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Chapter 21

HYDROCRACKING
Patrice Angela G. Abrea

History
Initial units came up during World War II for supplying
gasoline to Europe and America
Initial catalysts used were natural clays and operating
pressures were about 250 kg/cm2g
Continuous developments in catalysts has resulted in
lower pressure operation to produce desired quality
products
At present, more than 150 units are operating worldwide

Hydrocracking
Purpose: To process gas oil to break carbon- carbon
bonds of large
aromatic compounds and
remove contaminants
Hydrogenation (addition of hydrogen)
Cracking (carbon- carbon scission) of aromatic
bonds
Intent to create middle distillate products, not
gasoline range products

Primary Functions of Hydrogen:


Prevents the formation of polycyclic aromatic
compounds
Reduces tar formation
Prevents buildups of coke in the catalyst
Converts sulfur and nitrogen compounds present in the
feedstock by hydrogen sulfide and ammonia
Achieving high cetane number fuel

Hydrocracking Benefits
Produce Low Sulfur Products
Improves Combustion Quality of Products
Improves Downstream Processing
Middle Distillate yield is 80% compared to 45% in FCC
No coke or by- products

Feedstocks
Refractory (aromatic streams)
Coker oils
Cycle oils
Gas oils
Thermally cracked stocks
Solvent deasphalted residual oils
Straight run naphthas
Cracked naphthas

Catalysts
Acid sites (Amorphous Silica alumina, crystalline
zeolites, mixture of crystalline zeolite and amorphous
oxides)
- provide cracking activity
Metal sites (noble metals like palladium and platinum,
or non noble metal sufides like nickel, cobalt,
molybdenum, or tungsten)
- provide hydrogenation- dehydrogenation activities

Catalyst Poisons
Temporary poisons
Ammonia
Asphaltene, coke
Permanent Poison
Metals

Products
LPG
Motor gasoline
Reformer feeds
Aviation turbine fuel
Diesel fuels
Heating oils
Solvent and thinners
Lube oil
FCC Feed

Process Design
All hydrocracking processes are characterized by the
fact that in a catalytic operation under relatively high
hydrogen pressure, a heavy oil is treated to give products
of lower molecular weight.

Single- Stage, Once Through


Hydrocracker
Uses only one reactor
Any uncracked residual hydrocarbon oil from the bottom
of the reaction product fractionation tower is not
recycled for further cracking
Either the feedstock must first be hydrotreated to
remove ammonia, and hydrogen sulfide of the catalyst
used in the single reactor must be capable of both
hydrotreating and hydrocracking
60- 70% conversion

Single- Stage Hydrocracker with


Recycle
The uncracked residual hydrocarbon oil from the bottom
of the reaction product fractionation tower is recycled
back into the single reactor for further cracking
Either the feedstock must be hydrotreated and the
catalysts must be capable of both hydrotreating and
hydrocracking
97% conversion

Two- Stage Hydrocracker


Uses two reactors
The residual hydrocarbon oil from the bottom of the reaction
product fractionation tower is recycled back into the second
reactor for further cracking
The first- stage reactor accomplishes both hydrotreating
and hydrocracking
The second- stage reactor feed is virtually free of ammonia
and hydrogen sulfide
This permits the use of high performance noble metal
(palladium, platinum) catalysts which are susceptible to
poisoning by sulfur or nitrogen compunds
100% conversion

Process Options for Heavy


Feedstock
The major goal of residuum hydroconversion is
cracking of residua with desulfurization, metal removal,
denitrogenation, and asphaltene conversion. The
residuum hydroconversion process offers production of
kerosene and gas oil, and production of feedstocks for
hydrocracking, fluid catalytic cracking, and petrochemical
applications.

Process Options for Heavy


Feedstock
Asphaltenic Bottom Cracking (ABC) Process
H- Oil Process
Hydrovisbreaking (HYCAR) Process
Hyvahl Process
IFP Hydrocracking Process
Isocracking Process
LC- Fining Process
MAKfining Process
Microcrat- RC Process
Mild Hydrocracking Process
MRH Process
RCD- Unibon (BOC) Process
Residfining Process
Residue Hydroconversion (RHC) Process
Tervahl- H Process
Unicracking Process
Veba Combi Cracking Process

H- Oil Process
It is a catalytic process that uses a single- stage, twostage, or three-stage ebullated-bed reactor in which,
during the reaction, considerable hydrocracking takes
place.
The process is designed for hydrogenation of residua
and other high feedstocks in an ebullated bed reactor to
produce upgraded petroleum products.

IFP Hydrocracking Process


The process features a dual catalyst system: the first
catalyst is a promoted nickelmolybdenum amorphous
catalyst. It acts to remove sulfur and nitrogen and
hydrogenate aromatic rings. The second catalyst is a
zeolite that finishes the hydrogenation and promotes the
hydrocracking reaction.

Isocracking Process
The process has been applied commercially in the full
range of process flow schemes: single-stage, oncethrough liquid; single-stage, partial recycle of heavy oil;
single-stage extinction recycle of oil (100% conversion);
and two-stage extinction recycle of oil.

LC- Fining Process


It is a hydrocracking process capable of desulfurizing,
demetallizing, and upgrading a wide spectrum of heavy
feedstocks by means of an expanded bed reactor.
Operating with the expanded bed allows the
processing of heavy feedstocks, such as atmospheric
residua, vacuum residua, and oil sand bitumen.

MAKfining Process
The process uses a multiple catalyst system in
multibed reactors that include quench and redistribution
system internals (Hunter et al., 1997; Hydrocarbon
Processing, 1998, p. 86).

Mild Hydrocracking Process


It uses operating conditions similar to those of a VGO
desulfurizer to convert a VGO to significant yields of
lighter products.

MRH Process
The MRH process is a hydrocracking process designed
to upgrade heavy feedstocks containing amount of
metals and asphaltene, such as vacuum residua and
bitumen, and to produce mainly middle distillates (Table
21.10) (Sue, 1989; RAROP, 1991, p. 65).
The reactor is designed to maintain a mixed threephase slurry of feedstock, fine powder catalyst and
hydrogen, and to promote effective contact.

Residfining Process
A a catalytic fixed-bed process for the desulfurization
and demetallization of atmospheric and vacuum residua
(RAROP, 1991, p. 69; Hydrocarbon Processing, 1998).
The process can also be used to pretreat residua to
suitably low contaminant levels prior to catalytic
cracking.

Unicracking Process
It is a fixed-bed catalytic process that employs a highactivity catalyst with a high tolerance for sulfur and
nitrogen compounds and can be regenerated (Reno,
1997). The design is based on a single-stage or a twostage system with provisions to recycle to extinction
(RAROP, 1991, p. 79).

Fin