Petroleum Refining /3rd stage

Conversion Processes
The objective of the conversion processes is to convert low value atmospheric and
vacuum residues to valuable products such as naphtha, gasoline and gasoil.

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 oil.
- Typically cracking involves the thermal or catalytic decomposition of heavier
hydrocarbon feed stocks to lighter hydrocarbon feed stocks.
- Cracking can be carried out to any hydrocarbon feedstock but it is usually
applied for vacuum gas oil (VGO)
- Cracking can be with or without a catalyst.
- When cracking is carried out without a catalyst higher operating
temperatures and pressures are required. This is called as thermal cracking.
This was the principle of the old generation refineries.
- Now a day, cracking is usually carried out using a catalyst. The catalyst
enabled the reduction in operating pressure and temperature drastically.

Thermal Cracking
Thermal cracking is a refining process in which heat (~800°C) and pressure
(~700kPa) are used to break down, rearrange, or combine hydrocarbon molecules.
The first thermal cracking process was developed around 1913. Distillate fuels and
heavy oils were heated under pressure in large drums until they cracked into
smaller molecules with better antiknock characteristics. However, this method
produced large amounts of solid, unwanted coke. There are three types of industrial
thermal cracking processes.
1. A mild cracking (as in visbreaking) in which mild heating is applied to crack
the residue just enough to lower its viscosity and also to produce some light
products.
2. The second process is delayed coking in which moderate thermal cracking
converts the residue into lighter products, leaving coke behind.
3. The third process involves severe thermal cracking: part of the coke is
burned and used to heat the feed in the cracking reactor, as in fluid coking.

Petrochemical Dept. Page 1

 Petroleum Refining /3rd stage

Visbreaking
Visbreaking is a mild thermal cracking of vacuum or atmospheric residues to
produce light products and 75–85% cracked material of lower viscosity that can be
used as fuel oil. The process is mainly used to reduce the viscosities and pour
points of vacuum tower bottoms to meet the requirements of fuel oil. It is also used
to increase catalyst cracker feed stocks and gasoline yields. Middle distillates may
also be produced, depending on product demand. The thermally cracked residue
tar accumulates in the bottom of the fractionation tower
The possible reactions in visbreaking are:
 Cracking of the side chains attached to cycloparaffin and aromatic rings so
the chains are either removed or shortened to methyl or ethyl groups.
 Cracking of resins to light hydrocarbons (primarily olefins) and compounds
which convert to asphaltenes.
 At temperatures above 900°F (480°C), some cracking of naphthene rings.

Product Yield and Properties

Four products are produced in the visbreaking process: gases (C - 4), Naphtha C5
_ 166 oC, gas oil 166–350 oC , residue or tar +350‫‏‬oC.

Types of Visbreakers:
There are two types of visbreaker operation:
1. Coil or furnace visbreaker
It uses high furnace outlet temperature [885–930°F (473–500°C)], and reaction time
from 1-3 minutes.
The feed is heated in a furnace or coil and quenched as it exits the furnace with gas
oil or tower bottoms to slop the cracking reaction (Figure 1).
After quenching, the product enters the fractionation tower where it is separated
into gas, gasoline, gas oil and visbreaker tar (residue). The gas oil is steam-stripped
to remove volatile components. The visbreaker bottoms are withdrawn from the
fractionator, heat exchanged with the visbreaker feedstock, mixed with stripped gas
oil (optional) and routed to storage.

Petrochemical Dept. Page 2

 Petroleum Refining /3rd stage

Figure 1 Coil Visbreaker

2. Soaker Visbreaker
The process scheme described above is called furnace or coil cracking. Some
visbreakers use a soaker between the visbreaker furnace and the quenching step,
similar to the conventional thermal cracking processes. This type of operation is
termed soaker cracking as shown in the Figure 2. The soaker cracking uses lower
furnace outlet temperatures [800–830°F (427–443°C)] and longer reaction times.
In soaker visbreaking, the bulk of the cracking occurs not in the furnace but in a
drum located after the furnace called the soaker. The oil is held at a high
temperature for a pre-determined period of time to allow cracking to occur before
being quenched. The oil then passes to a fractionator.
The conversion is mainly a function of two operating parameters, temperature and
residence time. Coil cracking is a high temperature, short residence time route
whereas soaker cracking is a low temperature, long residence time route.
The product yields and properties are similar, but the soaker operation with its lower
furnace outlet temperatures has the advantages of lower energy consumption and
longer run times before having to shut down to remove coke from the furnace
tubes. Run times of 3–6 months are common for furnace visbreakers and 6–18
months for soaker visbreakers. This apparent advantage for soaker visbreakers is
at least partially balanced by the greater difficulty in cleaning the soaking drum.
Coil cracking yields are more stable. Soaker cracking usually requires less capital
investment, consumes less fuel.

Petrochemical Dept. Page 3

 Petroleum Refining /3rd stage

Figure 2 Soaker Visbreaker

Coking:
Coking are severe cracking operations designed to completely convert residual
products such as pitch or tar into gas, naphtha, heating oil, gas oil, and coke (The
process so completely reduces hydrogen that the residue is a form of carbon called
coke). Three typical types of coke are obtained (sponge coke, honeycomb coke,
and needle coke) depending upon the reaction mechanism, time, temperature, and
the crude feedstock.
The gas oil fraction represents the major product obtained used as a feed stock for
catalytic cracking units. The C5-220 oC naphtha may be used as a gasoline
blending agent, although its octane no. quality from 65 to 80 RON (unleaded), is
lower than the desirable, the coke is usually used as fuel.
The main uses of petroleum coke are as follows:
1. Fuel
2. Manufacture of anodes for electrolytic cells.
3. As chemical carbon source for manufacture of calcium carbide and silicon
carbide
4. Manufacture of electrodes for use in electric furnaces.
5. Manufacture of graphite

Petrochemical Dept. Page 4

 Petroleum Refining /3rd stage

Coking Types:
The major coking processes in use today are:
1. Delayed Coking:
A semi- continuous process (Figure 3) in which the heated charge is transferred to
large coking drums which provide the long residence time needed to allow the
cracking reactions to proceed to completion, the feed to these units is normally an
atmospheric residue, although cracked tars and heavy catalytic cycle oils may be
also used.
Initially the heavy feedstock is fed to a furnace which heats the residuum to high
temperatures (900°-950° F) at low pressures (25-30 psi) and is designed and
controlled to prevent premature coking in the heater tubes (Figure 3). The mixture is
passed from the heater to one or more coker drums where the hot material is held
approximately 24 hours (delayed) at pressures of 25-75 psi, until it cracks into
lighter products. Vapors from the drums are returned to a fractionator where gas,
naphtha, and gas oils are separated out. The heavier hydrocarbons produced in the
fractionator are recycled through the furnace.
After the coke reaches a predetermined level in one drum, the flow is diverted to
another drum to maintain continuous operation.

Process Description:
Hot fresh liquid feed is charged to the fractionator two to four trays above the
bottom vapor zone. This accomplishes the following:
1. The hot vapors from the coke drum are quenched by the cooler feed liquid thus
preventing any significant amount of coke formation in the fractionator and
simultaneously condensing a portion of the heavy ends which are recycled.
2. Any remaining material lighter than the desired coke drum feed is stripped
(vaporized) from the fresh liquid feed.
3. The fresh feed liquid is further preheated making the process more energy
efficient. Vapors from the top of the coke drum return to the base of the fractionator.
These vapors consist of steam and the products of the thermal cracking reaction:
gas, naphtha, and gas oils.

Petrochemical Dept. Page 5

 Petroleum Refining /3rd stage

Figure 3: Delayed Coking

2. Continuous (Fluid) Coking:

It is a continuous (contact or fluid) coking process which uses the fluidized - solids
technique to convert residues to more valuable products. The use of a fluid bed
permits the coking reaction to be conducted at higher temperature and shorter
contact times than those in delayed coking; steam is used for fluidizing the bed.
In continuous coking, thermal cracking occurs by using heat transferred from hot,
recycled coke particles to feedstock in a radial mixer, called a reactor, at a pressure
of 50 psi. Gases and vapors are taken from the reactor, quenched to stop any
further reaction, and fractionated. The reacted coke enters a surge drum and is
lifted to a feeder and classifier where the larger coke particles are removed as
product. The remaining coke is dropped into the preheater for recycling with
feedstock. Coking occurs both in the reactor and in the surge drum. The process is
automatic in that there is a continuous flow of coke and feedstock.

Petrochemical Dept. Page 6

 Petroleum Refining /3rd stage

Catalytic Cracking
Catalytic cracking is the most important and widely used refinery process for
converting heavy oils into more valuable gasoline and lighter products. Originally
cracking was accomplished thermally but the catalytic process has almost
completely replaced thermal cracking because more gasoline having a higher
octane and less heavy fuel oils and light gases are produced. It also produces
byproduct gases more valuable, than those produced by thermal cracking.
The produced light gases contain more olefins than those produced by thermal.
The catalysts facilitate the conversion of the heavier molecules into lighter products.
The catalysts are solid materials (zeolite, aluminum hydro-silicate, treated betonies
clay, 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.
Catalytic cracking rearranges the molecular structure of hydrocarbons to convert
heavy fractions into lighter fractions such as kerosene, gasoline, liquified petroleum
gas (LPG) and heating oil.
Use of a catalyst in the cracking reaction increases the yield of better quality
products under much less severe operating conditions than in thermal 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.

Petrochemical Dept. Page 7

 Petroleum Refining /3rd stage

The Thermafor catalytic cracking process (TCC) is representative of the moving-

bed units and the fluid 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 major fraction of the cracking reaction occurs.

1. 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
Orthoflow, 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 as the conveying media.

Figure 4 FCC Unit

Petrochemical Dept. Page 8

 Petroleum Refining /3rd stage

A typical FCC process (figure 4) 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.

Reactor
The "reactor" is a vessel in which the cracked product vapors are:
(a) separated from spent catalyst by flowing through a set of two-stage cyclones in
the reactor
(b) the spent catalyst flows downward through a stripping section to remove
hydrocarbon vapors by steam before the spent catalyst returns to the catalyst
regenerator.
The 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.
Spent catalyst is regenerated to get rid of coke that collects on the catalyst during
the process. Spent catalyst flows through the catalyst stripper to the regenerator,
where most of the coke deposits burn off at the bottom where preheated air and
spent catalyst are mixed. The regenerated catalyst leaves from bottom and mixed
with the feed stream.
Fresh catalyst is added and worn-out catalyst removed to optimize the cracking
process.

Regenerator
The catalyst is regenerated by burning off the deposited coke with air blown into the
regenerator. The regenerator temperature is about 715°C and a pressure of about
35 psi. The combustion of the coke is exothermic, it produces a large amount of
heat, a part is used for the vaporization of the feedstock and a part for endothermic
cracking reactions. For that reason, FCC units are heat balanced.
The hot flue gas exits the regenerator after passing through multiple sets of two-
stage cylones that remove catalyst from the flue gas.

Petrochemical Dept. Page 9

 Petroleum Refining /3rd stage

Distillation column
The reaction product vapors (at 535 °C and a pressure of 25 psi) flow from the top
of the reactor to the bottom section of the distillation column (fractionator) where
they are distilled into the FCC end products of cracked naphtha, fuel oil and off-gas.
After further processing for removal of sulfur compounds, the cracked naphtha
becomes a high-octane component of the refinery's blended gasolines.
The off-gas is sent to a gas recovery unit where it is separated into butanes and
butylenes, propane and propylene, hydrogen, methane, ethylene and ethane.
Many FCC fractionators produce a light cracked naphtha (lower boiling range) and
a heavy cracked naphtha.
The bottom product oil from the fractionator contains residual catalyst particles
which were not removed by the cyclones in the reactor. For that reason, part of that
bottom oil is recycled back into the main fractionators. The remaining oil is pumped
through a settler. The bottom oil contains most of catalyst particles and is recycled
back into the catalyst riser by combining it with the feedstock.

Petrochemical Dept. Page 10

 Petroleum Refining /3rd stage

Thermofor Catalytic Cracking

In a typical thermofor catalytic cracking unit, the preheated feedstock flows by
gravity through the catalytic reactor bed. The vapors are separated from the
catalyst and sent to a fractionating tower. The spent catalyst is regenerated, cooled,
and recycled. The flue gas from regeneration is sent to a carbon monoxide boiler
for heat recovery.

Process Variables:
In addition to the nature of the charge stock, the major operating variables affecting
the conversion process are the cracking temperature, catalyst/oil ratio, space
velocity, catalyst type and activity, and recycle ratio.
Generally increasing reaction temperature, catalyst / oil ratio, catalyst activity and
contact time results in an increase in conversion, while a decrease in space velocity
increases conversion. It should be noted that an increase in conversion does not
necessarily mean an increase in gasoline yield, as an increase in temperature
above a certain level can increase conversion, coke and gas yields, and octane
number of the gasoline but decrease gasoline yield.

Comparison between thermal and catalytic cracking

Catalytic cracking differences with Thermal Cracking
 Uses a catalyst
 Lower temperature
 Lower pressure
 More flexible
 Different reaction mechanisms
 High thermal efficiency
 High yields of gasoline and other distillates
 Low gas yields
 High product selectivity
 High octane number

Petrochemical Dept. Page 11