Petroleum Refinery

Engineering

CHAPTER 7
PETROLEUM PROCESSING
CONVERSION PROCESSES

Prepared by: Mr Ali Abbas

Conversion processes

Conversion processes in the petroleum industry are

generally used to:
1. Upgrade lower-value materials such as heavy residues
to more valuable products such as naphtha and LPG.
Naphtha is mainly used to supplement the gasoline
pool, while LPG is used as a fuel or as a petrochemical
feedstock.
2. Improve the characteristics of a fuel. For example, a
lower octane naphtha fraction is reformed to a higher
octane reformate product. The reformate is mainly
blended with naphtha for gasoline formulation or
extracted for obtaining aromatics needed for
petrochemicals production

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 Conversion processes

3. Reduce harmful impurities in petroleum fractions and

residues to control pollution and to avoid poisoning
certain processing catalysts.
For example, hydrotreatment of naphtha feeds to catalytic
reformers is essential because sulfur and nitrogen
impurities poison the catalyst.
 Conversion processes are either thermal, where only
heat is used to effect the required change, or catalytic,
where a catalyst lowers the reaction activation energy.
The catalyst also directs the reaction toward a desired
product or products (selective catalyst).

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THERMAL CONVERSION PROCESSES
 Thermal cracking was the first process used to increase
gasoline production. After the development of catalytic
cracking, which improved yields and product quality,
thermal cracking was given other roles in refinery
operations.
 The three important thermal cracking techniques are:
coking, viscosity breaking, and steam cracking.
Steam cracking is of special importance as a major
process designed specifically for producing light olefins

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Coking Processes
Coking is a severe thermal cracking process designed to
handle heavy residues with high asphaltene and metal
contents. These residues cannot be fed to catalytic
cracking units because their impurities deactivate and
poison the catalysts.
Products from coking processes vary considerably with
feed type and process conditions. These products are
hydrocarbon gases, cracked naphtha, middle distillates,
and coke. The gas and liquid products are characterized
by a high percentage of unsaturation.
Hydrotreatment is usually required to saturate olefinic
compounds and to desulfurize products from coking units.

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Thermal Cracking Reactions

The first step in cracking is the thermal decomposition of hydrocarbon

molecules to two free radical Fragments. This initiation step can
occur by a homolytic carbon-carbon bond scission at any position
along the hydrocarbon chain. The following represents the initiation
reaction:

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Thermal Cracking Reactions

Further β bond scission of the new free radical R˙ can

continue to produce ethylene until the radical is terminated..

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 Delayed Coking

 In delayed coking, the reactor system consists of a short

contact-time heater coupled to a large drum in which the
preheated feed “soaks” on a batch basis. Coke gradually
forms in the drum. A delayed coking unit has at least a
pair of drums. When the coke reaches a predetermined
level in one drum, flow is diverted to the other so that the
process is continuous.
 Vapors from the top of the drum are directed to the
fractionator where they are separated into gases,
naphtha, kerosene, and gas oil.

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 Delayed Coking

Operating conditions for delayed coking are 25–30 psi at

480–500°C, with a recycle ratio of about 0.25 based on
equivalent feed. Improved liquid yields could be obtained by operating
at lower pressures.

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 Fluid Coking

In the fluid coking process, part of the coke produced is

used to provide the process heat. Cracking reactions occur
inside the heater and the fluidized-bed reactor. The fluid
coke is partially formed in the heater.
Hot coke slurry from the heater is recycled to the fluid
reactor to provide the heat required for the cracking
reactions. Fluid coke is formed by spraying the hot feed on
the already-formed coke particles.

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 Fluid Coking

Reactor temperature is about 520°C, and the conversion

into coke is immediate, with complete disorientation of the crystallites
of product coke. The burning process in fluid coking tends to
concentrate the metals, but it does not reduce the sulfur content of
the coke.

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Viscosity Breaking (Vis-breaking)

 Viscosity breaking aims to thermally crack long-chain feed

molecules to shorter ones, thus reducing the viscosity and
the pour point of the product.
 In this process, the feed is usually a high viscosity, high
pour point fuel oil that cannot be used or transported,
especially in cold climates, due to the presence of waxy
materials.
 Wax is a complex mixture of long-chain-paraffins mixed
with aromatic compounds having long paraffinic side
chains.

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Viscosity Breaking (Vis-breaking)

Vis-breaking is a mild cracking process that operates at

approximately 450°C using short residence times. Long
paraffinic chains break to shorter ones.

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CATALYTIC CONVERSION
PROCESSES
 Catalytic conversion processes include naphtha catalytic
reforming, catalytic cracking, hydrocracking,
hydrodealkylation, isomerization, alkylation, and
polymerization. In these processes, one or more catalyst
is used.
 A common factor among these processes is that most of
the reactions are initiated by an acid-type catalyst that
promotes carbonium ion formation.
 Other important catalytic processes are those directed
toward improving the product quality through
hydrotreatment.

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 Alkylation

 Alkylation in the petroleum refinery is the reaction of a low

molecular weight olefin with an isoparaffin to produce a higher
molecular weight isoparaffin. Usually isobutylene and propylene are
used as olefins while isobutane is used as isoparaffin.
 The products are branched hydrocarbons having high octane
Ratings
 Hydrofluoric acid or sulfuric acid catalyst is employed.
Temperature of 5 to 21 oC or lower is used for sulfuric acid process
and 38 oC or lower for anhydrous hydrofluoric acid process.
Enough pressure is maintained to keep the hydrocarbons in
the liquid state

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Alkylation reactions

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 Isomerization

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 Isomerization

Isomerization is used to improve the octane number of the

n-paraffinic feeds by converting them into isoparaffins. As
an example, n-pentane has RON (research octane
number) of 61.7 while isopentane has a rating of 92.3. Light
straight run naphtha is used as a feed for the isomerization
and the following reactor conditions are maintained.

Reaction temperature = 95–205 oC

Reaction pressure = 250 – 500 Psi.
Catalyst is usually platinum supported on an acidic catalyst
such as zeolite or chlorinated metal oxide support.

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 Isomerization

Hydrogen is added to the feed to avoid the deposition of

coke on the catalyst surface and consumption of hydrogen is
negligible. Due to hydrogen presence in the feed, the
process is frequently called as hydroisomerization. A typical
feed and product composition of an isomerization unit is
given below:

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 Isomerization

 Some refineries do not have hydrocracking facility to

supply isobutane for alkylation unit. The required
isobutane can be obtained from n-butane using
isomerization.
 isomerization reaction:

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 Hydrotreating

 Hydrotreating is the removal of impurities from a petroleum fraction.

Hydrotreating primary purpose is to saturate olefins and/or reduce the
sulfur and/or nitrogen content (and not to change the boiling range) of the
feed.
 The process is used to stabilize (converting unsaturated
hydrocarbons such as olefins and diolefins to paraffins) a petroleum fraction
and to remove sulfur, nitrogen, oxygen, halides, and traces of metals from
the petroleum fraction.
Hydrotreating is applied to a wide variety of feedstocks.
Examples may include:
 Naphtha
 Kerosene
 Diesel (Gas oil)
 Atmospheric residues

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 Hydrotreating

 The process is generally carried out at moderately high temperature

and pressure and in the presence of a catalyst.

 Typical temperature and pressure are 270–340 oC and

690–20700 kPa respectively.

 Nickel/Cobalt and molybdenum oxides on alumina are widely used

catalysts.

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Catalytic Reforming
 Catalytic Reforming

The aim of this process is to improve the octane number of a

naphtha feedstock by changing its chemical composition.
 Hydrocarbon compounds differ greatly in their octane ratings due to
differences in structure.
In general, aromatics have higher octane ratings than paraffins and
cycloparaffins. Similar to aromatics, branched paraffins have high
octane ratings.
The octane number of a hydrocarbon mixture is a function of the
octane numbers of the different components and their ratio in the
mixture.

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Reformer Feeds

The feed to a catalytic reformer is normally a heavy naphtha fraction

produced from atmospheric distillation units. Naphtha from other
sources such as those produced from cracking and delayed coking
may
also be used. Before using naphtha as feed for a catalytic reforming
unit, it must be hydrotreated to saturate the olefins and to
hydrodesulfurize and hydrodenitrogenate sulfur and nitrogen
compounds

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Olefinic compounds are undesirable because they are precursors for
coke, which deactivates the catalyst. Sulfur and nitrogen compounds
poison the reforming
catalyst

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 Catalytic reforming

Typical feed and product PONA composition in vol% is:

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Catalytic reforming reactions

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Catalytic reforming reactions

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Reforming Catalysts

• The catalyst for the reforming process is a bifunctional catalyst

Pt/Al2O3 with Pt content usually of 0.2 to 0.6% by weight.

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Reforming Catalysts

• Catalytic reformers are normally designed to have a series of catalyst

beds (typically three beds). The first bed usually contains less catalyst
than the other beds. This arrangement is important because the
dehydrogenation of naphthenes to aromatics can reach equilibrium
faster than the other reforming reactions.

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Reforming Catalysts

• The second and third reactors contain more catalyst than the first
one to enhance the slow reactions and allow more time in favor of a
higher yield of aromatics and branched paraffins.

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Reforming Process

• Normally, catalytic reformers operate at approximately 500–525°C

and 100–300 psig

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Catalytic Cracking
Catalytic cracking

 Catalytic cracking is used to convert heavy fractions such as vacuum

gas oil to gasoline range and lighter products.

 Catalytic cracking has advantages over thermal cracking as more

gasoline having higher octane rating and less heavy fuel oils and light
gases are produced, this is due to the effect of the catalyst.

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Catalytic cracking

 Cracking is generally carried out in either a 1.Moving bed

reactor, or
2. Fluidized bed reactor

 The fluid catalytic cracking (FCC) is a fluidized bed cracking system

and is widely acceptable more than moving bed reactor system.

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Catalytic cracking

 Feed to FCC:
The gas oil from vacuum column and conversion processes boiling
between 316 oC and 566 oC is used. The gas oil can be considered a
mixture of aromatics, naphthenic, and paraffinic hydrocarbons.

 Atmospheric residue and vacuum residue may also be used.

 FCC products: Gasoline and lighter products, i.e., FCC is used to
produce gasoline, olefins, and LPG. Olefins produced can be used for
alkylation and polymerization.

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Catalytic Cracking Reactions

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Catalytic cracking catalyst

• The FCC catalyst is a powder with an average particle size of 75 μm. It

is zeolite (crystalline aluminosilicates) type catalyst. Y-zeolite and
ZSM-5 zeolite are common in catalytic cracking.

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Catalytic cracking catalyst

• Zeolites are aluminosilicate crystalline structures. They consist of

SiO4 and AlO4‒ In the interior of the structure there are water
molecules and mobile alkali metal ions such as of sodium that are
capable of being ion exchanged with other cations such as that of Pt.

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Cracking Process

• Catalyst size is important, because it acts as a liquid with the reacting

hydrocarbon mixture.

• The reactor temperature is usually held at about 450–520°C, and the

pressure is approximately 10–20 psig.

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THE END