HYDROCRACKING

CPE 656 PETROLEUM REFINING ENGINEERING

 HYDROCRACKING

 It 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 saturated
compounds.
 BACKGROUND

 Hydrocracking is the conversion of higher boiling point

petroleum fractions to gasoline and jet fuels in the presence
of a catalyst
 Hydrocracking process was commercially developed in
1927 by I. G. Farben (in Germany) for conversion of lignite
to gasoline
 Esso, and Chevron applied this process later in USA

 Due to the importance of this process, it has been heavily

researched and modified in petroleum industry
 WHY HYDROCRACKING?

 The increasing demand for gasoline and jet fuel compared

to diesel fuel and home heating oils was a dominant
factors in the development of hydrocracking process
 Hydrogen as a byproduct of catalytic reforming process
was available in large amounts and relatively cheap
 Environmental concerns about sulfur and aromatic
compounds were other factors in fast growth of
hydrocracking in recent years
ROLE OF HYDROCRACKER IN REFINERY

 Hydrocracking is one of the main conversion

processes in the refinery.
 It is mainly used to produce middle distillates of low
sulphur content e.g. kerosene and diesel.
 More recently, it has been used to remove wax by
catalytic dewaxing and for aromatic removal
by hydrogen saturation. This has been applied to the
lube oil plants and is gradually replacing the old
solvent dewaxing and aromatic solvent extraction.
 ADVANTAGES 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
 FEEDSTOCK

 VGO is the main feed for hydrocrackers, however a variety

of feeds can be used. The feedstock type influences the final
products.
 Hydrocracking is capable of using aromatics and cycle oils
and coker distillates as feed (these compounds resist FCC).
 Fluid Catalytic Cracking (FCC) takes more easily cracked
paraffinic atmospheric and vacuum gas oil.
 Cycle oils and aromatics formed in catalytic cracking (FCC)
becomes feedstock for hydrocracking.
 Middle distillate and even light crude oil can be used in
hydrocracking
 HYDROCRACKING FEEDSTOCK

 A typical hydrocracker feedstock is shown below.

LCGO = Light Coker Gas Oil

HCGO = Heavy Coker Gas Oil
LCO = Light Cycle Oil (produced in FCC, High in aromatics and sulfur)
 HYDROCRACKING PROCESS

 There are a number of hydrocracking processes available

for licensing
 These processes are fixed bed catalytic processes.

 The process employs either single stage or two stage

hydrocracking
 The temperature and pressure may vary with the age of
catalyst, desired products and the properties of feed stock.
 HYDROCRACKING PROCESS

Process Company
Unicracking UOP
GOFining Exxon Research & Eng.
Ultrcracking British Pet. Amoco
Shell Shell Development Center
BASF-IFB Badische Anilin, IFP
Unibon UOP, LLC
Isomax Chevron, UOP, LLC

There are other processes, such as LC-Fining, which are not based on
fixed bed reactors.
Hydrocracking Chemistry
Hydrocracking Chemistry
 Hydrocracking Catalyst

 Hydrocracking catalysts have a cracking function and a hydrogenation–

dehydrogenation function.
 The cracking function is provided by an acidic support, whereas the
hydrogenation–dehydrogenation function is provided by active metals.

Classification of hydrocracking catalyst (Secherzer and Gruia, 1996)

 The acidic support can be
 amorphous oxides (e.g. silica–alumina),
 a crystalline zeolite (mostly modified Y zeolite) plus
binder (e.g. alumina) or
 a mixture of crystalline zeolite and amorphous oxides.

 Cracking and isomerization reactions take place on

the acidic support
 The metals providing the hydrogenation–dehydrogenation
function can be
 noble metals (palladium, platinum) or
 non-noble metal sulphides from Group VI.A (molybdenum,
tungsten) and group VIII.A (cobalt, nickel).
 These metals catalyze the hydrogenation of the feedstock,
making it more reactive for cracking and heteroatom
removal and reducing the coking rate.
 They also initiate the cracking by forming a reactive olefin
intermediate via dehydrogenation.
 CATALYST

 The ratio between the catalyst’s cracking and

hydrogenation function can be adjusted to optimize activity
and selectivity.
 The relative strength of different hydrogenation and
cracking (acid) components in hydrocracking catalysts are
shown here:
 Dewaxing catalysts usually consist of a hydrogenation
metal (Pt, Pd, Ni) supported on a medium-pore zeolite (e.g.
ZSM-5) combined with a binder, commonly alumina.

 The reacting molecules pass inside the

cages and are brought in close contact
for reaction.
 The zeolite channels (or pores) are
microscopically small and in fact have
molecular size dimension such that
they are often termed ‘‘molecular
sieves.’’
Structure of Y-type zeolite
 Catalyst

 Co-Mo and Ni-Mo catalysts are used for desulfurization in

hydrotreating process
 One of the most common catalysts is the zeolite based
catalyst, which 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 γ-alumina is also widely applied as a catalyst
support due to its mechanical and thermal stability and
porous structure
 THERMODYNAMICS

 Aromatic hydrogenation, paraffin hydrocracking,

naphthenes hydrocracking and aromatic hydrodealkylation
reactions are all exothermic and careful control of the
fixed bed temperature is required, usually done by gaseous
quenches in the reactor. Catalyst partitioning of the bed
must be applied.
 The average heat of a reaction at 400°C (kJ/mol) of
different classes of reactions are:

Source: Billon and Bigeard,2001

 Factors Affecting Hydrocracking Process

 Process configuration: one stage (once-through or recycle)

or two stages
 Catalyst type
 Operating condition (depends on process objective)
 Conversion level
 Maximization of certain product
 Product quality
 Catalyst cycle
 Partial hydrogen pressure
 Liquid hourly space velocity
 Feed/hydrogen recycle ratio
 Process Configuration : One-stage

One-stage hydrocracking process A conversion of 40–

80% of the feed can be
achieved.
If high conversion is
required the product
from the bottom of the
distillation tower is
recycled back to the
reactor for complete
conversion.
This configuration can
be used to maximize a
diesel product.
It employs an
amorphous catalyst.
 Process Configuration: Two-Stage

Two-stage hydrocracking process

The effluent from the

first stage reactor is
sent to a separator and
fractionator.
The fractionator
bottoms are sent to the
second reactor.
In both configurations,
the hydrogen is
separated in the high
pressure separator and
recycled back to the
reactor.
 Process Configuration: Two-Stage

 The hydrocracking catalyst in the first stage has a high

hydrogenation/acidity ratio, causing sulphur and nitrogen
removal.
 In the second reactor, the catalyst used is of a low
hydrogenation/acidity ratio in which naphtha production is
maximized.
 If middle distillate, kerosene, diesel and jet fuel are to be
maximized, a high hydrogenation/acidity ratio is used.
Main reactions in two-stage hydrocracker
 Two-Stage Configuration

 A hydrotreatment reactor may be added before the first

hydrocracker to help in removing sulphur and nitrogen
compounds from the feed.
 Since H2S and NH3 are separated before entering the
second hydrocracker, this allows the selection
 of special catalysts in the second reactor without the
poisoning effect of sour gases.
 This will allow deep hydroconversion. The two-stage
configuration offers more flexibility than the single stage
scheme and is better suited for heavy feedstocks
Two-Stage Hydrocracking
 Hydrocracking Severity

 There are two levels of hydrocracking severity: mild and

conventional.
 Mild hydrocracking: the operating conditions are less
severe similar to desulphurization (hydrotreating)
conditions.

Comparison of
hydrotreating, mild
hydrocracking and
conventional
hydrocracking
operating conditions.
 Hydrocracking Severity

 A one-stage reactor without recycle is used in mild

hydrocracking.
 The major characteristics of this process are the
production of a high yield of fuel oil and a savings of
hydrogen, since the process is operated at almost
half of the hydrogen pressure used in conventional
hydrocracking.
 Usually mild hydrocracking is used to produce LSFO.
Products of Hydrocracking
 Catalytic Dewaxing

 Catalytic dewaxing is a particular hydrocracking process

used to improve cold flow properties of middle distillates
and lubricants by cracking normal paraffins that has high
melting points.
 Dewaxing can be achieved by isomerization, as carried out
by Chevron’s isodewaxing process.
 Isoparaffins have lower melting points than normal
paraffins.
 The properties targeted for improvement are pour point
and viscosity of middle distillates and lubricants, the cloud
point of diesel fuel, and the freeze point of jet fuel.
 Catalytic Dewaxing

 A single-stage, once through hydrocracking process

can be used for catalytic dewaxing, with or without
hydrotreating, depending on the S and N content of
the feedstock.
 The catalytic process is carried out as a trickle bed
reactor over a bifunctional zeolite catalyst under
hydrogen flow.
 A non-noble metal (e.g. nickel) supported on a
medium-pore zeolite, such as ZSM-5 can be used to
obtain a high selectivity.
HYDROCRACKING
PROCESS

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