Lecture 6

PETROLEUM REFINING &
PETROCHEMICAL PROCESSES
CONVERSION 1
Contents
Introduction
Cracking - Thermal
Cracking - Catalytic
Cracking - Hydro
Ing. Prof. Nana Derkyi Oil Ref & PChem Engg 2

Introduction

Conversion
 Having done all the physical separation processes on the crude oil,
such as distillation or deasphalting, dewaxing, we have pretty much
squeezed out what we could from the crude oil.
 But the yield of these products, particularly the light distallates like
gasoline or kerosene, does not really meet the demand.
 There are still many too heavy hydrocarbon molecules remaining

after the separation process.
 To meet demand for lighter products, the heavy molecules are

“cracked” into two or more lighter ones.
4
Ing. Prof. Nana Derkyi Oil Ref & PChem Engg
Conversion
 This process converts 75% of the heavy products into
gas, gasoline and diesel. The yield can be increased
further by adding hydrogen , a process
called hydrocracking , or by using deep conversion to
remove carbon.
 The more complex the operation, the more it costs and
the more energy it uses. The refining industry’s ongoing
objective is to find a balance between yield and the cost
of conversion.

Conversion
 Conversion processes change the size and structure of
hydrocarbon molecules in order to convert fractions into
more desirable products.
 The conversion processes, include:

1. Cracking
2. Combining
3. Rearranging

Petroleum Conversion Processes
 Cracking (thermal and catalytic)
 Coking
 Visbreaking
 Alkylation
 Polymerization
 Isomerization
 Reforming

 Cracking, coking, and visbreaking processes are used to
break large petroleum molecules into smaller ones.
 Polymerization and alkylation processes are used to

combine small petroleum molecules into larger ones.
 Isomerization and reforming processes are applied to

rearrange the structure of petroleum molecules to
produce higher-value molecules of a similar molecular
size.
CRACKING

Types of Cracking
1. Thermal cracking
2. Catalytic cracking
3. Hydrocracking

Thermal Cracking

Thermal Cracking
 Thermal cracking is a conversion process
principally to produce more motor gasoline from
crude oils and produce high-octane gasoline for
aircraft use, initiating an attempt to change the
composition of crude oil in petroleum refinery.
 Thermal cracking processes include visbreaking

and coking, which break heavy oil molecules by
exposing them to high temperatures.
Chemistry of Thermal Cracking
 Thermal cracking produces shorter straight chain
alkanes from longer straight chains found in gas
oils or other crude oil fractions.
 Free radicals (reactive species with unpaired
electrons, but no electronic charge) are the active
species that govern thermal cracking reactions.
 Because of the free radical chemistry, thermal
cracking of gas oil would produce gasoline with
relatively low octane Oilnumbers
Ing. Prof. Nana Derkyi Ref & PChem Engg 13
 Thermal cracking is a free radical reaction.
 The steps are: initiation, propagation, and termination.
 The free radical chain reaction starts with breaking the weakest C-
C bond in the reactant alkane (R-H) to form two free radicals
R1 and R2, each with one unpaired electron resulting from the
homolysis of the C-C bond (initiation).
 Once formed by the initiation step, each free radical can go

through two different propagation reactions:
1. Hydrogen abstraction
2. Beta (β) scission
 In a hydrogen abstraction reaction, for example, the radical
R1 removes (abstracts) a hydrogen atom from an alkane (R-H) to
produce a shorter chain alkane product (R1-H) and a new radical R
(hydrogen abstraction), thus propagating the free radical chain.
 Alternatively, the radical R1, (or R2) can go through a β scission

reaction to produce an olefin (ethylene) as a product, and a radical
R to propagate the chain.
 The β scission refers to the breaking of covalent bond in the β

position relative to the position of the unpaired electron as shown
below:

Thermal Cracking Process
COKING
 Despite the development of catalytic cracking
processes, coking processes have survived as a
popular refining process all over the world to refine
the heavy end of crudes or heavy oils through
carbon rejection as coke.
 Coking is the most severe thermal process used in

the refinery to treat the very bottom-of-the-barrel of
crude oil, i.e., vacuum residue.
COKING
 Three different coking processes are used in the
refineries: delayed coking, fluid coking, and flexi-
coking (a variation of fluid coking).
 The common objective of the three coking

processes is to maximize the yield of distillate
products in a refinery by rejecting large quantities
of carbon in the residue as solid coke, known as
petroleum coke.
Coking Process
 In the coking process, residue feed is introduced to the fractionator
after being heated in the heat exchangers with the coker gas oil
products.
 The bottoms from the fractionator, including the heavy ends of the
vacuum residue feed with heavy coker gas oil recycle, are mixed
with steam and sent to the tubular heater in the furnace to be heated
to approx 475°C at a pressure of 10-30 psi.
 Steam is added to prevent coking in the heater and the heated feed is
introduced from the bottom of one of the coke drums.
 The coking takes place in the insulated coke drum as the drum fills
up for a period of 16–18 h. 20
 While drum A is being filled up, drum B is decoked by using
hydraulic cutters and the drilling stem and the coke is removed
from the bottom of the drum.
 As the coking in drum A is completed, drum B should be decoked,

sealed, heated, and prepared for switching the feed.
 All of the heat necessary for coking is provided in the heater,

whereas coking takes place in the coke drum; hence, the process is
called “delayed coking.”

Two Kinds of Coke
 There are two kinds of coke produced by delayed coking of VDR:
high-density shot coke, and porous sponge coke
 The formation of shot coke is usually troublesome because of

difficulties in removing the coke from the drums and problems
with grinding, although shot coke has some niche applications
such as in titanium dioxide (TiO2) production.
 Sponge coke is used as solid fuel, and manufacturing anodes for

aluminum production, if its sulfur and metal concentrations are
sufficiently low.
VISBREAKING
 Visbreaking is a mild thermal cracking process applied to

reduce the viscosity of VDR to produce fuel oil and some
light products to increase the distillate yield in a refinery.
 Depending on the feedstock properties and thermal

severity in the reactor, the process will typically achieve
10–25% of conversion of the heavy ends to gas, gasoline,
and distillates while producing fuel oil with the desired
specifications.
Visbreaking Process
 Topped crude or vacuum residuals are heated and thermally cracked
(455 to 480°C, 3.5 to 17.6 kg/cm2) in the visbreaker furnace to
reduce the viscosity, or pour point, of the charge.
 The cracked products are quenched with gas oil and flashed into a
fractionator.
 The vapor overhead from the fractionator is separated into light

distillate products.
 A heavy distillate recovered from the fractionator liquid can be used

as either a fuel oil blending component or catalytic cracking feed.
 Conversion in visbreaking depends primarily on temp and time.
 As a measure of “thermal severity” under reactions conditions a

thermal severity index (TSI) is used as a function of temperature
and time.
28
 From the equation, conversion is related to the extent of
visbreaking and depends on (kt); and the TSI to establish the
interchangeability of T and t for a given conversion relates to (e(-
Ea/RT)t), where E is the apparent activation energy of the reaction,
a
R is the universal gas constant, T is the temperature, and t is time.
 In using the TSI for comparing thermal severity of different T and

t combinations as major operating variables of visbreaking, care
should be taken to use the right units for R and T.
 As a general convention, an apparent activation of energy of 50

kcal/mol is assumed for thermal cracking reactions involving the
homolysis of C-C bonds to produce free radicals.

 The exponential dependence of TSI on
temperature relates to the general exponential
term that constitutes the chemical reaction rate
constants.
 The chemical conversion in visbreaking reactions

can be expressed as the reduction in
concentration (cA) of long-chain alkane (or high-
molecular weight compounds) in the feedstocks.

CATALYTIC CRACKING

Catalytic Cracking
 As different from thermal cracking,

catalytic cracking:
1. uses a catalyst;
2. takes place at lower temperature and lower
pressure;
3. is more selective and flexible.

Catalytic Cracking
 Catalytic cracking, using heat, pressure, and catalysts, converts
heavy oils into lighter products with product distributions favoring
the more valuable gasoline and distillate blending components.
 Feedstocks are usually gas oils from atmospheric distillation,

vacuum distillation, coking, and deasphalting processes.
 These feedstocks typically have a boiling range of 340 to 540°C.
 All of the catalytic cracking processes in use today can be

classified as either fluidized-bed or moving-bed units.
Catalytic Cracking
 One particular catalytic cracking process, Fluid Catalytic

Cracking (FCC), has captured universal acceptance in the
refining industry because of its feed flexibility, ability to
modify product yields through minor changes in the
process operating conditions.
 FCC is used to produce high-octane gasoline mainly from

straight-run atmospheric gas oil and light vacuum gas oil
(LVGO)
Fluidized-bed Catalytic Cracking (FCC)
 FCC process uses a catalyst in the form of very fine

particles that act as a fluid when aerated with a vapor.
 Fresh feed is preheated in a process heater and

introduced into the bottom of a vertical transfer line or
riser with hot regenerated catalyst.
 The hot catalyst vaporizes the feed, bringing both to the

desired reaction temperature, 470 to 525°C.
 The high activity of modern catalysts causes most
of the cracking reactions to take place in the riser
as the catalyst and oil mixture flows upward into
the reactor.
 The hydrocarbon vapors are separated from the

catalyst particles by cyclones in the reactor.
 The reaction products are sent to a fractionator for

separation.
 The spent catalyst falls to the bottom of the reactor and is
steam stripped as it exits the reactor bottom to remove
absorbed hydrocarbons.
 The spent catalyst is then conveyed to a regenerator where

coke deposited on the catalyst as a result of the cracking
reactions is burned off in a controlled combustion process
with preheated air.
 Regenerator temperature is usually 590 to 675°C.
 The catalyst is then recycled to be mixed with fresh

hydrocarbon feed.
Moving-bed Catalytic Cracking
 In the moving-bed system, typified by the Thermafor Catalytic
Cracking (TCC) units, catalyst beads (~0.5 cm) flow into the top of
the reactor, where they contact a mixed-phase hydrocarbon feed.
 Cracking reactions take place as the catalyst and hydrocarbons move

concurrently downward through the reactor to a zone where the
catalyst is separated from the vapors.
 The gaseous reaction products flow out of the reactor to the

fractionation section of the unit.
 The catalyst is steam stripped to remove any adsorbed hydrocarbons.

 It then falls into the regenerator, where coke is
burned from the catalyst with air.
 The regenerated catalyst is separated from the

flue gases and recycled to be mixed with fresh
hydrocarbon feed.
 The operating temperatures of the reactor and

regenerator in the TCC process are comparable to
those in the FCC process.
Chemistry of Catalytic Cracking
 As opposed to thermal cracking governed by free radicals,
catalytic cracking proceeds through the formation of ionic species
on catalyst surfaces, and produces shorter, but branched-chain (not
straight-chain) alkanes by cracking the long straight-chain alkanes.
 The formation of branched-chain alkanes, or iso-alkanes, leads to

the production of gasoline with high octane numbers.
 This is the fundamental reason why catalytic cracking has replaced

thermal cracking as the central process in a refinery geared to
maximize gasoline production.
 The two types of ionic species, carbocations, that
are active in catalytic cracking reactions as
carbenium, and carbonium ions.
 Carbocations are the positively charged ions

made from hydrocarbons.

HYDROCRACKING

Hydrocracking
 Hydrocracking is a flexible catalytic refining process that can
upgrade a large variety of petroleum fractions.
 Hydrocracking is commonly applied to upgrade the heavier

fractions obtained from the distillation of crude oils, including
residue.
 The process adds hydrogen which improves the hydrogen to

carbon ratio of the net reactor effluent, removes impurities like
sulfur to produce a product that meets the environmental
specifications, and converts the heavy feed to a desired boiling
range.

Hydrocracking Chemistry
 The chemistry involves the conversion of heavy molecular
weight compounds to lower molecular weight compounds
through carbon-carbon bond breaking and hydrogen
addition.
 The main products have lower boiling points, are highly

saturated, and generally range from heavy diesel to light
naphtha.
 Hydrocracking processes are designed for, and run at, a

variety of conditions.
Hydrocracking Chemistry
 The process design will depend on many factors such as
feed type, desired cycle length, and the desired product
slate.
 Hydrocracking is a process that is suitable to produce

products that meet or exceed all of the present
environmental regulations.
 Hydrocracking reactions proceed through a bifunctional

mechanism.

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PETROLEUM REFINING &

Ing. Prof. Nana Derkyi Oil Ref & PChem Engg 2

Ing. Prof. Nana Derkyi Oil Ref & PChem Engg 3

 There are still many too heavy hydrocarbon molecules remaining

 To meet demand for lighter products, the heavy molecules are

Ing. Prof. Nana Derkyi Oil Ref & PChem Engg 5

 The conversion processes, include:

Ing. Prof. Nana Derkyi Oil Ref & PChem Engg 6

Ing. Prof. Nana Derkyi Oil Ref & PChem Engg 7

 Polymerization and alkylation processes are used to

 Isomerization and reforming processes are applied to

Ing. Prof. Nana Derkyi Oil Ref & PChem Engg 9

Ing. Prof. Nana Derkyi Oil Ref & PChem Engg 10

Ing. Prof. Nana Derkyi Oil Ref & PChem Engg 11

 Thermal cracking processes include visbreaking

 The steps are: initiation, propagation, and termination.

 Once formed by the initiation step, each free radical can go

 Alternatively, the radical R1, (or R2) can go through a β scission

 The β scission refers to the breaking of covalent bond in the β

Ing. Prof. Nana Derkyi Oil Ref & PChem Engg 16

 Coking is the most severe thermal process used in

 The common objective of the three coking

 As the coking in drum A is completed, drum B should be decoked,

 All of the heat necessary for coking is provided in the heater,

Ing. Prof. Nana Derkyi Oil Ref & PChem Engg 21

 The formation of shot coke is usually troublesome because of

 Sponge coke is used as solid fuel, and manufacturing anodes for

 Visbreaking is a mild thermal cracking process applied to

 Depending on the feedstock properties and thermal

 The vapor overhead from the fractionator is separated into light

 A heavy distillate recovered from the fractionator liquid can be used

 As a measure of “thermal severity” under reactions conditions a

 In using the TSI for comparing thermal severity of different T and

 As a general convention, an apparent activation of energy of 50

Ing. Prof. Nana Derkyi Oil Ref & PChem Engg 29

 The chemical conversion in visbreaking reactions

Ing. Prof. Nana Derkyi Oil Ref & PChem Engg 30

Ing. Prof. Nana Derkyi Oil Ref & PChem Engg 31

 As different from thermal cracking,

Ing. Prof. Nana Derkyi Oil Ref & PChem Engg 32

 Feedstocks are usually gas oils from atmospheric distillation,

 These feedstocks typically have a boiling range of 340 to 540°C.

 All of the catalytic cracking processes in use today can be

 One particular catalytic cracking process, Fluid Catalytic

 FCC is used to produce high-octane gasoline mainly from

 FCC process uses a catalyst in the form of very fine

 Fresh feed is preheated in a process heater and

 The hot catalyst vaporizes the feed, bringing both to the

 The hydrocarbon vapors are separated from the

 The reaction products are sent to a fractionator for

 The spent catalyst is then conveyed to a regenerator where

 Regenerator temperature is usually 590 to 675°C.

 The catalyst is then recycled to be mixed with fresh

 Cracking reactions take place as the catalyst and hydrocarbons move

 The gaseous reaction products flow out of the reactor to the

 The catalyst is steam stripped to remove any adsorbed hydrocarbons.

 The regenerated catalyst is separated from the

 The operating temperatures of the reactor and

 The formation of branched-chain alkanes, or iso-alkanes, leads to

 This is the fundamental reason why catalytic cracking has replaced

 Carbocations are the positively charged ions

Ing. Prof. Nana Derkyi Oil Ref & PChem Engg 41

Ing. Prof. Nana Derkyi Oil Ref & PChem Engg 43