W3V20 Refining Processes2 V2016 Handout

Oil & Gas
From exploration to distribution

Week 3 V20 Refining Processes (Part 2)
Jean-Luc Monsavoir
W3V20 - Refining Processes 2 p. 1

IFPEN - IFP School 2016 / TOTAL SA 2016
IFPEN - IFP School 2015 / TOTAL SA 2015 / IFP Training 2015
Refinery Objectives
The yield we can obtain from crude oil depends on the origin of the crude. For instance, for
an Arabian Light crude, from Saudi Arabia, we have, at the outlet of the Crude Distillation
Unit, 5% of gas, 20% of gasoline, 30% of Kerosene and diesel and 45% of heavy cuts.
But, these yields obtained at the outlet of the CDU do not correspond to the market demand
for final products.
If we compare the crude yields and the final market demands, in Europe, we can observe
that we have a lack of diesel, Jet fuel and gasoline. And a large excess of heavy products.
Lets see now how a refinery can solve this problem, and try to match the market demands.
The idea is to transform the heavy products recovered at the bottom of the CDU into lighter
products, according to the market demand.
For that, we feed the Vacuum Distillation Unit (VDU) with the atmospheric residue. By doing
that, we recover a vacuum distillate, with a carbon number between 25 and 50, and, at the
bottom, a vacuum residue, with a carbon number higher than 50.
The vacuum distillate is treated in a Fluid Catalytic Cracker called FCC, or in a Distillate
hydrocracker, called DHC. The vacuum residue will be treated in a delayed coker. We will
see later in detail these units. But for the moment, just remember that the basic objective is
to cut the long carbon chains into smaller ones.
In conclusion, the idea is to transform heavy cuts into diesel, kerosene, gasoline, as needed
by the market, in order to balance the offer and the demand.
We can list 3 main refinery objectives
1. to separate the crude, in a distillation column, into different petroleum cuts
2. to improve the quality of these cuts, in order to meet the commercial specifications

3. to improve the quantity, as requested by the market. FCC, DHC and delayed coker
units are able to change the yields of products, by transforming heavy products into
lighter ones, such as gasoline, kerosene or diesel oil.
Refining Processes
Gas Treatment
Gases are obtained at the top of the
Crude Distillation Unit. Then, they are
split again, in other distillation columns,
called a gas plant, to obtain first Fuel
gas. Fuel gas is used as internal fuel in
all the furnaces of the refinery. We also
obtain propane and butane, as final
products. But, it is mandatory to
eliminate sulfur compounds, which are
present in these cuts.
One of the most important compounds
is named H2S.
The H2S is eliminated in an amine unit. The gas, containing H2S, is put in contact with a
chemical reactant: an amine called DEA. A chemical reaction occurs between H2S and DEA.
The sweet gas goes to the outlet of the column. This unit is also largely used for the natural
gas treatment.
HDS unit
On the diesel cut, depending on the origin on the crude-oil, the cetane number obtained is
high enough to be within the specifications. Its the same for the cold flow properties. But

the sulfur content of the diesel cut from the crude distillation is too high to meet the target
specifications.
To decrease the sulfur content, below 10 ppm weight, to comply with European
specifications, we need to treat this cut in a unit called the hydrodesulfurization unit (or HDS
unit). At the outlet of the HDS unit, the diesel fuel complies with specifications such as
density, cetane number, cold flow properties and sulfur content. The diesel can be stored in
the final product tank, ready to be sold to customers of the refinery.
The desulfurization reactions take place inside a reactor filled with a catalyst. The catalyst is
a solid compound, designed to facilitate and accelerate the chemical reactions.
The hydrocarbons, containing the sulfur molecules, react at the surface of the catalyst with
hydrogen molecules in gas form.
At the end of the reaction, we obtain, on one hand a hydrocarbon without sulfur and, on the
other hand, H2S (Hydrogen sulphide) which is the product of the reaction between sulfur and
hydrogen.
We need a high enough temperature to activate the reactions: typically the temperature
inside the reactor is between 360C and 400C. We also need enough hydrogen pressure, to
help the hydrogen molecule go inside the catalyst, to react with the sulfur molecules.
Typically, the pressure of a Diesel HDS-unit is between 40 and 80 bar.
REFORMING unit
For gasoline fuels, remember that the main specifications to comply with are : density,
volatility, sulfur content and RON.
Density and volatility are regulated by operating the distillation column.
At the outlet of the CDU, the sulfur content is higher than the European specification, of 10
ppm weight. And, typically the RON, of this cut, is really low, in a range of 20 to 50.
To decrease the sulfur content of the gasoline cut, we install another HDS unit.
At the outlet of the HDS unit, the
sulfur content targeted is 0 ppm wt,
because sulfur is a poison of the
catalyst of the reforming unit, and
also to comply with the sulfur
specification of the gasoline. But the
Research Octane Number is still far
below the 95 targeted in Europe.
To increase the RON, the gasoline cut
is treated in a new unit, called the
Reforming unit.
At the outlet of the reforming unit, the gasoline is then within the specifications in terms of
density, volatility, RON and sulfur content. The gasoline can then be stored in the gasoline
final product tank.
The chemical reaction takes place again in a reactor, filled with another type of catalyst.

The paraffins react at the surface of the catalyst and are transformed into aromatics, with
production of hydrogen. The RON increases, because the RON of aromatics is higher
compared to the RON of paraffins. Another type of reaction is the transformation of
naphtenes into aromatics with, again, production of hydrogen. Aromatics are really
important bases for the petrochemical industry.
These reactions take place at high temperature, around 500C, and at a pressure of around
20 bar. In addition, the hydrogen produced during these reactions, in the reforming unit, is
directly used in the diesel, kerosene, and gasoline HDS-units.
Until now, we have seen the units which improve the quality of the products.
Lets now discover the units which increase the quantity and the yield of the desired
products.
FCC unit
At the bottom of the CDU, the atmospheric residue is distilled under vacuum, in a VDU, to
obtain a Vacuum distillate. The vacuum distillate is introduced into a Fluid Catalytic Cracking
unit, called FCC
The vacuum distillate is introduced at the bottom of the reactor, in a big pipe called a riser.
In the riser, the feed is in contact with a specific catalyst. The reaction occurs in the gas
phase at high temperature.
We recover the products of the reaction at the top of the reactor. The products of the
reaction are separated into different cuts in a distillation column.
The spent catalyst is recovered at the bottom of the reactor, and is regenerated in a
regenerator, before coming back again at the inlet of the riser. The catalyst is circulated in a
loop, between the reactor and the regenerator.
The catalyst is really specific. It looks like very small round particles, around 0,05 mm. This
catalyst is so small that is possible to fluidize it. To keep things simple , lets say that, under
some conditions, it moves like a liquid.
Under the operating conditions, the catalyst will break the long chain molecules into smaller
ones. By doing so, we transform the long molecules of the vacuum distillate into shorter
ones, and finally we produce additional gasoline and diesel fuel. We also obtain smaller
molecules with double bonds called olefins, like propylene. This molecule is really reactive,
and it is an important base for the petrochemical industry for the manufacturing of plastics.
In conclusion, you obtain, at the outlet of the FCC, a combination of different types of
shorter molecules, mainly composed of aromatics and olefins.
These reactions occur at high temperature, around 530C, and at low pressure, around 2 bar.
DHC unit
The vacuum distillate cut, can also be treated in a Distillate HydroCracker unit, called DHC.
The hydrocarbon molecules react at the surface of the catalyst with hydrogen. For example,
aromatic molecules are saturated with hydrogen, to form naphthene. Naphthene cracks
into linear compounds, under high pressure and high temperature.
And long chain molecules can again be cracked into smaller molecules.
Typical operating conditions are : temperature of the reactor is around 360C , and pressure
around 180 bar. In conclusion at the outlet of the DHC unit, we obtain mainly diesel, jet and
gasoline.
Until now, we have seen the treatment of the vacuum distillate. Lets see now what happens
with the heaviest cut of a refinery, the vacuum residue, recovered at the bottom of the VDU.

DELAYED COKER unit
To convert the heavy residue, we can treat it in a delayed coker unit.

The two main pieces of equipment of a delayed coker are the furnace, and the coker drum.
Inside the tubes of the furnace, the residue is heated, to around 500C.
At this temperature, the long chain molecules are thermally cracked into smaller molecules.
This chemical reaction also gives aromatics, olefins, and a lot of solid coke, as around 30 % of
the feed of the unit is converted into solid coke.
The coke accumulates very quickly in the drum. And thus, it is necessary, every 24 hours, to
remove the coke accumulated inside the drum, with specific equipment, using water
injection at a very high pressure, around 300 bar.
The coke produced in the drum can be sold, and used for different applications, depending
on the coke quality, for example to electrical power stations, or for electrode manufacturing.
The yield of products obtained depends on the unit type.

For an FCC, you can obtain up to 50% of gasoline from the feed.
A DHC is more adapted to produce diesel and Jet A1. It is possible, with a good catalyst
selection to obtain more than 60% of diesel and kerosene.
The delayed coker unit gives on average 20% of diesel and 10% of gasoline.
In addition, it is important to remember that the FCC unit also gives olefinic molecules, like
propylene, which are important for the petrochemical industry. Typically the yield of
propylene obtained is around 5% of the feed.
Summary - Refining Diagram

The first step of a refinery, is to cut the crude oil into different bases. This operation takes
place in the crude distillation unit (or CDU). All the cuts obtained, at the outlet of this
distillation column, are not within the desired quality specifications, and need extra
treatment, in additional refining units.
The second step, is to treat the cuts, in order to comply with the specifications, and market
demands. We have seen, the HDS units, used to remove sulfur compounds from gasoline,
kerosene and diesel. And, the reforming unit, to increase the RON of the gasoline.
We added, the FCC which treats the vacuum distillate, to produce mainly extra gasoline. And
the Hydrocracking unit (or DHC) to produce mainly diesel fuel and JetA1. At the end of these
treatments, we obtain several bases, ready to be blended to formulate the final commercial
products.
In conclusion, the third and last step of the refinery, is to blend all the bases, to obtain the
final commercial products, complying with the specifications.
Its during this operation of blending, that the refiner adds biofuels, like ETBE for gasoline
and FAME for diesel fuel.


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Oil & Gas

From exploration to distribution

W3V20 - Refining Processes 2 p. 1

W3V20 - Refining Processes 2 p. 2

W3V20 - Refining Processes 2 p. 3

W3V20 - Refining Processes 2 p. 5

W3V20 - Refining Processes 2 p. 7

DELAYED COKER unit

To convert the heavy residue, we can treat it in a delayed coker unit.

The yield of products obtained depends on the unit type.

Summary - Refining Diagram

W3V20 - Refining Processes 2 p. 9

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