What Goes On In An Oil

Refinery?
----REACTIONS - SEPARATIONS----

Crude Oil is fractionated to usable products
What shall we learn here?
Petroleum and natural gas are transported, stored near Refinery, then
What is the Purpose of an Oil Refinery?
What Goes In / Out of the Refinery?
How Do You Get from Crude Oil to Products?
Separations
Chemical Reactions cont...
here we shall learn - Cont.
How Do You Get from Crude Oil to
Products?
Separations
Chemical Reactions
Major Equipment
Minimizing Pollution
What do The Engineers Do?
Refer the following books also
1. Gary, J.H. and Handwerk, G.E Petroleum
Refining Technology and Economics, 4th
edition, Marcel Dekker Inc., New York, 2001.

1. Nelson, W.L. Petroleum Refinery
Engineering, 4th edition, McGraw-Hill, New
York, 1980.

1. Mayers, Robert A., editor Handbook of
Petroleum Refining Processes,2nd edition,
McGraw-Hill, New York, 1997, 3rd
edition,2003.

Overview
THE PURPOSE OF AN OIL REFINERY
IS TO TRANSFORM CRUDE OIL
INTO USEFUL PRODUCTS AS
EFFICIENTLY, PROFITABLY AND
ENVIRONMENTALLY SOUND A
WAY AS POSSIBLE
Overview - Cont.
The price and quality of crudes are variable. The
price and specifications of the products are to be
maintained. Government regulations add
constraints. There has to be a differential between
the price of crude and products; products are
essential in everyday life. Government subsidies
need to be kept to a minimum.
MY CUSTOMERS KEEP ME IN BUSINESS
How Do I Keep In Business ?
I need to design and erect the plants utilizing
logistics and use efficient technology.
I need to operate (control) the plant in the most
efficient manner possible.
Flow of feedstock to refinery, products to users
need to be done smoothly.
I need to keep the equipment running all the time.
I NEED PLANNERS, ENGINEERS!
OK, But...

WHAT GOES ON IN AN OIL
REFINERY?
Very Simplified
Petroleum and
Petrochemical
Flowchart
Oil
Well
Crude
Oil
Separations
C
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n
v
e
r
s
i
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n
s
S
e
p
a
r
a
t
i
o
n
s
a
n
d
P
u
r
i
f
i
c
a
t
i
o
n
s
Natural
Gas
Propane &
Butane
Naphtha
(C
5
- C
10
)
Gas Stove
Fuel
Gasoline
Jet Fuel
Fuel
R
X
Ethylene Polyethylene (Glad Bags)
R
X
R
X
Polymers (7 UP Bottles)
(Barbeque Grills)
R
X
R
X
Organic Chemicals
More Polymers
(Aspirin, Hair Spray)
(Football Helmet, Astro
Turf, Nylon)
Home Heating
Oil, Lubricating
Oil, Wax
Diesel Fuels
Kerosene &
Gas Oils (C
10
+)
Coke
(Carbon Material Similar to Coal)
Steel Making
Asphalt
Roads Pot Holes
Purifications remove sulfur and heavy metals
R
X
= Chemical Reactions
Graphite Fibers
(Tennis Racquets)
THE REFI NERY
Petroleum refining begins with: crude oil distillation,
followed by subsequent processing such as chemical
treating, catalytic reforming, hydrotreating,
hydrocracking, fluid catalytic cracking and thermal
cracking to produce a wide variety of petroleum
products.
The capacity of the refinery is typically defined by the
total capacity of atmospheric distillation units operating
in the refinery.

Fuels (motor gasoline, diesel and distillate
fuel oil, liquefied petroleum gas, jet fuel,
residual fuel oil, kerosene and coke)
Finished nonfuel products (solvents,
lubricating oils, greases, petroleum wax,
petroleum jelly, asphalt, and coke)
Chemical industry feed stocks (naphtha,
ethane, propane, butane, ethylene,
propylene, butylenes, butadiene, benzene,
toluene, and xylene).


The products of the refinery fall into three categories:
No two refineries are identical
Once the refinery is constructed switching to another type
of crude or change of the product distribution (because of
product demand pattern changes or specification
changes or environmental and health regulations) will be
difficult.
Refinery equipment are expensive and long life hence
not easy to replace or modify.
What Is Crude Oil?
Crude Oil is a liquid mixture of many
organic chemicals found underground. It is
the result of organic matter decaying over
thousands of years; hence the name fossil
fuel
Crude oil is found all over the world and
varies tremendously in its density,
aromatics, sulfur, and metals content
Major Refinery Products
LPG (Propane/Butane)
GASOLINE (hundreds of blends)
JET FUELS
DIESEL FUELS
LUBRICATING OILS AND GREASES
ASPHALTS
COKE (not the kind you drink )
FEED STOCK FOR CHEMICAL FERTILIZER
MANUFACTURE
FUEL FOR THERMAL POWER PLANTS
Gasoline Specifications
Gasoline (Petrol) must meet many criteria which
change with the time of year and geographic
location. Some critical specifications are:
Vapor Pressure
Octane
Aromatics / Benzene Content
Sulfur Content
Gasoline is always a blend of a number of streams in
the refinery
Other Specifications
Other refinery products must meet other
specifications such as:
Cetane number
Density
Pour Point
Flash Point
Viscosity
So, How Do You Make Good
Stuff Out Of That Gooey Crude?
So, How Do You Make Good
Stuff Out Of That Crude?
So, How Do You Make Good Stuff
Out Of That Crude?
THERMAL, CATALYTIC
REACTIONS
&
PHSICAL SEPARATIONS
Separation based on molecular size and
boiling point

Changing the molecular size of components

Changing the molecular shape of components

Removal of contaminants
Processing options
So, How Do You Make Good Stuff Out Of
That Crude?
Separate crude into light, middle and heavy
fractions
Convert low octane components to higher octane
components of petrol.
Blend intermediate streams together to meet
product specifications
Convert the very heavy stuff to heavy oils
Convert heavy oils, recover petrol, diesel, jet fuel
Remove sulfur/nitrogen through reaction
SEPARATIONS
SEPARATIONS -
CRUDE FRACTIONATION
HUGE DISTILLATION COLUMNS
ATMOSPHERIC DISTILLATION
VACUUM DISTILLATION
TYPICAL SIZE: 150,000 BARRELS/DAY
750 DEGREES F
OTHER SEPARATIONS
FLASH
DISTILLATION
ABSORPTION
ADSORPTION
LIQUID-LIQUID EXTRACTION
REACTIONS
REACTIONS
Almost all the reactions in the refinery use
special catalysts that increase the rate and
selectivity of the reaction. This improves
efficiency and reduces unwanted
byproducts.
Reactions to Make Higher Octane
ISOMERIZATION
C-C-C-C-C-C --> C C
nC6 C-C-C-C iC6
REFORMING
C-C-C-C-C-C-C --> C
nC7 C C-CH3
C C toluene
C

Reactions To Make Higher Octane
ALKYLATION

C C
C=C-C + C-C-C --> C-C-C-C-C
C
propylene isobutane isoheptane (2,2,dmp)
Reactions To Convert Heavy Oils
HYDROCRACKING
H2 + heavy oil --> gasoline + diesel
550 F 300 F 450 F
use boiling point to describe oils
CAT CRACKING
heavy oil --> gasoline + propylene, butane,
other light ends
550 F 300 F


Reactions To Convert Residue
Residue is the bottom of the barrel - the
material that is left in the bottom of the
crude/vacuum distillation towers

COKING
residue + heat --> coke + heavy oil
> 900 F solid 550 F
Reactions To Remove Sulfur
HYDRODESULFURIZATION
2 R-SH + H2 --> 2 R + 2 H2S
mercaptan hydrocarbon

SULFUR RECOVERY
convert H2S to elemental sulfur:
2 H2S + 2 O2 --> SO2 + S + 2 H2O
2 H2S + SO2 --> 3S + 2 H2O


MAJOR REFINERY EQUIPMENT
Vessels-Reactors, Separators, Storage Tanks
Pumps & Compressors
Furnaces
Heat Exchangers
Instruments (measure flow, temperature,
pressure, composition)
Control Systems
MINIMIZING POLLUTION
Operate Furnaces Efficiently
Waste Material Goes To The Flare Stack
Avoid Spills & Accidental Releases
Special Treatment of Sewer Water
Lots of Paper Work!

Crude oils may contain trace amounts of
metals such as nickel and vanadium, as well
as salts.
Most of the nonhydrogen, non-carbon
elements found in crude oils are undesirable
and are removed from the hydrocarbons in
total or in part during refinery processing.
WHAT ARE THE STUFF REMOVED FROM
THE CRUDE?
Sulfur
converted to elemental sulfur
in high sulfur fuel oil
in coke
Heavy Metals (nickel, vanadium)
in high sulfur fuel oil and coke
Nitrogen (organic nitrogen)
most is converted to ammonia and neutralized
in high sulfur fuel oil and coke
ENGINEERS PLAY AN IMPORTANT
ROLE IN THE REFINERY
What Roles Do Engineers Play?
Operations Engineer
Maintenance Engineer
Control Systems Engineer
Design Engineer
Health/Safety/Environmental Engineer
Planning / Scheduling Engineer
Reliability Engineer
Plant Manager
Other Ways Chemical Engineers
Support The Refining Industry
Research & Development Engineers
Technical Sales Engineers
Engineering & Construction Engineers
Governmental Regulators (EPA)
University Professors
Other Engineering Disciplines In
The Refinery
Mechanical Engineers - design &
maintenance of compressors, vessels
Electrical Engineers - electrical,
instrumentation, controls
Computer Scientists - main plant control &
information systems
Summary
Refineries are well designed chemical
processing plants that use reactions and
separations to convert crude oil into
gasoline and other valuable products
Chemical engineers play a role in keeping
these plants running safely and efficiently