this last equation, a VP vs Vapor compositon graph
can be constructed showing the composition of vapor
corresponding to a given liquid composition. We can
now relate these theoretical assumptions to the
behavior of a binary mixture of two HCs in the
Attachments already with you. This is the basis for both
batch and continuous distillations.

39
MASS OR MATERIAL BALANCE
A mass or material balance is an application of the Law
of Conservation of Mass to the analysis of physical or
chemical systems. By accounting for materials entering
and leaving a system, mass flows can be identified which
might have been unknown or difficult to measure
without this technique as will be illustrated in the Sugar
Plant later.
The exact techniques used in the analysis of the system
depends on the context of the problem but all revolve
around conservation of mass, that is , that matter can
not disappear or be created spontaneously.
Closely related and complementary analysis techniques
include Energy Balance and the somewhat more
complex Entropy Balance.
The general form for Mass Balance is The Mass that
enters a system must, by conservation of mass, either
leave the system or accumulate within the system.
Mathematically represented for a system without a
chemical reaction is as follows :
INPUT = OUTPUT + ACCUMULATION ---------------(1)
In the absence of a chemical reaction, the amount of any
species flowing in and out will be the same giving rise to
an equation for each species in the system since it must
be accounted for. However if this is not the case, then
the mass balance equation must be amended to allow
for the generation or depletion of any chemical species.

40
Mass is negative for depletion and positive for
generation.
What has been stated above is true for both batch
operation and also for continuous operation over any
chosen time interval.
The amended form is :
INPUT+GENERATION = OUTPUT+ACCUMULATION (2)
This simplifies to (1) if generation is 0.
In the absence of a nuclear reaction, the amount of
species flowing in and out must be the same, even in the
presence of a chemical reaction.
The boundaries of the system must be well defined.
Mass balances can be taken over systems in multiple
stages.
Mass balances can be simplified with the assumption
of steady state where accumulation is Zero.
Mass and Energy balances are very important in an
industry. Material balances are fundamental to the
control of processing, especially in the control of yields
of products.
The first material balances are determined in the
exploratory stages of a new process, improved on with
Pilot plant experiments when the process is being
planned and tested, checked out when the plant is
commissioned and then fine-tuned and maintained as a
control instrument as production continues. When

41
changes occur in the process, the material balances
need to be determined again.
Material and Energy balances can be simple, at times
can be very complicated, but the basic approach is
general. Experience in working with simpler systems
such as individual unit operations will usually help
develop the ability to extend the method to the more
complicated situations.
The increasing availability of computer programs has
made it possible to set up and manipulate very complex
mass and energy balances quite readily and therefore be
used in everyday process management to maximise
yields and minimise costs.
BASIC PRINCIPLES
If the Unit operation, whatever its nature, is seen as a
whole then it may be represented diagramatically as a
box as shown on the next page. The mass and energy
going in must balance with the mass and energy coming
out. Our focus, however, is Mass balance.

42
 MASS AND ENERGY BALANCE

Raw Materials Products out

in
mp1 mp2 mp3
mR1 mR2 mR3

Waste Products
Unit Operation
mw1 mw2 mw3
Stored Materials
ms1 ms2 ms3 Energy in
Products

Stored Energy Ep1 Ep2 Ep3

Es1 Es2 Es3 Energy in Waste

Energy in Heat,
Ew1 Ew2 Ew3
Work, Chemical,
Electrical
ER1 ER2 ER3
Energy losses to
Mass In = Mass Out + Stored Materials. surroundings
EL1 EL2 EL3
Raw Materials=Products+Wastes+Stored Materials.
mR = mP + mW + mS
(where (sigma) denotes the sum of all terms).
mR = mR1 + mR2 + mR3 = Total Raw Materials
mP = mP1 + mP2 + mP3 = Total Products.
mW = mW1 + mW2 + mW3 = Total Waste Products
mS = mS1 + mS2 + mS3 = Total Stored Products
And, that is, Total RM = Total P + Total W + Total SM.
If there are no chemical changes occuring in the plant,
the Law of Conservation of Mass will apply to each
component in the system and so for component A:
mA in entering materials = mA in exit materials + mA stored

For example, in Sugar producing plant, if the total

amount of sugar coming in is not equalled by total of
purified sugar and sugar in the waste liquors, then

43
something is wrong. Sugar is either being burned
(chemically changed) or accumulating in the plant or
going unnoticed down the drain somewhere. In this
case,
mA = mAP + mAW + mAU
where mAU is the unknown loss and needs to be
identified. So we now have :
RawMat = Products + Waste Products + Stored Products + Losses

where Losses are the unidentified materials

The first step is to look at the three basic categories :
materials in, materials out and materials stored. Then
consider the materials in each category to determine if
they are to be treated as a whole, a gross mass balance
or whether various constituents need to be treated
separately and if so which one. For example, it might be
to take dry solids as opposed to total material; meaning
separation into two groups of materials; Non-water and
water. More complete dissection can separate out into
chemical types.
The choice and detail depend on the reason for making
the balance and on the information that is required.
A major factor in industry is, of course, the value of the
materials and so, expensive raw materials are more
likely to be considered than cheaper ones and products
than wastes.
Having decided which constituent to be considered, the
basis for the calculations has to be decided. This might
be some mass of raw material entering the process on a

44
batch system or some mass per hour in a continuous
process. It could be some mass of a particular
predominant constituent (a given or assume mass of
flour entering in a bakery) or some unchanging
constituent, such as in combustion calculations with air
where it is helpful to relate everything to the inert
Nitrogen component.
Sometimes it is not important what basis is chosen and
in such cases, a convenient quantity such as the total
raw materials into one batch or passed in per hour to a
continuous process are ofen selected. Having selected
the basis, then the unit may be chosen such as mass or
concentration which can be weight or molar .
Material balances can be based on total mass, mass of
dry solid or mass of a particular component as shown in
the calculations examples below.

45
PROCESS FLOW CHARTS
The identification and drawing up a unit operation
/process is prerequisite for material balance and is
explained below.
Flow charts are schematic representation of the
production process , involving various input resources,
conversion steps and output and recycle streams.
The process flow may be constructed stepwise i.e. by
specifying the input / output / waste at each stage of the
process as shown in the figure below :

Inputs PROCESS Wastes

STEP -1

PROCESS
Inputs Wastes
STEP -2
Output
PROCESS FLOW CHART
Input of the process could include raw materials, water,
steam, etc,
Process Steps should be sequentially drawn from raw
materials to finished product. Intermediates and any
other byproducts should also be represented as well as
operating parameters such as temperature, pressure,
%concentration, etc.
The flow rate of the various streams should be stated in
the appropriate units ( m3/h, kg/h, lb(m)/f3, moles/h,
etc ) . Batch process should include total cycle time.

46
Wastes or Byproducts could include solids, water, etc.
For each process step ( unit operation ) as well as for an
entire plant mass balance should be drawn.

47
MASS BALANCE CALCULATIONS
Example 1
Using mass balance to check the results of an air
pollution monitoring study.
A fabric bag filter is used to remove dust from an inlet
gas stream so that the outlet gas stream meets the
required emission standards say in a cement or fertilizer
plant
During the study, the inlet gas flow to the bag is
169,920m3/h with a dust loading of 4577mg/m3. The
filter outlet is 185,040m3/h and the dust loading is
57mg/m3.
What is the maximum quantity of ash removed / hour
from the bag filter hopper based on these test results ?

169920 m3/hr FABRIC FILTER 185040 m3/hr

57 mg/Nm3
4577 mg/Nm3

ASH = x kg/hr
DUST REMOVAL

Solution
Based on dust balance :
Mass In = Mass Out.
Inlet gas stream dust = Outlet gas stream dust + Hopper Ash.

48
Calculate Inlet and Outlet dust quantities in kg/h.
Inlet Quantity = 169920m3/h x 4577mg/m3 x 1/106kg/mg
= 777.7kg/h
Outlet Quantity = 185040m3 /h x 57mg/m3 x 1/ 106 kg/mg
= 10.6kg/h
Ash Quantity Reqd to be removed /h is given by
Hopper Ash = Inlet dust quantity outlet dust quantity
= 777.7kg/hr - 10.6kg/h = 767.1kg/h
Example 2
Consider a slurry flowing into a settling tank to remove the
solids which are collected at the bottom of the tank using a
conveyor belt partly submerged in the tank and water exit via
an overflow pipe.
There are thus two species; solids and water which concentrate
in each output stream, ie. Water to solid ratio being higher in
the overflow than in the inlet and the solids concentration at
the exit of the belt is also higher than at the inlet as indicated in
the sketch.

49
Assume a steady state and a non-reactive system, accumulation
is zero
Analysis :
Analysis of slurry gives a mass composition of the inlet: 50%
solid and 50% water with a mass flow rate of 100kg/min and
combined solid and water outlet is 60kg/min.
Slurry removal efficiency of the tank is 60%.
What is the water/solid amounts in each output stream ?
Solution
Since efficiency is 60%, then the water outlet will contain
40% x 50%solids x 100kg/min = 20kg/min of solids
The amount of water leaving with solids on the conveyor
belt : ???
Example 3
Skim milk is made by removing some fat from whole milk. The
skim milk on analysis has the following composition :
90.5% Water, 3.5% Protein, 5.1% Carbohydrate,
0.1% Fat and 0.8% Ash.
Given that the whole milk contains 4.5% Fat and that only fat
was removed and no losses, calculate the composition of the
original whole milk .

INPUT: WHOLE MILK OUTPUT: SKIM MILK

FAT = 4.5%
SKIMMER WATER = 90.5%, PROTEIN = 3.5%,
FAT = 0.1%, ASH = 0.8%,
CARBOHYDRATE = 5.6%.

50
Solution
Basis : Assume 100kg of skim milk.
Fat content = 0.1%
Let the fat removed from the whole milk = x kg
Therefore total original fat = ( x + 0.1 ) kg
Total original mass = ( 100 + x ) kg
Since the original fat is 4.5%, then
( x + 0.1)/(100 + x) = 4.5/100= 0.045 kg and this gives
X = 4.6kg.
And total original mass = 100kg + 4.6kg = 104.6kg
Hence the composition of the whole milk will be :
Fat = 4.5%, 90.5/104.6% = 86.5%water,
3.5/104.6% = 3.3%protein, 5.1/104.6% = 4.9% carbohydrate
And 0.8/104.6% = 0.8%ash.
Example 4
A common salt solution was prepared by dissolving 20kg of salt
in 100kg of water to give a solution with a density of
1323kg/m3.
Calculate salt concentration in solution as :
a) weight fraction, b) weight/volume fraction, c) mole
fraction and d) molar concentration.
Solution
a) Weight fraction : 20/ 120 0.167, %wt/wt = 16.7%
b) Weight/volume : From the density, 1m3 of soln weighs

51
 1323kg, hence 1323kg of solution contains
20x1323kg salt/120 = 220.5kg/m3
Wt/volume fraction = 220.5/1000 = 0.2205 = 22.05%
c) Moles of water = 100/18 = 5.56
Moles of salt = 20/58.5 = 0.34
Total moles = 5.9
Hence mole fraction of salt = 0.34/5.9 = 0.058
d) Molar conc ( M ) = 220.5/58.5 = 3.77moles/m3
Note : For dilute solutions, mole fraction of solute approx =
moles of solute/moles of solvent. This applies to
solid/liquid mixtures. For solid/solid mixture,
concentrations are normally expressed as simple weight
fractions.
With gases concentrations are primarily expressed as
weight/unit volume or as partial pressures using the Gas
Law :
pV =nRT as illustrated below; R = 0.08206m 3atm/moleK and
1 atm = 100 kPa
Wt conc = nM/V, M = Gas molecular wt.
Example 5
Air consists of 77%wt nitrogen and 23%wt oxygen.
Calculate : a) mean molecular wt of air.
b) mole fraction of oxygen and
c) concentration of oxygen in mole/m 3 and kg/m3 at
25oC and 1.5 atm. Use R value supplied above.
Solution

52
Basis : 100kg of air
a) Moles of N = 77/28 = 2.75, moles of O = 23/32 = 0.72
Total moles = 2.75 + 0.72 = 3.47
Mean molecular wt of air = 100/3.47 = 28.8
b) Mole fraction of O = 0.72/3.47 = 0.21
c) pV = nRT, R = 0.08206m3atm/moleK, T = 298K, V = 1m3 and p=
1.5atm
Hence n = pV/RT = 1.5 x 1/ 0.0820 x 298 = 0.061
Wt of air = 0.061 x mean mol wt = 0.061 x 28.8 = 1.76kg/m3
Wt of O = 23% x 1.76 = 0.4kg/m3 = 0.4/32= 0.013mole/m3
When a gas is dissolved in a liquid, the gas mole fraction in the
liquid is calculated using the Gas law to obtain the number of
moles. The total volume is usually taken as that of the liquid
and then moles of liquid is determined.
Example 6
In the carbonation of a sof drink, the total amount of CO 2 reqd
is equivalent to 3 volumes of gas to one volume of water at 0 oC
and 1 atm P.
Calculate a) mass fraction and b) mole fraction of CO 2 in the sof
drink, ignoring all other components except CO2 and water.
Solution
Basis : 1m3 of water = 1000kg ( Density )
Therefore volume of carbon dioxide = 3m3
From Gas law, pV = nRT
Hence n = 3 x 1 / 0.08206 x 273 = 0.134
Wt of carbon dioxide = 0.134 x 44 =5.9kg

53
 Mass fraction = 5.9 / 1000 + 5.9 = 5.9 x 10-3
Mole fraction = 0.134/ ( 1000/18 + 0.134 ) = 2.41 x 10-3
CONTINUOUS PROCESSES
In continuous processes, time enters into consideration and
balances are related to unit time. If material holdup is constant
both in mass and composition, then quantities entering and
leaving in different streams in unit time are constant and a mass
balance can be written on this basis. Such analysis assumes the
process is in a steady state, i. e., flows and quantities held up do
not change with time.
Example 7 : MILK CENTRIFUGE A CONTINUOUS PROCESS
35,000kg of whole milk with 4% fat is to be centrifuged in 6
hours into skim milk containing 0.45% fat and cream with 45%
fat. What will be the flow rates of the two output streams from
the continuous centrifuge to accomplish this separation ?

INPUT: WHOLE MILK OUTPUT

35, 000kg, FAT = 4%
CENTRIFUGE SKIM MILK WITH 0.45% FAT.

CREAM WITH 45% FAT.

6 HOURS

Basis : 1 hours flow of whole milk.

Mass In :
Total mass of whole milk/hr = 35,000/6kg = 5833kg
Fat content + 0.04 x 5833kg = 233kg
Hence water and others = (5833 233)kg = 56,000kg
Mass Out :
If the mass of cream is x kg then its total fat = 0.45x kg

54
Therefore mass of skim milk = (5833 x) kg and its total fat
content is 0.0045(5833 x)kg
Mass Balance On Fat
Fat In = Fat Out
233 = 0.0045(5833 x ) = 0.45x
x = 465kg
Hence the flow of cream = 465kg/hr and
Skim milk = (5833 465)kg/hr = 5368kg/hr
Example 8
A srubber is used to remove fine particle or dust from the inlet
gas stream with a spray or a liquid, typically water, so that the
outlet gas stream meets the required process or emission
standard ( see figure below )

55
How much water must be continually added to wet the
scrubber in order to keep the unit running ?
Each stream is identified by a number within a diamond
symbol. Stream 1 is the recirculation liquid flow stream back to
the scrubber at 4.54m3/hr. The mass flow liquid being
withdrawn for treatment and disposal ( stream 4 ) is 0.454kg
m3/hr
Assume inlet gas stream ( #2 ) is completely dry and the oulet
stream ( #6 ) has 272.16kg/hr of moisture evaporated in the
scrubber. The water being added is stream #5.
Solution
Step 1 : Set up material balance around the scrubber
Convert form kg/hr to m3/hr for stream #6 to keep units
constistent; 272.16kg/hr x m3/1000kg = 0.272m3/hr.
Then set up MB equation and solve for stream #3, viz :
InputScrubber = OutputScrubber
Stream 1 + Stream 2 = Stream 3 + Stream 6
4.54 m3/hr + 0 = y m3/hr + 0.272 m3/hr
Hence Stream 3 ( y m3/hr ) = ( 4.54 0.272 ) m3/hr
= 4.27m3/hr
Step 2 : Do MB around the recirculation tank and solve for
Stream 5.
InputTank = OutputTank
Stream 3 + Stream 5 = Stream 1 + Stream 4
4.27m3/hr + x m3/hr = 4.54m3/hr = 0.454m3/hr
Hence Stream 5 = 4.994m3/hr - 4.27m3/hr

56
 = 0.724m3/hr
If it is to calculate only the makeup water , Stream 5, then
Stream 5 = ( 0.454 + 0.272 ) m3/hr = 0.73m3/hr
One of the key steps in solving this Example is drawing a simple
sketch of the system.
This is absolutely necessary so that it is possible to conduct
material balances. Drawings are a valuable first stpe when
solving a wide variety of porblems, even one that looks simple.
Drawing is a very useful way to summarise what we know and
what we need to know. It helps visualise the solution.
If the problem involves dimensional quantities, the dimensions
should be included on the sketch. They serve as reminder of
the need to convert the data into consistent units

57
FUELS REFINING PROCESSES

58
CONTENTS
PHYSICAL SEPARATION PROCESSES
CRUDE OIL DESALTING
CRUDE DISTILLATION
CRUDE DISTILLATION COLUMN INTERNALS
DIFFFERENT COLUMN OVERHEADS AND
PRODUCT DRAW OFFS.
STABILISATION, STRIPPING AND SPLITTING
VACUUM DISTILLATION
CONVERSION PROCESSES :
QUALITY IMPROVEMENT :
HYDROTREATING
CATALYTIC REFORMING
ISOMERISATION
DECREASING AVERAGE MOLECULAR WEIGHT:
CRACKING - THERMAL AND CATALYTIC,
HYDROPROCESSING ( HYDROGENATION
HYDROTREATING, HYDROCRACKING )
INCREASING AVERAGE MOLECULAR WEIGHT:
ALKYLATION AND DIMERISATION

59
AUXILLARY PROCESSES
HYDROGEN GENERATION
STEAM REFORMING AND
SHIFT CONVERSION
AMINE TREATMENT
SULFUR RECOVERY

60
PHYSICAL SEPARATION PROCESSES

61
CRUDE OIL DESALTING
This is the first process crude oil is subjected to in the
refinery. Crude oil ofen contains water, inorganic salts,
suspended solids, and water-soluble compounds of
some metals.
Desalters are sized to allow water and oil to settle and
separate according to Stokes law.
Desalting process helps to remove contaminants from
crude and hence helps to reduce corrosion, plugging and
fouling of equipment and to prevent poisoning the
catalysts in downstream processing units and therefore
improves on the reliability of these units and reduces
total cost of refinery operation.
The major contaminants The contaminants-salt, water,
added chemicals and solids if not removed from the
crude can cause serious damage to distillation
equipment, limit on-steam time, and cause inefficient
operation throughout the crude distillation unit. Specific
effects resulting from the salts in the crude are;
(a) hydrolysis to hydrochloric acid which will cause
severe corrosion in the crude distillation tower and lines;
(b) the salt acts as a catalyst for coke formation in
furnace tubes and transfer lines;
(c) salts and solids are deposited on heat exchanger and
furnace tubes causing plugging, reduced heat transfer
rates in the exchangers and hot spots in the furnace
tubes.

62
Residual products such as asphalt and fuel oils are
contaminated when effective desalting of the crude is
not accomplished.
This is due to the fact that inorganic salts remaining in
the crude tend to concentrate in the distillation
residuums. Such contamination in fuel oils can cause
clogging of burner or the deposition of slag on furnace
tubes and brickwork of boiler installations. The most
efficiently designed refinery will suffer from corrosion
and lost on-steam time if effective desalting equipment
does not function continuously.
Consequently, the separation of crude oil, salt, water
and other impurities has been a major refining problem.
One of the early methods of separating crude oil from
entrained impurities consisted primarily of settling.
Improvement was made by heating the oil before
settling. Sometimes the addition of chemical to the
mixture before settling gave further improvements.
However, obtaining consistently good results was
difficult and practically all refiners now use electrical
desalting equipment.
The major contaminants are :
-Chloride salts of Na, Ca and Mg
-Solids ; iron sulfides, sand, silts, clay from drilling mud
mostly responsible for exchanger and heater fouling.
-Water as brine from the oil field (Spec. 1 3% in water).
High BS&W reduces feed rate, increases energy cost,

63
contributes to downstream equipment corrosion and
increased waste water production
Benefits of desalting are:
-Protection of downstream equipment
-Reduces corrosion and hence maintenance costs
- Maximizes throughput
-Extends run length
-Stabilises unit operations
-Reduces energy cost
-Reduces slops treatment cost
Desalting Process:
Crude-oil desalting is usually by chemical injection and
electrostatic separation or precipitation.
a. Electrical desalting is the application of high-voltage
electrostatic charges to concentrate suspended
water globules in the bottom of the settling tank
( Desalter).
b. Water and chemical surfactant (demulsifiers) are
usually added to the heated crude, so that salts and
other impurities dissolve into the water which then
settles out.

64
PROCESS VARIABLES
(a)Water and salt content.
(b)Pressure drop across the mixing valve
Chemical addition.
(d)Wash water rates 3 to 10 volume per cent based on
crude oil charge.
(e)Settling time in accordance with stokes law.
(f)Temperature as determined by the viscosity of the oil.
(g)Alternating electric field.
(h)Pressure to keep the system from boiling.
(i)Desalter level.
(j)Ph which has effect on conductivity.
(k)Oleophobic impurities.
What can go wrong with desalting :
-Poor dehydration of the crude ( water carry over)
-Oil in desalter water ( oil carry over )

65
-Low voltage or high current
-Widely fluctuating voltage and current

66
REFINING PROCESSES - SEPARATION PROCESSES
ATMOSPHERIC DISTILLATION
The first step in crude oil refining is by a process known
as Distillation during which the crude is separated into a
number of streams called fractions, each one having a
certain boiling range and a distinct name. The Crude
Distillation Unit carries out this process.
Distillation Theory
A working knowledge of this topic is necessary in order
to have an understanding of the Crude Unit operation.
When a mixture of liquids is heated to boil, the first
vapors from the mixture almost always have a
composition that is different from the composition of
the liquid mixture.
Distillation is process in which a liquid or vapour
mixture of two or more substances is separated into its
component fractions of desired purity by the application
of and removal of heat.
Distillation is the most common separation technique.
It is used to separate mixtures by enrichment of phases
which occurs with boiling and depends on materials
having different boiling points. Any two liquids having
the same boiling points can not be effectively separated
by distillation.

67
The difference between liquid and vapor compositions
is the basis for distillation operation as earlier
discussed.
This is based on the fact that the vapor of a boiling
mixture will be richer in the components that have lower
boiling points ( higher volatilities ). Therefore, when this
vapor is cooled and condensed, the condensate will
contain more of the volatile components while the
original mixture will contain more of the less volatile
components.
Distillation columns are designed to achieve this
separation.
Therefore, the important variables in distillation are
composition, pressure and temperature. The boiling
point of a mixture is determined by composition and
pressure and since distillation is a boiling process,
distillation pressure and temperature are not
independent for a known composition.
For a binary system with a component boiling at 150 oC
and the second at 250oC, if the pressure and
composition are known then the BP is fixed and must be
between these two temperatures. For more complex
mixtures, the composition can only be estimated within
a certain range.
The dew point is the temperature at which saturated
vapor starts to condense and the bubble point is the
temperature at which the liquid starts to boil.

68
 Crude stills are the first major process unit in the
refinery. They are used to separate crude oils into
fractions according to boiling points so that the
downstream processing units will have feedstocks that
meet their particular specifications.
Crude distillation consumes enormous amounts of
energy, both in terms of cooling and heating
requirements and can constitute 40% to 50% of plant
operating costs.

Distillation Column
A distillation or fractionating column is a piece of
equipment designed to separate liquid mixtures
continuously by enrichment from boiling feature of
liquid mixtures in a multistage manner by continuously
boiling and condensing mixtures of different
compositions at different temperatures.
The feed mixture comes into the column some where in
the middle and products are removed from the top,
along the side and the bottom. The bottom is heated
while the top is cooled with cold liquid to create a

69
70
continuous temperature profile down the column for
boiling and condensing. In normal operation, the
pressure of the column is held constant and since every
component boils at a certain temperature and pressure,
and with the pressure set, an observation of the
temperature will indicate where in the column a
particular component is located.
Inside fractionating column are horizontal steel
trays( see the figure below) with openings in them to
allow vapors from the tray below to pass through the
top tray and to bubble through the liquid that is held up
on the top tray. On each tray the liquid boils and vapors
are condensed at the temperature of that tray.
Each tray has overflow pipe called the down comer.
When the liquid level on a tray reaches a certain height,
the liquid spills over the edge of the down comer and
drains the condensed liquids from each tray back to the
tray below, where the higher temperature causes re-
evaporation until the desired degree of product purity is
reached. The downcomer might be a circular pipe or
might be made of the column wall and a flat plate
mounted vertically at one side of the tray. The top edge
of the pipe or plate forms a Weir (usually about 2 high),
the height of which determines the height of liquid on
the tray.
Then side streams from certain trays are taken off to
obtain the desired fractions.

71
 Diameter and Height are proportional to vapour and
liquid rates and number of streams or fractions to be
withdrawn:
About 110f : 30 trays and 4 streams / fractions
and 160f : 50 trays and 6 streams / fractions.
Trays are usually spaced 12 inches ( 300mm ) to 24
inches ( 600mm ) apart.
Columns are generally higher and slimmer with lighter
materials but shorter and wider for heavy ones.

72
Column internal arrangements and configurations differ
depending on the service requirement and design
consideration
DIAGRAM OF A TYPICAL TRAY

The active area of a tray is about 70% of the tray and

provides the contact between up flowing vapor rich fluid
and counter flowing liquid while a settling portion
known as the free area serves as a flow pulsation
dampner. The space between the wall and the end of
the tray is hollow to allow for down flowing liquid from
one tray to another the downcomer. A weir is used to
create a little head of liquid on the tray to enhance liquid
/ vapor contact.
TRAY TYPES : There are three basic types performing
same function but using different methods;
Bubble Cap
Tray most
efficient
because
liquid /
vapor
contact is

73
much enhanced but more susceptible to fouling and
hence high maintenance cost.
Sieve Tray the simplest form with little efficiency since
there is no special arrangement for liquid / vapor mixing.
Valve Tray differs from the sieve tray by arrangement

of the holes. Movable covers are provided for the holes

with a device restricting the movement of the cover to
vertical movement in accordance with up flowing vapor
rate.

74
The column has many trays. The vapor bubbling through
the liquid on one tray comes from boiling on the tray
just below. The vapor condenses because the liquid on a
tray is cooler than the vapor from the tray below. The
heat of the condensation step causes some vapor to be
boiled off and this vapor in turn goes up to the next
higher tray. Hence each tray carries out an enrichment
(from the boiling step) and this is done on a continuous
basis.
Column operation must be kept in balance. Product
rates must be kept equal to the feed rate. Similarly, heat
removal rates must be kept equal to heat input rate. The
pressure has to be held constant so that temperatures
can be used to estimate compositions. Pressure is
controlled by balancing vapor input with output or
condensation, which is balancing heat input and output.
The overall goal is to have the desired product
composition. With the pressure constant, composition is
indicated by temperature; the top or bottom
temperature should be controlled to obtain the desired
composition.
The important variables are the flows of liquid and vapor
down and up the column compared to the feed flow
rate. The higher the internal rates, up to a certain limit,
the better the separation. In practice, this comes from
adjusting the reflux or the reflux ratio. This is the
amount of liquid returned to the top tray as compared
to the feed flow rate or top product rate. Usually
automatic controllers are used to adjust reflux rates in
order to maintain the column temperature profile.

75
Process Variables
Crude oil is usually pumped from storage tanks to the
Unit afer ensuring that it is fairly dry from the BSW
result. This is to minimize the chance of large amounts
of liquid water entering the unit. If this occurs, the water
will vaporize causing a high pressure drop in the column
or possibly derail or damage the trays.
In order to reduce the unit operating cost, as much heat
as possible is recovered from the hot streams from the
column by heat exchange with the cold crude charge,
which then goes to the Desalter. The crude, ex the
Desalter, is then heated to the desired feed temperature
in the Charge heater or Furnace. The Heater outlet
temperature is called Transfer Temperature or Coil
Outlet Temperature ( COT) and can vary from 600 oF
( 315oC ) to 800oF ( 425oC ) depending on the crude oil
feed.
The furnace supplies all of the additional heat input
necessary to the column in excess to that supplied by
the heat exchange train.
The crude oil exiting the furnace is in two phases and
hence some of it on entering the Flash Zone of the
column, at about atmospheric pressure, flashes into
vapor which rises up the column while the remaining
liquid residue drops downward. This flash is a very
rough separation; the rising vapors from the flash zone
still contain some heavy ends, which must be rejected
into the bottoms while the descending liquid contains
some light ends which must be stripped out.

76
The flashed vapors rise up the column counter-current
to the Internal Reflux flowing down the column. The
lightest materials of Naphtha range pass overhead and
are condensed into an overhead receiver.
Uncondensables leave the receiver as gases and can be
recovered by compression as required.
The fractionator top temperature is good measure of
naphtha end point and is controlled by returning some
naphtha as reflux along with naphtha side cut to the top
of the column. Increasing this reflux rate lowers the top
temperature and decreases the rate of the net overhead
product with a lower end point. This loss must be
recovered from the Kero draw off tray and this will
reduce the initial boiling point of the material from this
tray.
External reflux from the top of the column ( overhead
receiver ) moves downward against rising vapors. The
light ends from it are re-vaporised and move towards
the top while the heavy ends in rising vapors are
condensed and move down the column. This creates an
internal reflux stream flowing from the top all the way to
the flash zone and becoming progressively heavier as it
descends.
Products heavier than the net overhead are withdrawn
from portions of this internal reflux stream. The end
point of a side cut depends on the amount of liquid
being withdrawn. If the side cut withdrawal is increased,
the extra product is part of the material which was
formerly flowing down the column as internal reflux.
Since reflux flow to the tray below is now reduced,

77
heavier vapors can now rise to the tray above resulting
in heavier product.
Therefore varying draw off rate is the way side cut end
point specs are maintained.
The temperature of the draw off tray is a fair indication
of the product end point and an experienced operator
may increase/decrease his draw off rate to hold a
constant tray temperature and hence keep product on-
spec.
The degree of fractionation is generally judged by the
relationship between ASTM distillation temperature at
95% volume of the lighter product and 5% volume of the
adjacent heavier product. Some use IBP, which varies
with stripping and EP or FBP.
If the T > 0, it is called a Gap and shows good
separation.
If T < 0, there is an Overlap, a sign of poor separation.
Sometimes a gap is difficult to achieve and all one can do
is to reduce the overlap as much as possible.
Fractionation can be improved by increasing reflux rate
by an appropriate increase in the COT.
Reflux is the liquid stream returned to the column and
helps to achieve two purposes : extraction of heat from
the column while at the same time strips heavy ends
from the up flowing fluid (vapors). It also purifies the
distillate stream while providing column stability.

78
There may be occasions where internal reflux required
for good separation is so great that if it was all supplied
from the top, the top trays will flood. An Intermediate
Circulating Reflux or Side Reflux or Pump Around solves
the problem. Some internal reflux materials are
withdrawn, pumped through a cooler or an exchanger
and returned colder to a few trays higher in the column.
This cold reflux condenses extra vapors to liquid and
increase the internal reflux below the inlet point.
Sometimes a draw off tray is pulled dry, that is, product
withdrawal rate is greater than internal reflux rate. The
trays below become dry and no fractionation occurs.
Then either reducing product withdrawal rate or
increasing internal reflux by increasing the COT or
reducing the rate at which the next lighter product is
being withdrawn will correct the problem.

FACTORS AFFECTING COLUMN OPERATION :

The performance of a distillation column is determined
by many factors :
-Feed Conditions:- The state and composition of the feed
and presence of contaminants that can severely affect
the vapor-liquid equilibrium.
-Internal liquid and fluid flow conditions ( reflux )
-State of the trays and or packings and
-Weather conditions especially in temperate areas.

79
Other factors include changing operating conditions and
throughputs, imposed by changes in upstream
conditions and changes in the demand for products. All
of these plus associated control system should be
considered at the design stages because once a column
is built and installed, nothing much can be done to
rectify the situation without incurring significant costs.
CRUDE DISTILLATION: (See Diagram Below)
Crude oil is de-watered and desalted
Pre-Heating in heat exchangers
Fired Heater
Fractionation

80
81
CRUDE UNIT PROCESS FLOW DIAGRAM

82
DISTILLATION COLUMN WITH SIDESTREAM STEAM STRIPPER

83
Typical fractions from the Crude Tower are tabulated below :

FRACTION BP RANGE oC NIGERIAN VENEZUELAN

GULF: LAGOMAR:
%YIELD %YIELD
WHOLE 50 -170/175 21 17
NAPHTHA
SR KERO 165 20 16
245/250
LGO 230 360 26 15
HGO 300 370 5 7
LONG RESID >370 28 45

The Crude Unit overhead liquid distillate is called

Naphtha, which is the generic name for very many
different hydrocarbons with boiling range of 50 oC to
200/205oC and which contains paraffins, naphthenes
and aromatics ranging from those with four carbon
atoms to those with 10 or 11 carbon atoms.
Naphtha can be further separated into LPG ( C 3 / C4 ),
Light Naphtha ( C4 - C6 ) and Heavy Naphtha ( C6 C10 /
C11 ) with the boiling range of about 90oC to 205oC.

84
OVERALL REFINERY FLOW

85
REFINERY BLOCK FLOW DIAGRAM
VACUUM DISTILLATION
Distillation in refining process is in three classes:
Atmospheric distillation is the most known and occurs at
between 1 2 atmospheres which is enough to separate
petroleum products from crude oil. Further treatment of
the initial fractions to obtain improved quality is carried
out, for the medium to light distillates under the second
class, Pressure distillation. This can occur at 3 30
atmospheres or higher as in NHU Stripper and CRU
Stabiliser where LPG is separated from treated Naphtha
and Reformate respectively.
For the heavier materials, conventional distillation under
pressure will produce a lot of coke that is thermal
cracking without giving the right quality of desired
products.
The third class, Vacuum distillation allows separation
under negative or reduced pressure without thermal
cracking. For example material that will boil with
cracking at 350C/760mmHg can be made to boil
without decomposition at 230C/25-30mmHg. Vacuum
distillation produces Vacuum gas oils and distillates
( about 25% - 35% of total crude oil ) for catalytic
cracking units and lube base oils units in the purest
possible form and is therefore a very important chain in
maximizing crude oil utilization.
The diameter of the Vacuum Tower is usually much
larger than that of the Crude Tower in order to minimize
large fluctuations in pressure resulting from the volume
of vapors per unit volume of feed being much larger.
The principles are the same as those that govern
distillation. However, operations of a typical vacuum
tower presents as much difficulty to the operator as any
unit equipment. This is most prevalent at start up.
The most noticeable failure is vacuum loss with the
instant gas up of the pumps due to the low pressure and
high vapor expansion.
The most common problems include :
-insufficient NPSH for the bottom pump.
-pressure built up in the tower.
-faulty ejectors.
-product linkage.
-plugged seal legs.
 VGO = Vacuum Gas Oil
LVGO = Light Vacuum Gas Oil
HVGO = Heavy Vacuum Gas Oil
PA = Pumparound Circuit With Cooler

SIMPLIFIED DRAWING OF A TYPICAL VACUUM DISTILLATION COLUMN

CONVERSION PROCESSES
CONVERSION PROCESSES
These are refining processes that involve chemical
reactions and are of three types :
- those that improve quality; Hydrotreating, Reforming
Alkylation and Isomerisation.
-those that decrease average molecular weights of
hydrocarbons; Cracking process and
Hydrocracking/Hydrogenolysis.
Cracking processes make it possible to obtain more and
more valuable products from a given barrel of crude as
shown in the Table on page 13.
-those that increase average molecular weights of
hydrocarbons; Alkylation and Dimerisation
HYDROTREATING/HYDRODESULPHURISATION(HDS)
Hydrogenation is a class of chemical reactions in which
the net result is the addition of hydrogen.
Hydrogenolysis , a sweetening process, is type of
hydrogenation that removes hetero atoms by the
cleavage of the C-X bond, where C is a carbon atom and
X = S, N, O or even a metal atom leading to the
formation of a C-H and an H-X bonds, that is, S-H, N-H
and O-H bond.
Hydrotreating or Hydrodesulfurisation is widely used to
remove combined sulfur and nitrogen and other
contaminants ( Unsaturates and Organometallics ) from
natural gas and refined petroleum products ( gasoline,
jet fuels, kerosene, Diesel and fuels oils ). This results
from pressure to reduce from the environment SO 2
( sulfur dioxide ) and NOx (nitrogen oxides) emissions
resulting from using these fuels in vehicles, locomotive
engines, aircrafs, ships, Power Plants, industrial
furnaces and other forms of petroluem fuel combustion.
But the more important reason for sulfur removal from
Naphtha, is that even in very low concentrations, it
poisons Noble metal catalyst ( Platinum, Pt and
Rhenium, Re ) in the Reforming Units used in the
upgrade of octane rating of the heavy naphtha streams.
Hence HDS/HTU is a hydrogenolysis reaction and can,
using ethanethiol as an example, be expressed as :
C2H5SH + H2 C2H6 + H2S.
The Process : In industrial HDS unit, reactions occur in a
fixed bed reactor at high temperature ( 300 400 oC )
and a high pressure ( 30 130 atmospheres absolute )
typically in the presence of a catalyst consisting of
Alumina impregnated with oxides of Cobalt ( Co ) and
Molybdenum ( Mo ) or W/Al2O3 promoted with Ni
( 90%Ni-Mo, 10%Ni-W ) for Middle distillates or
Hydrodenitrogenation ( HDN ), which requires more
severe conditions. Ruthenium ( Ru ) is the most active
and of course the most expensive.
The liquid naphtha feed is pumped to the required
pressure and is joined by a stream of hydrogen rich gas
from the Reforming Unit. The liquid-gas mixture is first
preheated in the Reactor feed/effluent exchanger
enroute to the fired heater ( furnace ) where the mixture
is totally vaporised and heated to the required
temperature before entering the Reactor and flowing
through a fixed bed of catalyst where the reaction takes
place.
The hot products from the reactor are partially cooled in
the heat exchanger where the feed was preheated and
then flows through an air cooler and a water cooler
before going through a series of pressure reduction
processes. Then the liquid products are feed into a
Stripper where the dissolved gases and LPG are removed
and finally to the Splitter which separates Light Naphtha
from Heavy Naphtha, the main CRU feed.
NHU PROCESS VARABLES
Reactor Pressure
The unit pressure is chosen by catalyst life and product
quality considerations, the catalyst is generally effective
for a longer and the reactions are brought to a greater
degree of completion. For desulfurization, 20 to 35
kg/cm2 reactor pressure is normally used If feed
nitrogen and/or sulfur contents are higher than normal.
Similarly, higher operating pressures are necessary to
completely remove organic halides.
The selection of the pressure level is influenced to a
degree by the hydrogen to feed ratio set in the design,
since both of these parameters determine the hydrogen
partial pressure imposed on the catalyst. The hydrogen
partial pressure can be increased by operation at a
higher ratio of gas to liquid at the reactor inlet. The
extent of variation is determined by economic
considerations.
Most units have been designed so that the
desulfurization and denitrification reactions go
substantially to completion at the design reactor
temperature for a particular feedstock. Normal
variations in pressure or hydrogen gas rates in the unit
will not cause changes high enough to affect product
quality.
Temperature :
Temperature has a significant effect in promoting
hydrotreating raections. Its effect is however is slightly
different for each of the reactions that occur.
- desulfurization increases as temperature is
raised.
- The decomposition of chloride compounds in
low concentrations (<10ppm) will require
about the same temperature as sulfur
compound decomposition
- Olefin saturation behaves somewhat similar to
the desulfurization reaction with respect to
temperature except that olefin removal may
level off at somewhat higher temperatures.
The olefin content ofn feed must be limited to
keep reactor peak temperature within an
acceptable temperature range.
The higher the reactor inlet temperature the higher the
reaction rate but the greater the coke formation.
Therefore there is a temperature limit that must be kept
and this is dictated by the state of the catalyst, severity
of operations and feed rate.
Feed Quality:
For normal operation, daily changes in hydrotreater inlet
temperature to accommodate changes in feed quality
will not be necessary. However in cases when refinery is
purchasing outside crude from different sources, the
naphtha quality may change significantly to warrant
adjustment of reactor inlet temperature. In this case it is
essential that the PONA analysis (feed Quality) of the
new feed must carried out for comparison and
judgement of pocess variables adjustment

Space Velocity (SV) : this is the volume of hydrocarbon

feed/hr/unit catalyst volume and is calculated thus :
SV = Feed Rate (m3/hr at 15oC) / Catalyst Vol (m3)
The lower the SV (more feed/catalyst contact time), the
higher the reaction rate and since the amount of catalyst
is constant, SV can be changed by flow rate change. A
decrease in flow rate decreases SV making it possible to
operate at a lower temperature and vice versa.
Hydrogen Partial Pressure : The higher the hydrogen
partial pressure, the less is the catalyst coking tendency
and this is changed by acting on the system Total
pressure to a maximum compatible with the unit
vessels. The optimum value is equal to or greater than
6kg/sq.cm and is increased by increasing make up
hydrogen rate. Hydrogen PP is calculated thus :
PPH = P *[ {y(q mw)} {(Q MW) + (q mw)}]
P = pressure at the reactor outlet in kg/sq.cm.
y = mole fraction of hydrogen in the purge gas ( Lab).
q = total flow of purge gas from high pressure Separator
in kg/hr
mw = molecular weight of purge gas (Lab).
MW = molecular weight of the feed naphtha (Lab).
Q = Feed rate in kg/hr
End Of Run (EOR) : As a result of some unavoidable
hydrocracking occuring, coke gradually builds up on the
catalyst reducing its activity. Rust and other solid
materials from upstream equipment deposit on the top
of the catalyst bed restricting flow. Increasing T and
P across the reactor and reactor inlet temperature
approaching 370/4000C to obtain the desired less than
1ppm of sulfur in the treated heavy naphtha are
indicative of EOR conditions and the unit must be shut
down for catalyst regeneration or change out if a
previous regeneration(s) failed to achieve the desired
result.
NAPHTHA HDS UNIT PROCESS FLOW DIAGRAM
CATALYTIC REFORMING
One of the major problems of a refiner is inadequate
motor gasoline octane number.
One very important property of PMS is the octane
number, which influences "knocking" or "pinking"
behaviour in the engine of cars. Formerly, lead
compounds (especially Tetra-ethyl lead) were added
to petrol to improve the octane number. This has
been discontinued due to health/environmental
reasons.
One of the products of crude distillation process is a
low octane gasoline fraction, normally referred to as
Naphtha. Platforming is the process which reforms the
molecules in the low octane Naphtha feed to produce
a high-octane gasoline component, the Reformate.
Reforming is a refining process using controlled heat
and pressure in the presence of a catalyst to rearrange
or restructure the feed molecules thereby converting
paraffinic and naphthenic types of hydrocarbons (low
octane boiling range fractions) into petrochemical
feed stocks and higher octane stocks suitable for
blending into finished gasoline. The overall result is
that the product, Reformate, contains HCs with more
complex molecular shapes than in the naphtha feed.
The Reformate is a mixture of Paraffins, Naphthenes
and Aromatics containing C4 to C8 atoms.
In doing so, hydrogen atoms are separated from HC
molecules thereby making very significant amounts of
byproduct hydrogen gas (as will be discussed later)
available for use in a number of other processes in a
modern petroleum refinery. Other byproducts are
small amounts of small molecules of CH4, C2H6, C3H8
and C4H10, suggesting some cracking also occurs.
The Process : The feed is Treated Heavy Naphtha (with
6 10/11 carbon atoms), IBP 90/100oC and FBP
190/205oC. Heavy naphtha is used because Light
naphtha tends to crack easily to produce non-octane
enhancing molecules.
The Four basic Reforming reactions are :
Dehydrogenation of Naphthenes to Aromatics
e.g.Methylclohexane or Dimethylcyclopentane
to Toluene and Hydrogen at 80 - 90% volume
yield but decreases as the number of carbon
atoms increases such that about 5% remains
unconverted.
Isomerization of n-Paraffins to branched or
iso-Paraffins e.g. n-Octane to 2,5
Dimethylhexane or n-heptane to
Methylhexanes at almost 100% volume yield
but no hydrogen is produced and the ratio of
n- to iso- decreases with increasing molecular
weight.
Dehydrocyclization of n-Paraffins to Aromatics
e.g. n-Heptane to Toluene and Hydrogen at 70
80% volume yield. Reaction rate is low
requiring greater severity and hence coke
formation tendency. This reaction produces
 four moles of hydrogen per mole of paraffin
transformed.
Hydrocracking/Hydrogenolysis of paraffins,
especially higher ones, to smaller molecules
e.g. n-Heptane or Methylhexane or
Methylcyclohexane / Dimethylcyclopentane
( these two via ring opening ) to Methane,
Ethane, propane, butanes, pentanes and
hexanes. The net result is consumption of
hydrogen, low reformate yield, low hydrogen
purity and shorter catalyst life due to coke lay
down. Hydrocracking is promoted at high
severity (high temperatures) operation. Rate is
low at low temperature but increases faster
than other reactions as temperature increases.
Dealkylation e.g. Toluene to Benzene and
methane. This reaction does not increases
octane but consumes hydrogen. It increases
benzene production if aromatics are
involved.
Dismutation / Disproportionation e.g.
Toluene reacting with Methylcyclohexane to
produce Benzene and Dimethylcyclohexane
or two molecules of Toluene transformed to
Benzene and Xylenes.
Alkylation is promted at low pressure and
high temperature ( 500-550oC ). It does not
improve octane nor comsume hydrogen but
leads to the production of heavier
 molecules boiling higher than gasoline
range. These are coke precursors.
The first three reactions predominate as such the overall
net hydrogen product at 0oC/60oF and one atmosphere
is 50 200m3 or 300 1200f3 per 1m3 or 1barrel of
liquid Naphtha feed.
The first Reactor is usually the smallest containing the
least catalyst load than others because Naphthenes
Aromatics reaction equilibriates faster than the other
reactions. Dehydrocyclisation is slower equilibriating at
the exit of #3 Reactor. Isomerisation and Hydrocracking
are very slow reaching equilibrium at the exit of #4
Reactor. Hence other Reactors have progressively more
catalyst load than #1 Reactor, making #4 Reactor usually
the biggest.
THESE ARE POSSIBLE REACTIONS OF n-BUTYLBENZENE IN THE PRESENCE OF A
TYPICAL REFORMING CATALYST
 REFORMING CATALYST
Catalyst is noble metal, Platinum or combined
Platinum/Rhenium on chlorinated alumina support
base.The metal promotes hydrogenation/
dehydrogenation reactions while the alumina provides
the Lewis acid sites for carbonium ion formation. This
dual function is necessary for aromatisation and
isomerisation. Pt/Re catalyst has been found to have
greater stability, increased activity and selectivity
leading to lower pressure operations. Pt/Re ratio of
0.5 is better than a ratio of 1.0 and can tolerate higher
coke level (20-25% against 15-20%) and a higher sulfur
level in the Naphtha feed ( > 1.0 ppm) resulting in
increased run length.

REFORMING PROCESS
There are main types of Reforming process :
Semi-regenerative fixed bed Reactors (3 or 4 in
series).
Swing Reactor system (3 Reactors and 1 spare
regenerated Reactor on standby).
Continuous Catalyst Regeneration Reformer
(CCR).
CRU PROCESS VARIABLES :
System Pressure : Low pressure is favorable to all the
reactions that produce hydrogen. Higher pressures result
in cracking and lower pressures, coking. System pressure
is related to catalyst activity and life span and the
Recycle Gas compressor duty.
Temperature : Reactor inlet temperature is the same for
all the reactors and decreases across each reactor due to
the endothermic nature of most of the reactions. The T
is highest across Reactor #1. The reaction temperature is
a function of the catalyst activity at any point in time. If
other conditions are steady, the temperature has to be
increased to increase octane number, generally 1:1 at
the SOR to mid-Run and less so towards the EOR.
However, higher temperature is usually used at low
catalyst activity but results in lower yield of reformate
and lower hydrogen purity.
Weight Space Velocity ( SV ) : is related to the average
residence time of the feed on the catalyst and is defined
by the equation;
Feed Rate( tons/hr) Overall Catalyst Quantity(tons).
Any change in SV results in change of the feed rate and
hence in temperature change for the same severity and
octane number.
If SV is to be increased, the temperature, first and then
feed rate have to be reduced proportionally. The
situation is reversed but feed rate first then temperature
for any decrease in SV.
Hydrogen : Hydrocarbon Ratio : This is usually 6 and is
defined by:
Pure Recycle H2 (kmol / hr) Feed Rate(kmol/hr).
High hydrogen purity and high recycle gas compressor
capacity result in high H/HC ratio which results in lower
reactor inlet temperatures. Also high ratio increases
hydrogen partial pressure which extends catalyst life
since it prevents coke formation but has little or no
influence on product yield and octane rating.
Feed Quality: The physical properties of and the
presence of impurities in the feed affect unit
performance. In a fuels refinery where the criteria is to
increase the octane number of the gasoline by the
production of aromatics, the boiling range of the feed is
not as sensitive a variable as in the case of a
petrochemical refinery where production of BTX
(Benzene, Toluene and Xylene) is crucial.
Recycle Ratio (Mole Ratio, R) is defined by the equation:
R = GHM / Fm
R = kg mole H2/ kg mole Feed
G = Flow of Recycle Gas, kg/hr
H = Mole fraction of H2 in Recycle gas ( Laboratory)
M = Molecular Weight of feed ( usually about 110
depending on feed Quality)
F = Feed Flow Rate, kg/hr
m = Average Molecular Weight of Recycle Gas
( Laboratory )
FEED (TREATED HEAVY NAPHTHA) AND REFORMATE HYDROCARBON
TYPES

COMPONENTS HEAVY NAPHTHA REFORMATE

PARAFFINS 44 55% 30 50%
OLEFINS 0 - 2% 0%
NAPHTHENES 30 40% 5 10%
AROMATICS 5 10% 45 60%
OCTANE # 40 >90

CATALYTIC REFORMING SIMPLIFIED PROCESS FLOW

REFORMER PROCESS FLOW DIAGRAM
End Of Run For Semi-Regenerative CRU
With continued operations, the catalysts in the reactor
beds get progressively deactivated due coke lay down,
sulfur breakthrough and loss of acid sites resulting from
water breakthrough leaching out the chlorine, etc.
The net results are high P across the reactors, gradual
loss of negative T, decrease hydrogen purity, lower
H/HC ratio and finally continued increase in temperature
to obtain the same octane number which further
increases coke build up on the catalyst .
At this point the unit has to be de-commissioned for
catalyst regeneration. This can occur between 6 t0 24
months or more depending on the severity of operation.
CRACKING
Cracking is the process whereby complex high boiling
heavy Hydrocarbons are broken into simpler and
lighter molecules by the cleavage of C-C bonds, i.e
long chains into shorter ones leading to the increased
production of higher value Light and Middle distillates
and light hydrocarbon Gases.
Cracking was initially Thermal( Thermolysis). Pyrolysis
breaks down medium size alkanes into smaller more
useful alkanes and alkenes. Thermolysis has now been
displaced by Catalytic Cracking.
Examples of thermal cracking are Steam Reforming,
Pyrolysis, Visbreaker and Coking.
THERMAL CRACKING
VISBREAKER
A visbreaker is used to reduce the amount of low value
residuals with high viscosity and high pour point, which
can not be readily used or transported especially in cold
climates due to the presence of waxy materials, and
hence to increase the yield of more valuable middle
distillates (diesel and heating oils )
The unit thermally cracks large HC molecules in furnace
tubes to reduce viscosity and in the process produce
small amounts of light hydrocarbons ( LPG and gasoline).
The process name, visbreaker refers to the fact that it
reduces( i.e. breaks ) the viscosity of the feed yielding
gas, LPG, gasoline, gas oils and tar.
The tar can be processed in a Vacuum unit to produce
VGO which can be further processed in a Cat cracker,
Hydrocracker or other form of thermolysis. The vacuum-
flashed tar is a feed to a Delayed coker to produce some
specialty cokes such as Anode coke or Needle coke.
Vacuum Residue to the Visbreaker is composed of :
Ashaltenes : large polycyclic HCs suspended in oil in
colloidal form.
Resins : also polycyclic HCs but of lower molecular
weights than asphaltenes.
Aromatics : derivatives of benzene, toluenes and
xylenes.
Paraffins : mainly alkanes.
Cracking temperature is usually 425 - 650oC.
Properties Feed Visbreaker Tar
Density (kg/l) 1.020 1.048
Viscosity @ 100oC (cSt) 930.0 115.0
Sulfur( wt% ) 40.0 4.7
Product Yields( wt % )
Gas and LPG 3.0
Gasoline 6.0
Middle Distillates 15.0
Tar ( Residue ) 76.0
COKER
A coker converts Atmospheric Residue or Vacuum
Residue to low molecular weight HC gases, naphthas,
LGO, HGO and Petroleum Coke by thermal cracking
process.
The coke can be Fuel grade ( high in sulfur and metals )
or Anode grade ( low in sulfur and metals ). The straight
run coke, also called Green coke, is further processed by
calcining at 1302oC in a rotary klin to remove residual
volatile HCs. The calcined coke is then treated in an
Anode baking oven to yield anode coke of desired shape
and physical properties used mainly in the Aluminium
and Steel industries.
Chemistry of Thermolysis
One of the earliest thermal crackers was developed in
1912 and operated at 370 400oC and 90psia ( 620kPa ).
In 1921, an advanced thermal cracker was developed
and operated at 400 460oC. Modern high pressure
thermal cracker operates at 7,000kPa ( slightly over
1,000psia ).
The usual feeds are C30 to C50 HCs and the overall result is
the break down of heavy molecules into light ones.
The actual reaction is called Homolytic fission which
produces alkenes for the production of polymers.
A large number of chain reactions occur which are based
on Free Radicals, neutral or uncharged, lone or unpaired
electron species which are extremely reactive and short-
lived.
The main reactions include :
Initiation : where a single molecule divides into two free
radicals which then drives the rest of the reactions. The
bond broken is usually a C-C bond rather than a C-H
bond, eg , H3CCH3 2H3
Propagation :
Step 1 : H Abstraction in this reaction a free radical
abstract a hydrogen atom from a neutral molecule
thereby creating another free radical;
H3 + CH3 CH3 CH4 + H3CH2
Step 2 : Radical Decomposition - in which a free radical
breaks apart into two species, one alkene and one a free
radical; H3C H2 H2C =CH2 + H
Step 3 : Radical Addition is the reverse of
decomposition in which a radical adds on to an alkene to
form a single larger free radical which may lead to
polymerization ;
H2C=CH2 + H3C H2 H3C-CH2-CH2-H2
Step 4 : Alpha- and Beta- Scission the former a break
one carbon away from the free radical point while the
latter is two carbon away.
The alpha-scission produces diradical which abstract H
atoms from neutral HCs to produce methane and
another free radical.
Beta-scission produces an alpha-alkene and a primary
free radical with carbon atom number one being the
radical,
R-CH2-CH2-CH2-CH2-H2 R-CH2-H2 + H2C=CH-CH3
Termination : occurs when two free radicals react to give
products which are not free radicals in one of two ways :
Recombination : where two radicals combine to form
one larger molecule ;
H3 + H3C-H2 H3C-CH2-CH3
OR
Disproportionation where one free radical transfers a H
atom to another free radical to give an alkene and an
alkane;
H3C-H2 + H3C-H2 H2C=CH2 + H3C-CH3

STEAM REFORMING/CRACKING
This is thermal cracking process in which paraffins are
broken down into smaller ofen unsaturated
Hydrocarbons.
Light Hydrocarbon gases or liquids such as Ethane, LPG
or Light Naphtha (C6 and less) produce light Alkenes such
as Ethylene, Propylene, Propadiene, Butenes and
Butadiene mainly for the Petrochemical industry.
This process is uually carried out at very high
temperatures, 750 900oC or more. High temperature
gives more olefins of higher molecular weights and
Aromatics. High molecular weight hydrocarbons crack at
lower temperatures than the low molecular weight ones
( Ethane at 800C, Naphtha at 675-700C).
The HC feed is diluted with steam and then briefly
heated in a furnace at around 900oC. In modern pyrolysis
furnaces, the residence time is in milliseconds in order
to improve the yield of desired products. Afer the
cracking temperature has been reached, the vapors are
quickly quenched to stop the reaction.
The products depends on the feed composition, HC to
steam ratio, cracking temperature and the furnace
residence time.
Light HCs ( ethane, LPG and light naphtha) yield light
alkenes including ethene, propene and butadiene.
Heavier HCs ( full range or heavy naphtha and others)
not only produce these but also produce streams rich in
aromatics and materials suitable for inclusion in gasoline
or fuel oil.
The higher the cracking temperature ( severity ) the
more the ethene and benzene produced. Lower severity
produces relatively higher amounts of propene, C4 HCs
and liquid products .
The process usually result in coke deposit on the inner
wall of the furnace tubes and the furnaces have to be
de-commissioned one afer the other for de-coking.

Ethane Reforming
INITIATION :
CH3-CH3 2H3
CH3-CH3 CH3-H2 + H
CH3-CH3 + H3 CH3H2 + CH4
CH3-CH3 CH2=CH2 + H2
2C + 3H2
2C + 2H2O(v) 2CO + 2H2
PROPAGATION :
CH2=CH2 + H3 CH3CH2H2 CH3CH=CH2 + H
CH2=CH2 + CH3-H2 CH3CH2CH2H2

Butene-1 CH3CH2CH=CH2 + H
Higher hydrocarbons are produced from similar
sequence of reactions.
The following is an example of cracking of n-Butane :
#1 Possibility ( 48% ) : Breaking of a CH3CH2 bond to
produce: H + H-CH-CH free radicals which
afer a number of steps yields : CH and CH=CH-CH.
#2 Possibility ( 38% ) : Breaking of the CH-CH bond to
give the free radicals H-CH + H-CH eventually
leading to the production of CH-CH and CH=CH.
#3 Possibility ( 14% ) : Breaking of a C-H bond to give
H-CH-CH-CH + H leading to the formation of
CH-CH-CH=CH + H.
ENERGETICS OF THERMAL CRACKING
Thermal cracking energetics is dominated by entropy
change (S) rather than by enthalpy change (H) in the
Gibbs Free Energy equation : G = H TS
Minus Gmeans the reaction is feasible, zero value
means the process is in equilibrium and positive value
means the reaction is not feasible.
Although C-C bond energy is relatively high (375kJ/mol),
cracking is highly endothermic, producing large positive
entropy ( degree of disorder) resulting from the
fragmentation of one large molecule into several smaller
ones which together with the required high
temperature, make the TS term much larger than H
thereby favoring thermal cracking reactions
CATALYTIC CRACKING
Eugene Houdry, a French mechanical engineer ,
pioneerd catalytic cracking and developed the first
commercially successful process.
The first commercial plant was built in 1936. This
process almost doubles the amount of gasoline that
could be produced from a barrel of crude.
The FCC produces a high yield of gasoline and LPG while
the Hydrocracker is a major source of LPG, naphtha, jet
fuel and diesel oil. Catalytically cracked gasoline has
higher octane than Thermally cracked gasoline due to
the catalyst promoting isomerisation and
dehydrocyclisation reactions. Liquid products are also
more stable due to lower olefins content more
saturated components
Catalytic cracking uses acid ( equivalent to 90% sulfuric
acid ) silica-alumina and zeolite catalysts and moderately
high temperatures ( 400 500oC ) to aid the process of
breaking down large HC molecules into smaller ones by
heterolytic breakage of bonds yielding pairs of ions of
opposite charges, usually carbenium ion and very
unstable hydride anion. Carbon localized free radicals
and cations are very unstable and undergo processes of
chain rearrangement, beta-C-C scission and inter- and
intra-molecular hydrogen, hydride or methide transfer.
In either case, the corresponding reactive intermediates
(radicals or ions) are permanently regenerated and thus
they proceed by a self-propagating chain mechanism
which is eventually terminated by radical or ion re-
combination.
FLUID CATALYTIC CRACKING (FCC)
When heavy oil fractions, usually with IBP of 340oC and
above, are heated over clay type materials, cracking
reactions occur, which lead to significant yields of lighter
hydrocarbons.
The modern FCC unit is a continuous process which
operates 24 /7 for as much as 2 to 3 years between
shutdown for routine maintenance.
There are a number of proprietary designs, each one
available under a licence that must be purchased from
the developer by any refiner desiring to construct and
operate an FCC of a particular design
Basically, there two different configurations : the
stacked type where the reactor and the regenerator
are contained in a single vessel with the reactor above
the Regen and the side-by-side type where the reactor
and the Regen are in two separate vessels.
A typical FCCU is made up of many parts :
1. The Air Preheater for initial warm up of the entire
cold Converter.
2. The Feed Preheater which heats up the hydrocarbon
feed to between 300 to 400C.
3. The Riser where actual cracking occurs.
4. The Disengager and Stripper which ensure separation
of cracked HC vapors from the powdered catalyst.
5. The Main Fractionator which separates the cracked
vapor into the different fractions.
6. The Regenerator where coke deposited on the
catalyst is burnt off.
7. The Gas or Vapor Recovery System to maximize LPG
and gasoline yields.
8. Gasoline And LPG Merox Systems Sweetening
processes.
9. CO Boiler or Flue Gas Heater for heat recovery.
A very simplified process flow is shown below:

FLUID CATALYTIC CRACKING PROCESS

LEGEND
CT = CATALYST TRANSFER LINES
PS = PRODUCT SEPARATION
RG = REGENERATION
RX = REACTION
In FCC, heavy oil fractions are passed in vapor phase
through a bed of powdered zeolite catalyst at a suitable
velocity (0.1-0.7m/s). The catalyst and the HC vapor
form a system that behaves like liquid/fluid which can be
continuously transported from a reactor vessel, where
most of the cracking reactions take place, to the
disengager and the regenerator vessels and then back to
the reactor.
The Process:
The Reactor And The Regenerator
The preheated high boiling feed at about 315 to 430C,
made up of long chain HC molecules, is combined with
some recycle slurry from the bottom of the Main
Fractionator and injected into the Riser where it is
vaporized and cracked into smaller molecules of vapor
by contact and mixing with the very hot powdered
catalyst from the Regenerator. All of the cracking
reactions occur in the Riser. The HC vapors and
powdered catalyst flow upward in the Riser at around
520 - 535C and pressure of about 1.7barg and then
empty into the Disengager where the two are separated
by a set of two-staged cyclones. The spent catalyst flows
downward through a steam Stripper to remove adhering
HC molecules from the catalyst which then returns to
the Regenerator with the flow regulated by a Slide or
Plug valve in the spent catalyst line.
The cracking process produces carbonaceous material
( called Coke ) which deposits on the catalyst and which
very rapidly reduces the catalyst activity. The catalyst is
regenerated by burning off the coke with air blown into
the Regenerator, which is operated at about 700C and
2.41barg. The combustion of the coke is exothermic,
producing a large amount of heat that is partially
absorbed by the regenerated catalyst and provides the
heat required for the vaporization of the feed and the
endothermic cracking reactions.
The hot catalyst (at >700C) leaving the Regenerator
flows into the catalyst withdrawal well where entrained
combustion flue gas escapes and flows back to the upper
part of the Regenerator. Another Slide or Plug valve in
the regenerated catalyst line controls the flow of the
catalyst to the feed injection point just below the Riser.
The hot flue gas leaves the Regenerator afer passing
through multiple sets of two-staged cyclones that
remove entrained catalyst from it. This prevents
excessive catalyst losses.
The amount of catalyst circulating between the
Regenerator and the Riser is about 5kg per kg of feed
which is equivalent roughly to 4.66kg/ litre of feed.
Hence an FCC unit processing 75,000barrels / day (about
12,000,000 litre/ day) will circulate about 55,900metric
tons / day of catalyst.
Conversion is increased by higher temperature, longer
residence time and high catalyst/oil ratio although these
also promote coke lay down.
Distillation / Fractionation Column
The reaction product vapors at over 500C and 1.72barg,
flow from the top of the Disengager to the bottom of the
column where they are distilled into the FCC end
products: offgas, cracked naphtha, and heating/fuel oil
( Light Cycle Oil and Decanted oil) materials. Afer a
process of sulfur removal, the naphtha becomes a high
octane gasoline blend component.
The offgas is sent to the vapor recovery unit (VRU)
where it is separated into low molecular weight gases
( H2, methane, ethane and ethene), propane and
propene ( 65 70% ) and butanes and butenes (55
-60%).
The bottom product oil of the Fractionator contains
residual catalyst particles which were not completely
removed by the Disengager cyclones. This is why this oil
is called Slurry, part of which is recycled back to
fractionator above the disengaged vapor entry point to
cool and partially condense the reaction product vapors
as they enter the column and the balance of the slurry
used as fuel oil blend component and or manufacture of
Carbon Black.
Regenerator Flue Gas
The combustion air flow to the Regen is controlled to
have the desired ratio of carbon dioxide and carbon
monoxide in the hot flue gas (about 700C and 2-
41barg). This is then sent to the Seal Pot or a kind of
separator to remove 70 to 90% of the entrained catalyst
particles before the flue gas is either used first, in a
turbo-expander to generate power and then in the CO
Boiler / Flue Gas Heater to produce high pressure steam
or straight for steam generation only.
Chemistry
The figure below is a very simplified diagram of how high
boiling straight chain paraffins are broken down into
smaller straight and branched alkanes, branched alkenes
and cycloalkanes ( naphthenes).
Some of the smaller molecules are further converted
into still smaller alkenes and branched alkenes such as
ethane, propene, butenes and isobutenes for use as
petrochemical feedstocks. Propene, butanes and
isobutenes are also used in the Alkylation unit to
produce high-octane gasoline blending components.
The initially formed naphthenes are converted to
aromatics such as benzene, toluene and xylenes which
boil in the gasoline boiling range and have much higher
octane ratings than alkanes.
A very simplified series of chemical reactions occurring
during cracking is exemplified in the Figure :
Fluid Catalytic Cracking In Summary: (See Diagram
Below)
Maximizes Production of Gasoline.
Heating and Reaction.
Catalyst/Vapour Disengagment
Fractionation.
Gas Recovery for LPG production.
Catalyst Regeneration
UNICRACKER PROCESS FLOW DIAGRAM
COMPARISON BETWEEN CATALYTIC AND THERMAL CRACKING
Catalytic Cracking is different from Thermal Cracking in the following
ways:
Uses a catalyst
Lower temperature
Lower pressure
More flexible
Different reaction mechanisms
- ionic vs free radical
High thermal efficiency
Good integration of cracking and regeneration
High yields of gasoline and other distillates
Low gas yields
High product selectivity
Low n-alkane yields
High octane number
Chain-branching and high yield of C4 olefins
High yields of aromatics.

134
 UNICRACKER PROCESS FLOW DIAGRAM

ALKYLATION PROCESS
This is chemical process whose purpose is to use light olefins and light
iso-paraffins to produce high octane gasoline blend components and
is basically the reverse of cracking, that is, combination of olefins with
paraffins to form higher iso-paraffins, initially iso-butane with n-
butene to form iso-octane. In Alkylation, small molecules are
combined to produce larger molecules in the gasoline boiling range
leading to an increase in the average molecular weight.
The reaction is acid catalysed and proceeds by ionic ( carbenium ion)
mechanism similar to Cat Cracking. For example; Butenes react with
Iso-butane to yield mainly 2,2,4 trimethylpentane ( Iso-octane ).
Iso-butane is usually used instead of iso-pentane because the latter
already has a sufficiently high octane number while the olefins
usually used are propene, butenes / Isobutene and pentenes
(amylene) : Olefins is usually 3 : 12.
Butenes produce the highest octane, pentenes intermediate octane
and propene the lowest octane. However all give octane greater than
87.
Commonly used acids are concentrated (above 88%) sulfuric acid
(more widely used) and concentrated hydrofluoric acid (more risky).
Products are LPG grade propane liquid, n-butane liquid, C+ alkylate
and Tar (Heavy alkylate to Fuel oils materials).

135
 Alkylation Reactions:
Example: But 2 ene + Iso-butane
+
+
Initiation: C C = C C + H CC-C-C

C
+
H- Abstraction: C C C C + HCC
C
C
+
CCCC + CC
C
Addition:
C C C
C C+ + CCCCC
C C
2,2,3-Trimethylpentane plus other
isomers.

ISOMERISATION PROCESS
Isomerisation was initially meant to convert n-butane to iso-butane,
to provide feed for the Alkylation process. It is a small volume but
important refinery process to produce highly branched hydrocarbon
mixtures for gasoline blend. It converts normal paraffins components
of low octane light gasoline fraction ( C4, C5 and C6 ) high octane
constituents of gasoline in the presence of dual function catalyst
activated either by organic or inorganic chlorides are , e.g., Pt with
zeolite base or Aluminum chloride activated with hydrochloric acid
which promotes carbenium ion formation either by hydride ion
136
abstraction by the catalyst Lewis acid sites or olefins formed on the
catalyst surface protonated followed by 1,2-hydride/methide shif.
Hydrogen is usually added to inhibit side reactions (cracking and
olefins formation)
Normal Hexane yields 2,2-dimethylbutane + 2,3-dimethylbutane + 2-
methylpentane + 3-methylpentane and

137
AUXILIARY PROCESSES

138
HYDROGEN PRODUCTION
The hydrogen production from the CRU is generally not sufficient in a
high conversion Refinery for the Hydrotreating and Hydrocracking
processes. Consequently alternative source of more hydrogen has to
be found.
One of the methods used is :

139
Steam Reforming : Methane and steam are reacted together in an
exothermic reaction in the presence of catalyst made of 25 40% NiO
/ SiO /AlO at 760 816 C as follows : CH + HO CO +
3H.
Shift Conversion: This is a reaction between CO and steam in the
presence of CrO / FeO catalyst at about the same temperature
resulting in the formation of CO and H: CO + HO CO
+ H
Methanation Reaction: This is a side reaction and the reverse of the
reforming reaction leading to the formation of methane which
contaminates and reduces the yield of the produced hydrogen and
occurs especially over Ni / Al O catalyst at roughly 220C:
CO + 3H CH + H O
CO + 4H CH + 2HO
Consequently conditions are kept to reduce methanation as mush as
possible.

AMINE TREATMENT: Processes in the industry that remove hydrogen

sulfide and or mercaptans are usually called sweetening processes
because the products no longer have the sour, foul odor of hydrogen
sulfide and mercaptans.
Amine Treatment or Acid Gas Removal is one of these sweetening
processes. It uses aqueous solutions of various alkanolamines to
remove HS and CO from not only gases but also from liquid HCs and
LPG.
The different amine used could be one of the following:
140
 Monomethanolamine or Methanolamine, MEA.
Diethanolamine, DEA.
Methyldiethanolamine, MDEA.
Diisopropylamine, DIPA.
Aminoethoxyethanol or Diglycolamine ( DGA ).
Triethanolamine, TEA.
However the most commonly used ones are MEA, DEA and MDEA.
Gases containing HS or both HS and CO are referred to as sour or
acid gases which come mainly from hydrodesulfurisation and
cracking units.
Process: A typical amine treater consists of an Absorber column and
a Regenerator column and their accessory equipment. In the
absorber, a downflowing amine solution absorbs the two acids gases
from an upflowing sour gas stream yielding a sweetened gas at the
top and an amine solution rich in the absorbed acid gases at the
bottom. The rich amine solution is then routed into the regenerator
(a stripper with a reboiler) to produce regenerated or lean amine
that is recycled for reuse in the absorber. The stripped overhead gas
from the regenerator is concentrated HS and CO (see the flow
diagram below).
This HS-rich stripped gas stream is then normally sent to a Claus unit
to be converted to elemental sulfur.

141
142
SULFUR RECOVERY:
The Claus process, the most important gas desulfurisation process,
producing elemental sulfur from hydrogen sulfide, was invented some
100 years ago and has become the industry standard.
Substantial amount of the over 64 Million metric tons of sulfur
produced worldwide was byproduct sulfur from the refineries and
other hydrocarbon processing plants.
Gases with an HS content of over 25% are suitable for straight
through Claus unit while leaner feeds can be fed into a split-flow set
up or feed and air preheating unit.
The Claus technology is divided into two steps as shown in the
diagram below.
The first is the Thermal step where the acid gas reacts
stoichiometric ratio of air at over 850C such that elemental sulfur
precipitates in the downstream cooler. The Burner Reactor reaction in
this stage is :
2HS + 3O 2SO + 2HO
and 60 70% of the total amount of sulfur produced is from this
thermal stage:
This followed by the sulfur conversion reaction in fixed bed reactors
or converters packed with activated alumina or titanium dioxide
catalyst.
Typical inlet and outlet temperatures for the first reactor are about
230/232C ( > than dew point of sulfur to prevent condensation on
the catalyst ) and 315/330C respectively. The condenser outlet
temperature is at 177C, higher than the melting point of sulfur to
prevent premature solidification of sulfur. Ofen in the Burner side
reactions, COS (carbonyl sulfide) and CS are formed. However the
143
high temperature in the first converter stage helps to decompose
these compounds. The reaction for the catalytic stage is :
2HS + SO 3S + 2HO.
The overall sulfur yield is 95/97% on the input stream and over 2.6
tons of steam is usually generated for every ton of sulfur produced.
The tail gas from the SRU still has combustible components and sulfur
compounds ( HS, H and CO ) and is either incinerated or further
desulfurised in another tail gas treatment unit (e.g. an amine unit )
and the hydrogen sulfide recycled.

144
145
CRUDE OIL AND PRODUCT PIPELINES

A total of 166 tanks are available to handle crude,

Intermediate and finished products.
Product evacuation is by Road, Rail and Pipeline.
Capacity to load 192 trucks of 33,000 litres each daily.

146
Blending
Various Intermediate Components are Blended.
To Meet Market specifications.
And stored in Finished product tanks for evacuation.

147
LUBES BASE OILS, WAXES AND ASPHALT
REFINING

148
CONTENT
INTRODUCTION
CLASSIFICATION OF LUBRICANTS
LIQUID - OILS
SEMI SOLIDS GREASES AND THEIR PROPERTIES
CLASSIFICATION BASE OILS
FUNCTIONS
PROPERTIES
COMPOSITION
NAPHTHENIC
PARAFFINIC

ADDITIVES
CRUDE SELECTION FOR BASE OILS PRODUCTION
PROCESSING SCHEMES
FEED STOCK MANUFACTURE
HIGH VACUUM DISTILLATION UNIT (HVDU)
PROPANE DEASPHALTING UNIT (PDU)

VISCOSITY INDEX AND COLOR IMPROVEMENT

FURFURAL EXTRACTION UNIT (FEU)

149
 POUR POINT IMPROVEMENT
MEK/TOLUENE DEWAXING UNIT (MDU
WAXES: COMPOSITION, USES AND PRODUCTION
MEK/TOLUENE DEOILING UNIT (MDOU)
WAX HYDROFINISHING
GRADES OF WAXES

PRODUCTION OF ASPHALT
ASPHALT BLOWING UNIT (ABU)
GRADES OF ASPHALT : LIQUIDS AND SOLIDS

INTRODUCTION TO LUBRICATION
A metal surface, no matter how well polished, is never geometrically
flat but has some microscopic roughness due to asperities which tend
150
to interlock and prevent one surface from gliding over the other
when two metal surfaces are in contact. This resistance is called
friction and some force must be applied to overcome it for the
surfaces to glide.

Dry friction generates heat energy resulting in serious wears and

eventually seizure when the metals melt. Consequently rubbing
metal surfaces have to be separated by a film of lubricant which
serves to replace metal-metal friction with much lower internal
friction, measured by the viscosity of the lubricant separating them,
so that the asperities no longer touch. Hence a lubricant controls
friction and wear by introducing a friction reducing film between
moving surfaces thereby facilitating motion.

Another important function of a lubricant is to remove the heat

generated in the equipment being lubricated and solids from contact
area and protect against corrosion by moisture.

A lubricant can be a Fluid, Solid or Polymer

CLASSIFICATION OF LUBRICANTS
Fluids - Oils an gases
Solids - Graphite
151
 Semi Solid - Greases:
Greases are used where liquid lubricants can not provide required
protection. They are easier to apply and requires little maintenance.
Properties of Greases:
Stay in place.
Provide sealing action.
Provide extra film thickness.
Components of Greases:
Base Oils.
Thickners.
Additives.

CLASSIFICATION OF LUBE OILS:

Classification is based on sources:
Petroleum : Petro-lubes.
Biological : Animal and Plant Lubes. These no longer serve
modern requirements in nature and volume.
Synthetic Lubes.
Compounded Lubes.
Lube oils can be produced from most crude oils. They may be
distillates from Vacuum Distillation of Atmospheric Residue and range
from thin free-flowing Light Spindle oil to the thick viscous Cylinder
Oil or Bright Stock.
Consequently the Long Residue is regarded as the base material
for the manufacture of lube oils. Vacuum distillation of the residual
crude yields fractions of increasing boiling ranges and viscosities
152
and the Short or Vacuum Residue serves as the raw material very
viscous lube oil, Cylinder Oil or Bright Stock.

Petro Lubes are the most extensively used. Their uses are
numerous making it impossible to make the various grades directly.
Rather a limited number of Primary ( Base) oils are manufactured in
the Refinery and these are blended in various
proportions with or without additives to produce lube oils with the
desired properties.
Petro-lubes are classified in two ways : based on how they are
produced or on their application.
Classification Based On How Produced : as either
a) Distillates and
b) BS or CO.
a) Distillates fall into three sub-classes :
Low Viscosity Index (LVI) Oils with VI less than 30.
Medium Viscosity Index (MVI) Oils with VI of 30 to 85.
High Viscosity Index (HVI) Oils with VI greater 85.
LVI oils are from Naphthenic distillates and have low wax
content requiring little or no de-waxing to obtain the desired Pour
Point. Low VI oils are used where VI and oxidation stability are of
secondary importance.

153
MVI oils are from both Naphthenic (MVIN) and Paraffinic
Distillates (MVIP) with de-waxing of the paraffinic distillates.
They are general purpose lubricants for application where the use
LVI oils is a disadvantage.

HVI oils are produced by Solvent Extraction and De-waxing of

paraffinic diistillates. Solvent extraction improves VI, oxidation
and color stability. HVI oils are used where good VI and
oxidation characteristics are of import, e.g motor oil and turbine
oil.
b) Bright Stocks (BS) are obtained by de-asphalting of Vacuum
Residues in a Solvent Extraction process followed by the de-waxing of
the de-asphalted oil. BS are used as Cylinder oils but their major use
is as blend components for heavier motor and diesel oils.
Classification based On Applications :
Industrial Lubes: Spindle, Turbine, Machine, Gear, Compressor
Oils, etc.

Internal Combustion Engine Oils:

Land Petrol and Diesel Engine Oils.
Marine Cylinder and System Oils.
Hydraulic Oil Automatic Transmission Fluid (ATF).
154
 Metal Processing As Cutting, Grinding, Rolling and Pressing
Oils.
Preservation/Antirust Lubes.

The Functions of Liqiud Lubricants are :

Serve as an Antifriction.
Serve as a Coolant.
Serve as a Sealant .
Help to disperse Stress (Load carrying capacity).
Dust and Rust prevention.
Cleaning / Detergency.
Insulation (Transformer Oil).

Properties : The following properties are required for proper

functioning:
Viscosity during service should be constant.
A high flash point.
A low pour point.
Should be Non-corrosive.
Possession of oxidation stability: unstable oils discolor in
storage due to the formation of some insoluble materials;
exposure to oxygen a higher temperatures may cause formation
of corrosive acids and sludges resulting in increase in viscosity.
Resistance of an oil to oxidation is called oxidation stability.
Satisfactory and stable colour for marketing purposes.
Must have low cracking tendency.

Chemical Composition:
155
Lubes distillates consist of complex hydrocarbons of Paraffinic,
Naphthenic and Aromatic structures with carbon atom numbers
ranging from C24 to C34. Some distillates also contain Nitrogen,
Oxygen and Sulfur compounds. These various hydrocarbon types
differ considerably in their suitabilty as lube base stocks.,
Paraffins have very good VI characteristics. Normal paraffins in
luboil boiling range have high melting points and hence are not
suitable for use and are removed by De-waxing process.
Iso-paraffins have much lower melting points but are
unfortunately present as minor components in the lube oil boiling
range.

Aromatics have poor VI properties and are the least suitable for
use as luboil constituents.
Hybrid HC molecules with naphthenic rings and long iso-paraffin side
chains have been found to be the most suitable for use as luboils.
Some physical properties such as SG, VI and viscosity give some
rough ideas of the chemical composition of luboils.
When HCs of different type but of the same number of Carbon atoms
are compared :
SG increases in the order paraffins, naphthenes and aromatics.

156
Viscosity increases but VI decreases in the same order. As a result of
these, Naphthenic petro-lubes usually have nil or very low wax
content, low VI of 25 70 and are more oxidation stable while
Paraffinic petro-lubes on the other hand have high wax content, high
VI of 75 -105 but lower oxidation stability.
ADDITIVES : These are materials, usually chemical compounds,
added to a base stock to reinforce existing qualities or confer
additional characteristics and performance. They are usually named
afer their particular functions and some are multi-functional.
Examples are :
Low temperature detergents additives.
High temperature detergents additives.
Antioxidants.
VI improver.
Pour point depressants.
Anti-wear.
Anti-foamers.
Anti-rust.
Emulsifiers.
Load carrying improvers for mild and extreme pressure
conditions.

CRUDE OIL SELECTION FOR BASE OILS PRODUCTION

Scale of Operation For Lubricants :

Lubricants constitute 1 2% of total petroleum products consumed
and only 2-4% refinery output of Crude throughput.
157
Consequently their production is concentrated at selected Refineries
to benefit from Scale of Operation
The approximate boiling ranges of paraffinic base oil are:
OILS APPROXIMATE BOILING RANGES (oC)
Light Spindle Oil (LSPO) 100N 370 410
Heavy Spindle Oil (HSPO) 150N 410 450
Ligh Machine Oil (LMO) 250N 440 490
Medium Machine Oil (MMO) 500N 485 525
Bright Stock (BS) >525

For Naphthenic type of the same viscosity level, the boiling ranges are
about 20oC less.
Crude Oil Composition Influencing Lubes Properties:
The general composition cude oils had already been discussed in
some previous Module. Based on Lube oil production, Paraffinic
Crudes give high VI products while Naphthenic Crudes give low VI
products.

All finished base oils whatever be the viscosity, VI and pour point
already existed in the Crude Oil.
However, not all crude oils contain high boiling fractions present in
sufficient or desired quantity to be obtained by Refining treatments.
Hence only selected Crudes are used for lubes base oils production
placing some constraint on the Refinery for the sake of these special
products amounting to only 2 - 4% of Crude input.
158
PROCESSING SCHEMES
Base oils production from Crude oils is usually broken into three
Stages, viz,
1. Feed Stocks Manufacturing stage,
2. Viscosity Index and Color Improvement stage and
3. Pour Point Improvement stage

Feed Stock Manufacture

High Vacuum Distillation Unit (HVDU)
This unit separates Atmospheric Residue/Long Residue (AR/LRS), BP >
350/3700C, into Vacuum Gas Oil for FCCU, Waxy Distillates and
Vacuum or Short Residue. AR is distilled under vacuum (60
88mmHg abs at the column top and 120 150mmHg abs at Flash
Zone). Steam is injected into the last of coils in the furnace radiant

zone to reduce residence time to reduce coking (cracking) and into

the column bottom to aid fractionation.
HVDU is different from the Fuels Vacuum unit in that more fractions
are produced. Therefore its column has more trays requiring
intermediate cuts at varying heights along the column to supply the
necessary refluxes. Demister pads prevent entrainment of heavier
fractions into the Waxy distillates.

159
Vacuum Gas Oil (VGO) is the topmost stream and is an FCCU feed.
Four lube oil distillates (called Waxy Distillates) of increasing viscosity,
LSPO, HSPO, LMO and MMO are withdrawn respectively at selected
points down the column.
The Waxy distillates are steam stripped in separate strippers to
improve separation. Waxy distillates heavier than spindle oil solidify
at room temperature due to high wax content. The Black Vacuum or
Short Residue still containing highest viscosity oil (Bright Stock- BS) is
the column bottom product.
Propane Deasphalting Unit (PDU)
Short Residue of naphthenic crudes is usually disposed of as fuel oil
blend component or as bitumen. But Short Residue of waxy crudes,
containing the heaviest oil and asphalt is the feed for the production
of a valuable highly viscous base oil, Bright Stock (BS).
The extraction of this lubricating stock ( called De-asphalted oil, DAO)
in PDU is the first stage in the production of BS.
Raw very viscous lube oil (BS) is dissolved out of the Vacuum Residue
by counter current washing with liquid propane of 94% minimum
purity in a Rotating Disc Contactor (RDC). See diagram below. The
RDC has settling compartments both at the top and bottom. These
are separated from the turbulent section by calming grids. The oil
dissolves preferentially in liquid propane, the solubility increasing
wtih pressure but decreases with temperature. Asphalt solubility
decreases with increasing volume of liquid propane used.
The processes involved are :

160
Extraction
DAO Recovery
Asphalt Recovery
Propane Compression for re-use.
RDC temperature gradient is 70-75oC at the top and 39-40oC at the
bottom. Base pressure is about 29-32kg/cm2. Feed temperature is
about 65C. The .heavier vacuum residue feed (SG about 0.98), pre-
diluted with the solvent to reduce viscosity and promote distribution,
enters from the top and lighter liquid propane (SG 0.47 at 40oC) from
the bottom.
Liquid propane dissolves the oil and the Deasphalted oil (DAO) leaves
at the tower top (10% wt. Oil, 90% wt. liquid propane).
Propane asphalt (PAS) leaving the base contains about 23%wt of
liqiud propane.
The amount of propane used is between 5vols and 10vols/volume of
feed stock.
Both streams go to different evaporators and strippers for propane
recovery.
Propane vapour from both recovery sections is compressed, cooled
into an accumulator for recycling to the RDC.
The DAO is solid at room temperature due to its high wax content
and its storage tanks are therefore provided with steam heated coil.

161
The DAO is further processed in MDU to reduce the wax content and
the PAS is a blend component for the Asphalt Blowing Unit or for
Cutback asphalt production.

162
SETTLING COMPACTMENT

SETTLING COMPARTMENT

163
Viscosity Index And Color Improvement
Furfural Extraction Unit (FEU)
The waxy distillates for HVDU and the DAO from PDU contain
complex polynuclear aromatics resulting in their having poor
oxidation stability and poor VI. The non-aromatics oxidise especially
at high temperatures forming acids but little sludge. The aromatics
oxidise forming substantial amount of sludge.
These undesirable aromatics present in raw lube oils are removed in a
counter current Liquid Liquid extraction process using Phenol or
Furfural (most widely used as the solvent). The solvent preferentially
dissolves the aromatics.
Therefore FEU functions to reduce the aromatic content of its feed
with the aim of increasing VI, improving oxidation and color stability
and susceptibility to oxidation inhibitors.
The operation is carried out in an RDC similar to that of PDU. The
solvent allows two phases to form : a solvent rich Extract phase and a
solvent deficient Raffinate phase
The heavier Furfural enters from the top and the oil from the base of
the RDC.
Operation is batch wise or block operation, each feed processed
separately.

164
The extraction temperature at the top and bottom of the RDC and
Furfural to oil ratio are adjusted to suit each feed to obtain the
required VI.
Typically, the RDC top temperature is around 30 -110oC depending on
feed viscosity and the bottom temperature is about 90oC.
Ratio : Furfural to oil is 1.5 vol to 4 vols, more viscous oils requiring
heavier treatments.
The Raffinate stream leaving the top contains 15 20% of Furfural
and 85 80% Waxy Raffinate, while the extract stream leaving the
bottom contains 80 -90% Furfural and 20 - 15% Extract.
Both streams go through independent solvent recovery and steam
stripping to remove all Furfural which is condensed, neutralised to
reduce acidity, dried and recycled to the RDC.
By removing about 20% or more of aromatic extract from the feed,
the wax originally present has been concentrated by a corresponding
amount.
The oil products are referred to as Waxy Raffinates and are named :
100N from LSPO,
150N from HSPO,
250N from LMO,
500N from MMO and
BS from DAO.

165
They are fed to the De-waxing Unit in batch operation while the
Extracts are used for ABU feed or Fuel oil blend.

The figure below shows the structure of a typical RDC.

166
 SETTLING COMPACTMENT

our RAFFINATE OUTLET

FURFURAL INLET

OIL INLET

SETTLING COMPARTMENT

EXTRACT OUTLET

167
PourPoint Improvement
Solvent MEK/TOLUENE Dewaxing Unit (MDU)
Due to the high wax content of the waxy Raffinates, their pour points
are so high that they congeal easily at ambient temperatures.
The wax can not easily be removed by direct filtration because of the
high viscosity of the oils. Therefore, to separate the wax from oil,
solvent extraction followed by chilling then filtration is used. The
most commonly used solvent is a blend of Methylethylketone (MEK)
and Toluene the most moden dewaxing process.
Toluene dissolves the oil and wax, MEK is anti-wax, precipitating the
wax and not dissolving appreciable amount of oil.
The solvent mix ratio is 52/48% MEK/Toluene.
The waxy raffinate is mixed with solvent (primary dilution solvent)
and heated to a temperature of 25oC to ensure that the wax dissolves
completely. The charge mix is then cooled to the filtration
temperature, normally around -20oC, with the addition of further
amounts of solvent.
The charge mix is chilled in scraped-surface double pipe heat
exchangers and chillers.
Heat exchange is with cold filtration and the chilling medium is
usually evaporating propane, liquefied by compression and cooling.
The chilled mixture goes to the rotary filters where filtration takes
place under vacuum in continuous operation.

168
In the filters, the crystallized wax is separated from the oil in the form
of a thin cake which is continuously removed from the drum by
blowing back with inert gas, usually Nitrogen.
The size of the wax crystals that form as the feed is cooled influences,
in an important way, filtration and washing of the crystallized wax.
Washing is with solvent to recover the oil that remains trapped
between the wax crystals.
The total quantity of solvent (usually 3 5 vols./vol. of oil) added to
the charge oil is governed by its viscosity and the filtration
temperature. It is best to use the minmum quantity of solvent to
reduce operating cost.
The higher the solvent ratio, the lower the charge oil viscosity and the
larger the wax crystals. Large crystals result in good filtration rates but
the filter cake will be loose with a high pore volume and
consequently, a poor washing efficiency. Small crystals generally
produce tightly packed cakes with lower filration rates but improved
washing efficiency.
The dilution solvent can be a added to the oil feed in different ways
and in this way the crystal size of the separating wax can be
influenced.
The latest development in this field is the mutiple dilution system, in
which the solvent is added to the oil charge in increments before and
during chilling.
The incremental solvent addition ensures that the bond between the
wax crystals is dissolved and thus, no large aggregates are formed.
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The individual crystals so obtained give an improved filtration rate
and owing to the smaller pore volume, the cake will have improved
washability characteristics.
It is important that the temperature of the secondary solvent added
should be equal to that of the charge mix stream at the point of
injection. If the dilution solvent is too cold, shock chilling may occur
forming fine crystals. Higher temperature partially melts the wax
crystals.
The filtrate cake is transferred by conveyors to the wax boots, from
where it is pumped to the slack wax recovery section afer steam
heating.
The filtrate from the outlet of the filters first exchanges heat with the
incoming feed mix and then goes to the dewaxed oil recovery system.
In both recovery sections the bulk of the solvent is removed by
applying a double-effect evaporation system, additional heat being
supplied by hot-oil heaters. From the second (high-pressure) flash
column the oil or slack wax is transferred to a steam stripper, where
the final traces of solvent are removed.
The solvent recovered from all these sources is returned for further
use in the dewaxing process as moist or dry solvent, depending upon
the source from which it is recovered.
Any solvent losses are made good by the addition of fresh solvent.
The quantity of wax removed is typically 20 - 25% weight on waxy
feed.

170
Conditions are adjusted to obtain product oil desired pour point
usually -9 to -20oC.
Three grades of Slack waxes are produced in batch operation :
A grade from 100N and 150N waxy Raffinates.
B grade from 250N waxy Raffinates.
C grade from 500N waxy raffinates.
BS slack wax is FCC feed component.
The Table on the next page gives typical feed and product properties:

171
Waxes And Their Properties :
Refined waxes are solid or semi solid materials made up of a
mixture of hydrocarbons obtained or derived from petroleum

172
fractions. They are mixture of normal paraffins and iso-paraffins,
which may be attached to naphthene rings.
Waxes are grouped into three : Paraffin Waxes, Semi-
microcrystalline Waxes and Microcrystalline Waxes.
Paraffin waxes contain a high amount of n-paraffins and are from
Spindle and Light Machine oils Slack waxes; semi-microcrystalline
ones have lower n-paraffins content but greater amount of iso-
paraffins and naphtheno-paraffins and are from heavy distillate oil
Slack waxes and microcrystalline waxes contain predominantly iso-
paraffins and naphtheno-paraffins and are from de-asphalted oils
(DAOs).
Paraffin waxes have molecular weight in the range of 320 to 400,
melting or congealing point of 32C to 73C and oil content of less
than 0.5%. Finished paraffin waxes are odorless and colorless as
liquids and as white hard but fragile solids.
The molecular weight of microcrystalline waxes is between 450 to
1000 , congealing point of 60C to 85C and oil content of about
3%.. They are yellow or brown and plastic and sof as solids
Maximum oil content is 50% wt for Raw wax (Slack Waxes) and
0.5% to 1.0% wt maximum for commercial waxes.

Uses of Waxes: About 50% of commercial waxes is used in coating

and imprenating paper (water-proofing), 10% in the manufacture of
candles and the rest in textile, leather, cosmetics, electrical

173
 insulation, electrotyping, polish compounding, tyre manufacture,
etc.
These many uses of petroleum waxes explain why they are made in
different grades to meet the requirements of the different end
users.
Wax Production
Solvent MEK/TOLUENE Deoiling Unit (MDOU)
Slack waxes produced as by-products of refined lube oils in the MEK
Dewaxing Unit (MDU) still contain some oil components as well as
undesired low melting point waxes.
The melting/congealing point is always determined because it has
direct effect on many characteristics of waxes and their commercial
applications. The melting/congealing point is therefore, the main
property used for classifying waxes into different grades.
MDOU is designed to produce commercial paraffin waxes by deoiling
lube oil slack waxes produced in MDU. The oil product is called Foots
Oil and is usually routed to the FCCU feed tank.
In order to obtain waxes with the desired melting point and
penetration, it is necessary to remove the oil components and the
low melting point waxes; in this way the melting point of the deoiled
wax will increase and its penetration will decrease meeting the
required specification of commercial waxes.
The process used to remove the undesirable oil components from
the slack waxes is called deoiling.

174
The slack waxes are deoiled by using a solvent mixture (MEK and
Toluene). The process used to reduce the oil content in slack waxes
(deoiling) is very similar to that of dewaxing which has already been
discussed under MDU.
The feedstock is deoiled with a solvent mixture (MEK and Toluene).
The principle of the process is that the feed is mixed with the solvent
and chilled to a certain temperature and the wax which is crystallized
at this temperature is separated from the oil by filtration through a
rotary vacuum filter.
Everything regarding choice of the solvent is equally valid. In this
particular case, use is made of a MEK/Toluene mixture, the
composition of which varies from 60/40 (normal) to 70/30.
Methyl Ethyl Ketone is the agent which precipitates the waxes, i.e.
given that waxes are barely soluble in it, as the temperature falls they
separate in the form of crystals of a size suitable for the subsequent
filtration. However, as its solvency versus oil is also limited, a large
quantity of oil would also separate with the waxes.
The purpose of using toluene with the MEK is to keep the oil in
solution, at the same time reducing its viscosity at low temperatures
to aid separation during filtration. Toluene on its own would tend to
dissolve even large quantities of waxes, but the presence of MEK
prevents this.
The purpose of washing the wax cake is to remove the oil and the sof
wax that remain blocked between the wax crystals; it is thus obvious
that large crystals withhold large quantities of unwanted compounds

175
which worsen the properties of the finished wax (e.g. the melting
point falls and penetration increases).
In the multiple dilution system, the solvent is added to the feed in
incremental amounts before and during chilling.
For a particular slack wax feed the filtration temperature governs
the melting point, penetration and yield of deoiled wax. When the
filtration temperature is increased, the wax melting point is
increased, the penetration is reduced and the wax yield is reduced.
The opposite is the case when filtration temperature is decreased.
The Feed and product Hard Wax properties are shown in the Table in
the below.

GRADES

PROPERTIES A B C

Slack Wax Hard Wax Slack Wax Hard Wax Slack Wax Hard Wax

Flash Point (C) 195 195 220 220 225 225

Congealing Point 48 48 54 54 59 -62 60 66 70

(C)

Max. Oil Content 15 0.5 20 0.5 25 1.0

(%weight)

Wax Hydrofinishing Unit ( WHU )

176
The purpose of WHU is to produce food grade waxes by complying
with some health regulations and is the final step in the
manufacture of commercial waxes.
As earlier discussed, wax consists of redominantly n-paraffins ( above
70% ), the rest being mainly iso-paraffins and some aromatics,
polyaromatics and organic compounds of sulfur, nitrogen and oxygen.
The carbon chain length is usually 20 to 36, melting point ranges from
400c to 700c and sulfur content is usually between 0.01 and 0.5 %wt.
Hydrofinishing is a catalytic hydrogenation treatment of de-oiled
waxes ( hard waxes ) in order to improve their color, color and
oxidation stability, to reduce impurities ( O2, N2 and S compounds )
and to convert aromatics to naphthenes to meet FDA specifications .
The food and drug administration ( FDA ) test concerns the aromatic
content in waxes and this must be lower than a specified value to
pass the FDA test. This is because the product waxes are expected to
be of food grade and the aromatics are carcinogenic.
The reaction occurs in a fixed bed reactor packed with a catalyst
containing Nickel and Tungsten ( Wolfram, W ) on alumina support
base at temperature range of 2500C to 4000C and pressure of 50 to
100 kg / cm2.
The main reaction is the de-aromatisation of the aromatics and
polyaromatics to naphthenes and naphthenes fused with aromatics.
Break down of organo sulfur, nitrogen and oxygen compounds also
occurs to produce H2S, ammonia and water with a small amount of

177
hydrocarbons with lower molecular weights and lower boiling points
than the parent organic compounds.
Hydrocracking and isomerisation are also possible but because they
produce some oils which will affect the properties of the wax ( oil
content and melting point ), conditions are held such that these side
reactions are substantially minimsed.
The Table below gives the key properties of the hydrofinished waxes.

PROPERTIES GRADES

A B C

1. CONGEALING/ MELTING PT 0C 54 - 58 59 60 66 71

2. SULFUR %WT - - -

3. MAX. OIL CONTENT %WT 0.5 0.5 1.0

4. COLOR WHITE WHITE WHITE

5. FDA TEST PASSED PASSED PASSED

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ASPHALT BLOWING UNIT (ABU)
Asphalt is an amorphous dark brown to black, odorous, cement-like,
combustible mixture of fused polynuclear aromatics with cross-
linkages made of methylene, ether and thioether bonds.
It is usually obtained from petroleum processes and is insoluble in
most pure hydrocarbons. Crude oil composition is vital in refining for
asphalt beccause asphalt yields are practically set by crude oil
composition while asphalt quality is subject to processing. API
gravity and Carbon Residue can give a rough index of the quantity of
asphalt present in crude oil.
Raw asphalt has poor characteristic : high penetration, very low
softening point and other qualities.
Asphalt together with Resins (materials of similar composition but of
linear polymers and hydrocarbons soluble) make up 5 15% of Crude
Oil.
The oil fraction in asphalt is a mixture of oils similar to very heavy
lube oils. Resins are solids and semi solids.
The solid fraction is called Asphaltene which is responsible for the
consistency of asphalt: the more the asphaltene content the higher
the viscosity and sofening point but the lower the penetrattion.
Hence properties of asphalt vary over a wide range depending on the
properties and the nature of the various constituents.

179
Sources of Raw Asphalt:
Distillation: HVDU.
Air Blowing: ABU.
Precipitation or Solvent Extraction: PDU.
Distillation and Precipitation remove relatively fluid oils and waxes
without chemical conversion
Asphalt Product Types:
Solid grade : 80/100 Penetration.
60/70 Penetration.
50/60 Penetration.
Liquid (Cut back) grade: Medium curing (MC).
Rapid curing (RC).
Solid grades are usually produced by air blowing although 80/100
grade can also be produced by direct blend of PAS and Vacuum
Residue - 2.
Liquid or Cut back grade is produced by blending a petroleum solvent
with asphalt:
Volatile solvent like naphtha gives Rapid Curing (RC) grade which
hardens very quickly due to the solvent which evaporates easily.
Medium Curing (MC) grade uses less volatile solvent like kerosene to
blend and hence hardens less quickly.
RC and MC grade is each divided into 6 sub grades numbered 0, 1, 2,
3, 4 and 5 depending on the amount of solvent used in blending.
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The 0 sub grade has the greatest amount of solvent and is most fluid,
the 5 sub grade has the least amount.
The same sub grade in each class has the same fluidity i.e. RCO and
MCO have the same fluidity but differ only in the length of time
required for the solvent to evaporate.
Solid Grade Product Quality:
Sofening Point is determined using Ring and Ball tester and is the
temperature at which the ball placed on a ring of heated asphalt falls
through the ring and it varies from 45oC for 80/100 to 58oC for 50/60
grade.
Penetration is a measure of hardness and is the distance a needle
under a standard load will penetrate the asphalt in 5 seconds at a
specified temperature, usually 77oF (25oC), measured in 1/10mm unit.
The expression 50/60 Pen asphalt refers to an asphalt with a
hardness of between 50 and 60.
Flash Point varies from 225oC for 80/100 to greater 250oC for 50/60.
Fundamentals of ABU
The unit comprises of four (4) Sections:
the Oxidizer,
the Hot Oil System,
Oil Scrubbing System (to recover cracked oil) and
Fume Incinerator to burn foul smelling spent gases.

181
Air blowing is an oxidation reaction carried out in the oxidizer
column. The main reaction is dehydrogenation by the oxygen in the
blowing air and generation of water from reaction with hydrogen
from the dehydrogenated hydrocarbon in a Condensation
polymerization reaction.
Air blowing increases the asphaltene content at the expense of
resins and oils leading to higher softening point and lower
penetration.
The reaction is exothermic and temperature rises as the air rate
increases. Temperature control is therefore vital and usually kept at
300oC maximum.
Product properties depend on reaction temperature, air rate and
feed characteristics. Hence operation is carried out at appropriate
conditions to produce products with desired properties.
Flow through the oxidizer is counter current: Asphalt from the top
and air blowing from the bottom.
Asphalt product stream is withdrawn from the bottom and cracked oil
vapour and gases from the top. The oil is scrubbed to recover it as
FCCU feed. The scrubbed overhead vapour is burnt in the Incinerator.
Asphalt Blending :
Only Cutbacks and 80/100 grade are blended.
In-line blending is carried out based on laboratory bench result to
determine components ratio and regular tests for sofening point,
penetration and flash point are carried out as control measures.

182
183
 LUBES PLANT PROCESS SCHEME

SOLVENT
CRUDE UNIT VACUUM UNIT EXTRACTION DEWAXING FINNISHING

CRUDE OIL FINISHED

BASE OILS
1A 1B 2 3 4

LONG

RESID

1C
PROPANE
SURPLUS
DEASPHALTING
DISTILLATES ASPHALT EXTRACT SLACK
M WAX A
WAX W
D WAX B
FUEL OIL H WAX C
BLEND O
CRACKER
U
U
FEED

184
STAGE 1A, B, C: FEED STOCK MANUFACTURE

STAGE 2: VISCOSITY TEMPERATURE (VI) CHARACTERISTICS AND COLOR IMPROVEMENT

STAGE 3: POUR POINT IMPROVEMENT

STAGE4: STABILITY IMPROV EMENT, BLENDING, PACKAGING AND SHIPPING.

185
187
KRPC receives both local and foreign crude from Warri
through a 606 km pipeline.

188
Four crude tanks each are available for Local and
Foreign crude oils. Each set of crude tanks has a capacity
of 327,600 barrels or 6.5 days feedstock for Fuels Plant
at 60,000 Barrels Per Stream Day(BPSD).
A total of 166 tanks are available to handle crude,
intermediate and finished products.
Product evacuation is by Road, Rail and Pipeline and
there is
capacity to load 192 trucks of 33,000 litres each daily.

189
190
191
192
193
TANKAGE

194
FEATURES ASSOCIATED WITH VESSELS OPERATION

Sizing or Capacity (how long and for what service?)

Is it hot or very cold service (temperature sensitive)
lagging required?
It must have nozzles for inlet and outlet plus side
streams and sensors
It must breathe very important for self protection
(over pressure and under pressure can both be
experienced)
It must be accessible
It must be supported
Labels
Drains and Utility Connections

AS OPERATOR YOU MUST:

Know the service of the vessels you operate what

does it handle.
Understand the conditions inside each vessel.
Know the accessories and the linkages.
Understand the location does it pose any threats?
Is it near heaters?
Are associated auxiliaries well Located? Can they be
seen and serviced.
Where the vessel drains to.
How much material the vessel holds.
How to prepare the vessel for entry.

195
Grasp the associated risks with the vessel

PETROLEUM PRODUCTS AND THEIR USES

Category :

196
 Petroleum products are usually grouped into
three categories :
Light Distillates : LPG, Naphthas and Gasoline
Middle Distillates : Kerosine, Aircraf Jet Fuel and
Diesel Oil
Heavy Distillates and Residium : Fuel Oil,
Lubricating Oil, Waxes, Asphalt, Tar and coke
Liquefied Petroleum Gas (LPG)
LPG, which consists principally of propane and
butane, is produced for use as fuel (cooking gas).
LPG is also an intermediate material for the production
of light olefins used in the manufacture of
Petrochemicals.
Premium Motor Spirit (PMS)/Petrol/Gasoline
Motor gasoline is the most important refinery
product. It is a blend of hydrocarbons with boiling
ranges up to about 204OC. The important qualities for
gasoline are octane number (antiknock), volatility
(starting and vapor lock), and vapor pressure (storage
and environmental control).

Kerosene (Aviation, ATK and Domestic, HHK)

197
Straight Run Kerosene is used for cooking, lighting,
heating (Domestic) or as Aviation jet fuel (ATK) afer
further processing in KHU. It is also used as solvent.
o Automotive Gas Oil (AGO)/Diesel
Used as diesel engine fuels and domestic heating
oils.
Fuel Oils (LPFO and HPFO)
To power many marine vessels and Power Plants.
Commercial buildings and industrial facilities use a
blend of residual and diesel fuels (LPFO) for heating
and processing.
Asphalt ( Cured and Solid Grades)
Asphalt is used for road pavement and as roofing
materials because it is inert to most chemicals and
weather conditions.
Lubricants ( Oils and Greases )
Special refining processes produce lubricating oil base
stocks. Additives, such as demulsifiers, antioxidants,
pour point depressant and viscosity improvers,
thickners, etc are blended into the base stocks to
provide the characteristics required for motor engine
oils, industrial greases and other lubricants.

THE CHALLENGES

198
The major challenges being faced by the refining
industry are from the environmentalist in terms of :
Reduction in air pollution by reducing :
Carbon oxides emissions
Nitrogen oxides emissions
Sulfur oxides emissions.
Particulates emissions
Reduction in industrial noise pollution
Water pollution and sludge/solid Wastes
disposal.
Techonology is moving faster in the area of air
pollution much more than the others increasing initial
capital and mainteance costs as a result of refiners
having to install additional pieces of equipment
needed to comply with pertinent environmental
restrictions as laid down by government
Environmental Protection Regulatory Agencies.
Another important challenge is in the inadequacy of
technical personnel, especially experienced operators
and process engineers, resulting from aging work
force and recruitment not matching the spate of
retirementand other forms of staff attrition.

199
We also have the serious situation of responsibilty
given to the operational SBUs and CSUs not being
matched by adequate financial authority because
these entities are not yet being run as commercial
enterprises.

200
PETROCHEMICALS PROCESSES

201
CONTENT

INTRODUCTION
SOURCES OF RAW MATERIALS
EQUIPMENT
COMMON REACTIONS
PETROCHEMICALS PROCESSES
ANIONIC SURFACTANTS : DETERGENT ALKYLATES
LINEAR ALKYLBENZENES ( LAB ) PROCESS SCHEMES
CARBON BLACK PROCESS SCHEME
POLYMERISATION
POLYMERS
ALKENE MONOMER PRODUCTION
POLYETHENE PROCESS SCHEME
POLYPROPENE PROCESS SCHEME
USES OF POLYMERS

202
INTRODUCTION
The Petrochemicals industry is commonly called
molecular architecture.
This because finished products are built up of basic
building blocks e.g. CH3-, C2H5-, C3H7-, -COOH, -OH,
-NH2, -CONH2, -SO3H, -O.SO3H, - O -, - S-S -, etc.
Petrochemicals processes convert refinery products
/byproducts into intermediate or finished consumer
products several thousands of them.
Process plants are similar to those found in refining
Plants. Hence Refining and Petrochemicals Plants are
usually located next to each other and integrated into
one huge complex.
The major difference is in product purity which is
more important in Petrochemicals Plants and to
achieve this, equipment are usually smaller, e.g.
distillation columns are usually taller (more trays) but
thinner (process less volume).
SOURCES OF RAW MATERIALS
1. Primary Raw Materials :
Natural Gas :
Mixture of CH4 (Methane) with small amounts of
higher alkanes ( Ethane, Propane, C4 and C5 HCs),
CO2, N2 and S compounds, H2O and water vapour.
It can be Associated Wet, containing
comparatively large amounts of easily liquefied
HCs.

203
 Or Non associated Dry, although may have
appreciable amounts of C2 and higher alkanes
Where it is virtually CH4 (methane) the range of
uses is limited.
Where it contains higher paraffins, it is used as
major source of lower alkenes (Olefins) NGL.
Refinery Gases FCC LPG which is high in olefinic
content : 65-70% Propene and 55-60% Butenes.
Refinery Liquid Hydrocarbon Fractions : Naphtha,
Kerosene, Reformate for BTX and Ethylbenzene
extraction and Decanted oil ( Carbon Black ).
Secondary Raw Materials:
Ethane and higher Paraffins.
Ethene, Propene, Butenes and higher olefins.
EQUIPMENT
Typical Refinery pieces of equipment are also found
in the Pertochemicals Plant.
Other equipment found in the Petrochemicals
Industry are Crytallizers, Filters, Settling Tanks,
Cyclones, Leaching Plants and Evaporators.
Reactors :
Batch Stirred Tank Reactor (BSTR).
Continuous Stirred Tank Reactor (CSTR).
Tubular Reactor and Fixed Bed Reactors.

204
COMMON REACTIONS
Hydrogenation: Benzene to Cyclohexane.
Dehydrogenation: Isopropanol to Acetone and
Hydrogen.
Oxidation: Ethanol oxidised to acetaldehyde and
water.
Ethene oxidised to Ethylene
Oxide.
Reduction: Acetaldehyde is reduced to
Ethanol with H2
Halogenation: reaction involving F, Cl, Br and I.
Chlorination: CH4 + Cl2 CCl4 + HCl.
C2H4 + Cl2 ClCH2 CH2Cl.

Alkylation: Benzene + C8H18 (octane) Octyl

Benzene.
Isobutane and Propylene give
isoheptane.
Benzene reacts with Ethene to yield
Ethylbenzene.
De-alkylation: Toluene to Benzene or Benzene
reacting with Xylene to give two molecules of
Toluene.
Esterification: Ethanol + Acetic Acid give Ethyl
Acetate ( the Ester ) and water.

205
 Hydrolysis: EthylAcetate + H2O give Acetic and
Ethanol. This is the reverse of Esterification.
Sulfonation (Sulphuric Acid + Sulfur trioxide).
Benzene + H2SO4/SO3 give Benzene Sulfonic Acid
(R-SO2 OH).
Sulfation : To produce Sulfate Ester with Aq. Sulfuric
Acid)
Octene-1 + H2SO4 give Octyl, 2-Sulfuric Acid Ester
(R-O-SO2-OH). R = Octyl radical.
Condensation: Two molecules reacting to give a
more complex one and eliminating a
smaller molecule (e.g. water).
2 moles of Acetone give
Mesityloxide and water.
Polymerization:
Polymerisation is the most important reaction in the
Petrochemical Industry. It is used in the manufacture
of many consumer items called Polymers.
The word Polymer is derived from two Greek words :
Poly Many and Meros Parts / Segments.
Polymers are high molecular weight materials,
consisting of long chains of repeating single molecules
or slight modification of them called Monomers.
A monomer can be mono functional (Olefins) or
bifunctional (Amino acids) even trifunctional.

206
Polymerization is usually a catalysed reaction which
can be:
Addition: one monomer adding to each other or
one another (Olefins Homopolymers /
Copolymers / Terpolymer).
Condensation: monomer molecules combining
together with the elimination of small molecules
e.g. water.
Homopolymer Condensation Polymerization:
Amino acid to give Polyamide.
Copolymer Condensation Polymerization: Ethylene
glycol reacting with terephthalic acid give Terylene
or PTF or a diamine reacting with a dicarboxylic acid
producing Nylon material.
Polymerisation can occur via Free Radical reaction
or Ionic ( carbocation or carbanion )reaction. The
reaction occcurs in three steps for either
mechanism : Initiation. Propagation and
Termination.

207
SOME PETROCHEMICALS PROCESS SCHEMES
SURFACE ACTIVE MATERIALS ( SURFACTANTS }
Anionic surfactants are the most important synthetic
surfactant making up 60 70% of total production of
synthetic detergents
Usually used as sodium salt of the organic sulfonic
acids or less frequently sulphuric acid esters.
They are superior to soaps in that they form relatively
soluble Ca and Mg salts and are completely ionized
under all conditions of acidity.
They are ultimately derived from petroleum in most
cases and are also cheaper than soaps in many
applications.
The most important anionic surfactants are
Alkylbenzene sulphonates manufactured by a straight
forward Friedel-Crafs reaction between straight chain
alkenes and benzene in the presence of an acid
catalyst to produce alkylbenzenes which are then
sulphonated with a 4% SO3-air mixture at 40 50oC.
Straight chain alkenes yield largely biodegradable
products.
If a solid detergent is required the sulphonic acid is
neutralized with caustic soda, NaOH, the resulting
slurry mixed with builders, spray-dried to a smooth-
flowing powder to which heat sensitive ingredents
such as bleaches and enzymes may be added.

208
For liquid formulations, neutralization is effected with
caustic potash, KOH or alkanolamines.
LINEAR ALKYL BENZENE PRODUCTION
Process Scheme : Five Units involved are :
Kerosene Hydrodesulfurisation Unit (HDS) : For
Molex Feed Production.
The Molex Unit : Produces Normal Alkane.
The Pacol Unit : Produces Normal Alkene.
Benzene Production And Thermal Hydro-
dealkylation Unit (THDA) For Benzene
Optimisation .
The HF Alkylation Unit.
HDS
The feed to this unit is raw kerosene from the
Refinery Crude Units -1 and -2 but by design CDU- 2.
Its purpose is to remove S and N contaminants to
avoid poisoning the Molex unit molecular sieves
and Pacol unit catalyst.
The process is similar to NHU but operate at higher
pressure.
The raw kero is pre-fractionated to eventually
produce a four-carbon cut ( C10 C13 for light LAB or
C11 C14 for heavy LAB ) which actually is what is
desulfurised afer preheat in the reactor and then
fed as Treated Kero to the Molex Unit afer product
stripping to remove light ends.

209
MOLEX UNIT
A UOP licensed process separates normal paraffins
from isoparaffins and others using proprietary zeolite
molecular sieves which adsorbs C10 C14 (decane
through tetradecane) fractions which are then
desorbed using a low boiling hydrocarbon.
Products are Kero solvent raffinate, Isoparaffins and
normal paraffins ( nC10 to nC13 for light LAB and nC11 to
nC14 for heavy LAB ) as a ready stated.
PACOL UNIT
This is another UOP licensed process that converts
linear or normal paraffins from the Molex Unit to
linear Olefins using platinum on alumina support base
as the catalyst.
The linear Olefins thus produced, altogether forms,
one of the two feedstocks to the HF Alkylation Unit.
THDA UNIT
THDA produces benzene (the second feed) for HF
Alkylation unit.
The feed to this unit is the Reformate from the
Refinery CRU. The reformate is first stripped, to
remove as the overhead product, benzene and C4 and
lighter HCs as fuel gas.
The middle cut is Toluene, Xylenes, Ethylbenzene and
little benzene.
The bottom product contains mostly C9+ with little C8
materials and is returned to refinery gasoline pool.

210
The C6 and C8 middle cut is then subjected to
controlled hydrothermal cracking (hence the name ,
THDA ) resulting in increased yield of benzene from
a given quantity of reformate afer product
stripping plus byproduct, Toluene concentrate.
HF ALKYLATION UNIT
The linear Olefins from Pacol Unit are reacted with
benzene in the presence of Hydrofluoric (HF) acid
as the catalyst.
The main product is Linear Alkyl Benzenes which
are purified, freed from residual acid by
neutralisation and then sold to end users
( detergent manufacturers ).
Byproduct is Heavy Alkylates which afer being
freed from acid also by neutralisation and purified
are also sold to end users for the manufacture of
transformer oil, ATF, etc.

211
212
213
214
CARBON BLACK PRODUCTION ( CB )
CB is poduced mainly by controlled incomplete
combustion/thermal decomposition of the FCCU
Decanted or Conversion oil or gases. Yield is high
and control over CB properties (particle size and
structure) is wide.
CB comprises fine elemental carbon particles: 90
99% carbon.
Process Scheme
The Reactor feed is filtered in a high voltage
separator to remove entrained FCCU catalyst, coke
and metals.
Filtered feed goes to the Reactor where controlled
burning in pre-heated air and fuel gas (mainly C 3)
provide the heat necessary to crack DCO at about
1,000 1,200oC.
The residence time in reactor is controlled through
quenching with steam or water.
Potassium nitrate ( KNO3 ) solution is also injected
in controlled amounts to regulate carbon black
particle size.
KNO3 additive injection, control of residence time in
the reactor and control of temperature affect the
specific surface area and structure of the various
grades of CB produced.
The reactor effluent, comprising colloidal carbon
black particles suspended in the off-gas stream, is

215
used to pre-heat the feed and then cooled in
quench sprays.
The cooled CB is filtered in special fibreglass filter
bags, pulverised and discharged into a surge tank
afer which it is pelletized into the desired
spherical shape and dried to moisture level of less
than 1%.
The dried CB is conveyed in a bucket and screw
conveyors through a magnetic separator to remove
metals before being sent to storage silos for
bagging.
The capacity of the Plant is 104.51MT/DAY of
Decant Oil and product yield is :

S/N PRODUCT QUANTITY YIELD

( MT/D ) (%WT)
1 OFF GAS 50.01 47.85

2 HARD CARBON BLACK 54.50 52.15

3 TOTAL 104.51 100.00

216
 Two main types of CB are produced:

TYPES GRADES

High Abrasion Furnance (HAF) N326, N330 and N375

Intermediate Super Abrasion Furnance N220.

(ISAF)

TYPICAL FLOW SCHEME OF A CARBON BLACK PLANT

217
SOME USES OF CARBON BLACK :
o Coloring agent for Ink and Paints
o Black pigment for inkjet ink and toners
o Resins and Film coloring agents: because
of its high tinting strength, thermal
stability and excellent high UV absorbing
capacity, it is used with resins for the
manufacture of car bumpers, wire
coverings ( insullation ) and steel pipe
linings.
o Electric Conductive Agent : CB has
graphite type structure and hence has

218
 high electric conductivity. Hence its use as
conductive filler in plastics, elastomers,
paints, films, adhesives and pastes.
And in fuel tank caps and pipes in cars to
prevent generation of static electricity as
an excellent antistactic agent.
o Electronic Equipment Related Materials :
due to its stable resistance it is used in
display components and magnetic
recording materials.
o It has reinforcing capability and hence
imparts a high tensile strength and
abrasion resistance to rubbers, therefore
its use in tyre, fan belt and conveyor belt
manufacture.

POLYMERISATION AND POLYMERS

A Polymer ( Greek : polymeros many parts or
segments ) is high molecular weight (between a few
thousand and a few hundred thousand,say 10,000
200,000) material, consisting of long chains of
repeating single molecules or slight modification of
them called Monomers.
Classification
There are two ways of classifying Polymers
1. Based On The Source :

219
 Natural e.g. Proteins ( wool, silk, leader, muscle
fibers, enzymes, nucleic acids ), Polysaccharides
( starch, cellulose [ cotton, wood, paper, hemp, sisal
,linen ] and Rubber.
Synthetic e.g. Polyethylene, Terylene, Perspex,
Nylon etc.
About 80% of world organic chemical industry is
used in the production of synthetic polymers.
Synthetic polymers are as diverse as the natural ones.
We put on polyester clothes, sit on PVC chairs, write
on formica table top, work on formica kitchen table
top, our carpets and rugs are polymer materials, paint
our walls with latex paints and wooden floors with
polyurethane. Our cars have man made rubber tyres
and vinyl upholstery. Our dishes may be melamine.
Others are food and bread wrappers, shopping bags,
teflon coated frying pans, tooth brushes, hair brushes,
electrical insulators, plastic jugs, plates, cups, buckets.
Bowls, cutlery and heart valves, aircraf windshieds,
etc.
Therefore synthetic polymers (plastics, elastomers
and fibers) are the products of the chemical industry
with which the man in the street is most familiar and
which have had the greatest impact on his life.
2. Based On Structural Make Up :
Polymers are classified as Elastomers, Plastics and
Fibers depending on their initial moduli of
elasticity:

220
 Elastomers ( with elastic properties ): 15 150 psi;
e.g. Natural rubber, polychloroprene, polyisobutene
and polybutadiene, etc.
Plastics ( thin sheets, hard and mouldable solids,
coating, adhesives ): 1,500 15,000 psi; e.g. PVC,
PVA and polystyrene, etc.
Fibers ( thread-like ): 150,000 1,500,000 psi; e.g.
silk, cellulose, polyamides and terylene, rayon, etc.
Polymer properties of high viscosity, tensile and
impact strength and toughness depend on molecular
weight and chain length.
Mechanical strength develops from chain length of
about 50 monomers and increases up to a chain
length of 500 units afer which not much difference is
observed.
Synthetic polymers are usually named afer the
monomer / monomers with the prefix ; poly e.g.
polyethylene, polyvinyl chloride, polyvinylidene
chloride, polymethylmethacrylate, ABS ( poly
acrylonitrilebutadienestyrene ), etc.
PLASTICS
There are two major types: Thermoplastics and
Thermosets.
Thermoplastics : When heated melt to liquid which
on cooling forms a solid with no change in any of its
properties and these processes can be repeated
over and over again.

221
 Action of heat only makes the solid plastic and
pliable e.g. Polyethylene, Polyvinylchloride,
Polypropylene, Polystyrene etc.
Thermosetting Plastics : Set by the action of heat,
that is, once the polymer is heated, formed into a
shape and cooled down, no amount of heating will
cause the polymer to melt the second time.
Rather it will decompose or burn with increasing
temperature.
These is due to cross linkages in their structures e.g.
Bakelite: a Phenol -Formaldehyde polymer.

PLASTICS : POLYOLEFINS (POLYETHYLENE PE;

POLYPROPYLENE - PP)
Feed Stocks can be produced by :
Cracking of light alkanes e.g. NGL to
produce mainly Ethylene and
Propylene.
Cracking of Naphtha.
Cracking of Residual Oils
( Hydrocracking, Visbreaking and
Coking).

222
 Stripping of FCCU LPG which is rich
in Propene and Butenes ( see
Sourcces Of Raw Materials above ).
THE OLEFINS PLANT
The diagram below is a Process Flow Diagram of a
typical Olefins Plant where the feed NGL
( 89,900MTPA ) is steam reformed ( cracked ) and
98,000MTPA of Propylene Rich Feed ( PRF ) later
added to the cracked materials to produce polymer
grades of ethene ( 260,000MTPA ) and propene
( 126,000MTPA ) as the main products.
NGL at a pressure of about 36kg/sq.cm. and a
temperaure of 34C is first prefractionated in a
column from which Virgin C+ is taken at the bottom
and C - C alkanes are removed from the overhead.
These are then preheated and mixed with dilution
steam and DMDS to reduce coking before being
routed to the Pyrolysis furnaces; first through the
Convection section where the mixture is heated to
624C and then distributed into 192 radiant tubes
for cracking at about 1000C and very short
residence time ( milliseconds ) to produce olefin-
rich gas or vapor.
If there are six furnaces, five are usually in cracking
mode and the sixth on decoke afer about 12 days
in operation and then kept on standby to be put
back into service as soon as one other furnace is
ready for decoking.

223
The cracked vapor from the operating furnaces are
rapidly cooled by being used to generate ultra high
pressure steam at about 105kg/cm2 in a series of
quench heat exhangers to reduce secondary
cracking reactions which can reduce ethylene and
propylene yields.
In fact three levels of steam is generated in this
Plant :
Ultra High Pressure Steam at 105kg/sqcm and
505C.
High Pressure Steam at 46kg/sqcm and 400C and
Low Pressure Dilution Steam at 8kg/sqcm and
192C.
The vapors ex these exchangers are fed into a
Water scrubber to wash and further cool the
vapors. The HC ladden quench water is cooled to
around 80C before being sent to a separator where
Quench water, process condensates, light and
heavy oils are separated. The oils are pumped to
the Offsite for burning.
The gas or vapor exiting the top of the Scrubber is
compressed in five stages from 0.32kg/cm 2 and 38
C with interstage cooling and water draining from
the interstage knock out drums to 40kg/sq.cm.
The vapors are subjected to caustic wash afer the
fourth stage to remove Acid Gases ( mainly
hydrogen sulfide and carbon dioxide ).

224
The 5th stage discharge is then combined with a
Propylene rich feed ( PRF ), cooled to about 13C
and sent to a separator from the top of which the
Process gas goes to the Gas dryer packed with
molecular sieves and then a filtered to remove
water to less than 1ppm. The Process liquid from
the separator is sent to a coalescer and then to a
liquid dryer before joining the gas stream for a
series of cooling and chilling to -120C prior to
entering the De-methaniser. Here , the overhead
methane is sent to Fuel Gas and the 85% pure
hydrogen sent to a Hydrogen Purification unit to
yield 99.5% pure hydrogen for hydrogenation in the
Converters.
The bottom of the De-methaniser is fed to the De-
ethaniser. The top product is C2 material, containing
ethene and acetylene, is routed to the Acetylene
Converter where the acetylene content is mildly
catalytically hydrogenated to ethene, ethane and
Green oil. The green oil is removed in the Green Oil
Absorber and the C2- / C2= mixture goes to the C2
Splitter ( 75m high ) from where the top ethene
product is sent to storage tank or as direct feed to
the Polyethylene Plant . The bottom ethane product
is recycled to the furnaces for cracking.
The De-ethaniser bottom is sent to the De-
propaniser to remove propene/propane mixture
from the top. This mixture is sent to the
Methylacetylene/Propadiene ( MAPD ) Converter
where these compounds are mildly catalytically

225
hydrogenated to propene and propane. The
Converter effluent is then sent to the C3 Splitter ( a
2-in-1, 70m high fractionator with180 trays ) which
separates propene as the top product which is sent
to tank and the bottom propane is also recycled to
the furnaces for cracking.
The bottom of the De-propaniser goes to the De-
butaniser to remove C4 material as the top product
which is sent to the C4 Hydrogenation Reactor to
convert Butenes/Butadiene to Butane which is
recycled to the furnaces for cracking.
The De-butaniser bottom is heated, filtered and de-
watered before being sent to a coalescer and then
to a C5 Hydrogenation Reactor to produce Craked
C5+ as the main product.

226
OLEFINS PLANT BLOCK FLOW DIAGRAM

227
POLYETHYLENE ( PE ) PROCESS SCHEME
The process description applies to EPCL PE Plant with a
capacity of 270,000MTPA of Polyethylene and
22,000MTPA of but-1-ene.
The feed is ethene / hydrogen mixture with cyclohexane
as a carrier solvent .
The Plant is divided into Areas :
1. Synthesis Area The Reactors, etc.
2. Finishing Area Extrusion, Pelletisation, etc.
3. Solvent Recovery Area.
Ethylene from tank and or from the Olefins Plant is
admitted into a surge drum afer which it is
compreessed to 43kg/sq.cm., cooled and sent to a
purifier/dryer to remove water and other impurities. The
dried and cooled gaseous monomer is combined with
dried liquid mixture of cyclohexane and but-1-ene
forming a liquid-gas mixture which is also cooled before
being sent to an Absorber with a packed internals where
ethene and cyclohexane are absorbed in an exothermic
process requiring heat removal. The combined feed is
pumped to 34kg/sqcm then to 170kg/sqcm before being
cooled to the Reactor inlet temperature of slightly over
100C.
Three Ractors are used depending on the polymer grade
to be produced :

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Stirred Autoclave Reactor called Reactor #1.
Trimmer Reactor ( similar to the Tubular reactor ) called
Reactor #2.
Pipe or Tubular Reactor called Reactor #3.
The reaction is fast at about 290C and 170kg/sqcm and
ethylene conversion of upto 95% is achieve and most of
the co-monomer is also converted.
Hydrogen is added at a pressure depending on the
grade to control the grade and act as chain terminator.
Catalyst used is Ziegler-Natta type, mainly Titanium
tetrachloride blended with co-catalysts ;
triethylalumnium, diethylaluminium chloride and
tetraisobutyl-aluminoxane.
The grade of PE to be produced determines the relative
amout of catalyst and co-catalysts to be used.
Catalyst and co-catalyst are ususally injected to Reactor
#1 and de-activators, Pelargonic acid and Acetylacetone
added afer reactor #2 to help terminate the reaction
and make for easy separation of unused catalyst system
from the polymer in an Absober that absorbs the
catalyst system.
Product separation occurs in two stages at the
Intermediate Pressure Separator ( IPS ) and Low Pressure
Separator ( LPS ) where most of the solvent carrier,
cyclohexane and other vapors are flashed off.
The polymer exiting the LPS is fed to the Extruder where
additives are added. The extruder pushes the polymer to

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a Die Plate with 180 holes. A Pelletiser with 18 knives cut
the polymer into small pellets as it emerges from the
Die plate. A water current transports the pellets to the
Delumper to remove over size pellets/resins then to a
Stripper to remove residual cyclohexane which is routed
to the Recovery area.
The resins are then conveyed to Spin dryers where the
resins are separated from water using a stream of hot
air.
The dried product is sent to Hold-up Bins, then to the
Blenders and finally to product Silos ready for bagging
and packaging.

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231
POLYPROPYLENE ( PP ) PROCESS SCHEME
The capacity of the PP Plant is 80,000MTPA and it is
easily expandable to 120,000MTPA. The plant can also
produce co-polymer with ethylene.
The key points are :
The reaction is in liquid phase in tubular Reactors.
The process is continuous with short residence time in
the reactors.
The catalyst is ( Ziegler-Natta ) Titanium tetrachloride
supported in Magnesium chloride for stereo-specificity.
Co-catalysts used are Triethyl aluminium and
cyclohexane dimethyl silane.
An anti-foulant is added downstream of the reactors to
reduce the tendency of liquid polymer fouling the
reactor by sticking on their hot walls.
Hydrogen is added to the system as a chain terminator
and as such determines the molecular weight
distribution and the strength of the polymer.
The feed to the plant propylene from the outside battery
limit ( OSBL ) at about 95% purity. It is further purified
to around 99% purity within the Plant. The impurities
removed are mainly carbon monoxide, mercaptans and
moisture.

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Catalyst combination determines the stereo-regularity of
the finished product.
There are three kinds of PP which are characterised by
the regularity of the Methyl groups along the
hydrocarbon chain.
PP product is steroeregular, that is, the methyl groups
are oriented to the backbone of the molecule in a
regular way:
In the Isotactic form they all lie on one side of the chain.
In the syndiotactic form they are on alternate sides.
Stereoregular polymers pack together more easily than
non-stereoregular ( atactic ) ones in which the methyl
groups haphazardly arranged on the chain. This accounts
for why stereoregular products are more crystalline and
more rigid.
The best product to make is one that is 95% isotactic
and 5% atactic. This makes for easy processing by the
end users.
Catalyst slurry is prepared by adding special mineral oil
and petrolatum in a stirred drum for homogenisation.
The sequence of procedure at start up is :
Propene addition.
Add co-catalysts, triethylaluminium and the silane, afer
1 hour.
Add hydrogen afer another 1 hour.
Add the catalyst afer yet another 1 hour.

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This sequence makes for stability and prevents run-away
reaction.
The reaction occurs in three reactors :
The first is the Pre-polymer reactor where reaction is
initiated and the catalyst encapsulated. The reaction is
exothermic is controlled at 20C and 32kg/sqcm with a
residence time of 4 minutes.
The other two reactors are operated at 70C and same
pressure for 1-5 hours each. Conversion of 65% is
achieved in the second reactor and the balance of 35%
in the third reactor.
The reactor effluent then goes to the Primary Flash line
and is then routed to the Cyclone or Dynamic Separator
which is operated at 18kg/sqcm where unreacted gases
are separated from the heavy polymer slurry.
The polymer from the bottom of the cyclone is fed to
the Bag filters at 1 kg/sqcm for further flashing and
removal of entrained fines.
The solid polymer then goes to the steamer to remove
residual gases and de-actvate the catalyst. Drying is by a
stream of hot nitrogen.
Antioxidants are added to the powdery polymer before
going to the Extruder then to the Pelletiser from where
the pellets are moved in a stream of demin water to the
dryer. The dried resins are moved to the Blender and
finally to the storage Silos ready for bagging and
packaging.

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POLYPROPYLENE PLANT SIMPLIFIED FLOW DIAGRAM

235
POLYPROPYLENE PLANT EXTRUSION UNIT
236
SUMMARY
PE and PP are produced using low
temperature and low pressure
processes in the presence of Ziegler-
Natta catalyst (a mixture of
Triethylaluminium, Et3Al, and
titanium tetrachloride, TiCl4)
Reactions are quite exothermic so
heat removal is vital and must be
carefuly controlled.

Reaction conditions can be adjusted
to produce LLDPE or HDPE.

LLDPE molecular weight is 10,000
40,000 with density of 0.92gm/cm3.

HDPE has a density of 0.97gm/cm3

In both cases in PE Plant, reactor
effluent is fed to series of flash
drums to remove solvent (usually
cyclohexane) and unreacted feed.
Water is then added to destroy
residual catalyst and the slurry
centrifuged, dried and pelletized.

HDPE is unbranched and crystalline
and has higher tensile strength,
greater rigidity and high sofening
point than LDPE.

It can also withstand boiling water
and not readily attacked by solvents.

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LPDE has greater transparency.
PP has high strength, low density, high
resilence in moulded parts, high sofening
point, excellent resistance to moisture
and stress cracking and good electrical
properties.
However, because of branching, it is very
liable to oxidation promoted by light, heat
or trace metals; hence its use with anti-
oidants and light (UV) stablizers.

USES OF POLYMERS
Blow Moulding - Bottles.
Inject Moulding - Buckets, Bowls, Dustbins etc.
Roto Moulding
Filaments and Fibres.
Pipes, Conduit etc.
Electrical Insulation Materials.
Films and Sheets.
Engineering Plastics ( used in place of metals).
Furniture (formica), Upholstery ( PVC ) and Foams /
Mattresses ( Polyurethanes ).
Vending Cups, Cartoons and Packagings.
Household Wares and Toys.

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Fridge, TV, Radio Casings.
Business Machines/Telephone/Computer Casings.
Combs, Brushes etc.
Light Fittings and Signs.
Shoe Heels and Soles.
Flower Pots and Other Consumer Durables.

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