Catalysts

o Characteristics of good catalyst:

- ability to produce desirable product and not coke
- selective to valuable products (e.g. high octane
gasoline).
- stable, so it does not deactivate at the high
temperature levels in regenerators.
- resistant to contamination
 Catalysts
q Hydrocracking catalysts are dual functional,
(having metallic and acidic sites) promoting
cracking and hydrogenation reactions.
q The main reactions are:
q Cracking
q Hydrogenation of unsaturated
hydrocarbons obtained from cracking
q Hydrogenation of aromatic compounds
q Hydrogenolysis (breaking C-C bond by
the addition of hydrogen) of naphthenic
structure
 Catalysts
q Cracking is promoted by metallic sites of the
catalyst.
q Acid sites transform the alkenes formed into ions
q Hydrogenation reactions are also occur on
metallic sites
q Both metallic and acidic sites take part in the
hydrogenolysis reactions
q To minimize coke formation a proper balance
must be achieved with the two sites on the catalyst
(depending on the conditions of the operation)
 Catalysts

q High temperatures lead to more reactions on

acidic sites while increase in hydrogen partial
pressure enhances hydrogenation on metallic sites
q Conventional catalysts are composed of
transition metals deposited on acidic sites.
q The metals are those from group VIII (e.g.
molybdenum, cobalt, nickel,…)
 Catalysts

o Three classes:
(1) acid-treated natural aluminosilicates
(2) amorphous synthetic silica-alumina
combinations
(3) crystalline synthetic silica-alumina catalyst
called zeolite or molecular sieves
 Catalysts

q Zeolite-based catalyst is one of the most commonly

used catalysts in hydrocracking
q The use of zeolite catalyst minimizes coke formation
and improves catalyst stability
q Zeolites have large concentration of Brunsted acid
sites which enhances their hydrocracking activity
q Zeolites also need lower temperatures to achieve a
specified conversion
q Amorphous g-alumina is also widely applied as a
catalyst support due to its mechanical and thermal
stability and porous structure
Advantages of using Zeolite as Catalyst
o Higher activity
o Higher gasoline yield
o Higher octane number
o Lower coke yield
o Increased isobutane production
o Higher conversion without overcracking
Chuyển hóa phân đoạn nặng 149
HYDROCRACKING CATALYST
o There are a number of hydrocracking catalysts available and
the actual composition is tailored to the process, feed
material, and the products desired.
o Most of the hydrocracking catalysts consist of a crystalline
mixture of silica-alumina with a small uniformly distributed
amount of rare earths contained within the crystalline lattice.
o The silica-alumina portion of the catalyst provides cracking
activity while the rare-earth metals promote hydrogenation.
o Catalyst activity decreases with use, and reactor temperatures
are raised during a run to increase reaction rate and maintain
conversion.
o The catalyst selectivity also changes with age and more gas is
made and less naphtha produced as the catalyst temperature is
raised to maintain conversion.
o With typical feedstocks it will take from two to four years for
catalyst activity to decrease from the accumulation of coke
and other deposits to a level which will require regeneration.
o Regeneration is accomplished by burning off the catalyst
deposits, and catalyst activity is restored to close to its
original level.
o The catalyst can undergo several regenerations before it is
necessary to replace it.
o Almost all hydrocracking catalysts use silica-alumina as the
cracking base but the rare-earth metals vary according to the
manufacturer.
o Those in most common use are platinum, palladium,
tungsten, and nickel.
 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.
THE HYDROCRACKING PROCESS
o The hydrocracking process may require either one or two
stages, depending upon the process and the feed stocks used.
o The GOFining process is a fixed-bed regenerative process
employing a molecular-sieve catalyst impregnated with a
rare-earth metal.
o The process employs either single-stage or two-stage
hydrocracking with typical operating conditions ranging from
660 to 785°F and from 1000 to 2000 psig (350–420°C and
6900–13,800 kPa).
o The temperature and pressure vary with the age of the
catalyst, the product desired, and the properties of the
feedstock.
o The decision to use a single- or two-stage system depends
upon the size of the unit and the product desired.
o For most feedstocks the use of a single stage will permit the
total conversion of the feed material to gasoline and lighter
products by recycling the heavier material back to the reactor.
o The process flow for a two-stage reactor is shown in Figure
7.2. If only one stage is used, the process flow is the same as
that of the first stage of the two-stage plant except the
fractionation tower bottoms is recycled to the reactor feed.
o The fresh feed is mixed with makeup hydrogen and recycle
gas (high in hydrogen content) and passed through a heater to
the first reactor. If the feed has not been hydrotreated, there is
a guard reactor before the first hydrocracking reactor.
o The guard reactor usually has a modified hydrotreating
catalyst such as cobalt-molybdenum on silica-alumina to
convert organic sulfur and nitrogen compounds to hydrogen
sulfide, ammonia, and hydrocarbons to protect the precious
metals catalyst in the following reactors.
o The hydrocracking reactor(s) is operated at a sufficiently high
temperature to convert 40 to 50 vol% of the reactor effluent to
material boiling below 400°F (205°C).
o The reactor effluent goes through heat exchangers to a high-
pressure separator where the hydrogen-rich gases are
separated and recycled to the first stage for mixing both
makeup hydrogen and fresh feed.
o The liquid product from the separator is sent to a distillation
column where the C4 and lighter gases are taken off overhead,
and the light and heavy naphtha, jet fuel, and diesel fuel
boiling range streams are removed as liquid sidestreams.
o The fractionator bottoms are used as feed to the second-stage
reactor system.
o The unit can be operated to produce all gasoline and lighter
products or to maximize jet fuel or diesel fuel products.
o The bottoms stream from the fractionator is mixed with
recycle hydrogen from the second stage and sent through a
furnace to the second-stage reactor.
o Here the temperature is maintained to bring the total
conversion of the unconverted oil from the first-stage and
second-stage recycle to 50 to 70 vol% per pass.
o The second-stage product is combined with the first-stage
product prior to fractionation.
o Both the first- and second-stage reactors contain several beds
of catalysts.
o The major reason for having separate beds is to provide
locations for injecting old recycled hydrogen into the reactors
for temperature control.
o In addition, redistribution of the feed and hydrogen between
the beds helps to maintain a more uniform utilization of the
catalyst.
PROCESS VARIABLES
o The severity of the hydrocracking reaction is measured by the
degree of conversion of the feed to lighter products.
o Conversion is defined as the volume percent of the feed
which disappears to form products boiling below the desired
product end point
o The primary reaction variables are reactor temperature and
pressure, space velocity, hydrogen consumption, nitrogen
content of feed, and hydrogen sulfide content of the gases
o The effects of these are as follows:
q Reactor Temperature
o Reactor temperature is the primary means of conversion
control.
o At normal reactor conditions a 20°F (10°C) increase in
temperature almost doubles the reaction rate, but does not
affect the conversion level as much because a portion of the
reaction involves material that has already been converted to
materials boiling below the desired product end point.
o As the run progresses it is necessary to raise the average
temperature about 0.1 to 0.2°F per day to compensate for the
loss in catalyst activity.
q Reactor Pressure
o The primary effect of reactor pressure is in its effects on the
partial pressures of hydrogen and ammonia.
o An increase in total pressure increases the partial pressures of
both hydrogen and ammonia.
o Conversion increases with increasing hydrogen partial
pressure and decreases with increasing ammonia partial
pressure.
o The hydrogen effect is greater, however, and the net effect of
raising total pressure is to increase conversion.
q Space Velocity
o The volumetric space velocity is the ratio of liquid flow rate,
in barrels per hour, to catalyst volume, in barrels.
o The catalyst volume is constant, therefore the space velocity
varies directly with feed rate.
o As the feed rate increases, the time of catalyst contact for
each barrel of feed is decreased and conversion is lowered.
o In order to maintain conversion at the proper level when the
feed rate is increased, it is necessary to increase the
temperature.
q Nitrogen Content
o The organic nitrogen content of the feed is of great
importance as the hydrocracking catalyst is deactivated by
contact with organic nitrogen compounds.
o An increase in organic nitrogen content of the feed causes a
decrease in conversion.
q Hydrogen Sulfide
o At low concentrations the presence of hydrogen sulfide acts
as a catalyst to inhibit the saturation of aromatic rings.
o This conserves hydrogen and produces a product with a
higher octane number because the aromatic naphtha has a
higher octane than does its naphthenic counterpart.
o However, hydrocracking in the presence of a small amount of
hydrogen sulfide normally produces a very low-smoke-point
jet fuel.
o At high hydrogen sulfide levels corrosion of the equipment
becomes important and the cracking activity of the catalyst is
also affected adversely.
q Heavy Polynuclear Aromatics (HPNA)
o Heavy polynuclear aromatics are formed in small amounts
from hydrocracking reactions and, when the fractionator
bottoms is recycled, can build up to concentrations that cause
fouling of heat exchanger surfaces and equipment.
o Steps such as reducing feed end point or removal of a drag
stream may be necessary to control this problem
Chuyển hóa phân đoạn nặng 168
Chuyển hóa phân đoạn nặng 169
 Hydrocracking processes
q The fresh feed is mixed with hydrogen gas and recycle gas (high in
hydrogen content) and passed through a heater to the first reactor
q If the feed is high in sulfur and nitrogen a guard reactor is employed to
convert sulfur to hydrogen sulfide and nitrogen to ammonia to protect
precious catalyst in the following reactor.

gasoline
Jet fuel

Two-Stage Hydrocracking
 Hydrocracking processes
qHydrocracking reactors are operated at high temperatures to
produce materials with boiling point below 400 F
qThe reactor gaseous effluent goes through heat exchangers and
a high pressure separator where the hydrogen rich gases are
separated and recycled to the first stage.

gasoline
Jet fuel

Two-Stage Hydrocracking
 Hydrocracking processes
qThe liquid product from the reactor is sent to a distillation column
where C1-C4 and lighter gases are taken off and the gasoline, jet
fuel, naphta and/or diesel fuel streams are removed as liquid side
streams.
q The distillation bottom product is sent to the second
hydrocracker

gasoline
Jet fuel

Two-Stage Hydrocracking
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 vs FCC

q Fluid Catalytic Cracking (FCC) takes more

easily cracked paraffinic atmospheric and
vacuum gas oil
q Hydrocracking is capable of using aromatics
and cycle oils and coker distillates as feed
(these compounds resist FCC)
q Cycle oils and aromatics formed in catalytic
cracking (FCC) are satisfactory feedstock for
hydrocracking
q Middle distillate and even light crude oil can
also be used as feedstock for hydrocracking
Chuyển hóa phân đoạn nặng 175
Hydrocracking vs Hydrotreating

Chuyển hóa phân đoạn nặng 176