PETROLEUM INDUSTRY

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PETROLEUM
• commonly called crude oil
• also
refers to natural gas and the viscous or solid form known as
bitumen, which is found in tar sands.
• “rock oil” from the Latin petra, “rock” or “stone,” and oleum, “oil”)

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Chemical Constitution of Crude Oil

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 CRUDE OIL

HYDROCARBONS NON-HYDROCARBONS

ALIPHATICS AROMATICS NAPHTHENES SULFURS NITROGENS OXYGENS METALLICS

25% 17% 50% <8% <1% <3% <100PPM

C1 - C60 (C6H5)n O
CYCLOALKANES
SH

N
H COOH
S

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How important is Petroleum?
• largest fraction of primary energy
supply in the world
• transportation of people and
goods
• materialsthat are necessary for
operating combustion engines
• refineries
supply feedstock to the
petrochemicals and chemical
industry

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PETROLEUM INDUSTRY

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In the Philippines…
Active petroleum-producing fields in
the Philippines:
• Malampaya (gas and condensate)
and Galoc (oil) off shore north-west
Palawan
• Alegria (oil) onshore Cebu

Map of the Philippines showing active Petroleum Service Contract

areas in red. © Philippines Department of Energy.
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In the Philippines…
• The Philippines had a crude oil
refining capacity of 276,000 b/d at
the end of 2019.

• Pilipinas Shell Petroleum

Corporation, a subsidiary of Shell,
and Petron Corporation operate a
refinery in the Municipalities of
Tabango and Limay, respectively.
Petron Bataan refinery in Limay Bataan is the
largest refinery in the Philippines with a production
capacity of 180,000 barrels per day (bpd).
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• Shell temporarily shut its
Tabango refinery in May 2020.
• InAugust 2020, Shell announced
to permanently close the refinery
and convert the site into an
import terminal.
• The closure left the Bataan
Refinery of Petron as the sole
operating oil refinery in the
Philippines The Tabangao Refinery is an oil refinery in
Batangas with a production capacity to
process 110,000 barrels per day.
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PETROLEUM REFINING PROCESS

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OVERALL REFINERY
FLOW

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Desalting and Distillation

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DESALTING
• Crude oil pre treatment
• removes salt, water and solid particles

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DISTILLATION
Aims to separate this crude
oil into its component
hydrocarbons, or "fractions.“
Distillation of crude oil is
carried out in two units
1. ATMOSPHERIC
DISTILLATION UNIT
2. VACUUM DISTILLATION
UNIT

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Light Ends Unit

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Recall
Naphtha - any of various volatile, highly
flammable liquid hydrocarbon mixtures
used chiefly as solvents and diluents and as
raw materials for conversion to gasoline
containing principally aliphatic
hydrocarbons and boiling lower than
kerosene.

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Catalytic Reforming
• Heavy naphtha enter the
hydrotreater.
• From there it goes to the catalytic
reformer where Pt is used as a
catalyst
• turn cycloparaffins into aromatics
+ H2 and n-alkanes into i-alkanes.
• H2 goes back into the hydrotreater
and is removed as H2S.
• Products from the catalytic
reformer are called reformate and
are added to the gasoline pool.
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Octane Number
• also called Antiknock Rating
• measure of the ability of a fuel to resist knocking when ignited in a mixture with
air in the cylinder of an internal-combustion engine.
Knocking - spontaneous combustion; when gas ignites by compression rather
than because of the spark from the spark plug
• The octane number is determined by comparing, under standard conditions, the
knock intensity of the fuel with that of blends of two reference fuels: iso-octane,
which resists knocking, and heptane, which knocks readily.
• The octane number is the percentage by volume of iso-octane in the iso-octane–
heptane mixture that matches the fuel being tested in a standard test engine.

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 Reactions in Catalytic Reforming
1. dehydrogenation

2. isomerization

3. dehydrocyclization

All of these reactions significantly increase the octane number 21

Conversion of Heavy Gas Oil
Generic conversion processes for the heavy distillates C20 to C25

• aimed at reducing the

molecular size or the boiling
point of gas oil compounds,
involves
• thermal cracking
• visbreaking
• coking
• catalytic cracking
• hydrocracking
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Thermal Cracking
• high temperatures (450°C to 750°C) and
pressures (about 70 atm) are used to
break the large hydrocarbons into
smaller ones
• free radicals are formed
• mixturesof products containing high
proportions of hydrocarbons with
double bonds - alkenes

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Catalytic Cracking
• The concept of catalytic cracking is basically the same as thermal
cracking, but it differs by the use of a catalyst
• Produces shorter, but branched-chain alkanes by cracking the long
straight-chain alkanes. The formation of branched-chain alkanes, or
iso-alkanes, leads to the production of gasoline with high octane
numbers.

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 Conversion and Processing of Vacuum Gas
Oils
• A hydrocracking unit takes gas
oil, and cracks the heavy
molecules into distillate and
gasoline in the presence of
hydrogen and a catalyst.
• Hydrocracking provides high
yields of valuable distillates
without producing low-grade
byproducts (e.g., heavy oils,
gas, or coke)

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Conversion and Processing of Vacuum Gas
Oils
• The Heavy vacuum gas oil goes
into solvent extraction with
furfural which extracts the
heavy aromatics.
• Then the products go into
dewaxing which separates out
long-chain paraffins (wax). That
yields lube oil base stock which
becomes lubrication oils.

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 Processing and Conversion of Vacuum Distillation Residue

The heaviest and the most contaminated component of crude oil is the vacuum
distillation residue (VDR), also referred to as the bottom-of-the-barrel. There are
multiple processing paths to upgrade VDR into usable products. One process is
called deasphalting, which removes the heaviest fraction of VDR as asphalt that is
used mainly to pave roadways. The lighter fraction obtained in the deasphalting
process, deasphalted oil (DAO), can be used as fuel oil after hydrotreatment

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 Processing and Conversion of Vacuum
Distillation Residue
Visbreaking - mild thermal cracking process
applied to reduce the viscosity of VDR to
produce fuel oil and some light products to
increase the distillate yield in a refinery.

Coking - the most severe thermal process used

in the refinery to treat the very bottom-of-the-
barrel of crude oil. Maximizes the yield of
distillate products in a refinery by rejecting
large quantities of carbon in the residue as solid
coke or petroleum coke.

It is a fuel used for coke

furnaces
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OTHER CONVERSION
PROCESSES

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Alkylation
• The alkylation process combines light iso-paraffins, most commonly
isobutane, with C3–C4 olefins, to produce a mixture of higher molecular
weight iso-paraffins (i.e., alkylate) as a high-octane number blending
component for the gasoline pool.

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Polymerization
• Thepolymerization process combines propenes and butenes to
produce higher olefins with high-octane numbers for the
gasoline pool.
• Thelinking of similar molecules; the joining together of light
molecules.

Typical polymerization reactions 32

OTHER PROCESSES

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Product Blending
• Theobjective of product blending is to assign all available blend
components to satisfy the product demand and specifications to
minimize cost and maximize overall profit

For example, typical motor gasolines may consist of straight-run

naphtha from distillation, reformate, alkylate, isomerate, and
polymerate, in proportions to make the desired grades of gasoline
and the specifications.

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Sulfur Recovery
Objective: to convert H2S to elemental S

First stage: Modified Clause Process

-partial combustion of H2S
-primary S recovery
-works for acid gas with >50% H2S

Second Stage: SCOT Process – Claus tail gas clean-up

-removes COS and CS2 produced by side reactions in the Clause Process
-reduces COS and CS2 to H2S
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Modified Claus Process

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SCOT Process

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ENVIRONMENTAL IMPACTS OF THE OIL INDUSTRY
• Water contamination due to effluents
• rich in inorganic salts without appropriate treatment
• wash water and cooling water discharges, and
• seepage from storage and waste tanks

• Water contamination due to oil spills

• Particulate emissions into the atmosphere generated during operations
• Sulfur and nitrogen oxides, ammonia, acid mist and fluorine compounds gas
emissions from production and refining plants operations
• Noise pollution caused by equipment and operations that generate loud noise.

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