EP422

CHAPTER 5a

HYDROCRACKING
 CHAPTER 5a- 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
• Environmental concern
By-product limiting sulfur and
Environmental hydrogen aromatic compound
concern at low cost 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
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

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

Hydrogenation in fixed Followed by one or more reactors

with fixed hydrocracking catalyst
hydrotreating catalyst beds to dealkylate aromatic rings,
bed to improve H/C open naphthene rings &
ratios & remove feed hydrocrack parafin chains
contaminants
 Hydrocracking Process

Schematic diagram of single stage hydrocracking process

 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 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, naphtha
and diesel fuel streams are removed as liquid
side streams

Distillation bottom product is sent

back to hydrocracker
 Reactions

• Hundreds of simultaneous chemical reactions occurring in hydrocracking

Assumption – mechanism of hydrocracking

is that of FCC with hydrogen superimposed

Hydrogenation – Cracking – Hydrogenation –

In FCC, the C-C exothermic
H2 is added to endothermic
bond is broken reaction
C=C reaction
 MAIN CHEMICAL REACTIONS

CATALYTIC
CRACKING SATURATION
of heavy of the newly HYDRO
hydrocarbons formed CRACKIN
into lighter hydrocarbons G
unsaturated with 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.
 Hydrocracking Process
• The process is typically carried out in a series of fixed bed reactors at
300-4500C and 100-200 atm. The process is associated with large heat
release due to exothermic hydrogenation reactions which dominate the
endothermic cracking reactions. The major disadvantage of the process
is the requirement of very high pressure of hydrogen with large energy
consumption making the process rather expensive. A typical two-stage
hydrocracker is shown in Figure in the next page. In first stage 40-50
vol% of the feed is hydrocracked. The first stage also acts as a
hydrotreater, where poisonous nitrogen and sulfur compounds are
partially hydrogenated. The effluent from the first stage reactor passes
through heat exchangers to a high pressure separator where hydrogen-
rich gases are separated and recycled. The liquid from the separator is
fed to a fractionating tower and the tower bottoms form the feed to the
second stage. Usually fixed-bed reactors with liquid down flow are
used.
Schematic diagram of two-stage hydrocracking process
 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
The hydrocracking catalyst has to be a bi-functional catalyst:
– Acid sites to catalyze cracking reactions
– Metal sites catalyzing hydrogenation
Catalyst choice depends on the nature of feed and desired product distribution. CoO-
moO3-Al2O3 has been widely used for hydrocracking of heavy feed stocks such as
residual raffinate, solvent deasphalted residual oil and vacuum residue. Base metals
(Co, Mo, Ni, W) supported on Al2O3-SiO2 and zeolite are used for producing
lubricating oils and middle or heavy distillate. Typical catalysts consist of 2% CO 7
% Mo, 6% Ni, 20% W on Al2O3-SiO2. The Ni/SiO2-Al2O3 increased conversion of
heavy polynuclear compounds in the feed. Pt or Pd supported on zeolites are used for
clean and pretreated feeds and are highly selective towards gasoline, diesel or jet fuel.
Typical catalyst is 0.5 wt % Pt or Pd on zeolites prepared by ion exchanges. Ni-Mo-
zeolite and Ni-W-zeolite catalysts are used for maximizing gasoline and gas oil
production respectively. The Ni-W-impregnated rare earth exchanged X-type zeolite
was found to be more resistant to nitrogen and structurally more stable. Catalyst
poisoned by deposition of coke and other materials is usually regenerated by burning
off the deposits.
 Catalyst site functions

Cracking is promoted by metallic

sites of catalyst
To minimize coke
formation a proper
balance must be
Acid sites transform the alkenes achieved with the
formed into ions two sites on the
catalyst, depends
on the conditions of
the operation
Hydrogenation reactions also
occurs on metallic sites
 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.
• Catalyst deactivation mainly occurs by deposition of coke on catalysts
surface that can be removed by periodic burn-off. The other source of
deactivation is presence of sulfur, nitrogen and metals in feed. The S,
N and metals can be removed by feed pretreatment.