HYDROCRACKING

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.
 Hydro Conversion
Hydroconversion is a term used to describe
all different processes in which hydrocarbon reacts
with hydrogen.

Hydrotreating To describe the process of the removal of sulphur,

nitrogen and metal impurities in the feedstock by
hydrogen in the presence of a catalyst.

Hydrocracking The process of catalytic cracking of feedstock to

products with lower boiling points by reacting
them with hydrogen.

aromatics are saturated by hydrogen to the

Hydrogenation
corresponding naphthenes.
5
 PRINCIPLES
• Hydrogenation – oldest catalytic processes used in
petroleum refining.
• Why hydrocracking?
• Demand shifted to high
demand of ratios of gasoline and jet
petroleum fuel compared with
the usages of diesel fuel
products
and 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

• LCGO = light coker gas oil

• LCO = light cycle oil (produced in FCC, high in aromatics
and sulfur)
• HCGO = heavy coker gas oil
 HYDROCRACKING PROCESSES
• There are a number of hydrocracking
processes available for licensing.
• These processes are fixed bed catalytic
processes, in which liquid is moving
downward and gas is moving
upward/downward.
• 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 feedstock.
 HYDROCRACKING PROCESSES
PROCESS COMPANY
Unicracking UOP
GOFining EXXON Research & Eng
Ultracracking 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. (expanded bed reactor with
continuous on stream addition and
withdrawal of catalyst)
 HYDROCRACKING OBJECTIVE
NITROGEN

NAPHTHA

REMOVE FEED
CONTAMINANTS
CONVERT
METALS SULFUR LOW VALUE
GAS OILS
ULTRA
TO
CLEAN LUBE VALUABLE MIDDLE
BASE DISTILLATES
STOCKS PRODUCTS
 PRIMARY PROCESS TECHNIQUE

Hydrogenation in Followed by one or more

reactors with fixed hydrocracking
fixed hydrotreating catalyst beds to dealkylate
catalyst bed to aromatic rings, open naphthene
improve H/C ratios & rings & hydrocrack parafin chains
remove feed
contaminants
HYDROCRACKING BFD
 HYDROCRACKING PROCESS FLOW
Fresh feed is mixed with H2 and recycle gas
(high in H2 content) and passed through a
heater to the first reactor
Feed that high in sulfur & nitrogen a guard
reactor is employed to convert sulfur to H2S and
N2 to NH3 ( to protect precious catalyst in the
following reactor)
HC reactors are operated at high temp to
produce materials with boiling point below 400
F
 HYDROCRACKING PROCESS FLOW
Reactor gaseous effluent goes tru heat
exchangers and a high pressure separator
where the H2 rich gases are separated and
recycled to the first stage.

Liquid product from the reactor is sent to a distillation

column where C4 and lighter gases are taken off and the
jet fuel, naphta and diesel fuel streams are removed as
liquid side streams

Distillation bottom product is sent back to hydrocracker

 REACTIONS
• Hundreds of simultaneous chemical reactions
occuring in hydrocracking
Assumption – mechanism of hydrocracking
is that of FCC with hydrogen superimposed
In FCC, the C-C Hydrogenation – Cracking – Hydrogenation –
bond is broken H2 is added to endothermic exothermic
C=C reaction reaction
 MAIN CHEMICAL REACTIONS

CATALYTIC
CRACKING SATURATION
of the newly
of heavy formed HYDRO
hydrocarbo hydrocarbons CRACKING
ns into with
lighter hydrogen
unsaturated
hydrocarbo
ns
 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
alkenes formed into proper balance
must be achieved
ions with the two
Hydrogenation reactions
sites on the
also occurs on metallic sites catalyst, depends
conditions
on theof the
Both metallic and acidic operation
sites 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.