7

Catalytic Hydrocracking
PETROLEUM
REFINING
Technology and Economics
Fifth Edition

1
 OUTLINE
I. Principles
II. Hydrocracking
reaction
III.Feed preparation
IV.Process requirements
V. Hydrocracking Catalyst
 (1) the demand for petroleum
products has shifted to high
demand for gasoline, diesel, and
Why jet fuel compared with the
Hydrocracking usages of other products,
(2) by-product hydrogen at low
The interest in the use cost and in large amounts has
of hydrocracking has become available from
been caused by catalytic reforming operations,
several factors, and
including: (3) environmental concerns
limiting sulfur and aromatic
compound concentrations in
motor fuels have increased.
 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.
Advantages
1. Better balance of gasoline and distillate production
2. Greater gasoline boiling-range naphtha yields
3. Improved gasoline pool octane quality and
sensitivity
4. Production of relatively high amounts of isobutane
in the butane fraction
5. Supplementing of fluid catalytic cracking to
upgrade heavy cracking stocks, aromatics, cycle oils,
and coker oils to gasoline, jet fuels, and diesel
 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 and aromatics formed in FCC
oils
satisfactory make
feedstock for hydrocracking.
• Middle distillate and even light crude oil can be
used in hydrocracking.
 Feed Stock
• 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
Reactions
Aromatics which
are difficult to
process in FCC are
converted to
useful products
in Hydrocrackers.
 Feed Preparation
• Hydrocracking catalyst is sensitive to poisoning by
metallic salts, oxygen, organic nitrogen compounds, and
sulfur in the feedstocks.
• The feedstock is hydrotreated to saturate the olefins and
remove sulfur, nitrogen, and oxygen compounds.
• Molecules containing metals are cracked, and the metals
are retained on the catalyst.
• The nitrogen and sulfur compounds are removed by
conversion to ammonia and hydrogen sulfide.
• Although organic nitrogen compounds are thought to act
as permanent poisons to the catalyst, the ammonia
produced by reaction of the organic nitrogen compounds
with hydrogen does not affect the catalyst permanently.
 HYDROCRACKING
NITROGE
N

NAPHTHA

REMOVE FEED
CONTAMINANT
S CONVERT
METAL SULFU LOW VALUE
S R GAS OILS
TO
ULTRA
CLEANLUBE VALUABLE MIDDLE
BASE
STOCKS PRODUCTS DISTILLAT
ES
 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)
 PRIMARY PROCESS
TECHNIQUE

Hydrogenation in Followed by one or more

reactors with fixed
fixed hydrotreating hydrocracking catalyst beds to
catalyst bed to dealkylate aromatic rings, open
improve H/C ratios & naphthene 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
through
passed 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
convert 40 to 50 vol. % of the reactor effluent
to materials with boiling point below 400 OF
 HYDROCRACKING PROCESS
FLOW
Reactor gaseous effluent goes through
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 used as a

feedstock for second stage to bring total
conversion
 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.

Crackin
g

Hydrogenolysis Hydrogenation
of naphthenic – unsaturated
structure hydrocarbons

Hydrogenation
of aromatic
compounds
 CATALYST SITE
FUCNTIONS
Cracking is promoted
by metallic sites of
catalyst formationcoke
a
Acid sites transform the To minimize
proper
alkenes formed into must
balance
be
ions achieved
with the two
Hydrogenation reactions
sites on the
also occurs on metallic sites catalyst,
depends
conditions
on of
the
Both metallic and acidic the
sites take part in the 4th operation
reactions
 HYDROCRACKING
•
CA TAL YSTS
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.