✔ In the crude state, petroleum has minimal value, but when refined, it provides

high-value liquid fuels, solvents, lubricants, and many other products

✔ The fuels derived from petroleum contribute approximately one-third to one-half of
the total world energy supply and are used not only for transportation fuels (i.e.,
gasoline, diesel fuel, and aviation fuel, among others) but also to heat buildings.
✔ Petroleum products have a wide variety of uses that vary from gaseous and liquid fuels
to near-solid machinery lubricants.
 Petroleum refining is the separation of petroleum into fractions and
the subsequent treating of these fractions to yield marketable products.

As the basic elements of crude oil, hydrogen and carbon form the main input
into a refinery, combining into thousands of individual constituents, and the
economic recovery of these constituents varies with the individual petroleum
according to its particular individual qualities and the processing facilities of a
particular refinery.
 Three Categories of
Petroleum Products
In general, crude oil, once refined, yields three basic groupings of products that are
produced when it is broken down into cuts or fractions
● Naphtha, a precursor to gasoline and solvents, is produced from the
light and middle range of distillate cuts (sometimes referred to
collectively as light gas oil) and is also used as a feedstock for the
petrochemical industry.
• The middle distillates- products from
the middle boiling range of petroleum
and include kerosene, diesel fuel,
distillate fuel oil, and light gas oil. Waxy
distillate and lower-boiling lubricating
oils are sometimes included in the
middle distillates.
• The remainder of the crude oil includes
the higher-boiling lubricating oils, gas
oil, and residuum
 Refinery Process Categories
To convert crude oil into desired products in an economically feasible and environmentally acceptable manner, refinery
processes for crude oil are generally divided into three categories:
Separation Processes
Conversion Processes
Finishing Processes
Refinery Configurations
Topping Refinery
● Simplest refinery configuration
● Produce large quantities of unfinished oils
● Half of their output are residual fuel oils
 Conversion
Refinery
● most versatile refinery configuration
● produce two-thirds of their output as gasoline
● also produces high-quality jet fuel, liquefied
petroleum gas (LPG), diesel fuel, and a small
quantity of petroleum coke
Dewatering and
Desalting
● first step in petroleum
processing
● the goal is to remove water
and the constituents of the
brine that accompany the
crude oil from the
reservoir to the wellhead
during recovery
operations.
● fluids from the well are
separated into crude oil,
natural gas, and water
phases using a gas–oil
separator
Categories of general
refinery processes and
associated operations
 2. Petroleum 3.Petroleum treating
1. Separation processes conversion processes processes

a. Atmospheric distillation a.Cracking (thermal and a. Hydrodesulfurization

b. Vacuum distillation
c. Light ends recovery
catalytic) b. Hydrotreating
b. Reforming
c. Chemical sweetening
c. Alkylation
d. Acid gas removal
d. Polymerization
e. Deasphalting
e. Isomerization
f. Coking
g. Visbreaking
4. Feedstock and
product handling 5. Auxiliary facilities

a. Boilers
a. Storage b. Waste water treatment
b. Blending c. Hydrogen production
c. Loading d. Sulfur recovery plant
d. Unloading e. Cooling towers
f. Blowdown system
g. Compressor engines
Separation Process
Atmospheric distillation
● first and most fundamental step in the the refining
process
● primary purpose of the atmospheric distillation
tower is to separate crude oil into its components
● Products from CDU:

gas + naphtha, kerosene, light gas oil, heavy

gas oil and atmospheric residue.

● heavy hydrocarbon residue left at the bottom of

the atmospheric distillation column is sent to
vacuum distillation column
Vacuum distillation
● at reduced operating pressures
● 50 to 100 mm of mercury absolute
● primary advantage is that it allows for distilling
heavier materials at lower temperatures
● Reduced pressures decrease the boiling point of
compounds
● Products from VDU:

LVGO, HVGO and vacuum residue

https://www.youtube.com/watch?v=-0CwOvo3aKs
Conversion Process
Thermal Cracking
● involves a chemical cracking process followed
by the separation using physical principles
(boiling point differences)
● Products:

naphtha + gas, gasoil and thermal cracked

residue.

● https://www.youtube.com/watch?v=Xsqlv4rWnE
g&t=108s
● https://www.youtube.com/watch?v=Ujtg5TbBAz8
Catalytic Cracking
● breakdown of large compounds into small
hydrocarbons using an acid catalyst
● the operating of the processing unit is much easier
than that of thermal cracking due to less
temperature and pressure requirement
● Zeolite is used as catalyst
Catalytic Cracking
Hydrocraking
● heavier molecules react with hydrogen to
generate lighter hydrocarbons.
● Cycle oils and coker distillates are the typical
feedstocks
● High quality jet fuel and diesel production is
targeted
● Overall reaction is exothermic
● Cracking is promoted on silica-alumina sites
of the catalyst.
● Hydrogenation promoted by palladium,
molybdenum sulphide or tungsten sulphide
compounds
Reformer
● Heavy naphtha which does not have high
octane number is subjected to reforming
● Product: reformate product (with high octane
number)
● a combination of chemical and physical
processes
● converts (reforms) gasoline into higher-octane
gasoline
● same as for thermal cracking, but higher
temperatures are used
● https://www.youtube.com/watch?v=FQ0ImB6e
ozY
Types of Reforming Process
https://www.youtube.com/watch?v=FQ0ImB6eozY
 ● end-point naphtha or a straight-run
gasoline is heated to 510°C–595°C
(950°F–1100°F) in a furnace
● products of thermal reforming are
Thermal Reforming gases, gasoline, and residual oil or
tar
● higher the reforming temperature,
the higher the octane number, but
the lower the yield of reformate
 ● converts low-octane gasoline into
high-octane gasoline (reformate).
● catalytic reforming produces
Catalytic reformate with octane numbers on
the order of 90–95.
Reforming ● conducted in the presence of
hydrogen over hydrogenation–
dehydrogenation catalysts, which
may be supported on alumina or
silica–alumina.
 ● molybdena–alumina,
● chromia–alumina
Catalyst ● platinum on a silica–alumina or
alumina base
Isomerization
● upgrades the octane number of light naphtha
fractions and also simultaneously reduces benzene
content
● complements catalytic reforming process by
upgrading the octane number of refinery naphtha
streams
● is a simple and cost-effective process for octane
enhancement
● . Isomerate product contains very low sulfur and
benzene.
 metal catalyst- high-temperature
processes; aluminum chloride plus
Catalysts hydrogen chloride- low-temperature
processes.
Alkylation
● used to produce a high octane gasoline blending
stock from the isobutane formed primarily
during catalytic cracking and coking operations
● joins an olefin and an isoparaffin compound
using either a sulfuric acid or hydrofluoric acid
catalyst
● joins an olefin and an isoparaffin compound
using either a sulfuric acid or hydrofluoric acid
catalyst
Polymerization
● occasionally used to convert propene and
butene to high octane gasoline blending
components
● similar to alkylation in its feed and products,
but is often used as a less expensive alternative
to alkylation
● similar to alkylation in its feed and products,
but is often used as a less expensive alternative
to alkylation
● feed must be free of sulfur, which poisons the
catalyst
 Phosphates, liquid phosphoric acid,
phosphoric acid on kieselguhr, copper
Catalysts pyrophosphate pellets, and phosphoric
acid film on quartz
Visbreaking (viscosity breaking)
● convert about 15 percent of the feedstock
to naphtha and diesel oils and produce a
lower-viscosity residual fuel
● non-catalytic thermal process that converts
atmospheric or vacuum residues
● Products: Naphtha, Gasoil and a residue
Coking
● used primarily to reduce refinery production
of low-value residual fuel oils to gasoline and
diesel and coke.
● severe thermal cracking
● residue feed is heated to about 475 to 520 °C
(890 to 970 °F) in a furnace with very low
residence time
Types of Coking
 Delayed Coking
a semi-batch cyclic process that thermally
cracks a variety of residual oil feeds into
light gases, naphtha, diesel, heavy gas oil and
petroleum coke
 Fluid Coking
● continuous process that uses the
fluidized-solid technique
● greater quantities of more valuable
liquid product are recovered
Treating Process
Treating Processes
● stabilize and upgrade petroleum products by removing undesirable elements such
as:
● sulfur compounds are technically undesirable. In motor and aviation gasoline they
reduce the effectiveness of antiknock additives and interfere with the operation of
exhaust-treatment systems. In diesel fuel they cause engine corrosion and
complicate exhaust-treatment systems.
● nitrogen compounds, poison catalyst systems
● oxygenated compounds, can lead to colour formation and product instability.
Hydrodesulfurization
● catalytic chemical process (catalytic
hydrogenation) used to remove sulfur
compounds from refined petroleum products
with the sulfur compounds being converted to
hydrogen sulfide
● HDS feedstocks: naphtha, kerosene, diesel oil
and heavier oils
● hydrogen sulfide gas is then subsequently
converted into byproduct elemental sulfur or
sulfuric acid.
Hydrotreating
● carried out by charging the feed to the reactor,
together with hydrogen in the presence of catalysts
● it is more economical to hydrotreat high-sulfur
feedstocks prior to
● catalytic cracking than to hydrotreat the products
from catalytic cracking. The advantages are that
● (1) sulfur is removed from the catalytic cracking
feedstock, and corrosion is reduced in the cracking
unit;
● (2) carbon formation during cracking is reduced so
that higher conversions result; and
● (3) the cracking quality of the gas oil fraction is
improved
 ● tungsten–nickel sulfide
● cobalt–molybdenum
● alumina, nickel
Catalysts ●
●
oxide–silica–alumina
platinum–alumina.
 ● cobalt-modified molybdenum
disulfide together with smaller
Catalysts amounts of other metals.
● nickel and tungsten are also used,
depending on the nature of the feed
Hydrotreating
● reaction of organic compounds in the presence of
high pressure hydrogen to remove oxygen
(deoxygenation) along with other heteroatoms
(nitrogen, sulfur, and chlorine)
● removal of impurities such as sulfur and nitrogen
from distillate fuels—naphtha, kerosene, and
diesel—by treating the feed with hydrogen at
elevated temperature and pressure in the presence
of a catalyst.
● The feed types considered here are: Naphtha,
Kerosene, Gas oils, Atmospheric resids or reduced
crudes
● principal impurities to be removed are: Sulfur,
Nitrogen, Oxygen, Olefins, Metals
Chemical Sweetening
● treats sulfur compounds (hydrogen sulfide, thiophene
and mercaptan) to improve color, odor, and oxidation
stability. Sweetening also reduces concentrations of
carbon dioxide.
● accomplished by either extraction or oxidation (also
known as sweetening), depending upon the product.
● Extraction is used to remove sulfur from the very
light petroleum fractions, such as propane/propylene
(PP) and butane/butylene (BB).
● Sweetening, though, is more effective on
gasoline and middle distillate products.
 Merox Extraction
● an acronym for mercaptan oxidation
● used to remove mercaptans (organic sulfur
compounds) from PP and BB streams
● PP streams may undergo amine treating
before the Merox extraction to remove
excess H2S which tends to fractionate with
PP and interferes with the Merox process
● caustic prewash of the PP and BB removes
any remaining trace H2S prior to Merox
extraction
Acid Gas Removal
● Sour gas separated in the Gas Processing unit is sent to the Amine Unit for acid gas removal
using chemical solvents such as monoethanolamine (MEA), or diethanolamine (DEA)
● he sour gas is pumped from the bottom of an absorption column to get in contact with the basic
solution (typically 15-30wt% diethanolamine) to capture H2S (and other acidic gases such as
CO2) in the solution
Feedstock and Product
Handling
Feedstock and Product Handling

● consist of unloading, storage,

blending, and loading activities.
Auxiliary Facilities
Auxiliary Facilities

● wide assortment of processes and

equipment not directly involved in the
refining of crude oil is used in
functions vital to the operation of the
refinery

● products from auxiliary facilities

(clean water, steam, and process heat)
are required by most process units
throughout the refinery
Refinery Products
Gases
1. hydrogen- consumed in refinery
desulfurization
2. fuel gas- has a heating value similar to
natural gas and is consumed in plant
operations
3. ethane- may be recovered from the
refinery fuel system for use as a
petrochemical feedstock
4. propane and butane- convenient portable
fuel for domestic heating and cooking or
for light industrial use.
Gasoline
● a product of petroleum refining that varies in
composition and often includes additives such
as antiknock agents, antioxidants, lubricants,
and detergents.
● contains several other additives including
ethanol, methanol, formaldehyde, xylene,
1,3-butadiene, methyl tert-butyl ether (MTBE),
and hexane.
● also used as a diluent in paints, as a finishing
agent, and as an industrial solvent
Octane rating
● the measure of a fuel's ability to resist
"knocking" or "pinging" during combustion.
● Severe knocking can dissipate power output
and even cause damage to the engine
● https://www.youtube.com/watch?v=I8M1bKvi
6_c
Kerosene
● a medium weight distillate in the refining
process, and can be produced by distilling
crude oil (here it is known as straight run
kerosene) or by hydrocarbon cracking heavier
petroleum (here it is known as cracked
kerosene)
● a major component of aviation fuel, making up
more than 60% of the fuel.
Jet Fuel
● a type of aviation fuel designed for use in
aircraft powered by gas-turbine engines.
● It is clear to straw-colored in appearance.
Diesel
● for powering automobile, truck, bus, and
railway engines.
● any liquid fuel specifically designed for use in
diesel engines
● portion of the crude oil that distills out within
the temperature range of approximately 200 ºC
to 370 ºC
● may contain small amounts of hydrocarbon or
non-hydrocarbon additives to improve diesel
fuel performance
Fuel oils
● consists largely of residues from crude oil
refining.
● blended with other suitable gas oil fractions in
order to achieve the viscosity required for
convenient handling
● sulfur levels are naturally high because the
sulfur contained in the crude oil is concentrated
in the residue material.
● may contain large quantities of heavy metals
such as nickel and vanadium
Republic Act No. The minimum biodiesel blends under
the law are set at 10 percent for
9367 bioethanol (E10) and two percent for
biodiesel (B2).
Biofuels Act of 2006