Lecture 17 - Thermal Cracking-Merged

CHN-327 Petroleum Refining
Lecture 17
Dr. Hari Prakash Veluswamy

Assistant Professor
Depar tment of Chemi cal Engineering
IIT Roor kee
12 SEPTEMBER 2022
Recap…
Vacuum Distillation
Processing high TAN crudes
CHN-327 PETROLEUM REFINING 2

Outline of this presentation
 Thermal Conversion processes
 Thermal Cracking
 Steps
 Process
 Operating variables

Thermal Conversion Processes
• Cracking is the process whereby long-chain hydrocarbons are broken down into
simpler molecules such as light hydrocarbons, by the breaking of carbon-
carbon bonds
• Thermal cracking is performed at high temperatures (typically in the range of
450°C to 750°C) and pressures (up to about 70 atmospheres) to break the
large hydrocarbons into smaller ones
• 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
• 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.
• Because of the high severity of thermal cracking during coking, the residue
feed is completely converted to gas, light and medium distillates, and coke with
no production of residual oil
https://www.e-education.psu.edu/fsc432/content/average-boiling-points 4
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 numbers
• Three steps of free radical chain reactions exist
• Initiation
• Propagation and
• Termination
https://www.e-education.psu.edu/fsc432/content/chemistry-thermal-cracking-0 5
Chemistry of Thermal Cracking – Initiation step
• 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 of these free radicals contain one unpaired electron resulting from the
homolysis of the C-C bond
• R-H represents a paraffin chain which can be expanded such as (H-(CH2)n-H)

where n represents the number of carbon atoms in the alkane. In other words,
R represents a radical with an unpaired electron that becomes an alkane (R-H)
when combined with a hydrogen atom
• A Hydrogen atom with one proton and one electron is the simplest radical
Propagation step – Hydrogen abstraction
• Once formed by the initiation step, each free radical can go through two
different propagation reactions:
• Hydrogen abstraction
• 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
Propagation step – β scission
• 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
Termination step
• Initiation step produces two free radicals, the propagation step produces a
reaction product and one radical to continue the chain.
• The last step in the chain reaction, the termination step, removes two radicals
to produce one or two stable compounds depending on the termination
reaction
• The principal end result of the free radical chain reactions in thermal cracking
is to produce from long chain alkanes shorter-chain alkanes, light olefins, and
some aromatic compounds
Aspects of thermal cracking processes
• One important feature of free radical reactions is that isomerization reactions, e.g.,
shifting of the unpaired electron site from an edge atom of a molecule to the interior
atoms are not favored reactions
• Isomerization reactions take place at a slower rate than other propagation reactions,
e.g., β scission reaction
• The critical importance of this observation is that the thermal cracking reactions
produce shorter straight-chain alkanes and olefins without any significant formation
of branched-chain (or iso-alkanes)
• This is the reason why catalytic cracking processes have virtually replaced thermal
cracking processes to produce high octane number gasoline
Thermal cracking process
• Management of thermal reactivity is important in thermal cracking processes for
optimum conversion of the feeds with a wide boiling range.
• Typically, lighter products (gasoline and gas) and the heavier product (fuel oil) are
considered by-products in this process
• A heavy gas oil feedstock with a wide boiling range is fed to a fractionator to
separate the feed into a light oil and a heavy oil fraction depending on the desired
cut points.
• Light oil (which would have a relatively low thermal reactivity) is heated in a
separate furnace to higher temperatures so that the cracking takes place in a vapor
phase.
• Heavy oil fraction (with a high thermal reactivity) is heated to a lower temperature
for cracking in the liquid phase.
https://www.e-education.psu.edu/fsc432/content/thermal-reactivity-considerations-processing 11
• The heated feed streams are combined in a soak drum to provide sufficient time for
the completion of the cracking reactions
• After the soaker, the products are sent to a flash separator to separate the heavy end
as a side product (fuel oil) and the lighter products are sent to the fractionator for
separation into LGO, gasoline and the gaseous products
• Separating the feed into two fractions will avoid heating the reactive longer alkane
chains to high temperatures to keep coke formation and gas production under control
to maximize the LGO yield
• In naphtha cracking for ethylene production, all reactions are carried out in vapor
phase at low pressures to promote β scission reactions for high ethylene yields
• Coking of reactor tubes creates a major maintenance problem in naphtha cracking
for ethylene production
Lecture 18

Assistant Professor
IIT Roor kee
13 SEPTEMBER 2022
 Thermal Conversion processes
 Thermal Cracking

Operating variables in thermal cracking
• The major process variables are
1. Feedstock type.
2. Temperature.
3. Pressure.
4. Residence time.
• The majority of thermal cracking processes use temperatures of 455 to 540 deg C
• Mild cracking conditions, with a low conversion per cycle, favor a high yield of gasoline
components, with low gas and coke production, but the gasoline quality is not high
• More severe conditions give increased gas and coke production and
reduced gasoline yield (but of higher quality). With limited conversion per cycle, the heavier
residues must be recycled, but these recycle oils become increasingly refractory upon
repeated cracking.
• If they are not required as a fuel oil stock they may be coked to increase gasoline yield
James G. Speight, The Refinery of the Future, 2011, Chapter 5 - Thermal Cracking, https://doi.org/10.1016/B978-0- 3
8155-2041-2.10005-0.
Operating variables in thermal cracking
• When petroleum fractions are heated to temperatures over 350 deg C in the
absence of a catalyst, thermal decomposition proceeds at a significant rate
• The severity of thermal processing (the combination of reaction time and
temperature to achieve a given conversion) determines the degree of conversion and
the product characteristics.
• For example, sufficiently high temperatures and long residence times convert petroleum
constituents entirely to gases and coke.
• Cracking conditions can hence be manipulated to maximize production of the desired product, which
is usually gasoline, but may be cracked gases for petrochemicals, or a lower
viscosity oil for use as a fuel.
• The feedstock (cracking stock) can be almost any fraction of crude petroleum, but the greatest
amount of cracking is carried out on gas oil.
• Residua are also used as feedstocks for cracking, but the processes are somewhat different from
those used for gas oils.
• Thermal cracking processes may be classified by the types of products obtained, or by the physical
state (liquid and/or vapor phase) in which the decomposition occurs. The state depends on the
nature of the feedstock as well as conditions of pressure and temperature employed in the reactor
8155-2041-2.10005-0.
Thermal stability of different constituents
• The least thermally stable hydrocarbons are the paraffins, but the olefins
produced by the cracking of paraffins are reactive.
• Cycloparaffins (naphthenes) are less easily cracked.
• Their stability altering mainly if any side chains are present, but ring
splitting may occur, and dehydrogenation can lead to the formation of
unsaturated naphthenes and aromatics.
• Aromatics are the most stable (refractory) hydrocarbons, their stability
varying with the length and stability of side chains.
• Very severe thermal cracking of high boiling feedstocks can result in
condensation reactions of ring compounds, yielding a high proportion of
coke
8155-2041-2.10005-0.
Visbreaking
• Visbreaking is a mild thermal cracking process applied to reduce the viscosity of
VDR/ADR to produce fuel oil and some light products to increase the distillate yield in
a refinery
• Visbreaking produces Naphtha, Gas oil and a residue. The residue has lower
viscosity and pour point and hence can easily meet the requirements of the
fuel oil specifications in the fuel oil blending pool.
• Visbreaking basically breaks the long paraffinic side chains attached to aromatic
structures
• Due to this the residue pour point and viscosities are considerably reduced.
• Two classes of reactions occur during visbreaking
• Cracking of side chained aromatic compounds to produce short chained aromatics and paraffins
• Cracking of large molecules to form light hydrocarbons
Fahim, Mohamed A., Taher A. Al-Sahhaf, and Amal Elkilani. Fundamentals of petroleum refining. Chapter 6. Elsevier, 2009. 6
Visbreaking
https://www.e-education.psu.edu/fsc432/content/visbreaking 7
Visbreaking Reactions
• The main reaction in visbreaking is thermal cracking of heavy hydrocarbons,
since resins are holding asphaltene and keep them attached to the oil
• The cracking of resin will result in precipitation of asphaltene forming deposits
in the furnace and will also produce fuel oil.
• The cracking severity or conversion is limited by the storage stability of the final
residual fuel.
• The possible reactions in visbreaking are:
• Paraffinic side chain breaking which will also lower the pour point
• Cracking of naphthene rings at temperature above 482 C (900 F)
• Coke formation by polymerization, condensation, dehydrogenation and dealkylation
Visbreaking
• 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
• Carbon rejection in small quantities on the reactor surfaces during thermal
cracking helps reduce the viscosity of the fuel oil product
• This process decreases the demand for a cutter stock used as diluent (e.g.,
kerosene) that might otherwise be used to reduce the viscosity of the heavy
ends to meet the fuel oil specifications
• Adding a diluent may still be needed depending on the sulfur content of the
product and the fuel oil specifications
Thermal Severity Index (TSI)
• Conversion in visbreaking depends primarily on temperature and time.
• As a measure of “thermal severity” under reactions conditions, Thermal
severity index (TSI) as a function of temperature and time is used
TSI = Thermal severity index, TSI = f (T, t)
• Assuming an apparent first-order kinetics for the reaction, conversion in the
visbreaking reaction can be expressed by the integral
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
Ea is the apparent activation energy of the reaction, R is the
universal gas constant, T is the temperature, and t is time.
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
Types of visbreaking processes
• Higher visbreaking severity would produce a higher reduction in viscosity.
• Thermal severity is limited by the reactivity of the feedstock and the storage
stability of the residual fuel in accordance with the desired conversion level and
desired reduction in viscosity.
• Asphaltene content and concarbon of the feedstocks are important factors to
consider when selecting an appropriate thermal severity for the process to
prevent excessive coking in the visbreaking reactor.
• There are two types of visbreaking processes:
• Coil visbreaking in which thermal cracking occurs in the coil of the furnace and
• Soak visbreaking in which cracking occurs in a soak drum.
Coil visbreaking
• Vacuum or atmospheric residue feedstock is heated and then
mildly cracked in the visbreaker furnace.
• Reaction temperatures range from 885 to 930 F (470 to 500 C)
• Operating pressures vary from 3 bar to 10 bar.
• Higher temperatures and lower residence times are used in
the coil visbreaking process.
• For visbreaking, the feedstock is introduced into the coil
heated in the furnace where the thermal cracking reactions
take place
• At the furnace outlet, the reaction products are immediately
quenched using a portion of the gas oil product from the
fractionator to stop the thermal cracking reactions
• The quenching step is essential to prevent coking in the fractionation tower
• The gas oil and the visbreaker residue are most commonly used as quenching streams
• The quenched products are sent to the fractionator for separation into gas, gasoline, light gas oil, and
visbroken residue streams.
• A steam stripper can be used with the fractionator for better separation of the visbreaking products
https://www.e-education.psu.edu/fsc432/content/visbreaking-processes
Soak visbreaking
• Visbreakers employ a soaker between the
visbreaker furnace and the quenching step,
similar to the conventional thermal cracking
processes
• In soaker visbreaking, the bulk of the cracking
reaction occurs not in the furnace but in a drum
located after the furnace called the soaker
• Soaker visbreaking is a low temperature (430 to
455 deg C), long residence time route.
• Residence times can vary from 8-10 min in
comparison to only 1-3 min (associated with high
temperatures in coil visbreaking)
• The yield fractions achieved by both options
(coil and soaker visbreaking) are in principle the
same, as are also the properties of the products. https://ngic.hindustanpetroleum.com/ngic22/themes.html
Coil visbreaking Vs Soaker visbreaking
• The higher heater outlet temperature specified for a coil visbreaker is one of
its advantages, meaning significantly higher quantities of heavy visbroken gas
oil can be recovered
• In coil visbreaking, coke is deposited in the tubes of the furnace and will
eventually lead to fouling or blocking. Fouling, impedes heat transfer and/or
reduces throughput; diminishes efficiency and productivity
• The energy lost due to this inefficiency must be supplied by burning
additional fuel or reducing feed
• Fouling will also occur in the drum of a soaker visbreaker, though the lower
temperatures used in the soaker drum slows its deposition rate
• The lower temperatures used in the soaker approach implies that these units
use less fuel
• The soaker process is more difficult to adjust to changes in feedstock quality
because of the need to fine tune the temperature and residence time
James G. Speight, The Refinery of the Future, 2011, Chapter 5 - Thermal Cracking, https://doi.org/10.1016/B978-0-8155-2041-2.10005-0. 14
Lecture 19

Assistant Professor
IIT Roor kee
27 SEPTEMBER 2022
 Coking
 Process description
 Process types
 Delayed coking
 Fluid coking and
 Flexi coking

Coking
• 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
• 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.
• Because of the high severity of thermal cracking during coking, the residue
feed is completely converted to gas, light and medium distillates, and coke with
no production of residual oil
• 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.
https://www.e-education.psu.edu/fsc432/content/coking 3
Coke product
• Complete rejection of metals with the coke product provides an attractive
alternative for upgrading the extra-heavy crude and bitumen, and that is
particularly useful for initial processing of tar (or oil) sands for liberating the
hydrocarbons from the sand that is left behind with the coke
• Finding markets for the coke product as fuel or as filler for manufacturing
anodes for the electrolysis of alumina (possible only with petroleum coke from
delayed coking) makes the economics of coking more attractive by creating
value for the rejected carbon
• Sulfur and metal contents of the petroleum coke, as determined by the sulfur
and metal contents of the residue feed, are two important factors that affect
the commercial value of petroleum coke
https://www.e-education.psu.edu/fsc432/content/coking 4
Delayed 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 approximately 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
https://www.e-education.psu.edu/fsc432/content/delayed-coking 5
• The coking cycle is controlled such that the vacuum residue is continuously fed
to the unit (because the vacuum column works around the clock) and the fluid
products are recovered continuously, while coke is removed intermittently in a
semi-continuous process scheme.
• Therefore, there are at least two coke drums in every delayed coking unit, and
some units have more than two drums.
• 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”
Delayed coking
• The hot product vapors and steam from the top of the drum are quenched by
the incoming feed in the fractionator to prevent coking in the fractionator and
to strip the lighter components of the vacuum residue feed
• The fractionator separates the coking products into gases, coker naphtha,
coker light gas oil, and coker heavy gas oil.
• A side-steam stripper is used with the fractionator to ensure a good separation
between the coker naphtha and light gas oil streams
Operating variables of delayed coking process
• The delayed coking operating variables include heater outlet temperature,
pressure, recycle ratio, and cycle time.
• These variables are selected based on feed properties such as the
characterization factor, asphaltene content, and Conradson Carbon Residue
(CCR ) to ensure that coking in tubular heaters is minimized and liquid product
yield is maximized.
• The recycle ratio, which is typically 3–5%, is used to control the endpoint of the
coker heavy gas oil.
• The coke yield can vary from 20% to 30% depending on the feed properties
and coking conditions.
Types of coke
Shot coke
• There are two major kinds of coke produced by delayed
coking of VDR:
• High-density shot coke and
• Porous sponge coke.
• Shot coke consists of aggregates of ~5 mm diameter
spherical particles and sponge coke exhibits a porous
structure resembling a sponge
• The formation of shot coke is usually troublesome
because of difficulties in removing the coke from the Sponge coke
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
https://www.e-education.psu.edu/fsc432/content/two-kinds-coke 10
Needle coke
• Among the delayed coking products, needle coke is a
specialty coke produced mostly from coking of a highly
aromatic FCC decant oil.
• The major properties of the needle coke includes a low
coefficient of thermal expansion, a low puffing (sudden
volume expansion) tendency during graphitization
because of lower nitrogen and sulfur contents, and high
mechanical strength.
• The anode coke has limits on metal contaminants,
requiring less than 500 ppm of Ni and V in the coke.
• The price of fuel coke depends on its carbon purity (S,
N, and metal contaminants); however, the fuel coke is
traded at a price comparable to that of coal.
https://www.e-education.psu.edu/fsc432/content/two-kinds-coke
11
Image from https://www.gazprom-neft.com/
Lecture 20

Assistant Professor
IIT Roor kee
3 OCTOBER 2022
Recap…
 Coking
 Process description
 Process types
 Delayed coking
 Types of coke
 Shot coke
 Sponge coke
 Needle coke

Fluid coking and
Flexi coking
Introduction to catalytic cracking
Chemistry of catalytic cracking

Fluid coking and Flexi coking
• Fluid coking and flexi-coking are fluid-bed processes developed from the basic
principles of FCC, with close integration of endothermic (cracking, coking, or
gasification) and exothermic (coke burning) reactions.
• In fluid coking and flexi-coking processes, part of the coke product is burned
to provide the heat necessary for coking reactions to convert vacuum residua
into gasses, distillate liquids, and coke
• Flexi-coking, as a variation of fluid coking, provides the options of partial or
complete gasification of the coke product to produce a fuel gas with some or
no coke in the product slate
• Different from the bulk liquid-phase coking in delayed coking, coking takes
place on the surface of circulating coke particles of coke heated by burning the
surface layers of accumulated coke in a separate burner
https://www.e-education.psu.edu/fsc432/content/fluid-and-flexi-coking 4
Fluid coking
Fluid coking
Fluid coking
• Higher temperatures and short residence times in the reactor lead to higher
liquid and lower coke yields compared with those of delayed coking
• Coke is deposited layer by layer on the fluidized coke particles in the reactor
• Air is injected into the burner to burn 15–30 % of the coke produced in the
reactor, part of the particles are returned to the reactor, and the remainder is
drawn out as the fluid coke product
• Fluid coking can process heavier VDR and gives a higher distillate yield (and
lower coke yield) than delayed coking.
Yield in Fluid Coking process
Flexi coking
Flexi coking
• A gasifier is added for conversion of some or all coke produced in the coker in
reaction with air and steam to produce a synthesis gas
• The hot coke particles from the combustor are circulated back to the coking
reactor to provide the heat necessary for coking
• The distillate products from the coker are sent to the fractionator, as is done in
the fluid coking process
• On the gasifier outlet, after removing the fine particles from the gas by
cyclones, the gas is cooled in a direct-contact cooler to condense the sour water
and recover the flexi-gas
• The product gas can be used as fuel gas in the refinery. Depending on the
demand, the flexi-coking process can produce both fluid coke and fuel gas, or
gasify all the coke to produce only fuel gas
Lecture 21

Assistant Professor
IIT Roor kee
10 OCTOBER 2022
Catalytic conversion processes
• Catalytic conversion processes became important in petroleum refining after
the Second World War.
• Catalytic cracking has been developed to produce high yields of gasoline with
high octane # from high-boiling stocks using catalysts. As different from thermal
cracking, catalytic cracking
• uses a catalyst
• takes place at lower temperature and lower pressure
• is more selective and flexible
• One type of 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
https://www.e-education.psu.edu/fsc432/content/lesson-7-overview 2
Fluid Catalytic Cracking (FCC)
• FCC is used to produce high-octane gasoline mainly from straight-run
atmospheric gas oil and light vacuum gas oil (LVGO)
• This process involves breaking up long chains of n-alkanes into shorter chains
of branched alkanes (isoalkanes), cycloalkanes (naphthenes), and aromatics by
using acidic catalysts
• In addition to high-octane gasoline, catalytic cracking produces LPG, cycle oils,
and olefin-rich light hydrocarbons (C3, C4)
• The olefins are used as petrochemical feedstocks, or as reactants in alkylation
and polymerization reactions, to produce higher molecular weight branched
alkanes and olefins to contribute to the high-octane gasoline pool.
Hydrocracking
• Hydrocracking processes have been introduced for upgrading heavier crude
oil fractions such as heavy vacuum gas oil (HVGO) and vacuum distillation
residue VDR.
• The heaviest fractions of crude oil, HVGO and VDR, may not be easily
processed by FCC because of potential problems with excessive coking on
the catalysts.
• For upgrading these high-boiling and aromatic-rich feedstocks, hydrogen is
introduced in the hydrocracking process, along with bi-functional catalysts
systems, to keep coking under control while upgrading the heavy fractions
to light and middle distillates.
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.
• A high octane number of gasoline is needed for current spark-ignition engines
to run at high compression ratios without knocking. High compression ratios in
spark-ignition engines translate to high power and high efficiency.
https://www.e-education.psu.edu/fsc432/content/chemistry-catalytic-cracking 5
Chemistry of catalytic cracking
• 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.
• Removing a hydride ion (H-, a hydrogen atom with an additional electron)
from an alkane (e.g., methane) produces carbenium ions (path 1a).
• Also, adding a proton (H+, a hydrogen atom without the electron) to an olefin
(e.g., ethylene) can produce carbenium ions, as shown in path 1b
Carbocations – Carbonium ions
• Carbonium ions are produced by adding a proton to an alkane, say methane, as
shown.
• The resulting ion C+H5 is called methanium
• Carbocations are formed from hydrocarbons on two different acid sites:

Bronsted acid sites and Lewis acid sites
• Bronsted acid sites donate protons and Lewis acid sites accept electrons to form
carbocations from hydrocarbons.
Bronsted and Lewis acid sites
• Olefin (e.g., ethylene, C=C) produces an ethyl
carbenium ion (C+2H5) by reacting with a proton
donated from Bronsted acid site.
• Alternatively, a Lewis acid site accepts an
electron (or a hydride ion, H-) from an alkane
(e.g., ethane, C-C) to produce the same ethyl
carbenium ion (C+2H5).
• These two reactions that take place on the acid
sites of catalysts, along with the formation of
carbonium ions by protonation of hydrocarbons,
function as the initiation steps in the ionic chain
reactions that lead to the products obtained from
catalytic cracking.
https://www.e-education.psu.edu/fsc432/content/bronsted-and-lewis-acid-sites 8
Ionic chain reactions
https://www.e-education.psu.edu/fsc432/content/ionic-chain-reactions 9
Ionic chain reactions
• The initiation step includes the formation of a carbonium ion by proton donation from a
Bronsted acid site and/or the formation of a carbenium ion through hydride ion abstraction
by a Lewis acid site
• In a propagation step, the carbonium ion goes through cracking to produce an alkane
product and a carbenium ion, while the carbenium ion produced on the Lewis acid site goes
through a β-scission to produce an olefin product and another carbenium ion
• In additional propagation reactions, carbenium ions (secondary, or tertiary) react with
alkanes to produce i-alkane products and other carbenium ions, which can go through
isomerization reactions generating more stable ions and the ionic chain reaction continues.
• Finally, in termination steps, carbenium ions donate a proton to restore a Bronsted acid site
and produce an olefin as final product, or they abstract a hydride ion to restore a Lewis acid
site producing an i-alkane product
• Other reactions during catalytic cracking include dehydrocyclization and dehydrogenation
reactions to produce aromatic compounds
• Thermal cracking reactions may also take place during catalytic cracking because of the
sufficiently high temperatures used in the process. Some claim that initial thermal cracking
of alkanes to produce olefins serve as an initiation step in ionic chain reactions
https://www.e-education.psu.edu/fsc432/content/ionic-chain-reactions 10
Products obtained through Thermal & Catalytic Cracking
• Short chain paraffins constitute the principal products in both thermal and
catalytic cracking cases with one important difference – an abundance of iso-
alkanes (branched-chain alkanes) in catalytic cracking products.
• Catalytic cracking products contain higher concentration of aromatic
compounds. High octane number of gasoline produced by catalytic cracking
can be attributed to high concentrations of i-alkanes and relatively more
abundant aromatics present in the crackate (catalytic cracking product)
• Having no olefins larger than butylene (C4) from catalytic cracking processes,
also distinguishes catalytic cracking products from thermal cracking products
obtained from gas oil
• High yields of C1 and C2 gaseous products (methane, ethane and ethylene)
from thermal cracking are contrasted with high yields of C3- C6, with small
quantities of methane and essentially no olefins heavier than butylene, from
catalytic cracking
https://www.e-education.psu.edu/fsc432/content/distribution-products 11
https://www.e-education.psu.edu/fsc432/content/distribution-products 12
https://www.e-education.psu.edu/fsc432/content/comparison-products-type-hydrocarbon 13
ΔHf of Carbenium Ions
ΔHf of Carbenium Ions
• Isomerization of a primary propyl carbenium ion to a secondary propyl
carbenium ion releases (19.1- 1.5) = 17.6 kcal/mol. This is a very large
thermodynamic driving force for the isomerization of primary ion to a secondary
ion, and further to a tertiary ion with even a larger driving force
• Isomerization of the secondary propyl ion to the tertiary propyl ion, releases 1.5
kcal/mol of energy
• It is, therefore, clear that the initiation and propagation of carbocations in
catalytic cracking chain reactions on the catalyst surfaces will be dominated by
the formation of secondary and tertiary carbocations. The reactions of these
carbocations lead to the formation of branched-chain alkanes and olefins with
high octane numbers
• Another important feature of carbocation formation is the differences in the
enthalpy of formation which favors the formation of carbocations > C3 versus
C1 and C2 ions, because C1 and C2 ions are primary ions. This explains the low
yields of C1 and C2 species obtained from catalytic cracking
Lecture 22

Assistant Professor
IIT Roor kee
11 OCTOBER 2022
Recap…
 Chemistry of catalytic cracking
 Comparison of products obtained between thermal and catalytic cracking

 History and types of catalytic cracking processes
 Houdry and Thermafor catalytic cracking process

Time-Line for Catalytic Cracking Processes
• McAfee (1915)
• Batch reactor catalytic cracking to produce light distillates
• Catalyst: AlCl3 – A Lewis acid, electron acceptor
• Alkane – electron(abstracted by AlCl3)→ a carboca on(+)→ ionic chain reac ons to crack long chains
• Houdry (1936) - a commercial process
• Continous feedstock flow with multiple fixed-bed reactors
• Cracking/catalyst regeneration cycles
The evolution of catalytic cracking
• Catalyst: clays, natural alumina/silica particles
processes is an exemplary
• Thermafor Catalytic Cracking (TCC) (1942) showcase in chemical engineering
• Continues feedstock flow with moving-bed catalysts for discussing the advancement of
• Catalyst: synthetic alumina/silica particles reactor configuration, driven by
energy conservation and process
• Higher thermal efficiency by process integration kinetics.
• Fluid Catalytic Cracking (FCC) (1942)
• Continuous feedstock flow with fluidized-bed catalysts
• Catalyst: synthetic alumina/silica+zeolites (1965)
McAfee Catalytic Cracking
• The first catalytic cracking process was developed as a batch process (McAfee,
1915) shortly after the development of a thermal cracking process.
• The process used Lewis acid catalysts (e.g., AlCl3) for cracking
• These catalysts were expensive and corrosive
• In addition to these impediments, use of a batch reactor in the McAfee
process did not allow large-scale commercialization of this process
https://www.e-education.psu.edu/fsc432/content/houdry-catalytic-cracking 5
Houdry Catalytic Cracking
• The first full-scale commercial process, the Houdry Catalytic Cracking, used much less
expensive catalysts, such as clays, and natural alumina and silica particles.
• For cracking, gas oil feed was heated to 800oF and fed to a fixed-bed reactor packed with the
catalyst particles.
• Cracking products are sent to a fractionator to be separated into gas, gasoline, light cycle oil
(LCO) and heavy cycle oil (HCO) products.
• A series of swing reactors were needed to switch the feed flow from one reactor to another
after approximately 10 minutes of operation.
• The switch to a swing reactor was necessary because of rapid coking on catalysts which,
being natural materials, had a wide range of activity.
• Rapid coking on silica/alumina particles deactivated these catalysts and led to plugging of
the reactors.
• After the flow was switched to another reactor, the isolated reactor was stripped with steam
for five minutes to remove the liquid products adsorbed on catalyst particles.
• After stripping with steam, the deactivated catalysts were regenerated by
burning off the coke on catalysts with hot air introduced to the reactor
• Catalyst regeneration also takes approximately 5 minutes before the reactor
with regenerated catalyst is ready to accept the feed again.
• By this time, the second reactor would be ready for the 10-minute cycle of
steam stripping and catalyst regeneration.
• Having a third reactor in the plant would help deal with any delays/problems
in reactor preparation.
• Considering that catalytic cracking is an endothermic process, the heat
generated from burning the coke off the catalyst could be used partially to heat
the catalyst particles for the endothermic reaction.
• A large portion of the heat in the flue gases from coke combustion was not
available for the process. Therefore, the thermal efficiency of the Houdry
Process was low.
https://www.youtube.com/watch?v=EcdxPreDi_c&feature=youtu.be
Thermafor Catalytic Cracking (TCC)
https://www.e-education.psu.edu/fsc432/content/thermafor-catalytic-cracking-tcc
9
https://www.youtube.com/watch?v=retU8u1S6JU&feature=youtu.be
• Thermafor (also referred to as “thermofor” in some sources) Cracking Process
was introduced for better integration of thermochemistry (endothermic
cracking and exothermic catalyst regeneration) by introducing a moving-bed
configuration, rather than a fixed-bed
• Catalysts used in this process were synthetic alumina/silica beads that have
more homogeneous and consistent properties (e.g., activity) than the natural
minerals.
• Catalysts particles and the feed are introduced from the top of the reactor and
the catalyst particles move downward with gravity as the cracking reactions
take place on the catalyst surfaces
• Steam is injected from the bottom of the reactor to carry the cracking
products to the fractionator for recovery
https://www.e-education.psu.edu/fsc432/content/thermafor-catalytic-cracking-tcc 10
• As the particles move down the reactor, they are deactivated by coke build-up
on active sites.
• The deactivated catalysts removed from the bottom of the reactor are sent to
a regenerator unit where the coke on catalysts surfaces are burned off and the
heated catalysts particles are recycled to the top of the reactors by bucket
elevators
• Hot catalyst particles provide most of the heat necessary for the cracking
reactions in the reactor
• Although the thermal efficiency of TCC is higher than that of the Houdry
process, there was still a significant amount of heat loss during the transport of
heated catalyst particles by bucket elevators.
11
Lecture 23

Assistant Professor
IIT Roor kee
12 OCTOBER 2022
Recap…
 Chemistry of catalytic cracking
 History and types of catalytic cracking processes
 Houdry catalytic cracking
 Thermafor catalytic cracking

 Fluid catalytic cracking
 Zeolite catalysts
 Hydrocracking

• Fluid Catalytic Process, also introduced in 1942, offered an excellent
integration of the cracking reactor and the catalyst regenerator that provides
the highest thermal efficiency
• In FCC, a fluidized-bed (or fluid-bed) of catalyst particles is brought into
contact with the gas oil feed along with injected steam at the entrance (called
the riser) of the reactor
• The hot catalyst particles coming from the regenerator unit evaporate the feed
gas oil upon contact in the riser, and the cracking starts as the gas oil vapors
and the catalyst particles move upward in the reactor
• The temperature of the catalyst particles drops as the evaporation of gas oil
and endothermic cracking reactions proceed during the upward movement
• Cracking reactions also deposit a significant amount of coke on the catalysts,
leading to the deactivation of the catalyst
• After removing the adsorbed hydrocarbons by steam stripping, the coked
catalyst is sent to the regeneration unit to burn off the coke with air.
• Heat released from burning the coke deposit increases the temperature of the
catalyst particles that are returned to the riser to complete the cycle.
• Burning off the rejected carbon (coke) in the regenerator provides the energy
necessary for cracking without much loss, thus increasing the thermal
efficiency of the process.
• The cracking products are sent to the fractionator for recovery after they are
separated from the catalyst particles in the upper section of the reactor.
5
• In the reactor, the cracking reactions initiate on the active sites of the catalysts
with the formation of carbocations and the subsequent ionic chain reactions
produce branched alkanes and aromatic compounds to constitute the crackate
(cracked gasoline with high octane number), light olefins, cycle oils, and slurry oil
that are sent to the fractionator.
• A carbon-rich byproduct of catalytic cracking, termed “coke,” deposits on
catalyst surfaces and blocks the active sites.
• FCC is considered a carbon rejection process because the coke deposited on the
catalyst surface and eventually burned off for heat is rich in carbon and thus
enables the production of large quantities of a light distillate (crackate) in the
process without the addition of hydrogen
Configurations of FCC processes
• Two different configurations of the commercial FCC processes exist depending on
the positions of the reactor and the regenerator:
• they can be side by side or
• stacked, where the reactor is mounted on top of the regenerator.
•Major licensor companies that offer FCC processes with different configurations
include Kellogg Brown & Root, CB&I Lummus, ExxonMobil Research and
Engineering, Shell Global Solutions International, Stone & Webster Engineering
Corporation, Institut Francais du Petrole (IFP), and UOP.
• The UOP design of high-efficiency two-stage regenerator units offer advantages of
uniform coke burn, higher conversion of CO to CO2 and lower NOx emissions among
others.
• Another modification to FCC plants could be the installation of a catalyst cooler,
which may provide better control of the catalyst/oil ratio; the ability to optimize the
FCC operating conditions, increase conversions, and process heavier residual
feedstocks; and better catalyst activity and catalyst maintenance
Configurations of FCC processes
Zeolite catalyst for FCC
• One of the significant developments in FCC practice was the introduction of
zeolite catalysts in 1965.
• Catalysts and additives play a major role in the selectivity and flexibility of FCC
processes.
• FCC catalyst consists of a fine powder with an average particle size of 60–75
μm and a size distribution ranging from 20 to 120 μm.
• Four major components make up the catalysts: zeolite, active matrix, filler, and
binder.
• Each of these constituents has a unique role to play, but zeolite is the key
component that is more active and selective for high-octane number gasoline
production
Zeolite catalyst for FCC
Lecture 24

Assistant Professor
IIT Roor kee
13 OCTOBER 2022
Catalytic Hydrocracking
• Catalytic hydrocracking is one of the latest additions to petroleum refining
processes, with the first modern commercial unit started up by Chevron in
1958.
• The interest in hydrocracking has been attributed to the increasing demand for
light and middle distillates, the availability of byproduct hydrogen in large
quantities from catalytic reforming, and the environmental regulations limiting
sulfur and aromatic hydrocarbons in motor fuels
• The advantages of hydrocracking include its ability to handle a wide range of
feedstocks that may be difficult to process by catalytic cracking and its flexibility
in selectivity between light and middle distillates.
• The principal objective of hydrocracking is to decrease the molecular weight
and boiling point of heavy oils to produce saturated hydrocarbons (diesel and
jet fuel) from highly aromatic feedstocks (e.g., LCO from FCC) and distillation
residua.
Catalytic Hydrocracking
• The hydrocracking process has two dimensions: Hydrogenation of aromatic
rings and cracking of aliphatic compounds
• Aromatic rings cannot be cracked before they are saturated with hydrogen.
• With hydrocracking it is possible to convert an aromatic compound to a
paraffinic compounds without any loss of carbon
• As a hydrogen-addition process, hydrocracking provides high yields of valuable
distillates without producing low-grade byproducts (e.g., heavy oils, gas, or
coke) as experienced in carbon rejection processes such as coking.
3
Chemistry of catalytic hydrocracking
Hydrocracking catalysts
• The two different reaction systems in hydrocracking, hydrogenation and cracking, are
supported by bi-functional catalyst formulations
• Hydrogenation reactions are promoted by the metal component of the catalysts (e.g., Ni,
Co, Mo), and the cracking takes place on catalyst support consisting of silica/alumina
• Highly active noble metals (e.g., Pt, and Pd) can be used for hydrogenation of hydrocarbons
with extremely low sulfur contents as the noble metals are susceptible to sulfur poisoning.
•Hydrocracking processes most commonly include two reaction stages: Hydrotreating to
remove heteroatom (S, N, O) species and Hydrocracking to increase the H/C ratio of the
hydrocarbons in the feeds by hydrogenation and to decrease their molecular weight by
cracking.
• In most cases, the hydrotreating reactor (HT) packed with cobalt-molybdenum catalysts
precedes the hydrocracking (HC) reactor typically packed with nickel-tungsten catalysts (for
hydrogenation) supported on alumina/silica (for cracking).
Hydrocracking catalysts
Configuration of hydrocracking process
• Different configurations of hydrocracking processes, depending on the heteroatom
content of the feeds.
• For feeds with very low heteroatom contents, hydrocracking without hydrotreating
may be applied, but this is very rare.
• Other process configurations include single stage with dual catalysts, two-stage dual
and triple catalysts
• The hydrocracking reactions are performed at 300–400°C and 8–15 MPa of
hydrogen pressure.
• In a refinery, hydrocracking complements catalytic cracking by taking on the more
aromatic feedstocks that resist cracking, including the byproducts of FCC, such as light
cycle oil (LCO).
• Hydrocracking can also be used to upgrade residual fractions using different reactor
configurations and catalysts depending on the complexity of the upgrading tasks,
7
Configuration of hydrocracking process
Reactor configurations for hydrocracking process
• Hydrocracking a relatively light feedstock (e.g., atmospheric residue), a fixed-
bed configuration and relatively large-size catalyst particles can be used
• In extreme cases with very heavy vacuum residue, an expanded bed
configuration is used in which very fine catalyst particles are entrained in the
feed at high hydrogen pressures (high hydrogen/oil ratio)
• These extreme reaction conditions are necessary to prevent extensive coking
on catalysts that could shut down the process. For intermediate cases, an
ebullated (fluidized) bed configuration can be used
• In the United States, hydrocracking of LCO (from FCC) provides a large
proportion of the diesel fuel production because straight-run LGO is a preferred
stock for FCC to produce gasoline as the principal product
• The major licensors of hydrocracking processes include Chevron, UOP,
ExxonMobil Research and Engineering, BP, Shell, and BASF-IFP.
9
Reactor configurations for hydrocracking process
Salient aspects of hydrocracking
• Hydrocracking involves C-C bond cleavage to produce lighter HC's
• More liquid yield with Hydrocracking
• More hydrogenated products
• Cracking is less severe
• Secondary cracking reactions are minimized by stabilization of active species by
hydrogen
• Hydrocracking is more flexible w.r.t. the feedstock
• Refractory feedstocks (i.e. aromatics) can be processed
• C-C bond breaking after saturation with hydrogen
11
Hydrocracking vs. Catalytic Cracking
Lecture 25

Assistant Professor
IIT Roor kee
17 OCTOBER 2022
Catalytic Reforming
• Catalytic reforming converts low-octane, straight-run naphtha fractions, particularly
heavy naphtha that is rich in naphthenes, into a high-octane, low-sulfur reformate,
which is a major blending product for gasoline.
• The most valuable byproduct from catalytic reforming is hydrogen to satisfy the
increasing demand for hydrogen in hydrotreating and hydrocracking processes.
• Most reforming catalysts contain platinum as the active metal supported on
alumina, and some may contain additional metals such as rhenium and tin in bi- or
tri-metallic catalyst formulations.
• In most cases, the naphtha feedstock needs to be hydrotreated before reforming to
protect the platinum catalyst from poisoning by sulfur or nitrogen species.
• With the more stringent requirements on benzene and the total aromatics limit for
gasoline in the United States and Europe, the amount of reformate that can be used
in gasoline blending has been limited, but the function of catalytic reforming as the
only internal source of hydrogen continues to be important for refineries.
https://www.e-education.psu.edu/fsc432/content/catalytic-reforming 2
Catalytic Reforming
Catalytic Reforming
• The feedstock for catalytic reforming is straight-run (directly from the crude
oil) heavy naphtha that is separated in the naphtha fractionator of the Light
Ends Unit
• Hydrotreating heavy naphtha is often necessary before catalytic reforming to
protect the noble metal catalyst (e.g., Pt) used in the reforming process. The
intended product from catalytic reforming is the high-octane-number
reformate and the most significant by-product is hydrogen gas.
• Main purpose of the process is to increase the octane number of heavy
naphtha, conversion of naphthenes to aromatics and isomerization of
n-paraffins to i-paraffins are the most important reactions of interest.
• The catalysts used in reforming contains platinum (Pt), palladium (Pd), or, in
some processes, bimetallic formulations of Pt with Iridium or Rhenium
supported on alumina (Al2O3).
Chemistry of Catalytic Reforming
• Reactions of Interest
1. naphthenes → aroma cs
2. paraffins are isomerized
3. aromatics are unchanged
• Catalysts Used
•Platinum catalyst on metal oxide support (platforming) - Pt/Al2O3
•Bimetallic – Iridium or Rhenium [Pt-Re/Al2O3]
Feedstock: Heavy Naphtha Product: High Octane Gasoline
Paraffins ⇒ 45-55% Paraffins ⇒ 30-50%
Naphthenes ⇒ 30-40% Naphthenes ⇒ 5-10%
Aromatics ⇒ 5-10% Aromatics ⇒ 45-60%
https://www.e-education.psu.edu/fsc432/content/chemistry-catalytic-reforming
5
Desirable reactions of Catalytic Reforming
• Desirable chemical reactions of catalytic reforming including:
• dehydrogenation of naphthenes to aromatics,
• dehydroisomerization of alkyl-C5-naphthenes,
• dehydrocyclization of n-paraffins to aromatics, and
• isomerization of n-alkanes to i-alkanes
https://www.e-education.psu.edu/fsc432/content/desirable-chemical-reactions 6
Desirable reactions of Catalytic Reforming
• Aromatic compounds and large quantities of

by-product H2 are produced in the highly
endothermic Reactions 1–3.
• High temperatures, low hydrogen pressures,
low space velocity (SV), and low H2/HC ratio
strongly promote the conversion in Reaction
1-3.
• Although maintaining a low hydrogen
pressure is needed for promoting equilibrium
conversion in Reactions 1-3, it is, however,
necessary to maintain a sufficiently high
hydrogen pressure in the reactors to inhibit
coke deposition on the catalyst surfaces.
https://www.e-education.psu.edu/fsc432/content/desirable-chemical-reactions 7
Undesired reactions in catalytic reforming
• Hydrocracking is an undesired side reaction in catalytic reforming because it
consumes hydrogen and decreases the reformate yield by producing gaseous
hydrocarbons.
• Hydrocracking reactions are exothermic, but they can still be kinetically
favored at high temperatures, and favored, obviously, by high hydrogen
pressures.
• Typically, reformers operate at pressures from 50 to 350 psig (345–2415
kPa), a hydrogen/feed ratio of 3–8 mol H2/mol feed, and liquid hourly space
velocities of 1–3 h-1
• These conditions are chosen to promote the desired conversion reactions
and inhibit hydrocracking while limiting coke deposition on the catalyst
surfaces.
https://www.e-education.psu.edu/fsc432/content/undesired-reactions 8
Undesired reactions in catalytic reforming
n-C10+H2 → n-C6+n-C4
To inhibit this reaction, use
1.high T
2.high SV
3.Low H2P
Catalytic reformers are normally run at low H2 pressure to inhibit
hydrocracking!
Heats of Reactions:
• paraffin to naphthene → 44 kJ/mol H2 - endothermic
• naphthenes to aromatics → 71 kJ/mol H2 - endothermic
• hydrocracking → -56 kJ/mol H2 - exothermic
https://www.e-education.psu.edu/fsc432/content/undesired-reactions 9
Catalytic reforming reaction network
• The surfaces of metals (e.g., Pt) catalyze
dehydrogenation reactions, whereas the
acid sites on the support (e.g., alumina)
catalyze isomerization and cracking
reactions.
• Metal and acid sites are involved in the
catalysis of hydrocracking reactions.
• Achieving the principal objective of
catalytic reforming—high yields and
high quality of reformate—can be
achieved, to a large extent, by
controlling the activity of the catalysts
and the balance between acidic and
metallic sites to increase the selectivity
to desirable reactions in the reaction
network.
https://www.e-education.psu.edu/fsc432/content/reaction-network 10
Catalytic Reforming Process
• The first commercial catalytic reforming process was introduced by UOP in
1949 as the PlatformingTM process.
• Typical process employs two reactors. The reactors operate in series with
furnaces placed before each reactor to heat the feedstock and the reactor
effluents to 500–530°C before entering each reactor because the
predominant reforming reactions are highly endothermic.
• These units, called “semi-regenerative catalytic reformers,” need to be shut
down once every 6–24 months for the in-situ regeneration of catalysts that are
deactivated by coke deposition.
• Later designs included an extra reactor (a swing reactor) to enable isolation of
one reactor at a time to undergo catalyst regeneration, whereas the other two
reactors are running (Cyclic). This configuration enables longer on-stream times
(up to 5 years) before scheduled shutdowns for catalyst regeneration, but it has
not become popular.
https://www.e-education.psu.edu/fsc432/content/catalytic-reforming-processes 11
Catalytic Reforming Process
Catalytic Reforming Processes Based on Catalyst Regeneration
• Semi-regenerative (1949) – unit taken off-stream anywhere from every 3 to
24 months
• Cyclic (1960) – involves swing reactor. Basically, operate 3 out of 4 and use
extra reactor to take one offline.
• Continuous (1971) – catalyst is removed and replaced during the operation.
Maintains high activity. Expensive.
Continuous Catalyst Regeneration
• A continuous catalyst regeneration (CCR) scheme for reforming came on stream in 1971.
• The reactors are stacked with a moving bed of catalyst trickling from the top reactor to the
bottom reactor by gravity.
• Partially deactivated catalyst from the bottom of the reactor stack is continuously
withdrawn and transferred to the CCR regenerator.
• The regenerated catalyst is re-injected to the top of the first reactor to complete the catalyst
circulation cycle.
• Hydrotreated naphtha feed is combined with recycled hydrogen gas and heat exchanged
with the reactor effluent.
• The combined feed is then raised to the reaction temperature in the charge heater and sent
to the first reactor section. Because the predominant reforming reactions are endothermic,
an inter-reactor heater is used to reheat the charge to the desired reaction temperature
before it is introduced to the next reactor.
• The effluent from the last reactor is heat exchanged with the combined feed, cooled, and
separated into vapor and liquid products in a separator.
https://www.e-education.psu.edu/fsc432/content/continuous-catalyst-regeneration 14
• The vapor phase is rich in hydrogen gas, and a portion of the gas is
compressed and recycled back to the reactors.
• Recycling hydrogen is necessary to suppress coking on the catalysts. The
hydrogen-rich gas is compressed and charged together with the separator
liquid phase to the product recovery section.
• The performance of the unit (i.e., steady reformate yield and quality)
depends strongly on the ability of the CCR regenerator to completely
regenerate the catalyst.
• In addition to UOP’s Platforming process, the major commercial catalytic
reforming processes include PowerformingTM (ExxonMobil),
UltraformingTM and MagnaformingTM (BP), Catalytic Reforming (Engelhard),
Reforming (IFP), and RheniformingTM (Chevron).
Lecture 26

Assistant Professor
IIT Roor kee
18 OCTOBER 2022
Outline of today’s lecture
 Alkylation
 Polymerization
 Isomerization
 Introduction to Deasphalting process

Alkylation
• The alkylation process combines light iso-paraffins, most commonly isobutane,
with C3–C4 olefins, to produce a mixture of higher molecular weight iso-paraffins
(i.e., alkylate) as a high-octane number blending component for the gasoline pool.
• Iso-butane and C3–C4 olefins are produced as by-products from FCC and other
catalytic and thermal conversion processes in a refinery.
• The alkylation process was developed in the 1930s and 1940s to initially produce
high-octane aviation gasoline, but later it became important for producing motor
gasoline because the spark ignition engines have become more powerful with
higher compression ratios that require fuel with higher octane numbers.
• With the recent restrictions on benzene and the total aromatic hydrocarbon
contents of gasoline by environmental regulations, alkylation has gained favor as an
octane number booster over catalytic reforming. Alkylate does not contain any
olefinic or aromatic hydrocarbons.
https://www.e-education.psu.edu/fsc432/content/alkylation 3
Alkylation
Alkylation
• Alkylation reactions are catalyzed by strong acids (i.e., sulfuric acid [H2SO4] and hydrofluoric
acid [HF]) to take place more selectively at low temperatures of 70°F for H2SO4 and 100°F
for HF.
• By careful selection of the operating conditions, a high proportion of products can fall in the
gasoline boiling range with motor octane numbers (MONs) of 88–94 and RONs of 94–99.
• Early commercial units used H2SO4, but more recently, HF alkylation has been used more
commonly in petroleum refineries. HF can be more easily regenerated than H2SO4 in the
alkylation process, and HF alkylation is less sensitive to temperature fluctuations than
H2SO4 alkylation.
• In both processes, the volume of acid used is approximately equal to the volume of liquid
hydrocarbon feed. Important operating variables include acid strength, reaction
temperature, iso-butane/olefin ratio, and olefin space velocity.
• The reactions are run at sufficiently high pressures to keep the hydrocarbons and the acid in
the liquid phase. Good mixing of acid with hydrocarbons is essential for high conversions.
Acid catalyzed reaction mechanism
• These occur through ionic chain reactions initiated by donation of a proton
from the acid catalyst to an olefin to produce a carbocation that reacts with
iso-butane to form a tert-butyl cation.
• Subsequent propagation reactions involve the reactions of a tert-butyl cation
with olefins to form larger iso-paraffin cations that lead to final products
through reactions with iso-butane to form a new tert-butyl cation to sustain
the chain reaction.
• The alkylation reaction is highly exothermic; therefore, cooling the reactor
contents during alkylation is important.
Acid catalyzed reaction mechanism
UOP HF Alkylation Process
• Olefin and iso-butane feed streams are dried to remove water before they are mixed with the iso-
butane recycle stream. The mixture is fed to the reactor, where it is highly dispersed into an
incoming stream of acid catalyst.
• Conversion of reactants to high-quality alkylate takes place quickly, and the mixture flows up to
the settling zone.
• In the settler, the catalyst is separated out as a bottom phase and flows, by gravity, through the
catalyst cooler and returns to the reactor
• The hydrocarbon phase from the settler, which contains propane, recycled iso-butane, normal
butane, and alkylate, is charged to the main fractionator.
• High-purity propane is sent overhead to pass through the HF- propane stripper, de-fluorinator, and
potassium hydroxide (KOH) treater before it is recovered.
• Recycled iso-butane is drawn from the side of the fractionator and returned to the entrance of the
reactor after it is mixed with the dried olefin and isobutane feed. The n-butane product is taken
from the side of the fractionators as vapor, condensed and KOH- treated before recovery.
• The alkylate product is obtained from the bottom of the fractionator. The HF catalyst is
regenerated onsite in the regeneration section where heavy oils (tars) are removed from the
catalyst.
https://www.e-education.psu.edu/fsc432/content/uop-hf-alkylation-process 8
UOP HF Alkylation Process
Alkylation Process
• Transporting and working with concentrated acids pose safety risks.
• In particular, HF tends to form a vapor cloud that is difficult to disperse.
• The major licensor of the HF alkylation processes is UOP, whereas
ExxonMobil and Stratford Engineering Corporation license H2SO4 alkylation
processes.
• A newly designed alkylation process by UOP uses a solid catalyst called
Alkylene®
• Advantages of this new process over traditional HF alkylation processes
(liquid acid technology) include no acid transportation, no acid spills, no
corrosion, and reduced maintenance cost. Efforts to develop alternative
processes that use solid acid catalysts instead of concentrated HF and
H2SO4 for alkylation are underway.
Polymerization
• The polymerization process combines propenes and butenes to produce
higher olefins with high-octane numbers for the gasoline pool
• The polymerization process was used extensively in the 1930s and 1940s,
but it was replaced to a large extent by the alkylation process after World War
II
• It has gained favor after phasing out the addition of tetraethyl lead (TEL) to
gasoline, and the demand for unleaded gasoline has increased.
• The most commonly licensed polymerization process is the UOP
polymerization process, which uses phosphoric acid as catalyst. IFP licenses a
Dimersol® process that produces dimers from propene or butene using a
homogeneous aluminum alkyl catalyst.
https://www.e-education.psu.edu/fsc432/content/polymerization 11
Polymerization
https://www.e-education.psu.edu/fsc432/content/polymerization 12
Isomerization
• Isomerization processes have been used to isomerize n-butane to iso-butane used in
alkylation and C5 /C6 n-paraffins in light naphtha to the corresponding iso-paraffins to
produce high-octane number gasoline stocks after the adoption of lead-free gasoline.
• Catalytic isomerization processes that use hydrogen have been developed to operate
under moderate conditions
• Typical feedstocks for isomerization process include hydrotreated light straight-run
naphtha, light natural gasoline, or condensate.
• The fresh C5/C6 feed combined with make-up and recycled hydrogen is directed to a
heat exchanger for heating the reactants to reaction temperature.
• Hot oil or high-pressure steam can be used as the heat source in this exchanger. The
heated feed is sent to the reactor.
• Typical isomerate product (C5+) yields are 97 wt% of the fresh feed, and the product
octane number ranges from 81 to 87, depending on the flow configuration and
feedstock properties.
https://www.e-education.psu.edu/fsc432/content/isomerization 13
Lecture 27

Assistant Professor
IIT Roor kee
19 OCTOBER 2022
Outline of today’s lecture
 Deasphalting process
 Need
 Process
 Solubility concept

Deasphalting
• While distillation achieves separation/fractionation of the feed components with
respect to differences in their boiling point, deasphalting (as a solvent extraction
process) fractionates the feedstock, atmospheric, or more often vacuum distillation
residue (VDR), with respect to solubility/insolubility of molecular components in a
given solvent.
• A solvent fractionation scheme is used in laboratories to separate VDR into fractions
that are defined based on the solubility behavior
• VDR, which could be a solid at ambient temperature, is completely dissolved in
aromatic solvents such as benzene and toluene. The highest molecular weight
components of VDR classified as “asphaltene” can be separated by precipitation (as
solid material) when a light paraffin solvent is mixed with VDR solubilized in an
aromatic solvent (e.g., toluene)
• Paraffin solvent used (e.g., n-heptane) defines the identity of the separated
asphaltenes (e.g., toluene soluble and n-heptane insolubles)
• The portion of VDR that is soluble in the paraffin solvent is called maltenes, but also
labeled with respect to the solvent used in the separation, i.e., n-heptane maltenes
https://www.e-education.psu.edu/fsc432/content/deasphalting 3
Deasphalting
• The n-heptane solubles can further be separated using n-pentane (a lighter and a
weaker solvent) into insoluble (hard resin) and soluble (n-pentane solubles) fractions.
• The n-pentane solubles can also be separated using a lighter solvent yet (propane) to
soft resin and oil products.
• In refinery practice, only one stage of separation is used using the lightest solvent
(e.g., propane) to produce asphalt and deasphalted oil (DAO) fractions
• Asphaltenes consist of high-molecular weight compounds with strong aromatic
character and contain highest concentrations of heteroatom (S, N, and metal) species.
• Because of the low H/C ratio of asphaltenes and resins, the deasphalting process can
be considered as a “carbon rejection” process, yielding a high H/C ratio product (i.e.,
oil) after removing the asphaltenes and resins, as, typically, lower value byproducts
Solvent fractionation of vacuum distillation residue
Gradient solubility model
• Because of the large disparity in structure and properties of asphaltenes and
oil fractions in VDR, it is surprising that VDR appears as a solution (one-phase
material) rather than a suspension of discrete asphaltene particles in VDR.
• A commonly accepted hypothesis to explain the single phase observed with
VDR is known as the gradient solubility model, illustrated in Figure
https://www.e-education.psu.edu/fsc432/content/gradient-solubility-model 6
Gradient solubility model
• The gradient solubility model offers an explanation of how asphaltenes can be
forced out of the solution in VDR by solvent extraction.
• Briefly, the solubility of a compound in a given solvent depends on the strength of
the solvent that is measured by Hildebrand Solubility Parameters (HSP) for non-
polar solvents.
• The two definitions of HSP, indicating the dependence of the parameter values on
surface tension and molar volume of the solvent (1st Hildebrand parameter), or on
the energy of vaporization (heat necessary to evaporate the solvent under constant
volume conditions) and molar volume (2nd Hildebrand Parameter)
• Solubility parameter increases with the increasing density (decreasing molar
volume) and increasing surface tension, or increasing latent heat of vaporization.
• This explains why aromatic solvents have higher solvent power than aliphatic
hydrocarbons, and why the solvent power of paraffins decreases with the
decreasing carbon number.
Hildebrand Solubility Parameters
Deasphalting Process
• Deasphalting process in a refinery flow scheme as an intermediate process between
vacuum distillation and dewaxing processes, for producing the refinery output streams as
asphalt deasphalted oil (DAO), which can be directed to another separation process,
dewaxing, to produce lubricating oil base stock and wax, or can be sent to conversion units
such as hydrocracking to produce light and middle distillate fuels.
• It is important to note that the deasphalting process is an upgrading process to transform

VDR into marketable products, and/or convert it to distillate fuels that command high
demands
https://www.e-education.psu.edu/fsc432/content/deasphalting-process 9
Deasphalting Process
• The two objectives of the deasphalting process are:
• Produce asphalt - as final product.
• Remove asphaltenes to prevent coke, or metal buildup on catalyst in further processing of
DAO.
• Depending on the properties of the VDR and prevailing markets, the emphasis
could be placed on one of these objectives.
• Aromatic asphaltic crudes are more expensive to convert into distillate fuels
• Such crudes could be processed readily into making high yields of asphalt and
serve the asphalt market.
• With lighter crudes, the principal focus could be on removing the asphaltenes from
VDR so that DAO produced can be used in conversion processes with a lower extent
of problems caused by asphaltenes such as coke buildup, or metals buildup on
catalysts in, for example, hydrotreating or hydrocracking reactions.
Propane Deasphalting process
https://www.e-education.psu.edu/fsc432/content/simplified-flow-diagram-deasphalting-process 11
Propane Deasphalting process
• First step in deasphalting, residue (feedstock) is mixed with four to eight times
the volume of liquid propane.
• Heavier residua require a higher solvent to residue (S/R ) ratio for effective
separation of asphalt.
• Following the precipitation of asphalt, DAO and asphalt are separated, and
each stream is purified and flashed to recover and recycle the propane solvent
• The four-unit operations of deasphalting illustrated in the process flow diagram
are:
• Flocculation (& precipitation) of asphaltenes
• Asphalt decanting - separation
• Asphalt washing - to remove entrained oil
• Solvent recovery and recycle
Variables in Deasphalting process
• Independent variables in the deasphalting process include
• Solvent used
• Pressure
• Temperature
• Solvent/Residue (S/R) ratio and
• Contact time.
• These variables can be controlled to obtain the optimum conditions for the
desired separation in deasphalting.
• One of the important dependent variables in the process is the asphaltene
yield
• Qualitative plots of how asphaltene yield varies as a function of the process
parameters is provided
https://www.e-education.psu.edu/fsc432/content/asphaltene-yield 13
Asphaltene yield dependence on operating variables
• Solubility parameter of the solvent is a key a variable

that affects asphaltene yield • As temperature increases, solubility
• Asphaltene is completely soluble in toluene which parameter of the solvent decreases
has a high solubility parameter. Therefore, the
asphaltene yield with toluene will be zero
• Propane (C3,) which has the lowest solubility
parameter among the solvents given in the plot, will
give the highest asphaltene yield
Asphaltene yield dependence on contact time
• A sufficient amount of contact time with paraffin is

necessary for good asphaltene separation.
• The 8-10 h contact time refers to batch experiments

in laboratory.
• In flow systems of commercial deasphalting, the

contact time necessary for the desired separation of
asphalt is much shorter.
Asphaltene yield dependence on S/R ratio
• Asphaltene yield increases with the increasing solvent/residue ratio used in the process.
This is an unusual behavior for solvent extraction because, typically, the yield of an insoluble
fraction would decrease with the increasing quantity of solvent used in the extraction
behavior.
• The unusual behavior seen is termed as the “anti-solvent effect.”
• This relates to the gradient theory of asphaltene solubility in crude oil (or in VDR) such that
larger quantities of paraffin solvent used in the process more effectively disrupt the gradient
solubility by removing more oils from VDR, forcing the asphalt fraction (asphaltene+resin) to
separate out.
• Molecular composition of the asphaltenes would vary significantly along with the yield of
asphaltenes in the plot.
• As the yield of asphaltenes increases with the increasing S/R, lower molecular weight
asphaltenes would be progressively included in the separated asphaltenes. In other words,
for a given process, low yields of asphaltenes (obtained at low S/R) would contain the
highest molecular weight and highly aromatic compounds, whereas asphaltenes obtained at
high yield with high S/R ratio would include a broader range of molecular weight and
aromaticity in the separated asphaltenes.
• The consideration of variable asphaltene composition would also apply to
the asphaltenes separated with different paraffin solvents.
• In this case, lower yields of asphaltenes obtained with C7 (n-heptane) will be
associated with heavier and more aromatic asphaltenes than those obtained
with propane (C3).
• These observations relate to the absence of a precise molecular definition to
express the complex of asphaltenes, but the need to use an operational
definition on the basis of solubility/insolubility in a given solvent.
• It should, therefore, be remembered that the composition of the
asphaltenes, or asphalt produced in a refinery would not only depend on the
properties and composition of the parent crude oil, but also on the solvent,
as well as the S/R ratio used in the process among other factors, such as
temperature and pressure as they affect the solubility parameters of the
solvent
Lecture 28

Assistant Professor
IIT Roor kee
20 OCTOBER 2022
Dewaxing
• Dewaxing process in petroleum refining is removal of wax.
• The feedstocks to dewaxing include DAO from deasphalting, and HVGO from
vacuum distillation along with some compositional characteristics of the
feedstock and the dewaxing product.
• Wax (long-chain paraffins) obtained in dewaxing is a marketable by-product.
• Lubricating oil base stock is the principal product of interest
• The main purpose of dewaxing is to remove hydrocarbons that solidify readily
(i.e., wax) for making lubricating oil base stock with low pour points
https://www.e-education.psu.edu/fsc432/content/dewaxing 2
Feedstock for dewaxing and hydrocarbon composition
of the feed and the products
Desired properties of lube oil stock
• In addition to low pour points, other important properties of lube oil base stocks
include:
• Volatility – should be low to keep oil in the liquid phase during engine operation. Vapors are not
good lubricants.
• Viscosity– important to control because of lubrication and heat transfer considerations.
Moderate viscosities are desired. Low viscosity may not provide the required lubrication and
lead to high friction between metal parts. High viscosity causes loss of energy.
• Viscosity Index (change in viscosity with temperature) – small change in viscosity is desired over
a wide temperature oil, i.e., high viscosity index (HVI). HVI ensures that the lube oil functions
well at both cold start and at high temperatures generated by the engines.
• Thermal Stability – High thermal stability (or small degree of thermal degradation at high
temperatures) is necessary to minimize viscosity loss and coke deposition on metal surfaces
• All of these properties depend on the molecular composition of the hydrocarbons
constituting the lubricating oil base stocks. Commercial engine oils and other
commercial lube oils are formulated with chemical additives that would enhance the
performance of the base stocks.
Types of Dewaxing Process
• Two commercial methods of dewaxing are
• Solvent dewaxing - physical process; separation of wax by freezing and solvent
transport.
• Catalytic dewaxing - chemical process; removal of wax by selective reaction of long
chain n-alkanes (wax).
Solvent dewaxing
https://www.e-education.psu.edu/fsc432/content/solvent-dewaxing 6
Solvent dewaxing
• Stage-wise refrigeration of the feedstock after it is mixed with the solvent.
• The lowest temperature used in the refrigeration cascade depends on the desired
pour point of the lube oils base stock product
• Upon refrigeration, wax compounds solidify to form crystals. Wax crystals are
carried in the solvent to a rotary filter where wax is separated on a filter cloth
covering the rotating drum.
• The layer of wax (filter cake) on the drum is scraped from the filter by a blade and
carried away in a solvent stream to a steam-stripping unit to recover and recycle
the solvent separated from the wax product.
• The wax product, called slack wax, can be used to make paraffin wax for candles,
microwax used in the cosmetics industry, and petrolatum for petroleum jelly.
• The dewaxed oil from the filtration unit is also steam stripped to recover the
solvent to produce the lube oil base stock.
Solvent dewaxing
• The two principal solvents used in solvent dewaxing units are methyl ethyl
ketone (MEK) and propane
• Although the majority of dewaxing units in the U.S. refineries use MEK, some
advantages of using propane as a solvent compared to MEK include the
following:
• Propane is used both as a diluent and as a refrigerant
• Lower capital investment
• Refrigeration energy savings
• Higher filtration rates
• Rejection of asphaltenes and resins in the feed
• Higher VI than ketone dewaxing
Catalytic dewaxing process
• Although included under the separation processes, catalytic dewaxing is actually a
low-severity conversion process involving a selective catalytic cracking of n-paraffins.
• Because of removing wax (long chain n-paraffins) by chemical reaction, the process is
called dewaxing.
• The selective cracking of n-alkanes takes place in the pores of molecular sieve
catalysts (zeolites) with pore openings in the order of 0.6nm, which keep i-paraffins
out because of their larger size due to branching in the hydrocarbon skeleton.
• This selective cracking increases the ratio of i-paraffins to n-paraffins in the product
and lowers its pour point. Hydrogen is introduced along with the feed to prevent
coking on the catalyst surfaces.
• The cracking of n-paraffins produces distillate fuels such as gasoline as a by-product
from catalytic dewaxing.
Catalytic dewaxing process
https://www.e-education.psu.edu/fsc432/content/catalytic-dewaxing 10
Advantages of catalytic dewaxing process
• The advantages of catalytic dewaxing include:
• Production of lube base stock with lower pour point and in higher yield compared to the
product obtained from solvent dewaxing. Low yield from solvent dewaxing results from
the difficulty of separating the oil from the wax
• Lower capital investment
• Good product stability
• Flexibility to produce both lube oil base stock and light distillates
Chemistry and process flow sheet of catalytic dewaxing

Lecture 17 - Thermal Cracking-Merged

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CHN-327 Petroleum Refining

Dr. Hari Prakash Veluswamy

CHN-327 PETROLEUM REFINING 2

CHN-327 PETROLEUM REFINING 3

• R-H represents a paraffin chain which can be expanded such as (H-(CH2)n-H)

• In a hydrogen abstraction reaction, for example, the radical R1 removes

Dr. Hari Prakash Veluswamy

CHN-327 PETROLEUM REFINING 2

Dr. Hari Prakash Veluswamy

CHN-327 PETROLEUM REFINING 2

Dr. Hari Prakash Veluswamy

CHN-327 PETROLEUM REFINING 2

CHN-327 PETROLEUM REFINING 3

Dr. Hari Prakash Veluswamy

• Carbocations are formed from hydrocarbons on two different acid sites:

Dr. Hari Prakash Veluswamy

CHN-327 PETROLEUM REFINING 2

CHN-327 PETROLEUM REFINING 3

Dr. Hari Prakash Veluswamy

CHN-327 PETROLEUM REFINING 2

CHN-327 PETROLEUM REFINING 3

Dr. Hari Prakash Veluswamy

Dr. Hari Prakash Veluswamy

• Aromatic compounds and large quantities of

Dr. Hari Prakash Veluswamy

CHN-327 PETROLEUM REFINING 2

Dr. Hari Prakash Veluswamy

CHN-327 PETROLEUM REFINING 2

• It is important to note that the deasphalting process is an upgrading process to transform

• Solubility parameter of the solvent is a key a variable

• A sufficient amount of contact time with paraffin is

• The 8-10 h contact time refers to batch experiments

• In flow systems of commercial deasphalting, the

Dr. Hari Prakash Veluswamy

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