Fluid Catalytic Cracking

FCC
 Introduction to FCC process
• This is a low pressure and intermediate to high temperature process.
• Primary processing objective falls between either of the two:
✓Maximization of middle distillates (cracking essentially functions like visbreaker)
✓Maximization of LPG and gasoline

• This process converts HGOs like vacuum distillates into more valuable
products e.g. LPG, gasoline, cycle oils, olefin-rich light HCs, decant oil and
fuel oils.

Decant Oil: It is the heaviest product from the FCC unit, also known as Clarified Oil or Slurry Oil.
 What is concept behind the term “Fluid Catalyst” ?
• The catalyst in the form of fine powders are held in suspension by the
gaseous stream.
• By carefully controlling the catalyst particle size and the velocity of the gas
moving through it, a fluidized bed of catalyst would be formed.
• This fluidized bed thus formed, will have the properties of a static quantity
of the liquid.
• In fluidized systems, finely powdered catalyst is lifted into the reactor by
incoming oil which immediately vaporizes upon contact with the hot
catalyst..
• After catalytic reaction is complete, the hot catalyst is lifted into the
regeneration zone.
In summary, the catalyst cracker using POWDERED CATALYST in this fluidizing process is called FLUID CATALYST.
FLUIDIZATION
What kind of advancements may be expected in
this area of FCC ?
• Areas of Catalyst
• Reactor- Regenerator System
• Energy Recovery
Widely Accepted Designs Till Date:
1. Esso Model IV
2. Kellog Orthoflow
3. Kellog Orthoflow model-F converter with two-stage regeneration

WHY IS CATALYST REGENERATION NEEDED ?

1. The catalyst loses its effectiveness yet being active !!
2. The Carbon deposits on the surface of the catalyst need to be treated

WHEN IS THE CATALYST NEED TO BE THROWN AWAY ?

1. The activity of the catalyst loses out
 ESSO Model IV Design
• The design for the catalyst transferring system
R
in this design is unique.
e
g R • Reactor and Regenerator are connected by U-
e
n
e tubes, with one of its leg serving as a
e a standpipe and the other one is a riser.
r c
a
t t • Slide valves in this case, acts as a safety device
o
r
o which shuts off the lines automatically if
r there is a danger of reverse flow.
• Some elevation is always maintained for feed
and air inlet to prevent backflow during
pressure surges.
• The rate of air flow to the spend catalyst
Oil feed
transfer line establishes circulation rate in the
system (instead of the slide valves).
 Kellog Orthoflow Design
• It is a single vessel type unit, divided into two
sections: reactor-stripper (upper) and
regenerator (lower).
• The catalyst lines are located inside the
regenerator, thereby necessitating the
requirement of plug valve for controlling
catalyst flow.
• The plug valves consist of conical plugs which
can be moved into or out of conical seats,
thus varying the cross-sectional area for flow
of catalysts.
• The feed is injected into reactor riser through
hollow stem of the regenerator catalyst plug
valve.
 Kellog Orthoflow model-F
• This allows cracking in dilute phase gives better gasoline yield (at constant
conversion).

• The effective feature of riser cracker is its approach to concurrent flow of

catalyst and reacting vapors.

• There is no backmixing of catalyst, and each increment of cracking takes

place over the catalyst having the lowest Carbon deposit.

• This riser cracker provides highest effective activity for a given catalyst-to-oil
ratio.
 Kellog Orthoflow model-F

• The feed enters the riser through the nozzles

located at the periphery of the riser.
Flue Gas
to
Boiler Steam • Evenly mannered flow of HCs on catalyst is
realized initially by ensuring constant flow of
Riser
catalyst to the feed inlet, and providing a number
of feed introduction points.
Oil Feed
• The reaction time is controlled by using cyclones
at riser exit to separate HCs-vapors from catalyst
and discontinue catalyst cracking.
Plug Valve Steam
 Two-Stage Regenerator- in Kellog Orthoflow model F
• This two-stage regenerator permits obtaining extremely low Carbon or
regenerated catalyst levels at low inventories, and, at the same time,
promotes high activity maintenance.

• The first stage is operated at high velocities and low temperatures to

promote rapid burning without excessive high particle temperatures.

• The second stage accomplishes the final burning to very low levels of carbon
on catalyst at higher temperatures and lower velocity.

Catalyst activity represents the ability of a catalyst to increase the rate of a chemical reaction by reducing the energy
barrier between reactants and products. Improving the activity of a catalyst shortens the kinetic pathway and improves
efficiencies, accelerating the speed of reaction.
 Hydrotreating FCC feed
• Care has to be taken that the contaminant levels (PM, S, Asphaltene, N2) at
the feed should be as less as possible.
• To improve distillate yields and eliminate pollution problems, FCC feed can
be upgraded by hydrotreating.
• The removal of nitrogen prevents deactivation of acidic sites in catalyst by
basic nitrogen compounds.
• The reduction of metals (V and Ni) minimizes dehydrogenation reactions
and formation of coke.
Hydrotreating, also known as hydrodesulfurization (HDS), is a chemical process that removes impurities from petroleum
products and natural gas using hydrogen.
Revisit- Summary for Catalytic Cracking Reactions

Because of high degree

of isomerization
 • In addition, the formation of carbonium ions depends on the relative
stability which decreases in the following order:
Tertiary > Secondary > Primary > Ethyl > Methyl
Olefins

Responsible for
production of iso-
butane and high
octane iso-
paraffin in the
gasoline boiling
range

• These carbonium ions undergo several reactions like isomerization, C-

C bond scission, hydrogen transfer and termination.
• The reactivity preference for a same C-number HC is as follows:
Olefins > Alkyl-benzenes > Naphthenes > Poly-methyl-aromatics >
Paraffins > Unsubstituted aromatics
Usual Feed
 Feedstock Characteristics
• Among the different types of HCs in the feedstock, the paraffins and the naphthenes
crack at about the same rate.
• Unsubstituted aromatics crack very little, but side chains of substituted aromatics
crack at much higher rate than paraffins.
• Based on these aspects, the important feedstock characteristics are:
1. Specific Gravity
2. Boiling Range
3. Carbon Residue
4. Metals
5. Sulphur
6. Water Content → should be below 0.2 vol. % to prevent shocks and vibrations in
feedline due to flash vaporization of water droplets.
7. Color → ASTM D1500 color code of 4 is best
8. Asphaltene content → should be below 0.4 wt.% (pentane insoluble)
 Operating Conditions

• Reactor Temperature 470-540 ℃

• Regenerator Temperature 590-610 ℃
• Reactor Pressure 232 kPa
• Regenerator Pressure 274 kPa
• Fractionator Pressure 225 kPa
Typical Yield Pattern
 Principles of Operation
• Catalyst Recirculation- saves from frequent regeneration of catalyst
1. This recirculation uses the concept of fluidizing the system for
effective catalyst usage
2. To prevent Entrainment of HCs from reactor to regenerator, a
stripping section is used just before the entry to regenerator
3. The catalyst is kept fluidized in the reactor, stripper and regenerator,
by HC vapors, steam and air, respectively.

• Pressure Balance- Maintained through gravity or hydrostatic head.

Refer to the book by Ram Prasad- ch (8)

 Principles of Operation
• Heat Balance:
✓FCC unit is called HEAT BALANCED when the heat generated in the
regenerator is equal to the heat needed in the reactor, thus avoiding
the need to install catalyst coolers on the regenerator side and a fired
preheater on the reactor side.
✓Heat transport from the regenerator to the reactor is achieved by
circulating catalyst.
✓What will happen if the feed temperature reduces ? What can we
expect in that case for the heat of combustion in the regenerator ? Do
we need to increase the coke formation on the catalyst ? – are basic
non-trivial queries.
Refer to the book by Ram Prasad- ch (8)
 FCC Process Flow Diagram
Catalyst disengagement
Wet Gas Compressor
and flow of cracked
System
products Absorber-stripper
system
 Process Variables- Reactor Section (i)
• FRESH FEED RATE:
✓A FCC unit can accommodate wide range of feed rate at constant conversion.
✓In fact, greater variations are possible if a high conversion is desired at low
feed rates and a low conversion at high feed rates. This flexibility comes from
the setting up of optimum combined feed ratio which tends to keep the total
feed to the riser nearly constant.
✓It is generally advised to maintain a high combined feed ratio, at very low
feed rates.
WHSV → kg/h of feed divided by kg of catalyst hold up in the reaction zone (a
type of space velocity).
WHSV ↑ :: Catalyst surface available to the feed ↓. Hence, less cracking / lower
conversion.
 Process Variables- Reactor Section (ii)
• FRESH FEED TEMPERATURE: Increasing this will enhance the heat input to the
reactor.
• A 55.5℃ increase in feed will lead to:
❑Reduce conversion by 4%
❑Increase regenerator temperature by 11 ℃
❑Reduce coke yield by 5%
❑Reduce catalyst/oil ratio
 Process Variables- Reactor Section (iii)
• REACTOR TEMPERATURE (lower limit is 470 ℃): this value is determined by
heat content of combined feed and catalyst circulated through riser. An
increase in reactor temperature will produce:
❑Increase in lean gas yield (C2-)
❑An increase in C3-C4 yields
❑A decrease in gasoline yield of 1% for every 5.5 ℃ increase in reactor temp.
❑Increase in olefin content of all liquid products
 Process Variables- Reactor Section (iv)
• REACTOR LEVEL: it is the best measure of the weight of catalyst in reactor.
• Increasing the level will lead to:
❑An increase in conversion
❑A decrease in gasoline yield at constant conversion
❑Increase in regenerator temperature
❑Increase in coke yield
❑Decrease in olefin content of the liquid products
❑Increase in spent catalyst slide valve differential pressure and decrease in
regenerated catalyst slide valve differential pressure
 Process Variables- Reactor Section (v)
• STRIPPING Steam RATE: The quantity of steam required to strip the oil vapors
from spaces between the catalyst particle is determined by catalyst
circulation rate. During normal operation, an increase in stripping steam rate
will lead to following changes in process condition:
❑Increase fresh feed rate
❑Increase recycle rate (related to product recycled back e.g. cycle oil)
❑Decrease combined feed temperature
❑Increase in reactor pressure
❑Decrease in reactor temperature
❑Increase in spent catalyst slide valve differential pressure and decrease in
regenerated catalyst slide valve differential pressure
 Process Variables- Reactor Section (vi)
• Catalyst/oil ratio
• Recycle rate
• Recycle temperature
• Catalyst Activity:
1. Specific surface is used to measure the activity of catalyst. For FCC it may
be around 100 – 150 m2/g for catalytic crackers operating at high
conversion.
2. Low surface area means a large pore volume and pore diameter.
 Process Variables- Regenerator Section (i)
• AFTER BURNING- Coke is oxidized in this section to CO, CO2 and H2O through
exothermic process, thereby releasing heat. If the oxygen is more exposed to CO,
larger CO2 is formed with release of more energy. This is the afterburning reaction
which takes place above the regenerator bed and in the cyclones of the flue gas
lines.

• DENSE PHASE TEMPERATURE: depends of reactor conditions and feedstock quality

• REGENERATOR PRESSURE: the slide valves impose the magnitude
• REGENERATOR AIR RATE
• AIR DISTRIBUTION
• TORCH OIL: It is added in spray form; manages heat requirement to achieve proper
coke oxidation.
Typical Reactor- Regenerator setup !!
Reactor Mass Balance
Reactor Energy Balance
Regenerator Mass and Heat Balance

Hints for mass and energy balance !!!

H/W
Solution
H/W