Duhok polytechnic university

Technical college of engineering

petrochemical department

,, Naphtha Cracking ,,

Industrial training & Seminar

Dr. firas Salim Mohammed

Prepared by :
Berhat Kamal & Shavang Khoshavi & Sahand Nawzad 1
Over view :
What is naphtha
What is cracking
Steam cracking
Catalytic cracking
Naphtha cracking

2
Naphtha
Naphtha is a term used to refer to a group of volatile, flammable mixtures
of liquid hydrocarbons that are used mainly as solvents, diluents, or raw
materials for gasoline conversion. It is a light weight petrochemical feedstock
that is separated from crude oil in the fractional distillation process along
with kerosene and jet fuel.
There are many specific types of naphtha that vary in the amounts and types of
hydrocarbons contained in their unique blend. Refineries can produce various
forms of naphtha, and each has specific guidelines in how it should be handled
and stored. Generally speaking, the flammability and volatility of naphtha should
be taken into consideration as they are significant safety hazards.

3
Naphtha is the first petroleum product produced during the distillation
process and subsequently upgraded to make the major components of
gasoline. Virgin or straight-run Naphtha is the largest source of Naphtha
in most petroleum refineries. The virgin Naphtha is often further distilled
into two streams:

-a virgin light Naphtha SRLN

with an IBP of about 30 °C and a FBP of about 145 °C contains most
(but not all) of the hydrocarbons with 6 or less carbon atoms.

-a virgin heavy Naphtha SRHN

with an IBP of about 140 °C and a FBP of about 205 °C contains most
(but not all) of the hydrocarbons with more than 6 carbon atoms. Virgin
heavy Naphtha is usually processed in a catalytic reformer because the
light naphtha has molecules with 6 or less carbon atoms and lower
molecular weight hydrocarbons which are not useful as high-octane
gasoline blending components. 4
Naphtha Uses
Highly volatile and flammable, naphtha finds use in many human
industries as a solvent, and for industrial purposes. Humans
discovered it before the first century A.D. The term naphtha refers to a
broad category of chemicals, each a potentially dangerous solution of
hydrocarbons. Coal tar, shale and petroleum make up three distinct
forms of naphtha, each formed under different conditions and used for
different purposes for their chemical properties. In modern
production, naphtha often comes from crude oil distillation.
Naphtha has several other names including Enerade ED-6202, high-
flash aromatic naphtha, light aromatic solvent naphtha and petroleum
naphtha, although these terms can apply to a specific form of naphtha
with an intended use.

Humans use naphtha in three main ways: for industrial purposes, as a

solvent. And as a feedstock for steam and catalatic cracking, It is a
large class of chemicals that comes with some health and 5
environmental concerns.
Naphtha as a Solvent
Humans commonly use petroleum naphtha as a solvent. It can be
found in various cleaning agents where its low evaporation point
comes in handy and as a dilution agent for paints, varnish and
asphalt. Dry-cleaning businesses also use naphtha in their operations.

Naphtha as a feedstock for Steam or Catalytic Cracking

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Cracking
Cracking is a petroleum refining process in which heavy-molecular weight
hydrocarbons are broken up into light hydrocarbon molecules by the
application of heat and pressure, with or without the use of catalysts, to derive
a variety of fuel products. Cracking is one of the principal ways in which
crude oil is converted into useful fuels such as motor gasoline, jet fuel, and
home heating

The cracking products, such as ethene, propene, buta-1,3-diene and

C4 alkenes, are used to make many important chemicals. Others such as
branched and cyclic alkanes are added to the gasoline fraction obtained from
the distillation of crude oil to enhance the octane rating.
Cracking is conducted at high temperatures, by two processes
Steam Cracking which produces high yields of alkenes (Olifene) 7
Catalytic Cracking in which a catalyst is employed and which produces high
yields of branched and cyclic alkanes
8
Catalytic
cracking

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Steam cracking
Steam cracking plants use a variety of feedstocks, for example
• ethane, propane and butane from natural gas
• naphtha, a mixture of C5 to C10 hydrocarbons, from
the distillation of crude oil
• gas oil and residues, also from the primary distillation of oil.

steam cracking have 4 material balances cases:

1. Steam cracking light naphtha for max ethylene yield
2. Steam cracking light naphtha for max propylene yield
3. Steam cracking full range naphtha for max ethylene yield
4. Steam cracking full range naphtha for max propylene yield

• * if we have light naphtha or hydrocarbon from C1 to C7 is

better using steam cracking instead of catalytic cracking.
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Catalytic cracking :
A catalytic process that produces light olefins from naphtha was
developed to improve the yield of the conventional steam cracker. In
laboratory-scale tests, a newly developed zeolite-based catalyst at a
reaction temperature of 650 ◦C produced an ethylene-plus-propylene
yield of about 60%, which is about 10% higher than the conventional
process operated at around 820 ◦C. A feasibility study carried out for a
catalytic cracking process using the developed catalyst, that cracks
3000 tons-naphtha/day, indicated an energy saving of about 20%
compared with the conventional process.

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Figure 1. Catalytic cracking
of naphtha to light olefins
The catalysts facilitate the conversion of the heavier molecules into
lighter products. The catalysts are solid materials (zeolite, aluminum
hydro-silicate, treated be toniesclay, bauxite and silica-alumina) as
powders, beads, pellets or shaped materials.
The cracking process produces carbon (coke) which remains on the
catalyst particle and rapidly lowers its activity. To maintain the
catalyst activity at a useful level, it is necessary to regenerate the
catalyst by burning off this coke with air. As a result, the catalyst is
continuously moved from reactor to regenerator and back to reactor.
The cracking reaction is endothermic and the regeneration reaction
exothermic. Some units are designed to use the regeneration heat to
supply that needed for the reaction and to heat the feed up to
reaction temperature.
Use of a catalyst in the cracking reaction increases the yield of
better quality
products under much less severe operating conditions than in 14
thermal and steam cracking.
Temperature is 455°- 510° C at much lower pressures of 10-20 psi.
There are three basic functions in the catalytic cracking process:
• Reaction: Feedstock reacts with catalyst and cracks into different
hydrocarbons;
• Regeneration: Catalyst is reactivated by burning off coke; and
• Fractionation: Cracked hydrocarbon stream is separated into various
products.
The catalytic cracking process is very flexible, and operating conditions
can be adjusted to meet product demand. In addition to cracking,
catalytic activities include dehydrogenation, hydrogenation, and
isomerization.
The catalytic-cracking processes in use today can all be classified as
either moving bed or fluidized-bed units.
The Thermafor catalytic cracking process (TCC) is representative of the
moving bed units and the fluid (fluidized) catalytic cracker (FCC) of the
fluidized-bed units. There are very few TCC units in operation today and
the FCC unit has taken over the field. The FCC units can be classified as
either bed or riser (transfer line) cracking units depending upon where the 15
major fraction of the cracking reaction occurs.
Fluid Catalytic Cracking (FCC)
Fluid catalytic cracking is the most important conversion process used
in petroleum refineries. It is used to convert the high-boiling
hydrocarbon fractions to more valuable gasoline, olefinic gases and
other products. Fluid catalytic cracking or "cat cracking," is the basic
gasoline-making process. It uses high temperature (about 538 oC), low
pressure and a catalyst in the form of very fine particles [average
particle size about 70 micrometers (microns)] which behave as a fluid
when aerated with a vapor.
Two basic types of FCC units in use today are the ‘‘side-by-side’’ type,
where the reactor and regenerator are separate vessels adjacent to each
other, and the Or thoflow, or stacked type, where the reactor is
mounted on top of the regenerator. The cracker consists of a catalyst
section and a fractionating section. The catalyst section contains the
reactor and regenerator which, with the standpipe and riser, form the
catalyst circulation unit. The fluidized powdered catalyst is circulated
between the reactor and the regenerator using air, oil vapors, and steam 16
as the conveying media.
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A typical FCC process involves mixing a preheated hydrocarbon charge with
hot, regenerated catalyst as it enters the riser leading to the reactor. The charge is
combined with a recycle stream within the riser, vaporized, and raised to reactor
temperature (900°-1,000° F) by the hot catalyst. As the mixture travels up the
riser, the charge is cracked at 10-30 psi. In the more modern FCC units, all
cracking takes place in the riser. The "reactor" no longer functions as a reactor;
it merely serves as a holding vessel for the cyclones. This cracking continues
until the oil vapors are separated from the catalyst in the reactor cyclones. The
resultant product stream (cracked product) is then charged to a fractionating
column where it is separated into fractions, and some of the heavy oil is
recycled to the riser.

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Regenerator air
NAPHTHA CRACKING
Major plastics are manufactured from olefins, which are available either by
cracking of gases (gas-based petrochemicals), such as methane, ethane,
propane and butane, or from naphtha (naphtha-based petrochemicals). Due to
the larger availability of naphtha and the low energy requirement for cracking
as compared to gases, naphtha cracking is widely accepted for the manufacture
of olefins. Naphtha is a mixture of hydrocarbons boiling in the range of the
lowest boiling component (C5) to 150°C, which contains paraffins,
naphthenes, and aromatics in various proportions.

It is found that paraffins, i.e., straight chain hydrocarbons, yield olefins when
heated at a high temperature. The branched chain and aromatic hydrocarbons,
on the other hand, become heavier or decomposed to carbon.
It is also a fact that the yield of olefins decreases with the increasing molecular
weight (hence with boiling point) of the hydrocarbons.
For example, if ethane is thermally cracked, it will yield 80% ethylene, while
from propane, butane, naphtha, and gas oil as feedstocks, if cracked separately
the yields will be 45%, 37%, 30%, and 25%, respectively. Hence, the desirable 19
feedstock naphtha should have a very high content of paraffins and be in the
lower boiling range.
A suitable boiling range for feedstock naphtha for olefin production is below
100°C and should have a paraffin content of more than 75%.

Usually, naphtha in the boiling range of 90°C−150°C is catalytically

reformed in a refinery either to produce gasoline or aromatics. Hence, in the
refinery, C5−90°C cut is separated in the naphtha redistillation unit and is
sold to the petrochemical industry. Naphtha cracking is carried out in a tube-
still furnace at a temperature above 800°C. Due to thermal cracking, the
following cracking endothermic reaction takes place
Figure 3 Inside a tubular reactor being
used for steam cracking naphtha. The
temperature is about 1150 K.
1. Naphtha vapour flows through the
inside of the tubes in the furnace
2 Rows of furnace guns which burn
methane to generate heat inside the
furnace
3 A peephole
. 20
Light hydrocarbons obtained from the initial cracking reactions further
crack into lighter olefins and propagate until the reaction temperature is
brought down (quenched).
If the reaction is continued indefinitely, branched and cyclised heavy
hydrocarbons will be produced and coke will be generated as the ultimate
product.
Therefore, the cracking reaction is carried out in a very short residence time,
i.e., the naphtha feed passes the heater tubes at very high speed to avoid
undesirable heavy end products and coke.

Usually, residence time is maintained at <1 sec in the traditional cracker

furnaces and it is of the order of a few milliseconds in the modern
millisecond furnaces.

Since a coke layer develops inside the tube surface, the heat transfer rate is
rapidly reduced, causing reduced cracking and poor olefins yield. Steam is
introduced with the feed to remove the coke layer on the tube surface by
converting coke into carbon monoxide and hydrogen by water gas reaction,
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However, coke cannot be removed completely by steam and the thickness
grows during the operating period of the furnace.
When the coke layer reaches the point at which cracking operation shows poor
yield, the furnace is taken out of service and decoking is carried out with air and
steam to remove coke to the maximum extent.
Thus, a cracker furnace operates cyclically between the cracking and decoking
operations. Excess steam may also partially convert some of the hydrocarbons
or naphtha components to carbon monoxide and hydrogen and reduce the yield
of olefins.
By-products of cracking are propylene, butylene, butadiene, and aromatics, such as
benzene, toluene, xylene, isomeric paraffins, naphthenic components, and poly-
nuclear aromatics. Products from the cracking furnace are quenched by hot oil and
cooled before they are sent to the
separation units. The product
mixture then flows through a series
of separators, e.g., demethaniser,
de-ethaniser, depropaniser, and
debutaniser units, which are
multiplated distillation columns. 22
Table 2 shows the operating
parameters for a typical naphtha
cracker:
PRIMARY FRACTIONATOR OR STABILISER
Cracked liquids and gases are separated in a fractionating column the
bottom product of which is the heavy cracked oil rich in high boiling
aromatics.

This heavy oil is also partly used as the quenching medium for the
products from the furnace and partly sold as the carbon black feedstock
(CBFS) due to its heavy aromatic contents.

Cracked gases containing hydrocarbons, both saturated and unsaturated,

from methane to C7 hydrocarbons emerge from the top of the column,
which is then compressed and amine (or caustic) washed to remove
hydrogen sulfide and carbon dioxide gases.

This is illustrated in Figure (NEXT SLIDE)

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Figure 4 A view of the steam cracking unit at Wilton in the north-east of England.
The products from steam cracking include a mixture of C1 - C4 hydrocarbons and
are separated by fractional distillation. Some of the columns are:
1 A debutaniser which separates the C4 hydrocarbons from the C1 - C3
hydrocarbons
2 A depropaniser which separates out the C3 hydrocarbons
3 A deethaniser which separates out the C2 hydrocarbons 25
4 A demethaniser which separates out the methane
5 A C3 splitter which separates propene from propane
6 A C2 splitter which separates ethene from ethane
HYDROGEN SEPARATOR
Amine or caustic washed gases are then passed through a flash separator
vessel, where liquid hydrocarbon gases are separated from hydrogen at high
pressure and low temperature. Hydrogen from this vessel is used in the
hydrogenating units, such as pyrolysis gasoline and butadiene hydrogenation,
or as a fuel.
Demethaniser: Liquified gases from a hydrogen separator are then separated
from methane in a distillation column where methane (C1) emerges from the
top and is used as a fuel for the cracking furnace. The bottom of the column is
then passed to a de-ethaniser.

De-ethaniser: It is also a distillation column that separates ethane and ethylene

mixture (C2 mixture) as the top product from the rest of the liquified gases
containing propane, propylene, butane, butylenes, etc.

Ethane-ethylene separator: A C2 mixture from the top of the de-ethaniser

column is then passed through another distillation column that separates
ethylene as the top product and ethane as the bottom product. Ethylene is sent 26
to storage and is used up in the polyethylene (PE) synthesis plant. Ethane from
this column is recycled to a small cracking furnace to yield additional ethylene.
Depropaniser: The liquified gas mixture from the bottom of the de-
ethaniser is separated from propane and propylene (C3 mixture), which
leaves from the top of the column and enters the propane–propylene
fractionator. The bottom product contains the butanes, butenes, butadiene,
and heavier components, which are then separated from the butane–
butene mixture (C4 mixture).

Propane–propylene separator: In this column, propylene is recovered as

the top product and propane as the bottom product. Propylene is stored
and used for manufacturing polypropylene, and propane is sold as a
domestic fuel—liquified petroleum gas (LPG).

Debutaniser: Butane, butenes, and butadiene (C4 mixture) are recovered

as the top product and components heavier than the C4 mixture, i.e., C5
and heavier, are recovered as the pyrolysis gasoline (bottom product).
Pyrolysis gasoline is catalytically hydrode-sulfurised before it is sold or
blended as a gasoline component. A gasoline hydrode- sulfurisation unit
is similar to a naphtha pretreatment unit Typical yields of products from a
naphtha cracking unit is presented in next slide. 27
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