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HYDROCRACKING
CHAPTER 5c - OUTLINE
HYDROCRACKING
I. Principles
II. Hydrocracking reaction
III. Feed preparation
IV.Process requirements
V. Hydrocracking Catalyst
HISTORY
• 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 (rarely black coal) to
gasoline.
• Esso and Chevron applied this process later in
USA.
• Due to importance of this process, it has been
heavily researched and modified in petroleum
industry.
PRINCIPLES
• Hydrogenation – oldest catalytic processes used in
petroleum refining.
• Why hydrocracking?
• Demand shifted to high
ratios of gasoline and jet
demand of
fuel compared with the
petroleum
usages of diesel fuel and
products
home heating oils.
• By-product hydrogen at
low cost and in large
amounts has become
available from catalytic
WHY? reforming operations
By-product • Environmental concern
Environmental hydrogen limiting sulfur and
concern at low cost aromatic compound
concentrations in motor
fuels have increased.
ADVANTAGES OF HYDROCRACKING
• Hydrocracking is one of the most versatile process,
which facilitate product balance with the market
demand.
Improved gasoline
pool octane numbers
MODERN REFINERY
• Catalytic cracking (FCC) & hydrocracking work as a
team.
• FCC takes more easily cracked paraffinic gas oils as
charge stocks, while hydrocracker is capable of using
aromatics and cycle oils and coker distillates as feed
(these compounds resist FCC)
• Cycle oils and aromatics formed in FCC make
satisfactory feedstock for hydrocracking.
• Middle distillate and even light crude oil can be used
in hydrocracking.
FEEDSTOCK
• Typical hydrocracker feedstock is shown below
NAPHTHA
REMOVE FEED
CONTAMINANTS
CONVERT
METALS SULFUR LOW VALUE
GAS OILS TO
VALUABLE
ULTRA
CLEAN LUBE PRODUCTS MIDDLE
BASE DISTILLATES
STOCKS
PRIMARY PROCESS TECHNIQUE
CATALYTIC
CRACKING SATURATION
of the newly
of heavy formed HYDRO
hydrocarbons hydrocarbons CRACKING
into lighter with
unsaturated hydrogen
hydrocarbons
HYDROCRACKING REACTIONS
CRACKING & HYDROGENATION AS BELOW – the
scission of a C-C followed by hydrogenation
HYDROCRACKING REACTIONS
Aromatics
which are
difficult to
process in FCCU
are converted
to useful
products in
Hydrocrackers
HYDROCRACKING REACTIONS
• Cracking provides olefins for hydrogenation and
hydrogenation provides heat for cracking.
• Overall reaction provides excess of heat as
hydrogenation produces much larger heat than
the heat required for cracking operation.
• Therefore, the process is exothermic and
quenching (rapid cooling) is achieved by injection
cold hydrogen into the reactor and apply other
means of heat transfer
• Isomerization is another type of reaction, which
occurs in hydrocracking.
CATALYSTS
• Hydrocracking catalyst are dual functional
(having metallic and acidic sites) promoting
cracking and hydrogenation.
Cracking
Hydrogenolysis of Hydrogenation –
naphthenic unsaturated
structure hydrocarbons
Hydrogenation of
aromatic
compounds
CATALYST SITE FUCNTIONS
Cracking is promoted by
metallic sites of catalyst
To minimize coke
Acid sites transform the formation a
proper balance
alkenes formed into ions must be achieved
Hydrogenation reactions also with the two sites
on the catalyst,
occurs on metallic sites depends on the
conditions of the
Both metallic and acidic sites operation
take part in the 4th reactions
HYDROCRACKING CATALYSTS
• Generally a crystalline silica alumina base.
• Catalysts susceptible to sulfur poisoning if
hydrogen sulfide is present in large quantities.
• Catalysts not affected by ammonia.
• Sometimes necessary to remove moisture to
protect the catalyst.
• Catalyst deactivate and coke does form even with
hydrogen present.
• Hydrocarbons require periodic regeneration of
the fixed bed catalyst systems.