Cracking

 Dissociation of high molecular weight hydrocarbons into smaller fragments through

the introduction of heat is called as thermal cracking or pyrolysis.
 If this is done in the presence of the catalyst then it is said to be catalytic cracking and
though the reaction followed in this different with that of the thermal cracking but
yield similar products.
 Since in the increasing demands of the motor sprit or gasoline pushed refineries to
convert less valued fraction to more commercially important products.
 Developed countries like USA convert 70% of crude to motor spirit whereas in
countries like India thermal cracking is used to convert middle distillate to gasoline.
Theory Of Thermal Cracking Reactions
 In cracking, high molecular weight paraffins are divided when temperature exceeds
400oC
 paraffins having general formula CnH2n+2 where n ranges from and above 25 easily splits
into equally halves resulting in one saturated molecule and other unsaturated molecule
and upon increasing the conditions of the cracking this results in the formation of coke
and hydrogen

 And the fragmentation increases with increase in temperature , giving rise to often
simpler products to complex products occasionally.
 For a paraffins of less molecular order, the following reactions illustrate mode of
reaction
 Unsaturates continue with the cracking reaction again with the severity of conditions, like 
olefins give rise to diolefin or an alkyne
 Further severity in conditions lead to the production of methane, hydrogen and carbon, 
sine these are regarded as the most stable compounds and under congenial conditions 
thermal cracking forms dimers, trimers  etc.
 Hydrogenation also occurs to some extent
Aromatics and ring structure follow different pattern, like saturates are converted to
unsaturates

Sometimes under extreme conditions of cracking ring opens up 
 Light paraffins when subjected to cracking they undergo dehydrogenation reaction
dominates over other reactions of cracking.
 The tendency of hydrogenation becomes less when the molecule is above C4 and this
dehydrogenation results in the formation of isomers

 Based on all these reactions we conclude that the product of cracking may have
higher molecular weight than the feed itself, because of polymerization or
condensation
 Cracking proceeds via free radical mechanism and these are the atoms or group of
atoms with bare unpaired electrons and these differ from charged particles or ions
 These unpaired electrons are very active, and try to form stable compound by
acquiring unpaired electrons from sources available
 Hydrogen atoms usually refer to carbanium and carbonium depending on the charge
they carry

Only one radical is sufficient to bring  about series of changes
 Different radicals have different lives, out of which hydrogen free radical has the
highest stability and so a higher life. This increases with the decrease in size of the
molecule
 Due to high stability of tertiary carbonium ions, asymmetric carbon bonds can be
easily broken than that of the symmetric carbon atoms and hence isomerization
doesn’t take place in thermal cracking operation
Properties Of Cracked Materials
 Products of cracking has different properties because of unsaturation and they
entirely depend on the conditions of cracking
 For economic cracking, the heavy products from cracked stocks are mixed with the
incoming charge and are allowed to crack, hence they are called as recycle stocks
 Some of the properties are expected to change
1. Characterization factor decreases
2. Boiling point, pour point and viscosity decreases
3. Unsaturation and aromatization increases
4. Octane number increases
5. Sulfur in the cracked products may increase even though much of the sulfur
is removed as the hydrogen sulfide
6. Oxidation stability decreases
 Pressure, time and temperature are the important properties that govern the
cracking operations.
 At a given temperature and pressure, the yield of light fraction is a function of time,
time of cracking at a set conditions of temperature and pressure, increases with the
API gravity of the feed
 With increase in yield per pass the heat of decomposition decreases.
 If more gas were to be produced low pressure are desirable and with high pressure
gas to gasoline ratio becomes less.
 Reaction velocity is dependent on the temperature only,
 Recycle ratio increases the refractory nature of the stocks and hence recycling
should not exceed 2 to 3 times for economic operations.
Effect of pressure
 Pressure retards cracking operations but a positive pressure of 10 to 15 Kg/cm2 is
enclamped to minimize the coke formation. Increase in pressure deceases the
yields of the lighter fractions.
Depth of cracking and soaking factor
 In the initial stages of the cracking the concentration doesn’t change much as the
time progress
 Severity is mainly connected with the temperature where as soaking factor is
connected with the temperature and volume of feed per unit time
 Soaking factor is comparative term, which is compared by bringing the conditions
of operation to some standard conditions

v
KT dv
SV   R
0
K 426.7 F
Where
R=constant, correction factor when operating pressure differs from 52.7 Kg/cm2
KT /K426.7 relative cracking velocity at any temperature
dv/F= differential coil volume in liters per bbl. of feed stock daily throughput
Rate of Reaction
These reactions are described as first order reactions, when cracking per pass doesn’t
exceeds 25% 1 a
kt  ln
Where t ax
t in seconds
a% of material in feed 
x% of material that disappears in time t
Temperature and reaction rate‐constant are related by Arrhenius equation
E
ln K   c
RT
Where
R=8.314
t =K
E= energy of activation KJ
C=constant
Heat of Decomposition
It is not possible to ascertain in the accompanying heat changes in the cracking reactions
due to complexities involved in bond ruptures and formation
Cracking can be calculated by knowing the molecular weight of the charge stock and
products
C (M c  M p )
heat of cracking(KJ/gm)=
McM p

Where
C=‐1150.20
Mp/Mc= mole weight of charge and products
Heat of decomposition= Heat of combustion of products‐Heat of combustion of feed stock
Visbreaking
The name itself suggests that it is the reduction of viscosity which is the first stage of the
cracking operation
The advantages of visbreaker are listed as follows
1. Cheapest device
2. Can handle different feeds
3. Quality of feed is not deterrent for operation
4. Operating conditions are flexible
5. Not much technical knowledge is required for installation

Visbreaking works upon two parameters mainly residence time and cracking temperature,
based on this two types of units are very much popular. They are coil type and soaker
type
Coil type visbreaker
 In this coil is maintained at the cracking temperature and the reaction is allowed
to proceed in shortest possible time in the coil itself
 At the outlet the products are quenched and separated
 Sufficient time is permitted for the feed to complete the reaction accordingly the
time of travel of the stock in the coil is fixed

Soaker type visbreaker

 In this the reaction is initiated in the coil and reaction is completed in the drum
as the time is given
 The operating temperature is maintained at a less temperature than the coil type
visbreaker
Flow sheet for the Visbreaking  
Cracking for the production of Gasoline
 Each stock has certain characteristics that govern the operating conditions which will
yield the selected product to the desired level
 Mixed stocks require more stringent conditions, which require another coil exclusively.
 Modern refineries have anticipated this problem and instituted four coils, one for the
visbreaking operation, second for cracking heavy oils where temperature may be 520oC
 The other two coils were established for reforming operation. Pipe still heaters are
capable of raising the temperature of feed stock to 500oC in a short time.
 Production of gasoline from high boiling stocks was an old operation, at present Dubbs
two coil cracking operation is used
Dubbs Two Coil Cracking Process
Suspensoid catalytic cracking
 Mixing the catalyst in fixed proportion and passing through the heater.
 The main idea of this process is to deposit all the coke that is formed in the operation
on the catalyst itself.
 At the delivery the end products of the cracking are separated from the catalyst in a
separator.
 Carbon on the catalyst is burnt off and high temperatures are employed
 CATALYTIC CRACKING

 This is the most widely used technique for converting heavier fractions into gasoline of
high octane number
 This is differentiated from the thermal cracking by the reaction mechanism, carbonium
ion mechanism
 The product obtained from this method generally doesn’t have any ill effects as from
thermal cracking such as unsaturated compounds, high carbon formations, less yield
 This mechanism leads to the formation of more stable saturated compounds with the
abundance of isomeric reactions accompanying
 The stability of this mainly depends on the nature of the molecule undergoing cracking
than the conditions applied for cracking
Carbonium ion chemistry
 Most of the reactions like alkylation, polymerization, hydrocracking and reforming
etc. involve carbonium ion chemistry
 These are charged group ions unlike free radicals, electrophilic additions give these
kind of charged ions and the formation of such ions is known as protonation
Protonation of an olefin

RCH:CH 2 +H   RCH   RCH  CH 3 / RCH 2 CH 

Additions of Lewis Acid
Breaking of halogen

Addition of the electrophile to aromatics

 The life time of a carbonium ion may vary from fraction of seconds to many minutes
 As we go from primary to tertiary the stability of the carbonium ion decreases
 When protonation takes place, a primary carbonium ion may result

 This is governed by the Markovinkov’s rule

 Number of steps involved in this reaction are proton elimination, hydride shift,
methyl shift, addition, cracking, hydride transfer, termination of carbonium ion.
 This can be explained like this
 Carbonium ions are apt when chemical reactions proceed with the aldehydes and ketones

 Acid sites of catalysts provide such charges, Naphthenes undergo hydrogen transfer
to produce aromatics
 The heat of formation of methyl, ethyl ions have high values, because of this
catalytic cracking gives methane, ethane or ethylene
 Earlier catalyst were silica and alumina type and the introduction of zeolite catalyst
containing Ca, Mn or rare earth metals really boosted the industry with unexpected
divisions
Feed stock and catalytic cracking conditions
 Temperature in all cracking operations lies in between 450‐510oC and though doesn’t
exceed two atmosphere
 Catalyst to oil ratio is a set factor
 Feed of catalytic crackers is gas oils, blend of gas oils and modern tendency to use
even residuum
 Feed contain sulfur and nitrogen and traces of metal elements give trouble to the
refineries. This harms catalyst by reacting with the acid cites
 Metallic impurities like vanadium, nickel, iron copper etc. retrain the activity of catalyst
by blinding the active sites.
 Phillips Research and Development Facilities have developed a process to use ad
additive containing antimony that will passivate metal contaminants.
 Pretreatment of such stocks is immensely regarded to avoid the catalyst poisoning.
 Sulfuric acid treatment furnishes the removal of sulfur and nitrogen compounds and
85% strength acid is generally used
 Phenol or furfural is essential for aromatics rich stocks
 Deasphalting of residuum generally eliminate highly condensed structure.
 Sulfur present in aromatics usually favors more coke formation during cracking
Commercial Cracking Catalysts
 The first catalytic cracking catalyst were synthetic amorphous silica alumina's and
silica‐magnesia
 Later zeolites with rare earth exchanged ions were added to amorphous matrix to
improve the catalyst selectivity and activity.
 Noble metals are added to zeolite to assist the oxidation of CO to CO2 during
regeneration
 Heavy metal complexes like porphyrins increase coke deposits and these can
attended by two methods either by dematlization of feed or by adding metal
passivator like bismuth and sulfur
 Synthetic are found to possess high selectivity and give greater product distribution,
silica by itself doesn't possess active site, but by the addition of the aluminum the
active sites increases.
 Though they exhibit wide range of active site and porosity, due to ambiguous crystal
structure create problems for scientific correlations
 The zeolites have high adsorption capacity, high surface area and acid sites
 They are crystalline catalyst of aluminum and silicon atoms form tetrahedron which
are linked by shared oxygen atom
 There are almost 150 zeolite catalysts were explored but commercially occupy a
small spectrum.
 X and Y catalysts are explored for catalytic operations and they are represented by
NapAlpSi102‐pO384.g H2O, where p ranges from 96 to 74 for X and 74 to 48 for Y, while g
goes from 250 to 270 as aluminum decreases.
 Thermal stability of zeolite is a major concern and used catalyst always show less

activity because of the deposition of coke, metal traces and other acidic impurities.

 Presence of steam during regeneration decreases the surface area which causes the

loss of active site and eventually leading to a fused non porous inactive material

 If regeneration is done without steam, the hydroxyl group on the surface escapes

leading to the loss of active sites

 Chemical changes also occurs in combination with physical changes, here Brownsted

acid sites are converted to Lewis acid site and lost sites can be regenerated back by

the addition of water, if the activation temperature doesn’t exceed 700oC

 Zeolites are more resistant to heat and steam that amorphous catalyst
Motivation for zeolite catalyst
 More active site high adsorption capacity which increases cracking rates
 High selectivity for intermediate products like gasoline
 Hydrogen transfer at the primary steps which leads to the saturated products
 Commercial catalyst possess 100 to 400 M2/g surface area and pore volume range 0.2
to 0.5 ml/g and average pore dia is of 50‐80 Ao
 They are having sieving effect and can orient for specific molecules only
 ZSM‐5 is suitable for aromatics and alkylation reaction
 Asphaltenes are decomposed on the fluidizing medium to hydrocarbons, thus
increasing the liquid products
Types and working conditions of catalytic cracking
 Cracking is done on moving beds or fixed beds and as of now 20% is catalytic cracking
is by moving beds and remaining with the fluidized bed
 Pellet form are more suitable for fixed bed and beads form are well suited for moving
beds
 Zeolite catalyst crack ten times more than the low alumina catalyst or twice as much
as the high alumina catalyst
 Coke deposition is also effectively lowered by zeolites and at 70% conversion only 6%
of coke has been deposited with the low alumina catalyst
 Gulf FCC catalyst were developed to suit high temperatures that are usually used in
short contact risers and they help in producing rich gasoline.
 Perfect heat balance in the moving bed while fixed bed has to undergo constant
circulation of molten salts for uniform temperature.
 Recycle ratio is kept around 1:2 to 5:1
Reaction variables
 Pressure, temperature and oil to catalyst ratio is taken care during cracking
 Catalyst to oil factor should be varied for each operation as after every
regeneration the carbon ratio in the catalyst shouldn’t increase 0.25% which may
cause fatigue loss and improper cracking
 Sharp decrease in the cracking area and increase in the bulk density with increase
in cracking time reduce the conversion
 In short contact risers, a high octane quality gasoline can be obtained due to
cracking at high temperature
 Regenerator pressure is always coupled with the reactor system
 Since catalyst is a fine powder in cracking units excess pressure gives regeneration
problems
 60% of conversion can be achieved by in short time contact risers where time of
contact between oil to catalyst is around 4 sec
 Catalyst separation is done when effluents leave the reactor and this can be achieved
effectively by decreasing the velocity
 Back mixing leads to excessive coke formation which has to be avoided.
 The activity and selectivity of the catalyst is largely maintained in order to avoid coke
formation