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Petroleum Refining

What is it?
Petroleum Refining is the process of taking crude oil and
reprocessing it into a number of different products
Crude Oil - a yellow/black liquid found underneath the surface of the
earth which contains various hydrocarbons and other liquid organics
Typical refineries are very large industrial complexes made up of
many primary and auxiliary units
No two refineries are identical in that each handles varying amounts
of crude oil and produces vary amounts of products depending on
location and demand

Products
Light Distillates

Heavy Distillates

Liquid Petroleum Gas (LPG)

Heavy Fuel Oils

Gasoline (Petrol)

Bunker Fuel Oil

Light and Heavy Naphtha

Others (not all listed)

Middle Distillates

Petroleum Naphthas

Kerosine

Solvents

Diesel Fuels

Elemental Sulfur

Heating Fuels

Petrochemicals

Other Light Fuels

Asphalt and Tar

General Flow Diagram

Since gasoline is the
most desired product,
that is what a majority of
the crude oil is used to
produce
Aside from air and water,
hydrogen gas and H2S
are frequently used and
are thus produced on site

Crude Oil Distillation Unit

This is the first step for all refineries
The crude oil is heated up until it
boils, and then, by using fractional
distillation, the heavier hydrocarbons
(higher BP) can be separated from
the light ones (lower BP)
As the gases travel up the column,
they will condense and can be
pumped out
No reactions occur within the
distillation column

Crude Oil Distillation Unit

The products by temperature range and chain length are:

< 40 C - Petroleum Gas (C1 - C3)

o

40 - 200 C - Gasoline (C4 - C12)

o

200 - 250 C - Kerosene, Jet Fuel (C12 - C16)

o

250 - 300 C - Heating Oils (C15 - C18)

o

300-370 C - Lubricating Oils (C19 +)

o

370+ C - Residue, Asphalt (C25 +)

Vacuum Distillation
Vacuum distillation units are found in
80+% of refineries
At very low pressure, the leftovers from
the initial distillation tower can be
vaporized without cracking
These oils can later be cracked with
the aid of catalysts to control the
product formation
They are primarily used to produce
addition gasoline
No reaction occur during vacuum
distillation

Naphtha Hydrotreater
Naphtha - a flammable oil made up of various hydrocarbons with sulfur atoms
By treating the naphtha fraction with hydrogen, refineries are able to desulfurize the
hydrocarbons
The purpose of this is to reduce the SOx emissions generated from using the fuels
produced
Nitrogen and Olefins will be removed as well
Primary Reactions
C-S + 3/2 H2 > R-C-H + H2S
C=C + H2 > H-C-C-H
C-N + 2 H2 > C-H + NH3

Catalytic Reforming
Catalysts are used to convert the desulfurized naphtha into higher-octane
molecules know as reformates
N.B. - Octane rating measure the compression which can be withstood
before ignition
The reformates are rearranged and cracked versions of the hydrocarbons
These are a component of the final gasoline product
Primary Reactions:
R-R + H2 > R-H + R-H
R-C-R > C-R-R (and similar rearrangements)

Alkylation
Conversion of isobutane and butylene into alkylate,
another high-octane component of the gasoline product
The process is typically done in sulfuric acid of hydrofluoric
The product alkylate can either be used directly or farther
alkylated in order to produce a higher premium product for
aviation fuels
Primary Reaction: butene + isobutane > 2,2,4 trimethylpentane

Isomerization
The two distinct isomerization process are butane isomerization and pentane/
hexane isomerization
In this process, the straight chains are catalyticlly rearranged into their branched
isoparaffins of a higher octane number
For low temperature butane isomerization, aluminium chloride and HCl are
typically used, whereas with high temperature isomerization, platinum or other
metal catalysts are used
The reaction is simply a catalytic rearrangement similar to the following: R-C-R
> C-R-R
The above is a generic sense of the rearrangement. The catalyst will
determine the exact isomerization product

Distillate Hydrotreater
Similar to the Naphtha hydrotreater,
it uses hydrogen gas to desulfurize
other fractions of the crude oil
distillate in order to reduce the
production of Sox gases from use
It will also remove nitrogen and
aromatics; exactly what depends on
the feed
Primary Reactions:

C-S + 3/2 H2 > R-C-H + H2S

C-N + 2 H2 > C-H + NH3

Merox (Mercaptan Oxidizer)

These units also desulfurize fraction of the crude oil
distillation, specifically liquid petroleum gas, kerosene,
and jet fuels, but by oxidizing undesired mercaptans
(also known as thiols, the R-S-H group)
The overall reaction can be written:

Amine Gas Treater & Claus Unit

These two units are used in conjunction to create elemental sulfur
from the H2S byproduct of the hydrotraters
This process makes up the majority of all sulfur production worldwide
The Amine Gas treater also reduces the CO2 levels, which when
present in gas, sharply reduces its markability
Primary Reactions:
+

RNH2 + H2S > RNH3 + SH2 H2S + O2 S2 + 2 H2O

(Amine Gas Treater)

(Claus Unit)

Fluid Catalytic Cracking

Converts heavy, high-boiling fractions into
lighter products with a higher octane rating to
be used in gasoline
This used to be done by thermal cracking, but
the catalytic cracking allows the refineries to
control the product they produce, and as
such is now the common method
Carbon is deposited on the catalyst in this
process and reduces the performance of the
catalyst
This catalyst coke is burnt off in a regenerator

Hydrocracker
Uses hydrogen gas to break large
carbon chains into smaller ones of a
higher octane rating
The process works by pumping the
hydrogen gas and crude oil distillate
at high pressures over towers of
catalyst
The main products of this are jet fuel
and diesel
Primary Reaction:
R-R + H2 > R-H + RH

Visbreaker
This unit is responsible for thermally cracking
the heavy residual oils of the vacuum
distillation into more valuable products with a
reduced viscosity
While they are old, straight forward units, they
will continue to be present in refineries for
many years to come with more modernized
designs that help decrease energy losses and
increase conversion efficiencies
Thermal Cracking Reaction:
+

2C-C > [ 2C + C-C ] > 2C + C=C

The initial and final molecule will be longer
than ethyls and methyls, but it is the same
idea

Delayed Coking
Converts heavy residual oils into petroleum coke, a
carbonaceous solid, in addition to naphtha and other gas
oils
The coke is referred to as fuel grade, meaning it is high in
sulfur and metals) and anode grade (low in sulfur and
metals)
Coke that is primarily carbon can be sold for use in fuel,
whereas anode grade coke sees use in the aluminium
and steel industries

Sources
http://www.elmhurst.edu/~chm/vchembook/513refining.html
http://www.pavementinteractive.org/article/asphalt-production-and-oil-refining/
http://www.eia.gov/todayinenergy/detail.cfm?id=9130
http://www.eoearth.org/view/article/149994/
http://www.eoearth.org/view/article/153923/
http://www.pescova.com/oil_recovery/hydrotreating_system.shtml
http://www.uop.com/?document=uop-the-role-of-the-merox-process-in-ultra-low-sulfur-transport-fuels-production-techpaper&download=1
http://www.newpointgas.com/amine_treating.php
http://www.eia.gov/todayinenergy/detail.cfm?id=9150
http://www.refiningnz.com/visitors--learning/classroom--learning-resources/learning-centre/how-it-works---the-refining-process/
hydrocracker.aspx
http://www.sciencedirect.com/science/article/pii/S1026309812000612#
http://www.punjlloydgroup.com/landmark-projects-gallery/visbreaker-unit-and-sulphur-block