Chapter 9 Conversion Processes

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Chapter 9

Conversion Processes

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Chapter 9 Contents
9.1 Introduction

9.2 Catalytic Reformer

9.2.1 Chemical Reactions in the Reforming Unit
9.2.2 Reformer Catalyst
9.2.3 Semi-Regenerative Reforming process
9.2.4 Catalytic Reforming Process Description
9.2.5 Reforming Catalyst

9.3 Catalytic Cracking

9.3.1 Catalytic Cracking Reactions
9.3.2 Catalytic Cracking Catalysts
9.3.3 Process Variables

9.4 Hydrocracking Process

9.4.1 Hydrocracking Reactions
9.4.2 Hydrocracking Catalysts
9.4.3 Process Variables
9.4.4 Fixed Bed Catalyst Process
9.4.5 Safety Considerations
9.4.6 Corrosion Considerations

9.5 Thermal Cracking

9.5.1 Visbreaking
9.5.2 Coking Processes

9.6 Isomerization
9.6.1 Introduction
9.6.2 Methods of Isomerization

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9.7 Alkylation Process

9.7.1 Introduction
9.7.2 Sulfuric Acid Alkylation Process
9.7.3 Hydrofluoric Acid Alkylation Process
9.7.4 Safety & Corrosion Considerations

9.8 Polymerization
9.8.1 The Process
9.8.2 Safety & Corrosion Considerations

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Chapter 9
Conversion Processes
9.1 INTRODUCTION
Conversion processes are chemical unit processes where components and compounds
are subject to chemical reactions and new components and compounds, which extremely
different from the original ones are produced.

The purpose of conversion processes is to increase the production of light distillates,

intermediate distillates or both together by either breaking down of large hydrocarbon
molecules such as straight run fuel oil (bottom product of atmospheric distillation
columns), vacuum diesel oil and tar (side and bottom products of vacuum distillation
column) into smaller molecules or combining small hydrocarbons molecules to larger
molecules.

The breaking down of large hydrocarbon molecules into smaller molecules is usually
known as "destructive processes", while combining small hydrocarbon molecules to
larger molecules are known as "synthetic" processes on rebuilding hydrocarbon
molecules. The most used "destructive" processes are cracking (thermal, catalytic, and
hydrocracking) and reforming (thermal and catalytic reforming). The most used
"synthetic" processes (rebuilding hydrocarbon molecules) are polymerization, alkylation
and isomerization.

The above mentioned "conversion" processes are tools by means of which the petroleum
refiner can adjust the quantity and quality of the products obtained from a given amount
of crude oil to match the consumers' demands.

9.2 CATALYTIC REFORMER

Catalytic Reforming was introduced to the refining process to meet the increasing
demands of high octane gasolines.

The octane rating of gasoline is increased by "reforming" the molecules into molecules
which perform better in the gasoline engines:

 n-paraffins to iso-paraffins
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 naphthenes to aromatics

Paraffinic hydrocarbons have the lowest octane number, while the aromatics have the
highest.

The typical feedstocks going into catalytic reformers are:

1. Heavy straight-run naphthas (fractions boiling between 82-190 °C) and

2. Heavy hydrocracker naphthas.

These streams are composed of four major hydrocarbon groups: paraffins, olefins,
naphthenes and aromatics (PONA).

For the case of heavy straight run naphtha as the feedstock, the PONA analysis before
and after reforming is as follows:

Component Feed Product

Paraffins 45 - 55% 30 - 50%
Olefins 0 0
Naphthenes 30-40% 5 -10%
Aromatics 5 -10% 45 -60%

The paraffins and naphthenes undergo cyclization and isomerization to produce higher
octane components. The product from the catalytic reformer is usually called
"reformate". This is usually blended to straight run gasolines to produce higher octane
gasolines.

9.2.1 Chemical Reactions in the Reforming Unit

There are both desirable and undesirable reactions taking place in a reformer unit.
Desirable reactions in a catalytic reformer all lead to the formation of aromatics and iso-
paraffins as follows:

1. Paraffins are isomerized and to some extent converted to naphthenes. The

naphthenes are subsequently converted to aromatics.
2. Olefins are saturated to for paraffins which then react as in 1.
3. Naphthenes are converted to aromatics.
4. Aromatics are left essentially unchanged.

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Undesirable reactions in the reformer include:

1. Side chains on naphthenes and aromatics are broken off to form lighter gases.
2. Cracking of paraffins and naphthenes to lighter gases.

A very desirable by-product of the reformer is excess hydrogen, which is used in other
units (hydrotreaters and hydrocrackers).

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Reformer Reactions
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9.2.2 Reformer Catalyst

The reforming units usually use a stationary bed of catalyst in a reactor vessel.
The feed is heated to a vapor state and passed down through the catalyst bed. The high
temperatures and catalyst cause the chemical reactions go to completion.

The catalyst used in a reformer unit is usually a platinum material such as:
 platinum-iridium or
 platinum-rhenium

There have been several designs of reformer units in the refining industry, some of
which have special trademarked names such as:

 Platformer (licensed by UOP)

 Powerformer (licensed by Exxon)
 Ultraformer (licensed by SU Oil, Ind.)
 Catalytic Reformer (licensed by Engelhard)
 Houdriforming and Iso-Plus Houdryforming (licensed by Houdry)
 Rheniforming (licensed by Chevron)

A reforming reactor unit is shown diagrammatically as shown in the Figure 9.1.

Figure 9.1 Typical Fixed Bed Catalytic Reactor

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The catalyst beds are regenerated periodically (6 to 24 months) to get rid of the coke
deposits that form on the catalyst surfaces.

The catalyst must be removed and a new bed purchased every two to four years,
Reforming catalysts are very expensive.

In the reforming process, the higher the octane desired, the lower the yield and the more
light ends (low boiling compounds) are created.

Depending on how the reformer catalysts are regenerated, reforming processes are
classified into:

 semi-regenerative
 continuous
 cyclic

The semi-regenerative process is the most popular one of the three.

9.2.3 Semi-Regenerative Reforming process

In the semi-regenerative process (Figure 9.2), the pretreated feed and recycle hydrogen
are heated to 498 –542 °C before entering the first reactor. In the first reactor, the major
reaction is the dehydrogenation of naphthenes to aromatics (endothermic reaction) with
a large drop in temperature. To maintain reaction rate, the gases are reheated before
going to the second reactor. As the charge proceeds through the reactors, the reaction
rates slows down and the reactors become larger and the reheat necessary becomes less.

There are 3 to 4 reactors in series, each having a heater upstream of it. There can be
separate heaters or a single large heater with separate coils in it.

The gaseous products from the last heater are cooled and the products get condensed.
The hydrogen rich gases are separated from the liquid stream which goes to a
debutanizer tower (to be stabilized).

The hydrogen rich gas stream is split into hydrogen recycle stream and a net hydrogen
by-product used for hydrotreating and hydrocracker operations or as fuel.

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Operating pressures in the reformers range from 345 – 2415 kPa and the hydrogen
charge ratios are in the range of 3 – 8 mol of Hydrogen per mol of feed.

Feed Preparation

The active material in most catalytic reforming catalysts is platinum. Certain metals,
hydrogen sulfide, ammonia, and organic and sulfur compounds will deactivate the
catalyst. Feed pretreating, in the form of hydrotreating, is usually employed to remove
these materials. The hydrotreater employs a cobalt-molybdenum catalyst to convert
organic sulfur and nitrogen compounds to hydrogen sulfide and ammonia, which then
are removed from the system with the unreacted hydrogen. The metals in the feed are
retained by the hydrotreater catalyst. Hydrogen needed for the hydrotreater is obtained
from the catalytic reformer. If the boiling range of the change stock must be changed,
the feed is redistilled before being charged to the catalytic reformer.

Figure 9.2 Semi-Regenerative Reforming process

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9.2.4 Catalytic Reforming Process Description (Continuous Process)

The equipment for the continuous process is designed to permit the removal and
replacement of catalyst during normal operation. As a result, the catalyst can be
regenerated continuously and maintained at a high activity. As coke lay down and
thermodynamic equilibrium yields or reformate are both favored by low-pressure
operation, the ability to maintain high catalyst activities by continuous catalyst
regeneration is the major advantage of the continuous type of unit. This advantage has to
be evaluated with respect to the higher capital costs and possible lower operating costs
due to lower hydrogen recycle rates and pressures needed to keep coke lay down at an
acceptable level.

The semi regenerative unit is at the other end of the spectrum and has the advantage of
minimum capital costs. Regeneration requires the unit to be taken off-stream. Depending
upon severity of operation, regeneration is required at intervals of 3 to 24 months. High
hydrogen recycle rates and operating pressures are utilized to minimize coke lay down
and consequent loss of catalyst activity.

The cyclic process is a compromise between these extremes and is characterized by

having, a swing reactor in addition to those on-stream in which the catalyst can be
regenerated without shutting the unit down. When the activity of the catalyst in one of
the on-steam reactors drops below the desired level, this reactor is isolated from the
system and replaced by the swing reactor. In the cyclic processes, regeneration is
typically performed on a 24- or 48 hour cycle. The catalyst in the replaced reactor is
then regenerated by admitting hot air into the reactor to burn the carbon off the catalyst.
After regeneration it is used to replace the next reactor needing regeneration. Because of
these extra facilities, the cyclic processes are more expensive but offer the advantage of
low-pressure operation and higher yield of reformate at the same severity.

The Platforming process can be obtained as a continuous, cyclic, or semi-regenerative

operation and the other processes as either cyclic or semiregenerative. The Platforming,
semiregenerative process is typical of reforming operations and will be described here.

A simplified process flow diagram of the Platforming process is given in Figure 9.3. The
pretreated feed and recycle hydrogen are heated to 925 to 975 °F before entering the first
reactor. In the first reactor, the major reaction is the dehydrogenation of naphthenes to
aromatics and, as this is strongly endothermic, a large drop in temperature occurs. To
maintain rate, the gases are reheated before being passed over the catalyst in the second
reactor. As the charge proceeds through the reactors, the reaction rates decrease and the
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reactors become larger, and the reheat needed become less. Usually three reactors are
sufficient to provide the desired degree of reaction and heaters are needed before each
reactor to bring the mixture up to reaction temperature. In practice, either separate
heaters can be used or one heater can contain several separate coils. The reaction
mixture from the last reactor is cooled and the liquid products condensed. The hydrogen
rich gases are separated from the liquid phase in a drum separator and the liquid from
the separator is sent to fractionator to be debutanized.

The hydrogen-rich gas stream is split into hydrogen recycle stream and a net hydrogen
by product which is used in hydrotreating or hydrocracking operations or as fuel.

Figure 9.3 Platforming Unit

The reformer operating pressure and the hydrogen/feed ratio are compromises among
obtaining maximum yields, long operating times between regenerations, and stable
operation. It is usually necessary to operate at pressures from 200 to 500 psig and at
hydrogen charge ratios of 4,000 to 8,000 scf/bbl fresh feed. Liquid hourly space
velocities in the area of 2 to 3 are in general use.

9.2.5 Reforming Catalyst

All the reforming catalyst in general use today contains platinum supported on a silica or
silica-aluminum base. In many cases rhenium is combined with platinum to form a
more stable catalyst, which permits operation at lower pressures. Platinum is
thought to serve as a catalytic site for hydrogenation and dehydrogenation reactions
and chlorinated alumina provides an acid site for isomerization, cyclization, and
hydrocracking reactions.
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Reforming catalyst activity is a function of surface area, pore volume, and active
platinum and chlorine content. Catalyst activity is reduced during operation by coke
deposition and chloride loss. In a high pressure process, up to 200 barrels of charge can
be processed per pound of catalyst before regeneration is needed. The activity of the
catalyst can be restored by high temperature oxidation of the carbon followed by
chlorination. This type of process is referred to as semiregenerative and able to operate
for 6 to 24 month periods between regenerations.

The activity of the catalyst decreases during the on-stream period and the reaction
temperature is increased as the catalyst ages to maintain the desired operating severity.
Normally the catalyst can be regenerated at least three times before it has to be replaced
and returned to the manufacturer for reclamation.

Reactor Design
Reactors used for catalytic reforming vary in size and mechanical details, but all have
basic features as shown on Figure 9.1. Very similar reactors are used also for
hydrotreating, isomerization, and hydrocracking

9.3 CATALYTIC CRACKING

Catalytic cracking is the most important and widely used refinery process for
converting heavy oil into more valuable gasoline and lighter products.

Catalytic cracking involves the breaking of large, low value molecules into smaller, high
value molecules using high temperatures and catalyst.

The catalytic-cracking processes in use today can all be classified as either moving-
bed or fluidized-bed units.

The thermofor catalytic-cracking process (TCC) is representative of the moving-bed

units and the fluid catalytic cracker (FCC) of the fluidized-bed units.

The catalysts used in both processes are chemically similar and differ only in physical
configuration.

The cracking process produces carbon (coke), which remains on the catalyst particle
and rapidly lowers its activity.

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To maintain the catalyst activity at a useful level, it is necessary to regenerate the

catalyst by burning off this coke with air. As a result, the catalyst is continuously
moved from reactor to regenerator and back to reactor.

The process flows (Figure 9.4) of both types of processes are similar. The hot oil feed
is contacted with the catalyst in either the feed riser line or the reactor. As the
cracking reaction progresses, the catalyst is progressively deactivated by the
formation of coke on the surface of the catalyst. The catalyst and hydrocarbon vapors
are separated mechanically and oil remaining on the catalyst is removed by steam
stripping before the catalyst enters the regenerator. The oil vapors are taken overhead
to a fractionation tower for separation into streams having the desired boiling ranges.

Figure 9.4 Fluid Catalytic Cracking (FCC)

The spent catalyst flows into the regenerator and is reactivated by burning off
the coke deposits with air. Regenerator temperatures are carefully controlled to
prevent catalyst deactivation by overheating. This is generally done by controlling
the air flow to give a desired CO 2/CO ratio in the exit flue gases as the burning of CO
to CO2 does not remove coke from the catalyst but only produces excess heat.

Cyclone separators separate the flue gas and catalyst and the catalyst steam-stripped to
remove adsorbed oxygen before the catalyst is contacted wit the oil feed.

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9.3.1 Catalytic Cracking Reactions

[Link] molecular weight paraffins are cracked to paraffins of low molecular weight
and olefins.
Paraffins Paraffins + Olefins

[Link] molecular weight alkyl naphthenes are cracked to low molecular weight
naphthenes and olefins.

Alkyl naphthenes Naphthenes + Olefins

[Link] aromatics are cracked according to the following equation:

Alkyl aromatics Aromatics + Olefins

The products of the above mentioned reactions are subject to further cracking
reactions which are simply summarized below:

Naphthenes Aromatics + H 2
Olefins + H 2 Paraffins
Olefins + Olefins + H 2 Iso - paraffins
Olefins + Paraffins Iso-paraffins
Iso-paraffins Aromatics + H 2

Most of the above reactions products are in the range of gasoline (C 5 — C8) which
composed of high percentage of aromatics and iso-paraffins which have high octane
number.

9.3.2 Catalytic Cracking Catalysts

Commercial cracking catalysts can be divided into three classes:

[Link]-treated natural alumina silicates.

[Link] synthetic silica-alumina combinations.
[Link] synthetic silica-alumina catalysts called zeolites or molecular sieves.

Catalysts are handled in the form of (beads) or powder. Most catalysts used in
commercial units today are either class (3) or mixtures of classes (2) and (3) catalysts.
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The advantage of the zeolite catalysts over the natural and synthetic amorphous
catalysts are:

[Link] activity.
[Link] gasoline yields at a given conversion.
[Link] of gasoline containing a larger percentage of paraffinic and aromatic
hydrocarbons.
[Link] coke yield (and therefore usually a larger throughput at a given
conversion level).
[Link] iso-butane production.
[Link] to go to higher conversions per pass without over cracking.

The high activity of zeolitic cracking catalysts permits short residence time cracking
and has resulted in many cracking units being adapted to riser cracking operations.

Basic nitrogen compounds, iron, nickel, vanadium and copper in the oil act as poisons
to cracking catalysts.

9.3.3 Process Variables

In addition to the nature of the charges stock, the major operating variables
affecting the conversion and product distribution are the cracking temperature,
catalyst/oil ratio, space velocity, catalyst type and activity, and recycle ratio. For
better understanding of the process, several terms should be defined.

Activity: Ability to crack gas oil to lower boiling fractions.

Catalyst/oil ratio = C/O = lb catalyst/lb feed.

Conversion = 100 (Volume of feed — volume of cycle stock)

Volume of feed

Cycle stock: Portion of catalytic- cracker effluent not converted to naphtha and
lighter products (generally the material boiling above 430 °F).

Efficiency = (% gasoline) x 100

% conversion

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Recycle ratio = Volume recycle/volume fresh feed

Selectivity: The ratio of the yield of desirable products to the yield of undesirable
products (Coke and Gas).

Space velocity: Space velocity may be defined on either a volume (LHVS) or a weight
(WHSV) basis. In a fluidized-bed reactor, the LHSV has little meaning because it is
difficult to establish the volume of the bed. The weight of the catalyst in the reactor
can be easily determined or calculated from -the residence time and C/O ratio.

LHSV= liquid hour space velocity in volume feed / (volume catalyst) (hr).

WHSV= weight hour space velocity in lb feed / (lb catalyst) (hr). If it is the catalyst
residence-time in hours, then WHSV = l/ (t) (C/O)

The general effects of the operating variables are the same for both the moving and
fluidized-bed units but each type of unit has special limitations, which affect their
importance. Within the limits of normal operations, increasing:

[Link] temperature.
[Link]/oil ratio.
[Link] activity

Feed for a catalytic cracker

 Straight run heavy gas oil (often called HAGO heavy atmospheric gas oil)
 Vacuum gas oils (HVGO and LVGO)

Feed to the cat reactor is at about 260-425°C. The hot catalyst in the reactor is at about
650 to 815°C and the reaction occurs at about 480-540°C.

When the molecules crack, there is a deficiency of hydrogen to fill the open spaces. This
causes:

 Some coking (pure carbon molecules)

 Production of olefinic hydrocarbons: molecules such as ethylene, propylene and
butylene.
 Large aromatics with side chains are broken where the side chain is attached.

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The cracked product is separated from the catalyst and sent to a fractionator.

Coke on the catalyst must be burned off in a regenerator unit.

There are three main parts to a cat cracker system:

 Reactor (catalyst and hydrocarbon)

 Regenerator (catalyst and air)
 Fractionator (hydrocarbon separation)

9.4 HYDROCRACKING PROCESS

Hydrocracking process is one of the most versatile of all petroleum refining processes.
Any fraction from naphtha to non-distillable can be processed, producing almost any
desired product with a molecular weight lower than that of the charge stock At the
same time, that hydrocracking takes place, sulfur, nitrogen, and oxygen are almost
completely removed and olefins are saturated, thereby giving products that are a
mixture of essentially pure paraffins, naphthenes and aromatics.

Hydrocracking is carried out at moderate temperatures and pressures over a fixed

catalyst bed in which the fresh feed is cracked in hydrogen atmosphere.

Exact process conditions vary widely ending on the feedstock properties and the
products desired. However, pressures usually range between 1500 and 3000 psig and
temperature between 280 and 475 °C.

Following are some of the advantages of hydrocracking process:

[Link] balance of gasoline and distillate production.
[Link] gasoline yield.
[Link] gasoline pool octane quality and sensitivity.
[Link] of relatively high of isobutane in the butane fraction.

9.4.1 Hydrocracking Reactions

There are hundreds of simultaneous and complicated chemical reactions occurring

during hydrocracking process. Main hydro cracking reactions are summarized as
following:
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(1) Cracking reactions:

Paraffins, Naphthenes and aromatics of high molecular weight

Heat, Catalyst
Cracking
paraffins, naphthenes, aromatics of low molecular weight + olefins

(2) Hydrogenation reactions:

Hydrogenation
Olefins + H2 Corresponding Paraffins + Heat
(Saturation)

(3) Isomerization reactions:

H2
Olefins+ low molecular weight paraffins isoparaffins
Catalyst

The above-mentioned reactions show that cracking and hydrogenation are

complementary, for cracking provides olefins for hydrogenation, while hydrogenation in
turn provides heat for cracking. The cracking reaction is endothermic and the
hydrogenation reaction is exothermic. The reaction actually provides an excess of
heat because the amount of heat released by the exothermic Hydrogenation reaction
is much greater than the amount of heat consumed by the endothermic cracking
reactions.

This surplus of heat causes the reactor temperature to increase and accelerate the
reaction rate. Injecting cold hydrogen into the reactors to absorb the excess heat of
reaction controls this.

9.4.2 Hydrocracking Catalysts

There is a number of hydrocracking catalysts available and the actual composition

is tailored to the process, feed material, and the product desired. Most of the
hydrocracking catalysts consist of crystalline mixture of silica-alumina with a small
uniformly distributed amount of rare-earth metals. The Silica-alumina portion of the
catalyst provides cracking activity while the rare-earth metals, encourage
hydrogenation.
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Almost, all hydrocracking catalyst use silica-alumina as the cracking base but the
rare-earth metals vary according to the manufacturer. Those in most common use are
Platinum (PE), Palladium (Pd), Nickel (Ni), and Tungsten (W).

9.4.3 Process Variables

[Link] Temperature
Reactor temperature is the primary means of conversion control at normal reactor
conditions a 20 °F increase in temperature almost double the reaction rate but not
affect the conversion level as much.

[Link] Reactor Pressure

The primary effect of reactor pressure is on its effects on the partial pressures of
hydrogen and ammonia. Conversion increases with increasing hydrogen partial
pressure and decreasing with increasing ammonia partial pressure. The hydrogen
effect is greater, however, and the net effect of raising total partial pressure is to
increase conversion.

[Link] Space Velocity

The volumetric space velocity is the ratio of liquid flow rate in barrels per hour to
catalyst volume in barrels. The catalyst volume is constant; therefore the space
velocity varies directly with feed rate. As the feed rate increases, the time of catalyst
contact for each barrel of feed is decreased and conversion is lowered. In order to
maintain conversion at the proper level when the feed rate is increased, it is necessary
to increase the temperature.

[Link] Nitrogen Content

The organic nitrogen content of the feed is of great importance as the hydro-cracking
catalyst is deactivated by contact with organic nitrogen compounds. An increase in
organic nitrogen content of the feed causes a decrease in conversion.

[Link] Hydrogen Sulphide

Hydrocracking in the presence of a small amount of hydrogen sulphide normally
produces a very low smoke point jet fuel. At high hydrogen sulphide levels corrosion
of the equipment becomes important and the cracking activity of the catalyst is also
affected adversely.

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9.4.4 Fixed Bed Catalyst Process

There is a number of hydrocracking processes available for licensing. With the

exception of the H-Oil and HY-C processes all hydrocracking processes in use today
are fixed-bed catalytic processes with liquid down flow. The hydro cracking process
may require either one or two stages, depending upon the process and the feedstocks
used.

The process flows of most of the fixed-bed processes are similar and the
Unicracking/JHC process will be described as a typical fixed-bed hydro cracking
process.

The Unicracking/JHC process is a fixed-bed regenerative process employing a

molecular-sieve catalyst impregnated with a rare-earth metal. The process employs
cither single-stage (Figure 9.5) or two-stage (Figure 9.6) cracking with typical
operating conditions ranging from 500 to 800 °F and from 1,000 to 2,000 psig. The
temperature and pressure vary with the age of the catalyst, the product desired, and the
properties of the feedstock.

The decision to use a single or two-stage system is dependent upon the size of the unit
and the product desired. 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. The process flow for a two-stage reactor system is
shown in Figure 9.6. If only one stage is used, the process flow is the same as for the
second stage of the two-stage plant.

In a modem refinery, catalytic cracking and hydrocracking units work as a team. The
catalytic cracker takes the more easily cracked paraffinic gas oils (from the atmospheric
and vacuum towers) as feed. The hydrocracker, on the other hand, is capable to handle
the more aromatic feedstocks (from the fractionators of the cat cracker and coking
units), which are difficult to be processed in a cat cracker.

Hydrocrackers are excellent at helping to control the volumes of gasoline vs. diesel
produced from a refinery. Thus a hydrocracking unit can be used to swing production
to meet demand.

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The Process;

There are different hydrocracking processes, but the common units are fixed bed
reactors filled with catalysts. Catalysts commonly employed are a mixture of crystalline
silica-alumina with a small amount of rare earth metals (platinum, nickel, etc.) within
the crystalline lattice. The silica-alumina (portion of the catalyst) causes the cracking
reactions while the rare earth metals promote hydrogenation.

The fresh feed is mixed with makeup hydrogen and recycles gas (high in hydrogen
content) and passed through a heater to the first reactor. The first stage reactor is
operated at a sufficiently high temperature to convert 40 to 50 vol. % of the reactor
effluent to material boiling below 400°F. 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. The liquid product from the separator is sent to a distillation column where the
gasoline and lighter fractions are taken overhead and the bottoms used as feed to the
second stage reactor. If jet fuel or diesel fuel is one of the products desired, then the
distillation column separation is made with the jet fuel or diesel fuel going overhead.
The bottoms from the distillation column are mixed with recycle hydrogen and sent
through a furnace to the second stage reactor. Here the temperature is maintained to
bring the total conversion of the unconverted oil from the first stage and second stage
recycles to 50 to 70 vol. % per pass. The second stage product is combined with the
first stage product prior to fractionation.

Both the first and second stage reactors contain several beds of catalysts. The major
reason for having separate beds is to provide locations for injecting cold recycled
hydrogen into the reactors for temperature control. In addition, redistribution of the
feed and hydrogen between the beds helps to maintain a more uniform utilization of
the catalyst.

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Figure 9.5 Single Stage Hydrocracking

(Once Through Operation)

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 Figure 9.6 Schematic of a two-stage hydrocracking unit 

Process Company
Isomax Standard Oil Co. (Calif.) and UOP
Union Oil Co. and Esso Research and
Unicracking/JHC
Engineering Co.
Gulf OH Co. and Houdry Process and
H-G hydrocracking
Chemical Co.
Ultra cracking Standard Oil C0. (Indiana)
Hydrocarbon Research, Inc, and Cities
Hy-C, H-Oil
Service Research
Shell Shell Development Co.
Badische Aniline and Soda Fabric, and
BASF-IFP hydrocracking
Institute Francis Petrole

Table 9.1 Hydrocracking Processes Available For License

9.4.5 Safety Considerations

Because this unit operates at very high pressures and temperatures, control of both
hydrocarbon leaks and hydrogen releases is important to prevent fires. In some
processes, care is needed to ensure that explosive concentrations of catalytic dust do
not form during recharging. Inspection and testing of safety relief devices are
important due to the very high pressures in this unit. Proper process control is needed
to protect against plugging reactor beds. Unloading coked catalyst requires special
precautions to prevent iron sulfide-induced fires. The coked catalyst should either be
cooled to below 120° F before dumping, or be placed in nitrogen-inerted containers
until cooled.

There is a potential for exposure to hydrocarbon gas and vapor emissions, hydrogen
and hydrogen sulfide gas due to high-pressure leaks. Large quantities of carbon
monoxide may be released during catalyst regeneration and changeover. Catalyst
steam stripping and regeneration create waste streams containing sour water and
ammonia.

9.4.6 Corrosion Considerations

Because of the operating temperatures and presence of hydrogen, the hydrogen
sulfide content of the feedstock must be strictly controlled to a minimum to reduce
the possibility of severe corrosion. Corrosion by wet carbon dioxide in areas of
condensation also must be considered. When processing high-nitrogen feedstock, the
ammonia and hydrogen sulfide form ammonium hydrosulfide (bisulfide), which
causes serious corrosion at temperatures below the water dew point. Ammonium
hydrosulfide is also present in sour water stripping.

9.5 THERMAL CRACKING

Thermal processing generally refers to those petroleum-refining processes, which
change the molecular structure of hydrocarbons by application of heat without the use
of catalysts. When thermal cracking process is based on cracking straight run fuel oil
(bottom product of atmospheric distillation column) or vacuum diesel oil and tar (side
and bottom streams of vacuum distillation column) under severe thermal conditions
to produce desirable products e.g. gas oil, gasoline and coke, the process is called
"delayed coking".

Visbreaking is another thermal cracking process used under mild thermal conditions
to reduce the viscosity of straight run fuel oil without coke formation. The visbroken
fuel oil is mainly used as fuel for furnaces.

9.5.1 Visbreaking

This is a mild thermal cracking operation used mainly to reduce the viscosity and
pour points of vacuum reduced crudes. This process is often referred to as the poor
man's cracker, because the cost of a visbreaker is quite less compared to catalytic
cracking processes. By having a visbreaker process, a refinery can reduce the
production of heavy fuel oil by 20 to 30 percent.

The main reactions that take place during visbreaking are:

1. Breaking off and cracking of side chains attached to cyclo-paraffins and

aromatic rings.
2. Cracking of resinous materials to light hydrocarbons (mainly olefins).
3. Some cracking of naphthene rings (above 480 °C).

The amount of cracking in a visbreaker is limited, because too severe operation can
make the resulting product unstable leading to formation of gummy materials by
polymerization.

The product yield of a visbreaker for a sample of vacuum residue from Kuwaiti crude
is shown below:

 Butane and lighter products 2.5 (wt %)

 C5 – 180 °C naphtha 5.9 (wt %)
 Gas oil, 320 °C EP 13.5 (wt %)
 Tar 78.1 (wt %)

There are two types of visbreaker operations: coil and furnace cracking (Figure 9.6)
and soaker cracking (Figure 9.7). Coil cracking uses higher furnace outlet
temperatures (473 – 500 °C) and reaction times from one to three minutes, while
soaker cracking uses lower furnace outlet temperatures (427 – 443 °C).

Figure 9.6 Coil Visbreaking

 Figure 9.7 Soaker Visbreaking

9.5.2 Coking Processes

Coking units convert heavy feedstocks into a solid coke and lighter molecules.
Processing of heavier crudes and lack of fuel oil market for heavy residual oil is
forcing more utilization of cokers.

The feed to the coking unit is vacuum reduced crude and cat cracker fractionator
bottoms of all the coking processes, delayed coking is the most popular one. Fluid
coking and Flexicoking are two other common coking processes.

[Link] Delayed Coking

The name for this process comes from the process of heating the feed in a very high
velocity stream. It reaches coking temperature without cracking. The cracking occurs
in the next vessel, so the process is considered delayed coking.

Hot fresh liquid feed is charged to the fractionator tower above the bottom of the
vapor zone. Liquids from the feed and molecules condensed from the vapor enter a
furnace at a high velocity.

In the furnace the feed is heated to 500°C and enters the coke drum where the coking
takes place. Heavy molecules crack to form light molecules and pure carbon coke
solid. When the coke drum is nearly full, feed is switched to the next drum while the
coke is removed from this one.

Light hydrocarbons (gas oil, naphtha and light ends) leave the top of the coke drum
and enter the fractionator as a vapor stream. The vapor contacts the incoming feed,
which cools the vapor and prevents further cracking.

The feed is heated and stripped of light ends.

Coke drum reaction vapor is cooled and heavy ends are condensed.
The fractionator separates the gas oils, naphtha and light ends.
The cokes formed in the delayed coking process are of different types (sponge coke,
needle coke) and are used for graphite manufacture, electrodes, and other chemicals.

Typical yields from a delayed coker:

 Coke 45.76 (wt %)
 Gas (Butanes and lower) 11.92 (wt %)
 Naphtha 20.50 (wt %)
 Gas oil 21.82 (wt %)

[Link] Flexicoking and Fluid Coking

In the Flexicoking process, the feed (e.g. vacuum residue) is preheated to about 315-
370 °C and sprayed into the reactor where it contacts a hot fluidized bed of coke
particles (T = 510 to 540 °C ). These hot coke particles is recycled to the reactor from
the coke heater at a rate sufficient to maintain the reactor bed temperature. The coke
recycle from the heater thus provides sensible heat, heat of vaporization for the feed,
and the endothermic heat for the cracking reactions.

The cracked vapor products pass through cyclone separators in the top of the reactor
vessel (to separate the entrained coke particles), and are then quenched in the
scrubber vessel located at the top of the vessel. Some of the high-boiling (> 495 °C)
vapors are condensed in the scrubber and are recycled back to the reactor.

The balance of the cracked vapors flow to the coker fractionator where the various
cuts are separated.

The coke produced by the cracking process is deposited as thin films onto the of the
existing coke particles in the reactor fluidized bed. The coke is steam-stripped in the
baffled section at the bottom part of the reactor to prevent reaction products, other
than coke to leave the reactor.

The coke particles flow from the reactor to the heater where they are heated to about
593 °C. The coke heater is also a fluidized bed and its primary function is to transfer
heat from the gasifier to the reactor.

Some coke particles flow from the coke heater to a third fluidized bed (gasifier)
where it is reacted with air and steam to produce a fuel gas product consisting of CO,
H2, CO2, and N2. Sulfur in the coke is converted mainly to H2S and nitrogen to NH3.
This gas flows from the top of the gasifier to the bottom of the heater where it
fluidizes the heater bed and provides the heat needed in the reactor. The heat
requirement is also supplemented by the recirculating hot coke particles from the
gasifier to the heater. Approximately 60 to 90 % of the coke produced in the reactor
is gasified in the gasifier.
[Link] Fluid coking

Fluid coking is a simplified version of the flexicoking process. In this process, only
enough coke is burned to satisfy the heat requirements of the reactor and the feed
preheat. Generally, this means burning 20 to 25 percent of the coke produced in the
reactor. The balance of the coke is withdrawn from the burner vessel and is not
gasified as in the flexicoker. As a result, only two fluid beds are used in a fluid coker
a reactor and a burner (which replaces the heater).

Typical yields of the two processes are as follows:

Flexicoking (wt %) Fluid Coking (wt %)

Gas 11.8 11.8

Light naphtha 1.9 1.9

Heavy naphtha 7.8 7.8

Gas oil 50.4 50.4

Gross coke 28.1 28.1

Total 100.0 100.0

Net coke 22.4 2.3

 Figure 9.8 Delayed Coking Unit

Figure 9.9 Simplified Flow Diagram for a Flexicoker

9.6 ISOMERIZATION
9.6.1 Introduction

The light straight run gasoline "LSR" (C 5-180 °F.) can have its octane number
improved by the use of an isomerization process to convert normal paraffins in to
their isomers. This results in a significant octane increase as n-pentane has an
unleaded RON of 61.7 and isopentane has a rating of 92.3 in once-through
isomerization the unleaded RON of LSR gasoline can be increased from 70-84.

9.6.2 Methods of Isomerization

There are two methods used to perform isomerization depending on the feedstock
state.

a. Vapor-Phase Isomerization Process

In this case feed stock in vapor state. This method is used for the
isomerization of normal butane (n-C 4) to isobutene (i-butane), which is used
as a feedstock for alkylation unit.

b. Liquid Phase Isomerization Process

[Link] Butane Isomerization Process

The isomerization reaction of paraffins and olefins have been known for a long
lime, but the reaction was not considered to be important, until the higher octane
number of branched chain hydrocarbon compared with the straight chain types was
realized. The reaction become important when the reactivity of iso-butane for
alkylate production was realized, and it was found that large quantities of normal
butane were available.
 Figure 9.11 Butane Isomerization

The most efficient catalyst for isomerization of n-butane to iso butane is a mixture
of aluminium chloride and hydrogen chloride. The reaction is carried out at about
200 °F and under a pressure of 150 to 500 psi. Under these conditions the butane is
liquid and is passed in part, through an aluminium chloride saturator, in which it
dissolves some catalyst for effecting conversion in the succeeding reactor, hydrogen
chloride being introduced to promote the reaction. Sludge containing aluminium
chloride and heavy hydrocarbons is withdrawn from the bottom of the
reactor, whilst vapour containing light hydrocarbons, aluminium chloride and
hydrogen chloride passes to an aluminium chloride fractionator, from which n-
butane and aluminum chloride is withdrawn from the base and returned to the top of
the reactor. The vapours containing iso-butane and some n-butane, and hydrogen
chloride are condensed and passed to a hydrogen chloride stripping column, where
the hydrogen chloride is removed and returned to the process. The hydrocarbons are
then soda-washed, to remove any remaining acid, and finally fractionated to obtain
the iso-butane.

[Link] Pentane Isomerization Process

Normal paraffins hydrocarbons heavier than butane can also be isomerized using a
similar process and catalyst, other catalyst containing aluminium chloride are also
used, e.g., aluminium chloride in antimony trichloride. The isomerization of
Pentane-Hexane mixtures is practiced commercially, by introducing the
hydrocarbons containing hydrogen into a mixture aluminium chloride and
hydrocarbons. Temperatures of 220° to 250°F and pressure of 650 to 750 psi are
normally used. The product is known as "isomerate" and must be fractionated to
give the isomerized pentanes and hexanes.

As the molecular weight of the normal subject to isomerization is increased, there is

a tendency for cracking of the molecules to occur with the formation of lower
molecular weight iso-paraffins. There is also a tendency to form olefins, which
Polymerize to large molecules than are desired.

Figure 9.12 Pentane/Hexane Isomerization

9.7 ALKYLATION PROCESS

9.7.1 Introduction
Alkylation combines low-molecular-weight olefins (primarily a mixture of propylene
and butylene) with isobutene in the presence of a catalyst, either sulfuric acid or
hydrofluoric acid. The product is called alkylate and is composed of a mixture of
high-octane, branched-chain paraffinic hydrocarbons. Alkylate is a premium blending
stock because it has exceptional antiknock properties and is clean burning. The
octane number of alkylate depends mainly upon the kind of olefins used and upon
operating conditions.

9.7.2 Sulfuric Acid Alkylation Process

In cascade type sulfuric acid (H2SO4) alkylation units (Figure 9.13), the feedstock
(propylene, butylene, amylene, and fresh isobutane) enters the reactor and contacts
the concentrated sulfuric acid catalyst (in concentrations of 85% to 95% for good
operation and to minimize corrosion). The reactor is divided into zones, with olefins
fed through distributors to each zone, and the sulfuric acid and isobutanes flowing
over baffles from zone to zone.

The reactor effluent is separated into hydrocarbon and acid phases in a settler, and the
acid is returned to the reactor. The hydrocarbon phase is hot-water washed with
caustic for pH control before being successively depropanized, deisobutanized, and
debutanized. Alkylate obtained from the deisobutanizer can then go directly to motor-
fuel blending or be rerun to produce aviation-grade blending stock. The isobutane is
recycled to the feed.

Figure 9.13 Schematic of sulfuric acid alkylation process

9.7.3 Hydrofluoric Acid Alkylation Process

Phillips and UOP are the two common types of hydrofluoric acid alkylation processes
in use.

[Link] Phillips Process

In the Phillips process, olefin and isobutane feedstock are dried and fed to a
combination reactor/settler system. Upon leaving the reaction zone, the reactor
effluent flows to a settler (separating vessel) where the acid separates from the
hydrocarbons. The acid layer at the bottom of the separating vessel is recycled. The
top layer of hydrocarbons (hydrocarbon phase), consisting of propane, normal butane,
alkylate, and excess (recycle) isobutane, is charged to the main fractionator, the
bottom product of which is motor alkylate. The main fractionator overhead,
consisting mainly of propane, isobutane, and HF, goes to a depropanizer. Propane
with trace amount of HF goes to an HF stripper for HF removal and is then
catalytically defluorinated, treated, and sent to storage. Isobutane is withdrawn from
the main fractionator and recycled to the reactor/settler, and alkylate from the bottom
of the main fractionator is sent to product blending.

[Link] UOP Process

The UOP process uses two reactors with separate settlers. Half of the dried feedstock
is charged to the first reactor, along with recycle and makeup isobutane. The reactor
effluent then goes to its settler, where the acid is recycled and the hydrocarbon
charged to the second reactor. The other half of the feedstock also goes to the second
reactor, with the settler acid being recycled and the hydrocarbons charged to the main
fractionator. Subsequent processing is similar to the Phillips process. Overhead from
the main fractionator goes to a depropanizer. Isobutane is recycled to the reaction
zone and alkylate is sent to product blending.

Figure 9.14 Schematic of hydrogen fluoride alkylation

Besides manufacturing plenty of high octane gasoline, a catalytic cracking unit also
produces a large number of smaller molecules like propylene and butylene.

The "alky" plant takes 2 olefins, propylene and butylene and reacts them with
isobutane to form an iso-paraffin called alkylate.
The total volume of materials entering the alkylation process is greater than the
volume of products out. This is because larger molecules are produced from the
smaller varieties.

The catalysts used in the Alkylation unit to facilitate the reactions are either:

 Sulphuric acid (H2SO4), or

 Hydroflouric acid (HF acid).

Alkylate Product

 Boiling range is controlled to gasoline specifications.

 The API gravity is about 70
 It is high in octane. MON 88-94, RON 94-99.
 Alkylate is blended with LSR Naphtha (gasoline) to produce higher octane
gasoline.

9.7.4 Safety & Corrosion Considerations

Sulfuric acid and hydrofluoric acid are potentially hazardous chemicals. Loss of
coolant water, which is needed to maintain process temperatures, could result in an
upset. Precautions are necessary to ensure that equipment and materials that have
been in contact with acid are handled carefully and are thoroughly cleaned before
they leave the process area or refinery. Immersion wash vats are often provided for
neutralization of equipment that has come into contact with hydrofluoric acid.
Hydrofluoric acid units should be thoroughly drained and chemically cleaned prior to
turnarounds and entry to remove all traces of iron fluoride and hydro-fluoric acid.
Following shutdown, where water has been used the unit should be thoroughly dried
before hydrofluoric acid is introduced.

Leaks, spills, or releases involving hydrofluoric acid or hydrocarbons containing

hydrofluoric acid can be extremely hazardous. Care during delivery and unloading of
acid is essential. Process unit containment by curbs, drainage, and isolation so that
effluent can be neutralized before release to the sewer system is considered. Vents
can be routed to soda-ash scrubbers to neutralize hydrogen fluoride gas or
hydrofluoric acid vapors before release. Pressure on the cooling water and steam side
of exchangers should be kept below the minimum pressure on the acid service side to
prevent water contamination.

Some corrosion and fouling in sulfuric acid units may occur from the breakdown of
sulfuric acid esters or where caustic is added for neutralization. These esters can be
removed by fresh acid treating and hot-water washing. To prevent corrosion from
hydrofluoric acid, the acid concentration inside the process unit should be maintained
above 65% and moisture below 4%.

9.8 POLYMERIZATION
Polymerization in the petroleum industry is the process of converting light olefin
gases including ethylene, propylene, and butylene into hydrocarbons of higher
molecular weight and higher octane number that can be used as gasoline blending
stocks. Polymerization combines two or more identical olefin molecules to form a
single molecule with the same elements in the same proportions as the original
molecules. Polymerization may be accomplished thermally or in the presence of a
catalyst at lower temperatures.

9.8.1 The Process

The olefin feedstock is pretreated to remove sulfur and other undesirable compounds.
In the catalytic process the feedstock is either passed over a solid phosphoric acid
catalyst or comes in contact with liquid phosphoric acid, where an exothermic
polymeric reaction occurs. This reaction requires cooling water and the injection of
cold feedstock into the reactor to control temperatures between 300 and 450 °F at
pressures from 200 psi to 1,200 psi. The reaction products leaving the reactor are sent
to stabilization and/or fractionator systems to separate saturated and unreacted gases
from the polymer gasoline product.

Polymerization is used in the petroleum industry to indicate the production of

gasoline components, hence the term "polymer" gasoline. Furthermore, it is not
essential that only one type of monomer be involved. If unlike olefin molecules are
combined, the process is referred to as "copolymerization." Polymerization in the true
sense of the word is normally prevented, and all attempts are made to terminate the
reaction at the dimer or trimer (three monomers joined together) stage. However, in
the petrochemical section of a refinery, polymerization, which results in the
production of, for instance, polyethylene, is allowed to proceed until materials of the
required high molecular weight have been produced.
 Figure 9.15 Schematic of polymerization Process

9.8.2 Safety & Corrosion Considerations

The potential for an uncontrolled exothermic reaction exists should loss of cooling
water occur. Severe corrosion leading to equipment failure will occur should water
make contact with the phosphoric acid, such as during water washing at shutdowns.
Corrosion may also occur in piping manifolds, reboilers, exchangers, and other
locations where acid may settle out. There is a potential for exposure to caustic wash
(sodium hydroxide), to phosphoric acid used in the process or washed out during
turnarounds, and to catalyst dust.