CPE656

PETROLEUM REFINING
ENGINEERING

CHAPTER 6
Hydrocracking

6.1. Feedstock and products

6.2. Process and mechanisms
6.3. Process Variables
6.4. Catalyst used
6.5. Health and safety considerations
IR. TS. MOHD FADHIL BIN MAJNIS
SCHOOL OF CHEMICAL ENGINEERING
COLLEGE OF ENGINEERING
UNIVERSITI TEKNOLOGI MARA (UiTM)
https://www.linkedin.com/in/fadhilmajnis/
 Background
• 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

Background
developed in 1927 by I. G. Farben (in Germany)
to convert lignite to gasoline.
The hydrocracking unit consists of one or more
• Esso and Chevron applied this process later in downflow hydrocracking reactors.
USA. The reactor configuration and the presence of
internals (‘distributor and redistributor trays’, ‘mixing
trays’, ‘catalyst support grids’ and ‘outlet collectors’)
• Due to the importance of this process, it has allow the fluids to flow downwards in the reactor,
favouring the reactions for dealkylation of the
been heavily researched and modified in the aromatic rings, the opening of the naphthenic rings
petroleum industry. and the breaking of the paraffin bonds.
https://www.costacurta.com/applications/refining/hydrocracking/

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 Reason

• The increasing demand for gasoline and jet fuel compared to diesel fuel
and home heating oils was a dominant factor in developing the
Whyhydrocracking process.

Hydrocracking?
• Hydrogen, a byproduct of the catalytic reforming process, was available in
large amounts and relatively cheap.

• Environmental concerns about sulfur and aromatic compounds were other

factors in the fast growth of hydrocracking in recent years.

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 Role of Hydrocracker in Refinery

• Hydrocracking is one of the main conversion processes in the refinery.

Role Of
• It is mainly used to produce middle distillates of low sulphur content, e.g.
Hydrocracker In
kerosene and diesel.

• Refinery
More recently, it has been used to remove the wax by catalytic dewaxing and for
aromatic removal by hydrogen saturation. This has been applied to the lube oil
plants and is gradually replacing the old solvent dewaxing and aromatic solvent
extraction.

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 Advantages of Hydrocracking
Better balance of gasoline and distillate production.

Greater gasoline boiling-range naphtha yields.

Advantages of
hydrocracking
Improved gasoline pool octane quality and sensitivity.

Production of relatively high amounts of isobutance in the butane

fraction.

Supplementing of FCC to upgrade heavy cracking stocks,

aromatics, cycle oils and coker oils to gasoline, jet fuels and diesel.
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Hydrocracker in Refinery
• VGO is the main feed for hydrocrackers. However, a
variety of feeds can be used. The feedstock type
influences the final products.

• Hydrocracking can use aromatics, cycle oils, and

coker distillates as feed (these compounds resist
FCC).

• Fluid Catalytic Cracking (FCC) takes more easily

cracked paraffinic atmospheric and vacuum gas oil.

• Cycle oils and aromatics formed in catalytic cracking

(FCC) become feedstock for hydrocracking.

• Middle distillate and even light crude oil can be

used in hydrocracking

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Feed preparation

• Hydrocracking catalyst is susceptible to poisoning by metallic salts, oxygen,

organic nitrogen compounds and sulfur in the feedstocks.

• To remove heteroatoms and oxygen, the feedstock is hydrotreated to saturate

the olefins and remove sulfur, nitrogen and oxygen compounds.

Suggest a process unit that can remove

heteroatoms and oxygen in the feedstocks
and elaborate on it in detail.
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Hydrocracking Feedstock
A typical hydrocracker feedstock is shown below.

LCGO = Light Coker Gas Oil

HCGO = Heavy Coker Gas Oil
LCO = Light Cycle Oil (produced in FCC, High in
aromatics and sulfur)
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 Hydrocracking Process

• There are several hydrocracking processes available for licensing.

Hydrocracking
• These processes are fixed bed catalytic processes.
Process
• The process employs either single-stage or two-stage hydrocracking.

• The temperature and pressure may vary with the age of the catalyst,
desired products and the properties of feedstock.

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Hydrocracking Process
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

Other processes, such as LC-Fining, are not based on fixed bed

reactors.
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 Hydrocracking Chemistry

Hydrocracking
Chemistry

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Process Configuration
• Aromatic hydrogenation, paraffin hydrocracking, naphthenes hydrocracking, and
aromatic hydrodealkylation reactions are all exothermic and careful control of
the fixed bed temperature is required, usually done by gaseous quenches in the
reactor. Catalyst partitioning of the bed must be applied.
• The average heat of a reaction at 400°C (kJ/mol) of different classes of reactions
are:

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Factors Affecting Hydrocracking Process
• Process configuration: one stage (once-through or recycle) or two stages
• Catalyst type
• Operating condition (depends on process objective)
Conversion level
Maximization of certain product
Product quality
Catalyst cycle
• Partial hydrogen pressure
• Liquid hourly space velocity (LHSV)
• Feed/hydrogen recycle ratio

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Process Configuration: Single-stage

• A conversion of 40–80% of the feed

can be achieved.
• If a high conversion is required, the
product from the bottom of the
distillation tower is recycled back to
the reactor for complete
conversion.
• This configuration can be used to
maximize a diesel product.
• It employs an amorphous catalyst.

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Process Configuration: Two-stage

• The effluent from the first stage

reactor is sent to a separator and
fractionator.
• The fractionator bottoms are
sent to the second reactor.
• In both configurations, the
hydrogen is separated in the
high-pressure separator and
recycled back to the reactor.

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Process Configuration: Two-Stage

• The hydrocracking catalyst in the first stage has a high

hydrogenation/acidity ratio, causing sulphur and nitrogen removal.
• In the second reactor, the catalyst used is of a low
hydrogenation/acidity ratio in which naphtha production is
maximized.
• If middle distillate, kerosene, diesel and jet fuel are to be maximized,
a high hydrogenation/acidity ratio is used.

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Main reactions in the two-stage hydrocracker

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Two-Stage Configuration
• A hydrotreatment reactor may be added before the first hydrocracker to help
remove sulphur and nitrogen compounds from the feed.
• Since H2S and NH3 are separated before entering the second hydrocracker,
this allows the selection of special catalysts in the second reactor without
the poisoning effect of sour gases.
• This will allow deep hydroconversion. The two-stage configuration offers
more flexibility than the single-stage scheme and is better suited for heavy
feedstocks.

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Two-Stage Hydrocracking

Search on current technology of

hydrocracking process unit and share
your findings.

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Hydrocracking Severity
•There are two levels of hydrocracking severity: mild and conventional.
•Mild hydrocracking: the operating conditions are less severe similar to
desulphurization (hydrotreating) conditions.

Comparison of hydrotreating, mild hydrocracking and conventional

hydrocracking operating conditions.

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Hydrocracking Severity

• A one-stage reactor without recycling is used in mild

hydrocracking.
• The major characteristics of this process are the production of a
high fuel oil yield and savings of hydrogen since the process is
operated at almost half of the hydrogen pressure used in
conventional hydrocracking.
• Usually, mild hydrocracking is used to produce LSFO.

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Products of Hydrocracking

Products of
Hydrocracking

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Hydrocracking Catalyst
• Hydrocracking catalysts have a cracking function and a hydrogenation–
dehydrogenation function.
• The cracking function is provided by acidic support, whereas the hydrogenation–
dehydrogenation function is provided by active metals.

Classification of hydrocracking catalyst (Secherzer and Gruia, 1996)

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Hydrocracking Catalyst
• The acidic support can be:
• amorphous oxides (e.g., silica-alumina),
• a crystalline zeolite (mostly modified Y zeolite) plus binder (e.g., alumina) or
• a mixture of crystalline zeolite and amorphous oxides.
• Cracking and isomerization reactions take place on the acidic support
• The metals providing the hydrogenation–dehydrogenation function can be
• noble metals (palladium, platinum) or
• non-noble metal sulphides from Group VI.A (molybdenum, tungsten) and group VIII.A (cobalt,
nickel).
• These metals catalyze the hydrogenation of the feedstock, making it more reactive for cracking and
heteroatom removal and reducing the coking rate.
• They also initiate the cracking by forming a reactive olefin intermediate via dehydrogenation.

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 Hydrocracking Catalyst
• The ratio between the catalyst’s cracking and hydrogenation function can be
adjusted to optimize activity and selectivity.
• The relative strength of different hydrogenation and cracking (acid) components in
hydrocracking catalysts are shown here:

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 Catalyst
• Dewaxing catalysts usually consist of a hydrogenation metal (Pt, Pd, Ni) supported on a
medium-pore zeolite (e.g. ZSM-5) combined with a binder, commonly alumina.

• The reacting molecules pass inside the cages and

are brought in close contact for reaction.
• The zeolite channels (or pores) are microscopically
small and in fact have molecular size dimension
such that they are often termed ‘‘molecular
sieves.’’

Structure of Y-type zeolite

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Catalytic Dewaxing

• Catalytic dewaxing is a particular hydrocracking process used to improve cold

flow properties of middle distillates and lubricants by cracking normal
paraffins that have high melting points.
• Dewaxing can be achieved by isomerization, as carried out by Chevron’s
isodewaxing process.
• Isoparaffins have lower melting points than normal paraffins.
• The properties targeted for improvement are the pour point and viscosity of
middle distillates and lubricants, the cloud point of diesel fuel, and the
freezing point of jet fuel.

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Catalytic Dewaxing

• A single-stage, once-through hydrocracking process can be used for

catalytic dewaxing, with or without hydrotreating, depending on the S
and N content of the feedstock.
• The catalytic process is carried out as a trickle bed reactor over a
bifunctional zeolite catalyst under hydrogen flow.
• A non-noble metal (e.g., nickel) supported on a medium-pore zeolite,
such as ZSM-5, can be used to obtain a high selectivity.

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Catalyst
• Co-Mo and Ni-Mo catalysts are used for desulfurization in the hydrotreating
process
• One of the most common catalysts is the zeolite-based catalyst, which
minimizes coke formation and improves catalyst stability
• Zeolites have a large concentration of Bronsted acid sites, enhancing their
hydrocracking activity. Zeolites also need lower temperatures to achieve a
specified conversion
• Amorphous -alumina is also widely applied as catalyst support due to its
mechanical and thermal stability and porous structure

Compare the hydrocracking and catalytic cracking in terms of

process principle, operating temperature, operating pressure,
catalyst used, reactor types, feedstock and products
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Health and safety considerations
Hydrocracking offers a safer alternative to thermal cracking but still presents potential hazards. Here's a
breakdown of the key health and safety considerations:

Exposure Hazards:
•Hydrogen: Hydrocracking uses hydrogen gas, which is a flammable and asphyxiant gas. Leaks can displace
oxygen, causing suffocation, and ignite easily in the presence of an ignition source.
•Hydrocarbons: Similar to other cracking processes, leaks or spills can expose workers to crude oil
components, causing skin, eye irritation, and respiratory problems.
•Hydrogen Sulfide (H2S): As with thermal and catalytic cracking, sour crudes can contain H2S, requiring
proper detection and respiratory protection to prevent exposure.
•Other Chemicals: Depending on the specific process and additives used, workers might encounter
ammonia, caustics, acids, or other hazardous materials.

Physical Hazards:
•Heat and Pressure: Hydrocracking units operate at high temperatures (around 700°F to 1000°F) and high
pressures. This combination poses a risk of burns from contact with equipment or releases and potential
equipment failures due to pressure overload.
•Fire and Explosion: Similar to other cracking processes, flammable hydrogen and hydrocarbons, along
with high temperatures and potential ignition sources, create a fire and explosion hazard.
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Health and safety considerations
Risk Mitigation Strategies:
The same mitigation strategies used in other cracking processes apply to hydrocracking, with some emphasis
on hydrogen hazards:

•Personal Protective Equipment (PPE): Equipping workers with appropriate gloves, respirators suitable for
hydrogen exposure, eye protection, and flame-resistant clothing is crucial.

•Process Safety Management (PSM): A comprehensive PSM program is essential for identifying and
managing hazards throughout the hydrocracking process.

•Training: Workers should receive thorough training on safe work practices specific to the hydrocracking
unit, including hazard recognition, proper PPE use, emergency response procedures for hydrogen leaks and
fires, and handling procedures for high-pressure equipment.

•Monitoring and Testing: Regular monitoring of the crude feedstock, products, process streams, and
emissions helps identify potential issues and maintain safety. This includes monitoring for H2S and hydrogen
gas leaks.

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Health and safety considerations
•Ventilation: Proper ventilation systems are crucial to remove hazardous vapors
and heat from the work environment, with a particular focus on removing
hydrogen gas buildup.

•Pressure Relief Systems: Hydrocracking units should be equipped with properly Hydrogen Leak Detection - Schoonover Inc.

functioning pressure relief systems to prevent catastrophic failures.

•Hydrogen Leak Detection and Mitigation: Specific measures to detect and

address hydrogen leaks are crucial, including:
• Hydrogen-specific gas detectors continuously monitor for hydrogen leaks
in the atmosphere.
• Double block and bleed (DB&B) valves systems allow for isolating Double Block & Bleed Valves | Alco Valves | UK
Valve Manufacturers (alco-valves.com)
sections of piping for maintenance or leak mitigation while minimizing
releases.

By implementing these measures, refineries can significantly reduce the health

and safety risks associated with hydrocracking.
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 RECAP:
• Hydrocracking is normally a two-stage process combining cracking and
hydrogenation, wherein heavier feedstocks are cracked in hydrogen to
produce more desirable products.

• The process employs high pressure, high temperature, a catalyst, and

Hydrocracking
hydrogen.

• Hydrocracking is used for feedstocks that are difficult to process by catalytic

cracking since these feedstocks usually have a high aromatic content and/or
high concentrations of sulfur and nitrogen compounds, which are two
principal catalyst poisons.

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