DOWNSTREAM

OUTLINE

 Refining
 Petrochemical
 Supply chain, distribution, retailing, and products.
 DOWNSTREAM

downstream activities through operations:

 in refining, trading and marketing of crude oil and petroleum
products,
 manufacturing and marketing of petrochemical products, gas
processing and transportation, regasification, utilities
marketing, power generation
 the provision of technical and engineering solutions
 DOWNSTREAM – IN MALAYSIA

Refining and Trading

 DOWNSTREAM – IN MALAYSIA

Retail and Lubricants

 DOWNSTREAM – IN MALAYSIA

Petrochemicals
 DOWNSTREAM – IN MALAYSIA

Petrochemicals
 DOWNSTREAM – IN MALAYSIA

Petrochemicals
 DOWNSTREAM – IN MALAYSIA
Gas and Infra
 REFINING

 Refining aims to provide a defined range of products

according to agreed specifications.

 A refinery is a production facility composed of a group of

chemical engineering unit processes and unit operations
refining certain materials or converting raw material into
products of value.
 REFINING

 Simple refineries use a distillation column to separate crude

into fractions, and the relative quantities are directly
dependent on the crude used.

 Refineries in the United States produced an average of about

12 gallons of diesel fuel and 19 gallons of gasoline from one
barrel (42 gallons) of crude oil in 2014. Many other petroleum
products are also refined from crude oil.

 Therefore, it is necessary to obtain a range of crudes that can

be blended to a suitable feedstock to produce the required
quantity and quality of end products
 REFINING

 The economic success of a modern refinery depends on its

ability to accept almost any available crude. A refinery that is
able to handle multiple types from heavy to light crude is said
to have to have a large swing. Trade specifications such as
”West Texas Intermediate” (W TI) API 38.3 °, “Brent Blend” API
38.3°, “Heavy Arab Crude” API 27.7 ° or “Grane” API 18.7° are
examples of such crudes.

 Medium light crudes can be used directly in early engines and

burners. Modern consumers, such as gas and diesel engines,
aviation turbojet engines and ship bunkers need fuels
manufactured to precise specifications . This includes
removing contaminants and pollutants, such as sulfur.
 REFINING

 With a variety of processes such as cracking, reforming,

additives and blending, it can provide product in quantity and
quality to meet market demand at premium prices.
 The refinery operations often include product distribution
terminals for dispensing product to bulk customers such as
airports, gasoline stations, ports and industries.
 REFINING - FRACTIONAL DISTILLATION

 The basic refinery uses fractional distillation. Incoming crude

is heated to its boiling point. It then enters the distillation
column, which separates the dif ferent fractions. The column
is of the reflux type, where colder condensed fluids running
down are reheated by rising vapors that in turn condense. This
produces clear thermal zones where the dif ferent products
can be drained.

 The fractions are a mix of alkanes and aromatics and other

hydrocarbons, each fraction contains a distribution of carbon
numbers and hydrocarbons.
Fractional Distillation
 REFINING - FRACTIONAL DISTILLATION

 Naphtha, or full range naphtha, is the fraction with boiling points

between 30 °C and 200 °C and molecules generally having carbon
numbers 5 to 1 2. The fraction is typically 15–30% of crude oil by
weight. It is used mainly as a feedstock for other processes:
• In the refinery for producing additives for high octane gasoline
• A diluent for transporting very heavy crude
• Feedstock to the petrochemical olefins chain
Feedstock for many other chemicals. As a solvent in cleaning etc.

 Gasoline has carbon numbers mainly between 4 and 1 2 and boiling

points up to 1 20 °C. Its main use is as fuel for internal combustion
engines. Early on, this fraction could be sold directly as gasoline for
car s, but today’s engines require more precisely formulated fuel, so
less than 20% of gasoline at the pump is the raw gasolin e fraction.
Additional sources are needed to meet the demand, and additives are
required to control such parameters as octane rating and volatility.
Also, other sources such as bioethanol may be added, up to about 5%.
 REFINING - FRACTIONAL DISTILLATION

 Kerosene has main carbon numbers 10 to 16 (range 6 to 16)

boiling between 150 °C and 275 °C. Its main use is as
aviation fuel, where the best known blend is Jet A -1 . Kerosene
is also used for lighting (paraf fin lamps)and heating.

 Diesel oil, or petrodiesel, is used for diesel engines in cars,

trucks, ships, trains and utility machinery. It has a carbon
number range of 8 to 21 (mainly 16-20) and is the fraction
that boils between 200 °C and 350 °C.
 REFINING - FRACTIONAL DISTILLATION

 White and black oils: The above products are often called
white oils, and the fractions are generally available from the
atmospheric distillation column . The remaining fraction below
are the black oils, which must be further separated by vacuum
distillation due to the temperature restriction of heating raw
crude to no more than 370-380°C. This allows the lighter
fractions to boil of f at a lower temperatures than with
atmospheric distillation, avoiding overheating.

 Lubricating oils, or mineral base lubricating oil (as opposed to

synthetic lubricants), form the basis for lubricating waxes and
polishes. These typically contain 90% raw material with
carbon numbers from 20 to 50 and a fraction boiling at 300-
600 °C. 10% additives are used to control lubricant
properties, such as viscosity.
 REFINING - FRACTIONAL DISTILLATION

 Fuel oils is a common term encompassing a wide range of

fuels that also includes forms of kerosene and diesel, as well
as the heavy fuel oil and bunker that is produced at the low
end of the column before bitumen and coke residues
 REFINING - FRACTIONAL DISTILLATION

 Bitumen and other residues like coke and tar has carbon
numbers above 70 and boiling points above 525 °C. Low
sulfur coke can be used for anodes in the metals industry
(aluminum and steel) after processing (calcining). The
remainder is a problem fuel, because of high sulfur content
and even higher CO2 emissions than coal (typically 15%
higher). Bitumen in the form of asphalt boiling above 525 °C
is used for roofing and road paving. Asphalt concrete
pavement material is commonly composed of 5%
asphalt/bitumen and 95% stone, sand, and gravel
(aggregates).
 REFINING - CRACKING

 Self-reading!
REFINING - UPGRADING AND ADVANCED
PROCESSES
 The Refinery make up dif fers from an upstream plant, in that
the overall site is divided up in to process types or 'units'.

 The following figure gives a more detailed process flow

diagram of an actual modern refinery. It shows the extent of
treatment that takes place after initial fractional distillation ,
to improve fuel yield and functional properties, and an
explanation of why modern gasoline at the pump contains less
than 20% raw gasoline straight from the column. Additional
processes may also be included, e.g., for crude pre -treatment
to be able to source lower quality crudes with less processing
at the production site.
Typical PFD of a modern refinery
REFINING - UPGRADING AND ADVANCED
PROCESSES
 Most of these reactions take place at elevated temperature and
pressure over a catalyst such as platinum or rhenium or
sometimes iron, and need precise control for optimal throughput.
A few process flow diagrams have been included to give an
indication of the complexity of these processes compared to the
relative simplicity of many upstream processes.

 Atmospheric distillation is the fractional distillation unit already

described. In actual designs, it is combined with vacuum
distillation. Raw crude cannot be heated to more than
370-380 °C. It is often called the Crude Oil Distillation Unit
(CDU)

 Vacuum distillation unit (VDU) further distills the black oils into
fuel oils and residual bitumen and coke to avoid overheating the
crude and to extract additional valuable product that could be
upgraded.
REFINING - UPGRADING AND ADVANCED
PROCESSES
 Naphtha hydrotreater : Various sulfur compounds are present in the
hydrocarbon mixture and, if burnt with the other carbons, will cause
sulfuric emissions. The hydrotreater uses hydrogen to remove some of
these compounds. As an example, the hydrodesulfurization (HDS)
reaction for ethanethiol can be expressed as:

ethanethiol + hydrogen → ethane + hydrogen sulfide

C 2 H 5 SH + H 2 → C 2 H 6 + H 2 S

 A catalytic reformer unit is used to conver t the naphtha molecules (C5-

C1 2) into higher octane reformate (reformer product). These are mixed
with raw gasoline to achieve a higher octane product . The process
creates more aromatics (ring formed hydrocarbons) by
dehydrocyclization or more complex hydrocarbons with double bonds or
side groups by dehydrogenation. These processes release hydrogen
which is recovered and can be reused in hydrotreater s or
hydrocrackers .
REFINING - UPGRADING AND ADVANCED
PROCESSES

Catalytic reformer
REFINING - UPGRADING AND ADVANCED
PROCESSES
 Distillate hydrotreater units desulfurize distillates (such as
diesel) after fractional distillation, in the same way as the
naphtha hydrotreater.

 Fluid catalytic crackers (FCC) units upgrade heavier fractions

into lighter, more valuable products. Long chain molecules
(high carbon numbers) are split into shorter molecules to
achieve more of the high value fuel components. A typical
design uses a reactor and a regenerator. A fine powdered
porous catalyst with zeolite (silicate and alumina) is fluidized
in the hydrocarbon vapor, where a reaction takes place at
535 °C and 0.172 MPa.
REFINING - UPGRADING AND ADVANCED
PROCESSES
 The catalytic reaction takes place within a few seconds, after
which the reformate and catalyst is separated in a cyclone.
The spent catalyst then goes back to a regenerator that heats
it to 715 °C at 0.241 MPa and releases flue gas. The catalyst
powder can then be reused. The reformates go to a distillation
column for separation into fractions.
REFINING - UPGRADING AND ADVANCED
PROCESSES
 A hydrocracker unit performs essentially the same function as
the FCC when more saturated hydrocarbons are desirable in
the product. This means alkane carbon chains with single
bonds, not double bonds or cyclic rings like aromatics, or
more complex molecules. For this, additional hydrogen is
needed. The reaction takes place with hydrogen under
pressure over a catalyst. The relative market need for diesel,
kerosene and gasoline will influence the choice of FCC versus
hydrocracker. In the US, with a higher relative volume of
gasoline, more FCC capacity is needed, while in Europe and
Asia, with higher diesel consumption, more hydrocracking is
used.
REFINING - UPGRADING AND ADVANCED
PROCESSES
 Visbreaking units upgrade heavy residual oils by thermally
cracking them into lower viscosity product that can be
blended into lighter, more valuable products . Visbreaking is
characterized by its thermal severity, ranging from mild
cracking at 425°C to severe cracking at 500 °C. Depending on
the residual oil, as much as 15-25% lighter fractions like
diesel, kerosene and gasoline could be obtained . The residue
is tar and coke.

 The Merox unit treats LPG, kerosene or jet fuel by oxidizing

thiols (mercaptans) to organic disulfides. The purpose is to
reduce strong odors caused by thiol presence .
REFINING - UPGRADING AND ADVANCED
PROCESSES
 Coking units (delayed coking, fluid coker, and flexicoker), like
the visbreaker, uses thermal cracking of very heavy residual
oils into gasoline and diesel fuel . The residue is green coke,
and is further processed to fuel coke or, if too low in sulfur
and contaminants, to anode coke for the metallurgic
industries.

 An alkylation unit produces high-octane components for

gasoline blending. The main use is to convert isobutane
(C 4 H 10 , but arranged dif ferently than n84 butane) to alkylates,
mainly isooctane or isoheptane by adding an alkyl group such
as propene or butene over a strong acid catalyst, such as
sulfuric or hydrofluoric acid.
REFINING - UPGRADING AND ADVANCED
PROCESSES
 Dimerization is similar to alkylation, but uses a dimer group
instead of an alkyl group. For example, butenes can be dimerized
into isooctene, which may be hydrogenated to form isooctane.
Isomerization units convert linear molecules to higher -octane
branched molecules by rearranging the same atoms arranged in
a different way. For example, C 4 H 10 n-butane has the carbon
atoms in a chain, while isobutane has a central carbon with one
hydrogen and three CH 3 groups attached. The isobutane can then
be fed to the alkylation unit.

 Steam reforming produces hydrogen for the hydrotreaters or

hydrocracker. Typical is the steam methane reformer (SMR),
where steam reacts with Methane at 425 °C with a nickel
catalyst to produce syngas, which is a source for many different
reactions:

CH 4 + H 2 O ↔ CO + 3H 2
REFINING - UPGRADING AND ADVANCED
PROCESSES
 If more hydrogen is needed, followed by a gas shift reaction
with CO:

CO + H 2 O ↔ CO 2 + H 2

 Amine gas treater, Claus unit, and tail gas treatment converts
hydrogen sulfide from hydrodesulfurization into elemental
sulfur, which is a valuable traded product.
REFINING - UPGRADING AND ADVANCED
PROCESSES
 The Claus process is the most common with the overall
reaction:

2H 2 S + O 2 → S 2 + 2 H 2 O

 The reactor runs at 1 ,000 °C and 0.15 MPa, with three steps:
one thermal and two catalytic to improve yield. Using these
processes, a modern refinery can raise the basic gasoline
yield depending on crude quality from 10 -40% to around to
70%.
REFINING - UPGRADING AND ADVANCED
PROCESSES

Claus process
 REFINING - BLENDING AND
DISTRIBUTION
 After the refining processes, the various fractions are stored
in intermediate tanks, then blended into marketable products
for loading onto railcars, trucks or ships, and distribution to
gas stations or industries.
 REFINING - BLENDING AND
DISTRIBUTION
 Each product is blended to a specification of up to 25
parameters such as octane rating, energy content, volatility
and sulfur content. The task is to achieve the specification
(and not exceed, where applicable) with the minimum amount
of over-spec “giveaway.”

 The blending quality is managed with infrared or

chromatograph type process analyzers. These can determine
the precise fractions of a sample by molecule type.
 REFINING - BLENDING AND
DISTRIBUTION
 The standard specification gasoline is therefore standard from
company to company in the individual markets, ensuring
compatibility with vehicle manufacturer requirements . Also,
the terminal operator may be an independent third party or
run as co-distribution, so that a terminal in one region
distributes for several companies based on the same products
in the same tanks.
 REFINING - BLENDING AND
DISTRIBUTION
 Each company then seeks to dif ferentiate its product by
adding small quantities of unique additives that are marketed
to increase engine performance , lifetime, clean combustion
and so forth. These additives are added as the product is
dispensed to trucks for delivery to that brand gasoline station.
 REFINING - BLENDING AND
DISTRIBUTION
 The terminal management system tracks batches of product
received or dispensed, as well as those eventually received by
gasoline stations, airports or other consumers and
consolidates with stored volumes. Each operation should be
validated against orders, bills of lading and positive
identification of trucks, vessels and their operators.

 In countries where this process is not well managed, losses of

product due to theft and other factors can be as high as 15%
or more in the distribution operations. Eventually the main
goal is to ensure that orders are met, and stakeholders pay or
get paid in the form of VAT, taxes, product, delivery charges,
etc.
 PETROCHEMICAL

 Chemicals derived from petroleum or natural gas –

petrochemicals – are an essential part of today’s chemical
industry. Petrochemical plants produce thousands of chemical
compounds.

 The main feedstock is natural gas, condensates (NGL) and

other refinery byproducts such as naphtha, gasoil, and
benzene.
 PETROCHEMICAL

Petrochemical plants are divided into three main primar y product groups
according to their feedstock and primar y petrochemical product

 Olefins include ethylene, propylene, and butadiene. These are the main
sources of plastics (polyethylene, polyester, PVC), industrial chemicals
and synthetic rubber.

 Aromatics include benzene, toluene, and xylenes, which also are a

source of plastics (polyurethane, polystyrene, acr ylates, nylon), as well
as synthetic detergents and dyes.

 Synthesis g as (syngas) is formed by steam reforming between methane

and steam to create a mixture of carbon monoxide and hydrogen . It is
used to make ammonia, e.g., for fer tilizer urea, and methanol as a
solvent and chemical intermediar y. Syngas is also feedstock for other
processes such as the Fischer–Tropsch process that produces synthetic
diesel.
 PETROCHEMICAL

Petrochemical tree: feedstock and primary petrochemicals

 PETROCHEMICAL

 The primar y petrochemicals are not end products , but form building
blocks for a wide range of materials. Therefore, each primar y
petrochemical gives name to a chain of reactions leading to those
materials. There are almost 200 petrochemicals that can be described
this way. There are more processes than end products, as each product
may require multiple steps .

 Many of these processes are based on polymerization, which means

that it is based on processes that fir st form monomers then let these
bind together to form polymers as long chains or a three dimensional
network .

 Petrochemicals are of ten made in cluster s of plants in the same area .

These plants are of ten operated by separate companies, and this
concept is known as integrated manufacturing . Groups of related
materials are of ten used in adjacent manufacturing plants, to use
common infrastructure and minimize transpor t . E.g, in Ker teh and
Gebeng.
 PETROCHEMICAL - AROMATICS

 Aromatics, so called because of their distinctive perfumed

smell, are a group of hydrocarbons that include benzene,
toluene and the xylenes. These are basic chemicals used as
starting materials for a wide range of consumer products.
Almost all aromatics come from crude oil , although small
quantities are made from coal.
 PETROCHEMICAL - AROMATICS

 Xylene and polyester chain

Aromatics – xylene and polyester chain, derivatives

PETROCHEMICAL - AROMATICS
 PETROCHEMICAL - OLEFINS

 Olefins are petrochemical derivatives produced by cracking

feed stocks from raw materials such as natural gas and crude
oil. Lower olefins have short chains with only two, three or
four carbon atoms, and the simplest one is ethylene. The
higher olefins have chains of up to twenty or more carbon
atoms. The main olefin products are ethylene, propylene,
butadiene and C 4 derivatives. They are used to produce
plastics, as chemical intermediates, and, in some cases, as
industrial solvents.
 PETROCHEMICAL - OLEFINS

 Ethylene, derivatives
PETROCHEMICAL - OLEFINS
PETROCHEMICAL - OLEFINS
 PETROCHEMICAL - SYNTHESIS GAS

 Synthesis gas (syngas) is a mixture of carbon monoxide and

hydrogen. It can be created from coal or methane reacting
with steam at high temperatures :

 From coal:
C + H 2 O → H 2 + CO

Or from methane:

CH 4 + 1/2O 2 → CO + 2H 2 Lean combustion

CH 4 + H 2 O → CO + 3H 2 Steam reforming
PETROCHEMICAL - SYNTHESIS GAS
 PETROCHEMICAL

 Syngas is used for production of methanol or ammonia. It is

also used for production of synthetic fuels, both diesel
(Fischer–Tropsch process) and gasoline
 PETROCHEMICAL

 Ammonia is a pungent, colorless, gaseous alkaline compound of

nitrogen and hydrogen ( NH 3 ) that is very soluble in water and can
easily be condensed to a liquid by cold and pressure. It is
manufactured by the direct combination of hydrogen and
nitrogen under pressure over a catalyst. The main process is still
the Haber-Bosch synthesis invented in 1915, operating at 15 –25
MPa and between 300 and 550 °C in four reaction chambers with
catalyst. Anhydrous ammonia is mainly used for the manufacture
of nitrogenous fertilizers. It is also a building block for the
synthesis of many pharmaceuticals, for explosives, and is used in
many commercial cleaning products.
 Urea CO(NH 2 ) 2 is synthesized from ammonia and carbon dioxide.
It is named for its presence in human and most land animal
urine (except fish and birds). Dissolved in water, it is neither
acidic nor alkaline. Urea is widely used in fertilizers as a
convenient source of nitrogen. Urea is also an important raw
material for the chemical industry in animal feed, plastics and
resins.
PETROCHEMICAL
 UTILIT Y SYSTEMS

Process control systems

 A process control system is used to monitor data and control
equipment on the plant.

 Very small installations may use hydraulic or pneumatic

control systems, but larger plants with up to 250,000 signals
to and from the process require a dedicated distributed
control system.

 The purpose of this system is to read values from a large

number of sensors, run programs to monitor the process and
control valves, switches etc. to control the process. Values,
alarms, reports and other information are also presented to
the operator and command inputs accepted.
UTILIT Y SYSTEMS

The main function of the

control system is to make
sure the production,
processing and utility systems
operate efficiently within
design constraints and alarm
limits.
 UTILIT Y SYSTEMS

 The system is operated from a central control room (CCR) with a

combination of graphical process displays, alarm lists, repor ts and
historical data cur ves. Smaller per sonal screens are of ten used in
combination with large wall screens as shown on the right. With
modern systems, the same information is available to remote
locations such as onshore corporate operations suppor t centers.
UTILIT Y SYSTEMS

Piping and
instrumentation
diagrams (P&ID) show
the process. Additional
information is needed
for the specification of
the process control and
safety systems design
and their control logic.
These include: Loop
diagram, Instrument
datasheet, Cable
schedule and
Termination list
 UTILIT Y SYSTEMS

 Metering section
To make sure readings
are accurate, a fixed
or movable prover
loop for calibration is
also installed. The
illustration shows a
full liquid hydrocarbon
(oil and condensate)
metering system. The
analyzer instruments
on the lef t provide
product data such as
density, viscosity and
water content .
Pressure and
temperature
compensation is also
included.
 UTILIT Y SYSTEMS

 Control and safety configuration

 Telemetry/SCADA Supervisory control and data acquisition

(SCADA

 Information management systems (IMS)

 Safety systems and functional safety

 Emergency shutdown and process shutdown

 Fire and gas system