Hydrocracking

What is Hydrocracking?

Hydrocracking is the conversion process of

higher boiling point petroleum fractions to light
hydrocarbons (mainly gasoline and jet fuels) in
the presence of a catalyst
 Hydrocracking
 Hydrocracking is catalytic cracking in
the presence of hydrogen. The extra
hydrogen saturates, or
hydrogenates, the chemical bonds of
the cracked hydrocarbons and
creates isomers with the desired
characteristics.

Hydrocracking
 Hydrocracking is also a treating
process, because the hydrogen
combines with contaminants such as
sulphur and nitrogen, allowing them
to be removed
 Feed
• The straight run
• Coker gas oil
• FCC cycle oil

Hydrocracking
• Uses high pressure and large
amount of hydrogen
• Hydrogenation reaction
suppress coke formation
• Products high in liquid yield and
low in sulfur and olefins
 Process: Hydrocracking
The two reactions that occur are
1. Cracking (endothermic) and
2. Hydrogenation (exothermic).

Heat of cracking is supplied by the hydrogenation

reaction  autothermal reaction.
 Why Hydrocracking?
 The increasing demand for gasoline and
jet fuel compared to diesel fuel and home
heating oils was a dominant factor in the
development of hydrocracking process
 Hydrogen as a byproduct of catalytic
reforming process was available in large
amounts and relatively cheap
Benefits of Hydrocracking
 Hydrocracking is one of the most versatile
process, which facilitate product balance with the
market demand
 Other advantages are:
 Very high gasoline yield
 High octane numbers
 Production of large amount of isobutane
 Supplementing FCC (Fluid Catalytic
Cracking) to upgrade heavy stocks,
aromatics and coker oils
 Hydrocracking vs FCC
 Fluid Catalytic Cracking (FCC) takes more
easily cracked paraffinic atmospheric and
vacuum gas oil
 Hydrocracking is capable of using aromatics
and cycle oils and coker distillates as feed
(these compounds resist FCC)
 Cycle oils and aromatics formed in catalytic
cracking (FCC) are satisfactory feedstock for
hydrocracking
 Middle distillate and even light crude oil can
also be used as feedstock for hydrocracking
 Hydrocracking processes
 The fresh feed is mixed with hydrogen gas and recycle gas (high in
hydrogen content) and passed through a heater to the first reactor
 If the feed is high in sulfur and nitrogen a guard reactor is employed to
convert sulfur to hydrogen sulfide and nitrogen to ammonia to protect
precious catalyst in the following reactor.

gasoline
Jet fuel

Two-Stage Hydrocracking
 Hydrocracking processes
Hydrocracking reactors are operated at high temperatures to
produce materials with boiling point below 400 F
The reactor gaseous effluent goes through heat exchangers and
a high pressure separator where the hydrogen rich gases are
separated and recycled to the first stage.

gasoline
Jet fuel

Two-Stage Hydrocracking
 Hydrocracking processes
The liquid product from the reactor is sent to a distillation
column where C1-C4 and lighter gases are taken off and the
gasoline, jet fuel, naphta and/or diesel fuel streams are removed as
liquid side streams.
 The distillation bottom product is sent to the second
hydrocracker
gasoline
Jet fuel

Two-Stage Hydrocracking
 Hydrocracking Reactions

There are hundreds of simultaneous chemical

reactions occurring in hydrocracking
 It is assumed that the mechanism of
hydrocracking is that of catalytic cracking with
hydrogen superimposed
 In catalytic cracking the C – C bond is broken,
while in hydrogenation, H2 is added to a carbon-
carbon double bond
 Cracking is an endothermic reaction
 Hydrogenation is an exothermic reaction
 Hydrocracking Reactions

 Cracking and hydrogentation are complementary

as shown below
Hydrocracking reactions

Aromatics which
are difficult to
process in FCC are
converted to useful
products in
Hydrocrackers.
 Hydrocracking Reactions
 Cracking provides olefins for hydrogenation and
Hydrogenation provides heat for cracking
 The overall reaction provides an excess of heat as
hydrogenation produces much larger heat than the
heat required for cracking operation
 Therefore the overall process is exothermic and
quenching is achieved by injecting cold hydrogen
into the reactor and apply other means of heat
transfer, e.g. intermediate heat exchanger
 Isomerization is another type of reaction, which
occurs in hydrocracking
 Hydrocracking Reactions

 As a result of isomerization, the olefinic products

formed are rapidly hydrogenated which provides high
octane isoparaffins
 The volumetric yield can be as high as 125% as the
hydrogenated products have a higher API gravity
 Hydrocracking reactions are normally carried out
at an average catalyst temperature between 550 and
750 F
 Hydrocracking Reactions
 The reactor pressure ranges from 8275 – 13800
kPa (1200 to 2000 psig)
 Large quantity of hydrogen is circulated in
order to prevent excessive catalyst fouling
 Catalyst poisons are removed from the
feedstock to enhance catalyst life
 The feedstock may be hydrotreated to reduce
the sulfur and nitrogen levels as well as metals
 In recent designs, the first reactor in the reactor
train may be used for sulfur and nitrogen removal
 Reaction Kinetics

 Kinetic modeling of reactions in hydrocracking is

difficult due to the complexity of feedstock and
products
 In general, adsorption of hydrogen to the active
sites on the catalyst surface can be shown as

kA
H2 + S H2.S
k-A
S = vacant adsorption site on the catalyst surface
kA = adsorption rate constant
k-A = desorption rate constant
 Reaction Kinetics
 The rate of adsorption ra is proportional to the
concentration of active sites Ca and the partial
pressure of hydrogen
ra = kA pH2 Ca

 The desorption rate would be

rd = k-A CH2S
 The net rate of adsorption is
ra - rd = kA pH2 Ca - k-A CH2S
The total concentration of active sites is constant
C =C + C
 Reaction Kinetics

 At equilibrium, the net rate will be zero

CH2S = (KA PH2 CT )/(1 + KA PH2)
Where KA = kA/k-A

Once the molecules have been adsorbed, they

undergo several possible types of surface reactions
The rate constant is also related to activation
energy of the reaction
 In general, the rate of hydrocracking follows a
first order kinetics
 Catalysts

• Characteristics of good catalyst:

- ability to produce desirable product and not coke
- selective to valuable products (e.g. high octane
gasoline).
- stable, so it does not deactivate at the high
temperature levels in regenerators.
- resistant to contamination
 Catalysts
 Hydrocracking catalysts are dual functional,
(having metallic and acidic sites) promoting
cracking and hydrogenation reactions.
 The main reactions are:
 Cracking
 Hydrogenation of unsaturated
hydrocarbons obtained from cracking
 Hydrogenation of aromatic compounds
 Hydrogenolysis (breaking C-C bond by
the addition of hydrogen) of naphthenic
structure
 Catalysts
 Cracking is promoted by metallic sites of the
catalyst.
 Acid sites transform the alkenes formed into ions
 Hydrogenation reactions are also occur on
metallic sites
 Both metallic and acidic sites take part in the
hydrogenolysis reactions
 To minimize coke formation a proper balance
must be achieved with the two sites on the catalyst
(depending on the conditions of the operation)
 Catalysts

 High temperatures lead to more reactions on

acidic sites while increase in hydrogen partial
pressure enhances hydrogenation on metallic sites
 Conventional catalysts are composed of
transition metals deposited on acidic sites.
 The metals are those from group VIII (e.g.
molybdenum, cobalt, nickel,…)
 Catalysts

• Three classes:
(1) acid-treated natural aluminosilicates
(2) amorphous synthetic silica-alumina
combinations
(3) crystalline synthetic silica-alumina catalyst
called zeolite or molecular sieves
 Catalysts

 Zeolite-based catalyst is one of the most commonly

used catalysts in hydrocracking
 The use of zeolite catalyst minimizes coke formation
and improves catalyst stability
 Zeolites have large concentration of Brunsted acid
sites which enhances their hydrocracking activity
 Zeolites also need lower temperatures to achieve a
specified conversion
 Amorphous -alumina is also widely applied as a
catalyst support due to its mechanical and thermal
stability and porous structure
Advantages of using Zeolite as Catalyst
• Higher activity
• Higher gasoline yield
• Higher octane number
• Lower coke yield
• Increased isobutane production
• Higher conversion without overcracking
End of Chapter Six