THERMAL CRACKING

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Purpose of Thermal Cracking:

To make more light & middle distillates from heavier ends by

pyrolysis, or thermolysis.
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Process conditions and parameters

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 Process conditions and parameters

Vapor phase Liquid phase

Low pressure (<200 psig) High pressure (350 – 1500 psig)
High T’s (1000 - 1200° F) Low T (750 - 950° F)
Low gasoline yield High gasoline yields
High octane # (aromatics & olefins) Low octane #
Extensive coke formation Low gas yield
High gas yields
Materials problems

Products
Products include paraffins, olefins, naphthenes, and aromatics. Amount of
shorter straight chain alkanes (such as C2, C3 ) is relatively high.

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 PROCESS DIAGRAAM

FRACTIONATOR

Gasoline

SOAKER
LGO

1000 – 1100° F
350 – 700 psig

Light oil
Vapor phase

750 – 900° F
350 – 700 psig

Heavy oil Liquid phase

Fuel oil

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 Chemistry of Thermal Cracking

1) Free radicals (not ions) are the active species

Neutral species; unpaired electrons

2) Free radical chain reactions

Initiation
R–H R1• + R2• homolysis – homolytic bond cleavage

Propagation
R1• + R–H  R1 – H + R • hydrogen abstraction–favored at high pressures
R1•  olefin + R  scission – favored at low pressures

Termination
R4• + R5•   R–R Radical Combination
2R4•  olefin + alkane Disproportionate

3) Isomerization
C – C – C – C – C – C  C – C – C – C – C – C -not favored
 – scission  C = C + C – C – C – C - faster than isomerization

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 VISBREAKING PROCESS

Feedstock From Process Typical products - to - unit

Residual Atmospheric Decompose Gasoline or distillate To

tower & Hydrotreating
Vacuum tower Vapor To Hydrotreater
Residue To Stripper or
recycle
Gases To Gas plant

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Schematic of
visbreaking unit

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STEAM CRACKING

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COKING PROCESSES

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 DELAYED COKING

GAS

HEAVY FEED LIQUID

COKE

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Schematic of delayed coking unit
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CONTINUOUS COKING

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 COKING PROCESSES

Feedstock From Process Typical products - to - unit

Naphtha, Distillation Decomposition •Gasoline or distillate To

gasoline column, Hydrotreating
blending •Vapor To Hydrotreater
•Residue To Stripper or
recycle
•Gases To Gas plant

Clarified oil Catalytic   Coke to Shipping, recycle

Tars cracker Gas oil to Catalytic cracking
Various units

Wastewater, Treatment    
(sour) Gases Gas plant

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 SAFETY CONSIDERATIONS

Because thermal cracking is a closed process, the primary

potential for fire is from leaks or releases of liquids,
gases, or vapors reaching an ignition source such as a
heater.
In coking, temperature control must often be held within
a 10°-20° F range, as high temperatures will produce coke
that is too hard to cut out of the drum.
Conversely, temperatures that are too low will result in
high asphaltic-content slurry.
Water or steam injection may be used to prevent buildup
of coke in delayed coker furnace tubes.
Water must be completely drained from the coker, so as
not to cause an explosion upon recharging with hot coke.

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Provisions for alternate means of regress from the
working platform on top of coke drums are important in
the event of an emergency.

The potential exists for exposure to hazardous gases

such as hydrogen sulfide and carbon monoxide, and
trace polynuclear aromatics (PNA's) associated with
coking operations.

When coke is moved as a slurry, oxygen depletion may

occur within confined spaces such as storage silos,
since wet carbon will adsorb oxygen.

Wastewater may be highly alkaline and contain oil,

sulfides, ammonia, and/or phenol.
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 CORROSION CONSIDERATIONS
When sour crudes are processed, corrosion can occur
where metal temperatures are between 450° and 900°
F. Above 900° F coke forms a protective layer on the
metal.

The furnace, soaking drums, lower part of the tower,

and high-temperature exchangers are usually subject
to corrosion.

Hydrogen sulfide corrosion in coking can also occur

when temperatures are not properly controlled above
900° F.

Continuous thermal changes can lead to bulging and

cracking of coke drum shells. 23
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CATALYTIC CRACKING

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CATALYTIC CRACKING

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The three types of catalytic cracking processes are;

1. Fluid catalytic cracking (FCC),

2. moving-bed catalytic cracking, and
3. Thermofor catalytic cracking (TCC).

The catalytic cracking process is very flexible, and

operating parameters can be adjusted to meet
changing product demand.

In addition to cracking, catalytic activities include;

1. dehydrogenation,
2. hydrogenation, and
3. isomerization.
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 CATALYTIC CRACKING PROCESSES

Feedstock From Process Typical products - to - unit

Deasphalted Deashpalter Decompositio •Middle distillates To

oils n, alteration Hydrotreat, blend, or recycle
•Petrochem feedstock To
Petrochem or other
•Residue To Residual fuel
blend

Gas oils Towers, coker Decompositio •Gasoline To Treater or blend

visbreaker n, alteration •Gases To Gas plant

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Feedstocks:

 straight – run gas oil

 vacuum gas oil
 atmospheric residue
 heavy ends (coker gas oil,
DAO)
 vacuum residue

Pretreatment:

 deasphalting – to prevent excessive coking on

catalyst surfaces
 demetallation (Ni, V) – prevent catalyst deactivation
 hydrocracking – to prevent excessive coking

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Products from Catalytic Cracking

n-paraffins, i-paraffins, aromatics, naphthenes, and

olefins.

I-paraffins come from ionic reaction, is branched chain,

have high Octane number.
C3 – C4 gases
C5 – C10 isoparaffins (gasoline), olefins, aromatics,
napthenes
> C10 – light cycle oil
> C14 – decant oil

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 FLUID CATALYTIC CRACKING

The most common process is FCC, in which the oil is

cracked in the presence of a finely divided catalyst,
which is maintained in an aerated or fluidized state by
the oil vapors.
The fluid cracker consists of a catalyst section and a
fractionating section that operate together as an
integrated processing unit.
The catalyst section contains the reactor and
regenerator, which, with the standpipe and riser, form
the catalyst circulation unit.
The fluid catalyst is continuously circulated between
the reactor and the regenerator using air, oil vapors,
and steam as the conveying media.
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A typical FCC process involves mixing a preheated
hydrocarbon charge with hot, regenerated catalyst as it
enters the riser leading to the reactor.
The charge is combined with a recycle stream within the
riser, vaporized, and raised to reactor temperature
(900°-1,000° F) by the hot catalyst.
As the mixture travels up the riser, the charge is
cracked at 10-30 psi.
In the more modern FCC units, all cracking takes place
in the riser.
The "reactor" no longer functions as a reactor; it
merely serves as a holding vessel for the cyclones.
This cracking continues until the oil vapors are
separated from the catalyst in the reactor cyclones. 33
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The resultant product stream (cracked product) is then
charged to a fractionating column where it is separated
into fractions, and some of the heavy oil is recycled to
the riser.
Spent catalyst is regenerated to get rid of coke that
collects on the catalyst during the process.
Spent catalyst flows through the catalyst stripper to
the regenerator, where most of the coke deposits burn
off at the bottom where preheated air and spent
catalyst are mixed.
Fresh catalyst is added and worn-out catalyst removed
to optimize the cracking process.

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Schematic of FCC unit
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 FCC PROCESS DIAGRAM

Fluid Catalytic Cracking (FCC)

Introduced in 1942
Different process configurations (Fig 6.1 G&H)

Introduction of zeolites in 1965

greatly improved this process.
Zeolite particles are 70 µm in dia.
CO Boiler

Flue gas 1650° F

Flue gas
2nd stage riser
13
00
°F
Regenerator
1000° F
1st stage
1300 - 1400° F

Feed (300 ° F)
Air Steam
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 Moving Bed Catalytic Cracking

The moving-bed catalytic cracking process is similar to

the FCC process.

The catalyst is in the form of pellets that are moved

continuously to the top of the unit by conveyor or
pneumatic lift tubes to a storage hopper, then flow
downward by gravity through the reactor, and finally to
a regenerator.

The regenerator and hopper are isolated from the

reactor by steam seals.

The cracked product is separated into recycle gas, oil,

clarified oil, distillate, naphtha, and wet gas.
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 Thermofor Catalytic Cracking

In a typical thermofor catalytic cracking unit, the

preheated feedstock flows by gravity through the
catalytic reactor bed.

The vapors are separated from the catalyst and sent to

a fractionating tower.

The spent catalyst is regenerated, cooled, and recycled.

The flue gas from regeneration is sent to a carbon-

monoxide boiler for heat recovery.

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 Safety Considerations
Liquid hydrocarbons in the catalyst or entering the heated
combustion air stream are controlled to avoid exothermic
reactions.
Because of the presence of heaters in catalytic cracking
units, the possibility exists for fire due to a leak or vapor
release.
In some processes, caution is taken to prevent explosive
concentrations of catalyst dust during recharge or disposal.
When unloading coked catalyst, iron sulfide may ignite
spontaneously when exposed to air.
It is usually wetted with water to prevent it from igniting
vapors.
Coked catalyst may be either cooled below 120° F before it
is dumped from the reactor, or dumped into containers that
have been purged and inerted with nitrogen and then cooled
before further handling. 39
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Because the catalytic cracker is a closed system, there is normally little
opportunity for exposure to hazardous substances during normal
operations.

The possibility exists of exposure to extremely hot (700° F)

hydrocarbon liquids or vapors during process sampling or if a leak or
release occurs.

In addition, exposure to hydrogen sulfide and/or carbon monoxide gas

may occur during a release of product or vapor.

Catalyst regeneration involves steam stripping and decoking, and

produces fluid waste streams that may contain varying amounts of
hydrocarbon, phenol, ammonia, hydrogen sulfide, mercaptan, and other
materials depending upon the feedstock, crudes, and processes.

Inadvertent formation of nickel carbonyl may occur in cracking

processes using nickel catalysts, with resultant potential for hazardous
exposures.
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 CORROSION CONSIDERATIONS

Corrosives or deposits in the feedstock can foul gas

compressors.

Inspections of critical equipment including pumps,

compressors, furnaces, and heat exchangers may be
conducted as needed.

When processing sour crude, corrosion may be expected

where temperatures are below 900° F.

Corrosion takes place where both liquid and vapor phases

exist, and at areas subject to local cooling such as nozzles
and platform supports.

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When processing high-nitrogen feedstock, exposure to
ammonia and cyanide may occur, subjecting carbon steel
equipment in the FCC overhead system to corrosion,
cracking, or hydrogen blistering.

These effects may be minimized by water wash or corrosion

inhibitors.

Water wash may also be used to protect overhead

condensers in the main column subjected to fouling from
ammonium hydrosulfide.

Inspections should include checking for leaks due to erosion

or other malfunctions such as catalyst buildup on the
expanders, coking in the overhead feeder lines from
feedstock residues, and other unusual operating conditions.
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SUMMARY
History of Catalytic cracking
1). Batch reactor catalytic cracking to produce light distillates
(1915)
Catalyst: AlCl3 - A Lewis acid, electron acceptor
Alkane - electron (abstracted by AlCl3 )-> a
carbocation(+)
-> ionic chain reactions to crack long chains
2).Houdry (1936) - a commercial process
Continuous feedstock flow with multiple fixed-bed
reactors
Cracking/catalyst regeneration cycles
Catalyst: clays, natural alumina/silica particles
3). Thermoform Catalytic Cracking (TCC) (1942)
Continuous feedstock flow with moving-bed catalysts
Catalyst: synthetic alumina/silica particles
Higher thermal efficiency by process integration
4). Fluid Catalytic Cracking (FCC) (1942)
Continuous feedstock flow with fluidized-bed catalysts
Catalyst: synthetic alumina/silica +zeolites (1965)
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 Chemistry of Catalytic Cracking

A) Acid Sites

Carbocations are generated on acid sites on the catalysts

Lewis acid sites – accept electrons
Bronsted acid sites– donate protons

Bronsted site
H+
Lewis site
O O O O O

Al- Si Al Al Si+ Al- +H20

O O O O O O

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B) Ionic Chain Reactions and Products
i. Initiation

+ Carbonium ion
+H
d
nst e
o
Br
Alkanes
-H -

Lewi Carbenium ion

s

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ii) Propagation

Carbenium + alkane i-alkane (product) + Carbenium

ii) Termination

isomerization
-H
+
Carbenium carbenium Olefin (product)

(Restore
Bronsted Site)

+H
(i- alkane
(Product)
(Reform
Lewis site)

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 Comparison between thermal and catalytic cracking

Catalytic cracking exhibit the following compared to thermal cracking;

 uses a catalyst
 lower temperature
 lower pressure
 more flexible
 different reaction mechanisms
ionic vs. free radical
High thermal efficiency
Good integration of cracking and regeneration
High yields of gasoline and other distillates
Low gas yields
High product selectivity
Low n-alkane yields
High octane number
Chain-branching and high yield of C4 olefins
High yields of aromatics

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LECTURE 5

CATALYTIC REFORMING

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 CATALYTIC REFORMING

Catalytic reforming is an important process used to convert low-

octane naphthas into high-octane gasoline blending
components called reformates (increase the octane number
of straight run heavy naphtha)

Reforming represents the total effect of numerous reactions

such as cracking, polymerization, dehydrogenation, and
isomerization taking place simultaneously.

Depending on the properties of the naphtha feedstock (as

measured by the paraffin, olefin, naphthene, and aromatic
content) and catalysts used, reformates can be produced
with very high concentrations of toluene, benzene, xylene,
and other aromatics useful in gasoline blending and
petrochemical processing.
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Hydrogen, a significant by-product, is separated from the
reformate for recycling and use in other processes.

A catalytic reformer comprises a reactor section and a

product-recovery section.

More or less standard is a feed preparation section in

which, by combination of hydrotreatment and
distillation, the feedstock is prepared to specification.

Most processes use platinum as the active catalyst.

Sometimes platinum is combined with a second catalyst
(bimetallic catalyst) such as rhenium or another noble
metal.

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Feedstock and Product

Feedstock: Heavy Naphtha

 Paraffins 45-55 %
 Olefins 0-2 %
 Naphthenes 30-40 %
 Aromatics 5-10 %

Product: High Octane Gasoline

 Paraffins 30-50 %
 Olefins 0 %
 Naphthenes 5 –10 %
 Aromatics 45-60 %
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There are many different commercial catalytic reforming
processes including;
platforming, powerforming, ultraforming, and
Thermofor catalytic reforming.

In the platforming process, the first step is preparation

of the naphtha feed to remove impurities from the
naphtha and reduce catalyst degradation.

The naphtha feedstock is then mixed with hydrogen,

vaporized, and passed through a series of alternating
furnace and fixed-bed reactors containing a platinum
catalyst.

The effluent from the last reactor is cooled and sent to a

separator to permit removal of the hydrogen-rich gas
stream from the top of the separator for recycling. 52
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The liquid product from the bottom of the separator is
sent to a fractionator called a stabilizer (butanizer).

It makes a bottom product called reformate; butanes and

lighter go overhead and are sent to the saturated gas
plant.

Some catalytic reformers operate at low pressure (50-200

psi), and others operate at high pressures (up to 1,000
psi).

Some catalytic reforming systems continuously regenerate

the catalyst in other systems.

One reactor at a time is taken off-stream for catalyst

regeneration, and some facilities regenerate all of the
reactors during turnarounds. 53
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 Catalytic Reforming Process

Feedstock From Process Typical products - to - unit

Desulfurized Coker Rearrange, •High octane gasoline . .

naphtha dehydrogenat Blending
e •Aromatics To Petrochemical

Naphthene- Hydrocracker, Rearrange, •Hydrogen To Recycle,

rich fractions hydrodesulfur dehydrogenat hydrotreat, etc.
e

Straight-run Atmospheric Rearrange, •Gas To Gas plant

naphtha fractionator dehydrogenat
e

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Schematic of platforming process

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 CATALYTIC REFORMING PROCESS DIAGRAM

Catalytic Reforming Processes

Platforming

H2

Feed

Heater
925-975°F
Gas (C3, C4)

Reactor-1

Separator

Reformate

Reactor-2 Fractionator

Heat Exchanger 56
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REACTIONS

1) a. Dehydrogenation

+ 3H2

b. Dehydroisomerization

+ 3H2

c. Dehydrocyclization

n-C7H16 + 4H2

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2) ISOMERISATION

O.N. 91 83 100

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PROCESSES

low severity low paraffin conversion

high severity high paraffin conversion

lean naphtha high n-paraffinic content

- difficult to process
rich naphtha low n-paraffinic (high
naphthene) content
- easy to process

Ways to promote these reactions

1) high Temp
2) low Pressure
3) low SV
4) low H2/HC ratio
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 Safety Considerations
This is a closed system; however, the potential for fire
exists should a leak or release of reformate gas or
hydrogen occur.
Operating procedures are developed to ensure control of
hot spots during start-up.
Safe catalyst handling is very important.
Care must be taken not to break or crush the catalyst
when loading the beds, as the small fines will plug up the
reformer screens.
Precautions against dust when regenerating or replacing
catalyst should also be considered.
Small emissions of carbon monoxide and hydrogen sulfide
may occur during 60
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 Corrosion Considerations

Also, water wash should be considered where stabilizer

fouling has occurred due to the formation of ammonium
chloride and iron salts. Ammonium chloride may form in
pretreater exchangers and cause corrosion and fouling.
Hydrogen chloride from the hydrogenation of chlorine
compounds may form acid or ammonium chloride salt

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 ALKYLATION & POLYMERISATION

Alkylation

1). Purpose : use light olefins and light iso-paraffins to produce high octane
gasoline. Basically, the reverse of cracking; small molecules are combined
to produce larger molecules in the gasoline boiling range.

2. Principal Reactions

C–C=C + C–C–C  C–C–C–C–C

. C=C–C + C–C–C  C–C–C–C–C

Use isobutane instead of isopentane because i-C 5 already has a

sufficiently high octane number

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MECHANISM

C–C=C–C + H2SO4 C–C–C–C + HSO4 Initiation - carbenium ion

C C
Tert-butyl cation
C–C–C–C + C–C–C C–C–C–C + C–C
H C
C C C
C–C + C–C=C–C C–C–C–C- C Other trimethylpentyl
C C cations by isomerization

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3). Feedstock

Olefins and isobutane are used as alkylation unit feedstocks

*Chief sources of olefins are catalytic cracking and coking
operations
- most common olefins used are butenes and propene
*Isobutane is produced by hydrocrackers and catalytic crackers
- Catalytic reformers, crude disillation and natural gas
processors also produce some isobutane fed to the
alkylation unit

4). Products
LPG grade propane liquid,
Normal butane liquid,
C5 + alkylate and Tar

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