Petroleum Refining Technology

(CHE F422)
 Options for upgrading of VGO/Heavy stocks

• Thermal cracking
• Catalytic cracking
• Hydrocracking
Why catalytic cracking
• Cost effective as compared to hydrocracking.
• Higher yields of gasoline of 91+ octane number
through highly olefinic.
• Relatively flexible in terms of feed quality.
• High yields of C3 & C4 olefins
 Catalytic cracking
Solution of
• Unsaturation of products
• High carbon formation
• Low yield of gasoline
during Thermal cracking
 Chemistry of catalytic cracking

• Proceeds through the ionic species • Protonation

• It forms branched chain alkanes • Proton elimination
• Iso-alkane • Hydride shift
• High octane gasoline • Termination of carbonium ions
Chemistry of catalytic cracking

• Cracking: (+ ve) Endothermic

• H-transfer: (- ve) Exothermic
• Isomerization: (- ve) Exothermic
• Cyclization: (- ve) Exothermic
Acid Site of Catalyst
Acidic Catalyst
 Acidic Catalyst
Addition of Lewis acid:

• Paraffinic reactivity
• Rate of reaction & coke formation increases with C number
• High production of C3 & C4
• Olefinic reactivity
• Cracks at faster rate
• Rapid isomerization
• Naphthene reactivity
• Cracks faster compared to paraffinic
Cracking reactions
 Cracking catalyst
Acid catalyst: which can supply proton

Advantages of zeolite catalyst

Cracking catalyst
 History

1. Batch reactor cat cracking to produce light distillates

(1915); Cat: AlCl3 .
2. Houdry (1936) - Commercial process; Continuous feed
with multiple fixed-bed reactors; Cracking / cat
regeneration cycles; Cat: clays, natural alumina / silica
particles.

3. Thermoform Catalytic Cracking (TCC) (1942);

Continuous feed, moving-bed cat; Cat: synthetic
alumina/silica particles.

4. Fluid Catalytic Cracking (FCC) (1942); Continuous feed

flow with fluidized-bed catalysts; Cat: synthetic
alumina/silica + zeolites (1965).
 FCC
• Ability to circulate catalyst
• Hold catalyst in unit and not lose it
• Yield from unit important after above considerations
• FCC catalyst
• Cat cracking have many compromise
 FCC
• Crime to reduce reactor stripping steam rate at
expense of increased bed temp

• Soft cat may not stay in unit, hard catalyst own

problems

• Crime to have steam in torch oil nozzles without

restriction orifice present
 FCC CATALYST

• Good stability to high temperature

and to steam
• High activity
• Large pore sizes
• Good resistance to attrition
• Low coke production
 FCC CATALYST
FILLER
(CLAY)

BINDER
ZEOLITE

MATRIX

Zeolite: 15 to 50 wt%
 Fluid Catalytic Cracking Unit (FCCU)
• FCCU chemical engineering precision operation marvel
turning heavy feed stocks in lighter products with large
process margin.

• Reaction and regenerator of FCCU operate in fluidized

state at ~ 480– 5200 C for catalytic reactions in riser /
reactor and 680 to ~ 7000 C for regeneration of cat by air,
both sections separated by slide valves.

• Typical units large number of components as ~75 pumps,

> 35 exchangers, ~ 35 vessels, ~120 CV, ~ 45 PSVs, 7
columns, ~75 orifice plates, air blower and compressor
• Turnaround preferred after about 4- 5 years operation.
• Introduce in 1965
• Role: Selectivity & flexibility
• Fine powder: average 60-70 µm, ranging from 20-120 µm
• zeolite, active matrix, filler, and binder
Used catalyst: less activity because of coke deposited, heavy metals
Regeneration, steam stripping: loss of active site
 Amorphous Catalyst & Zeolite
• Zeolite:
• more active sites and adsorption capacity.
• More selectivity to gasoline.
• Favors hydrogen transfer lead saturated products.
• Acid strength depends on Si/Al ratio.
• Commercial catalyst:
• Surface area: 100-400 m2/g,
• Pore volume: 0.2-0.5 ml/g
• Pore dia.: 50-80Å
• Si/Al: 4.5
• 5 Å zeolite: crack only n-paraffins.
• ZSM-5: suitable for aromatics.
At 70% conversion of feed over zeolite: only 6% coke formed
 Catalytic Cracking Processes
Historical Time-Line for Catalytic Cracking Processes
1. McAfee (1915)
• Batch reactor catalytic cracking to produce light distillates
• Catalyst: A1Cl3 – A Lewis acid, electron acceptor
• Alkane – electron(abstracted by A1Cl3)→ a carbocation(+)→ ionic chain reactions
to crack long chains

2. Houdry (1936) - a commercial process

• Continous feedstock flow with multiple fixed-bed reactors
• Cracking/catalyst regeneration cycles
• Catalyst: clays, natural alumina/silica particles

3. Thermafor Catalytic Cracking (TCC) (1942)

• Continues 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)
Catalyst: AlCl3 Lewis acid: Expensive & Corrosive.
Late: Clays, and natural alumina and silica particles.
 Operation condition
Reactor temperature: 450-520 C
Operating velocity: 1-2 kg/cm
Space velocity: 1-1.75 /hr
Regeneration temp.: 520C
Catalyst shape: Beads/pellets
 Operation condition
Catalyst temp: 515
Reactor temperature: 600 C
Recycle ratio: 0-0.5 Vol./vol.
Space velocity: 0.7 V/hr
Catalyst to oil: 2 to 7
Regeneration temp.: 600C
Catalyst shape: Beads
 Catalytic Cracking Unit (FCCU)
 Major reactions: cracking, isomerization,
hydrogen transfer, alkyl transfer, cyclization,
dehydrogenation
FG
500 - LPG
550°C
Nap
FCC LCO
HCO
GO Coke

• % Conv
• Delta Coke
• C/O ratio: 5-10
 Operation condition
Temp: 470-500 C
Pressure:1.5 to 2.2 atm
Regeneration temp.: 580-610C
Catalyst to oil: 2.5 t0 5 kgs/bbl
Catalyst shape: Beads
 Catalytic Cracking
• Fixed bed: obsolete
Pellets form of catalysts
• Moving bed: 20%

• Fluidized bed: 80% Powder

Low alumina High alumina Zeolites

Conversion, % 61 68 74
C1+ C2+H2 1.674 1.672 1.755
C3 % Vol. 8.4 8.2 7.4
C4 % Vol. 6.2 7.4 9.4
Gasoline, % Vol. 50.5 58.0 63.5
LCO, % Vol. 12 14 13
Coke % Wt. 6 6 6
 Reaction variables
• Temperature, Pressure, & Cat to Oil ratio.

• Temperature is independent variable.

• Contact time : 1-4 sec.