Higher Institute of Engineering and Technology in Tanta

Chemical engineering Department

Petrochemical Industries (CHE361)
Lecture (6)

Lecture (6)

Thermal Cracking
❖ Thermal cracking is a chemical process used in the petrochemical industry to break down
large, heavy hydrocarbon molecules into smaller, more useful molecules by applying high
temperatures.
❖ It is commonly used in refining crude oil to produce valuable products like gasoline, diesel,
and olefins (ethylene, propylene), which are essential for manufacturing plastics and other
chemicals.

Thermal cracking Overview:

❖ In thermal cracking, heavy hydrocarbons are heated to high temperatures (typically

between 450°C and 750°C) under high pressure.
❖ The intense heat and pressure cause large hydrocarbon molecules to break apart into
smaller ones.
❖ This process may involve both homolytic cleavage (where molecular bonds break evenly,
producing free radicals) and reforming reactions.

Types of Thermal Cracking:

1. Vis breaking:
❖ A mild form of thermal cracking aimed at reducing the viscosity of heavy residual oil,
making it easier to transport and further process.
❖ The primary goal of vis-breaking is to convert these heavier fractions into lighter, more
manageable products, thereby enhancing their value and making them easier to transport
and process further.

Process Overview:

❖ Heating:

The heavy oil feedstock is heated to moderate temperatures (typically between 400°C and 500°C)
under controlled conditions.

❖ Residence Time:

The oil is held in a visbreaking unit for a specific duration, allowing for partial thermal cracking
to occur.

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 Higher Institute of Engineering and Technology in Tanta
Chemical engineering Department
Petrochemical Industries (CHE361)
Lecture (6)

❖ End Products:

The process results in lighter hydrocarbons and a reduction in the overall viscosity of the feedstock,
producing products that are easier to process.

Operating Conditions:

❖ Temperature:

Typically maintained at lower temperatures compared to more severe thermal cracking processes
(e.g., delayed coking).

❖ Pressure:

Generally operated at atmospheric pressure, although some configurations may use slight
pressures.

❖ Reaction Time:

Short residence times are used, often in the range of seconds to a few minutes.

Types of Vis-breaking:

❖ Batch Vis-breaking: Involves processing batches of heavy oil sequentially.

❖ Continuous Vis-breaking: A more common industrial approach where the feedstock is
continuously fed through the reactor, allowing for a steady output of products.

Products of Visbreaking:

1. Light Fuel Oils:

Such as naphtha and kerosene, which can be used as fuels or further processed into gasoline.

2. Gas Oil:

A valuable fraction that can be further treated or used as a feedstock for catalytic cracking.

3. Reduced Residual Oil:

The remaining heavy oil has lower viscosity, making it easier to transport and process.

Advantages of Vis-breaking:

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 Higher Institute of Engineering and Technology in Tanta
Chemical engineering Department
Petrochemical Industries (CHE361)
Lecture (6)

❖ Improved Product Quality:

Reduces the viscosity of heavy oils, making them more suitable for refining or transportation.

❖ Cost-Effective:

Vis-breaking units are generally less expensive to operate than more complex processes like
catalytic cracking.

❖ Flexibility:

Can be integrated into existing refining operations without significant modifications.

Disadvantages of Vis-breaking:

❖ Limited Conversion:

The process does not completely break down heavy hydrocarbons; some residue remains.

❖ Coke Formation:

Some solid carbon (coke) can form during the process, potentially requiring equipment
maintenance.

❖ Lower Yields of Light Products:

Compared to more severe cracking processes, visbreaking yields lighter products but may not
maximize the production of desired olefins.

Applications:

❖ Refinery Optimization:

Vis-breaking is often employed in refineries to improve the economics of processing heavy crudes
and residues, allowing refineries to handle a broader range of crude oil types.

❖ Pre-treatment for Further Processing:

The lighter fractions produced can serve as feedstocks for catalytic cracking or hydrocracking,
maximizing refinery output.

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 Higher Institute of Engineering and Technology in Tanta
Chemical engineering Department
Petrochemical Industries (CHE361)
Lecture (6)

Vis-breaking is an essential process in modern refining, especially for maximizing the value of
heavy crude oils and residues. By reducing viscosity and creating lighter hydrocarbons, vis-
breaking enhances the overall efficiency and profitability of refining operations.

Delayed Coking:

❖ Delayed coking is a thermal cracking process used in the petroleum refining industry to
convert heavy residual oils, such as those left over after distillation, into lighter products
and petroleum coke.
❖ It is particularly useful for maximizing the value of heavy crudes and heavy fuel oils that
are otherwise difficult to process.

Process Overview:

❖ Delayed coking involves heating heavy feedstock in a coking drum at high temperatures
(typically between 450°C and 550°C) under atmospheric or slightly elevated pressure.
❖ The process consists of two main stages: coking and quenching.

Coking Process:

❖ Heating:

The heavy oil is first heated and vaporized in a furnace before entering the coking drum.

❖ Residence Time:

The heated feedstock is allowed to stay in the coking drum for a certain period (generally several
hours), where thermal cracking occurs, breaking down the hydrocarbons into lighter products and
solid coke.

❖ Coke Formation:

As cracking occurs, solid carbon (petroleum coke) begins to form and settle at the bottom of the
drum.

Quenching:

❖ After the desired residence time, the coking drum is cooled (quenched) to stop the reaction.
❖ The solid coke is then removed, typically by mechanical means, and the lighter products
are collected.

Products of Delayed Coking:

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 Higher Institute of Engineering and Technology in Tanta
Chemical engineering Department
Petrochemical Industries (CHE361)
Lecture (6)

1. Light Distillates:

Such as naphtha and kerosene, which can be further processed or blended into gasoline.

2. Gas Oil:

A valuable middle distillate used in diesel production or as a feedstock for catalytic cracking.

3. Petroleum Coke:

A carbon-rich solid product used in various applications, including as a fuel source, in aluminum
production, and in the manufacturing of electrodes.

Advantages of Delayed Coking:

❖ High Conversion Rates:

Capable of converting a significant portion of heavy feedstock into valuable lighter products and
solid coke.

❖ Effective Residuum Processing:

Allows refineries to handle heavy residues that would otherwise be uneconomical to process.

❖ Flexible Feedstock Options:

Can utilize a wide variety of heavy oils and residues.

Disadvantages of Delayed Coking:

❖ Energy-Intensive:

Requires substantial energy input to heat the feedstock and maintain the desired temperatures.

❖ Coke Handling:

The formation of solid coke necessitates regular removal, which can complicate operations and
maintenance.

❖ Environmental Concerns:

The combustion of petroleum coke can lead to emissions, and the production process can generate
other pollutants.

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 Higher Institute of Engineering and Technology in Tanta
Chemical engineering Department
Petrochemical Industries (CHE361)
Lecture (6)

Applications:

❖ Refinery Integration:

Delayed coking is often integrated into refinery configurations to improve the yield of valuable
products from heavy crude oils and residues.

❖ Petroleum Coke Production:

The solid coke produced can be marketed for various industrial applications, including use as a
fuel, in cement manufacturing, or as a feedstock for the aluminum industry.

Delayed coking is a crucial process in modern refining that allows for the efficient conversion of
heavy residual oils into lighter, more valuable products. By transforming heavy feedstocks into
petroleum coke and lighter distillates, delayed coking enhances the overall profitability and
flexibility of refining operations, making it a key component in the management of heavy crude
oil resources.

Fluid Coking:

❖ A more advanced form of coking that is continuous produces lighter hydrocarbons and
coke.
❖ Fluid coking is an advanced thermal cracking process used in the petroleum refining
industry to convert heavy residues from crude oil into lighter hydrocarbons and petroleum
coke.
❖ It is similar to delayed coking but operates in a continuous flow manner, allowing for
greater efficiency and flexibility in processing.

Process Overview:

❖ Fluid coking utilizes a fluidized bed reactor, where the feedstock (heavy oil residues) is
injected into a bed of hot, solid particles (coke) that are maintained in a fluidized state by
the upward flow of gas or vapor.
❖ The process operates at high temperatures (typically between 480°C and 600°C) and can
handle a variety of heavy feedstocks.

Coking Reaction:

❖ Cracking:

As the heavy hydrocarbons come into contact with the hot coke particles, thermal cracking occurs,
breaking down larger molecules into lighter products and forming additional solid coke.

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 Higher Institute of Engineering and Technology in Tanta
Chemical engineering Department
Petrochemical Industries (CHE361)
Lecture (6)

❖ Fluidized Bed:

The fluidized bed enhances heat transfer and provides good mixing, which leads to more uniform
temperatures and efficient reaction conditions.

Product Recovery:

❖ The lighter cracked products are vaporized and separated from the solid coke particles.
❖ Separation:

The vapors are sent to a fractionation unit to separate the valuable distillates, including naphtha,
kerosene, and gas oil.

Coke Handling:

❖ The solid coke particles accumulate in the reactor and must be removed periodically.
❖ Fluid coking systems typically include a discharge system that allows for continuous
removal of coke, maintaining a consistent level of coke in the reactor.

Products of Fluid Coking:

1. Light Hydrocarbons:

Such as naphtha and diesel, which can be further processed or blended for fuel production.

2. Gas Oil:

Can be used as a feedstock for catalytic cracking or other refining processes.

3. Petroleum Coke:

A high-carbon solid product used in various industrial applications, including aluminum

production and as a fuel source.

Advantages of Fluid Coking:

❖ Continuous Operation:

Unlike delayed coking, which operates in batches, fluid coking allows for continuous processing,
improving efficiency and throughput.

❖ Higher Yields:

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 Higher Institute of Engineering and Technology in Tanta
Chemical engineering Department
Petrochemical Industries (CHE361)
Lecture (6)

Can achieve higher yields of valuable lighter products due to better heat transfer and mixing in the
fluidized bed.

❖ Flexible Feedstock Processing:

Can handle a wide range of heavy oils and residues.

Disadvantages of Fluid Coking:

❖ Complexity:

The fluidized bed system requires more sophisticated equipment and control mechanisms
compared to delayed coking.

❖ Operating Conditions:

High temperatures and the need for solid coke circulation can pose operational challenges.

❖ Coke Quality:

The quality of petroleum coke produced may vary based on feedstock and operational conditions,
affecting its marketability.

Applications:

❖ Refinery Optimization:

Fluid coking is often integrated into refineries to maximize the conversion of heavy feedstocks
and improve overall refinery efficiency.

❖ Petroleum Coke Production:

The solid coke produced can be marketed for various applications, including as a fuel source, in
cement manufacturing, and in the production of electrodes.

Fluid coking is a vital technology in modern refining, enabling the efficient conversion of heavy
oil residues into valuable lighter hydrocarbons and petroleum coke. Its continuous operation and
ability to handle a variety of feedstocks make it an attractive option for refineries looking to
optimize their processes and maximize the value of heavy crude oil resources.

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 Higher Institute of Engineering and Technology in Tanta
Chemical engineering Department
Petrochemical Industries (CHE361)
Lecture (6)

Steam Cracking:

❖ A process that uses steam along with heat to break down naphtha or gas oils, particularly
for producing ethylene and propylene.
❖ Steam cracking is a petrochemical process that uses high temperatures and steam to break
down large hydrocarbon molecules into smaller, more valuable products.
❖ It is one of the primary methods for producing olefins, such as ethylene and propylene,
which are fundamental building blocks for various chemicals and plastics.

Process Overview:

❖ Feedstock:

The process typically uses light hydrocarbons like naphtha, ethane, propane, or gas oil as
feedstocks.

❖ Heating:

The feedstock is mixed with steam and heated to extremely high temperatures, usually between
750°C and 900°C, in a tubular reactor.

❖ Cracking Reaction:

The heat causes the hydrocarbons to undergo thermal cracking, breaking the larger molecules into
smaller ones.

Reaction Mechanism:

❖ Free Radical Mechanism:

The process primarily relies on a free radical mechanism, where high temperatures generate free
radicals that initiate the cracking of carbon-carbon bonds.

❖ Steam Role:

Steam serves two main purposes: it dilutes the feedstock to prevent premature reactions and carries
the cracked products out of the reactor.

Products of Steam Cracking:

❖ Olefins:

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 Higher Institute of Engineering and Technology in Tanta
Chemical engineering Department
Petrochemical Industries (CHE361)
Lecture (6)

❖ Ethylene: The primary product, used in the production of polyethylene,

ethylene glycol, and other chemicals.
❖ Propylene: Used to produce polypropylene, acrylonitrile, and various
chemicals.

❖ By-products:

❖ Butenes and Butadiene: Used in synthetic rubber and other chemical

processes.
❖ Aromatics: Such as benzene, toluene, and xylene, which are important in
the production of various chemicals and solvents.

Operating Conditions:

❖ Temperature:

High temperatures (around 800°C to 900°C) are essential for achieving sufficient cracking.

❖ Pressure:

The process is generally conducted at low pressures, close to atmospheric pressure, to facilitate
the rapid escape of gaseous products.

❖ Residence Time:

The time the feedstock spends in the reactor is typically short (seconds), which helps to minimize
secondary reactions that can produce unwanted by-products.

Advantages of Steam Cracking:

❖ High Yields of Olefins:

It produces a significant amount of ethylene and propylene from relatively small amounts of
feedstock.

❖ Versatility:

Can use a variety of feedstocks, including natural gas liquids (NGLs) and heavier oils.

❖ Established Technology:

Steam cracking is a well-developed and widely used process in the petrochemical industry.

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 Higher Institute of Engineering and Technology in Tanta
Chemical engineering Department
Petrochemical Industries (CHE361)
Lecture (6)

Disadvantages of Steam Cracking:

❖ Energy-Intensive:

The high temperatures required lead to substantial energy consumption.

❖ Environmental Impact:

The process generates greenhouse gases and other pollutants, necessitating appropriate emissions
control measures.

❖ Coke Formation:

Some solid carbon (coke) may form on the reactor tubes, requiring regular maintenance and
cleaning.

Applications:

❖ Production of Chemicals:

Steam cracking is essential for producing various petrochemical feedstocks used in manufacturing
plastics, fibers, and other materials.

❖ Integration with Other Processes:

The olefins produced are often further processed in other petrochemical reactions, such as
polymerization or alkylation, to create end products.

Steam cracking is a crucial process in the petrochemical industry, responsible for producing key
building blocks like ethylene and propylene. Its ability to efficiently convert a wide range of
hydrocarbon feedstocks into valuable products makes it an integral part of modern chemical
manufacturing and plastics production.

Operating Conditions of thermal Cracking :

❖ Temperature:

High temperatures facilitate the breaking of molecular bonds.

❖ Pressure:

High pressure in some forms of thermal cracking, but steam cracking typically uses lower
pressures.

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 Higher Institute of Engineering and Technology in Tanta
Chemical engineering Department
Petrochemical Industries (CHE361)
Lecture (6)

❖ Residence Time:

Adjusting the amount of time the feedstock remains in the high-temperature zone impacts the
product yield and composition.

Questions on lecture (6)

Answer the following questions:
1. write short notes on the Thermal Cracking .
2. what are the various types of Thermal Cracking?
3. Write briefly about the Delayed Coking.
Best wishes
Asso.Prof :Wafaa Ahmed

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