Chapter 6
Thermal and catalytic
conversion process
Cracking
Cracking processes break down
heavier hydrocarbon molecules
(high boiling point oils) into lighter
products such as petrol and diesel.
These processes include:
1. Thermal cracking(Pyrolysis)
2. catalytic cracking
3. hydrocracking
Feed Material
RCO from ADU
Thermal cracking
The general reaction of thermal
cracking:
CnBased
H2n ---------Cn/2
Hn+2radical
+ Cn/2Hn
on the
free
mechanism
Radical production
C5H12 ------ C5H11* + H*
O2 ------- O* +O*
Propagation
C5H12 + H* ----- C5H11* +H2
Termination
C5H11* + C3H7* ------ C8H18
Thermal cracking
Thermal cracking of reduced crude/vacuum
residue at 460-520C and Pressure of 700
kPa
Major products- Gasoline & middle
distillates
Thermal cracking of Reduced crude oil
Cracking is endothermic reaction. It needs
heat
Product yields (Vol%) based on T,P, time.
Time of cracking with API gravity. So
heavier fraction easily cracks.
Gas
1.0
Naphtha
42.0
57.5
Thermal cracking
Properties of cracked materials
1. K value decreases
2. Boiling Point, pour point and decreases
3. Un-saturation and aromatics increases
4. Octane no increases
5. Oxidation stability decreases.
6. Produce large amount of solid,unwanted
coke. Longer period for cleaning.
Thermal cracking
Cracking reaction are generally first order reactions, so rate
constant
is given by
k = 1/t ln a/(a-x) where
a - % of material in feed
x - % of material that disappears in time t.
As per arrhenius eqn rate constant is,
ln k = -E/RT +Constant
Thermal cracking
The heat of decomposition by empirical formulae
Heat of cracking (KJ/gm) = C (Mc-Mp)/McMp
C = - 1150, M-Mol wt of charge and Product
Heat of decomposition = heat of combustion of products-heat of
combustion of feed stocks
In the present days
thermal cracking is
working in refineries in
the form of vis-breaking
Visbreaking
Viscosity-breaking- Cracking to reduce the
viscosity
Heavy crudes or residuum's (bottom of the
barrel ) are the feed for this operation. Residue
from Atmos. / Vac. distillation units can be used
In india capacity touches 6 lakh barrels per day
to get middle distillate.
10-15 kg/cm2 pressure at 425-500C to reduce
viscosity/ pour point.
Visbreaking
Coil/Furnace type- high temp. & short residence
time cracking
T : 470-500 C
Time: 5-6 min
P 10 Kg/cm2
Visbreaking
Soaker type- Low temperature & Long
residence time cracking
Light gases
T : 425-460 C
Time: 15-20 m
P 10 Kg/cm2
Visbreaking- Yield pattern (Based on feed stock)
FEED
PRODUCT
Luisiana Vacuum
Residue
Arabian Light
Atmos.residue
Feed stock
Gravity API
Carbon residue
Sulfur wt %
11.9
10.6
0.6
16.9
Product yields
Naphtha
6.2
7.8
Light gas oil
6.3
Heavy gas oil
Residuum
Gravity API
Carbon residue
Sulfur wt %
3.0
70.8
88.4
11.4
15.0
0.6
20.9
1.3
5.0
Vis-breaking - Comparison
De-coking
Coil type requires frequent de-coking as
coke deposit,
fouling on tubes/coils. This is quite labor
intensive .
Coil type, tubes are de-coked sequentially
without the need to shutdown the visbreaking operation.
In soaker type require far less frequent decoking but their being taken out of service
normally requires a complete halt to the
operation.
CATALYTIC CRACKING
While thermal splitting of C-C bond proceeds
via radical mechanism, mainly producing
linear cracking products,
Catalytic cracking proceeds in the presence
of acid catalysts via carbocations giving
much more branched products with high
octane number
1.Houdry fixed bed CC
2.Moving bed
3.Fluidized bed
Houdrys Fixed bed CC
Each reactor was equipped with molten
salt heat removal system to remove the
heat from regeneration step and it was
FCC
Started in the 1930s finely divided solids
flow like liquids.
Refinery process that provides ~50 % of all
transportation fuels indirectly.
Provides ~35 % of total gasoline pool directly
from FCC produced naphtha.
~80 % of the sulfur in gasoline comes from
the FCC naphtha.
FCC
Major Secondary Refining Process
Conversion of heavy fractions ( VGO -370 C+)
into lighter fuel products (LPG, Gasoline,
Diesel)
Circulating fluid bed reactor system (Reactor
Regenerator configuration)
Multi component catalyst system
FCC IS THE WORKHORSE FOR REFINERY MOST PROFITABLE TOO!
Main Reactions in FCC
Cracking
of
Paraffins,Naphthenes
and
side chain of aromatics
Isomerisation of olefins
Dehydrogenation
of
Naphthenes and Olefins
Hydrogen Transfer
Cyclization
and
condensation of olefins
Alkylation and dealkylation
Main Reactions in FCC
FCC
Catalyst in FCC
For cracking of C-C bonds,
the acid catalysts are added.
First Alcl3 is used, but due to
corrosion,
and
waste
treatment was great.
Zeolite-Y was added to the
active
alumina
catalyst
(silica-alumina)
structure.
(Si/Al =2.5-3)
Catalyst in FCC
Broensted Acid centre
In regenerator more than 700 C, the
hydrolysis of framework aluminium
occurs, causing partial and even
total collapse of zeolite structure
Catalyst in FCC
Partial Dealumination of
framework at
800 C with steam
OR
Dehydroxylat
ed at 750 F to
Formation of bronsted acid sites
form Lewis
Next slide
Solid Acid Catalyst-Final structure
Partial de-alumination
Catalyst in FCC
In order to increase the thermal and
hydrothermal stability , the rare earth
salt solution (mixture of Lanthanum,
cerium, neodynium and praseodimium
chloride) added to replace the sodium
ion present in the structure.
CO combustion promotors
To facilitate the oxidation of CO to CO2
in regenerator pt or palladium based
combustion promoters are used.
Catalyst in FCC
SOx reducing additives
To reduce the SOx emission by adding
Inorganic oxide (Al2O3 or MgO )
Oxidation of SO2 to SO3 and formation
of metal sulphate on the additive.
In the reactor metal sulphate are
reduced to H2S which leaves the FCC
unit with cracked products.
Composition of FCC catalyst
Stacked FCC Design
CATALYTIC
HYDROCRACKING
Hydro-cracking (HC) Process
The feedstocks are not suitable for
catalytic cracking because of their
high metal, sulfur, nitrogen, and
asphaltene contents used in HC.
The process can also use feeds with
high aromatic content.
Products from hydrocracking
processes lack olefinic hydrocarbons.
The product slate ranges from light
hydrocarbon gases to gasolines to
residues.
Hydrocracking
Hydrocracking is a catalytic hydrogenation process in
which high molecular weight feedstocks are
converted and hydrogenated to lower molecular
weight products.
The catalyst used in hydrocracking is a bifunctional
one. It is composed of a metallic part, which
promotes hydrogenation, and an acid part, which
promotes cracking.
Hydrogenation removes impurities in the feed such as
sulphur, nitrogen and metals.
Cracking will break bonds, and the resulting
unsaturated products are consequently hydrogenated
into stable compounds.
Hydrocracking Chemistry
1. Alkane hydrocracking
2. Hydrodealkylation
3. Ring opening
4. Hydroisomerization
5. Polynuclear aromatics
hydrocracking
- Products from hydrocracking are saturated. i.e.
gasolines from hydrocracking units have lower
octane ratings. They have a lower aromatic content
due to high hydrogenation activity.
- Products from hydrocracking units are suitable for
jet fuel use.
Hydrocracking also produces light hydrocarbon
gases (LPG) suitable as petrochemical feedstocks.
Hydrocracking Process
Mostly single stage, with the possibility of two
operation modes. Once-through and a total
conversion of the fractionator bottoms by recyling.
In once-though operation, low sulfur fuels are
produced and the fractionator bottom is not recycled.
In the total conversion mode the fractionator bottom
is recylced to the inlet of the reactor.
In the two-stage operation, the feed is
hydrodesulfurized in the first reactor with partial
hydrocracking. Reactor effluent goes to a highpressure separator to separate the hydrogen-rich gas,
which is recycled and mixed with the fresh feed. The
liquid portion from the separator is fractionated, and
the bottoms of the fractionator are sent to the second
stage reactor.
Hydrocracking reaction conditions vary widely,
depending on the feed and the required products.
Temperature and pressure range from 400 to
480C and 35 to 170 atmospheres. Space
velocities in the range of 0.5 to 2.0 hr-1 are
applied.
Catalytic hydrocracking
Demerits
Initial
investment and
operating cost
1.5 times more
than FCC
52
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