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4.

Alkylation

4.3.1 Introduction
The alkylation reaction is the addition of an alkyl
group to any hydrocarbon. In the petroleum
industry, however, the term alkylation is used for
the reaction of low molecular weight olefins with a
light isoparaffin to form a liquid hydrocarbon. The
alkylation process was commercialized during the
second half of the 1930s to convert the light
hydrocarbons in the Fluid Catalytic Cracking
(FCC) off-gases into more useful, liquid products.
During the Second World War, it experienced a
tremendous growth due to the need for high-octane
aviation fuel. From 1950 to 1970, the world
capacity remained relatively flat due to the
comparative cost of other gasoline blending
components. The lead phase-down in many
countries and additional environmental regulations
after the 1970s increased the demand for alkylate
as a blending stock for motor gasoline.
In addition, the phase-out of MTBE (methyl
tert-butyl ether) in some US states has further
increased the need for high-octane clean streams. At
the beginning of the millennium, 13% of the US
gasoline marked was alkylate. In fact, alkylate is a
high-octane blend-stock (RON, Research Octane
Number, 93-98; MON, Motor Octane Number, 90-95)
free of undesirable components such as sulphur,
benzene and other aromatics. It is mostly made up of

C7 to C9 highly branched paraffins and is produced


primarily by reacting isobutane with light olefins in
the presence of strong acid catalysts, such as
hydrofluoric and sulphuric acid.
Due to safety and corrosion problems caused by
the use of liquid strong acids, a number of companies
have carried out research to commercialize a solid
alkylation catalyst. In fact, though the process has
been a reliable and safe producer of a prime highoctane gasoline for many decades, in recent years it
has been the object of environmental concerns and of
research and development efforts.

4.3.2 Process chemistry


and thermodynamics
The alkylation unit is traditionally fed with the FCC
off-gases and is normally installed in refineries
equipped with catalyting cracking units. The usual
feedstocks are isobutane and light olefins, mostly C3
and C4; the olefins from cokers (if available) are also
sent as feeds to alkylation. Table 1 shows the
composition of two typical olefinic feedstocks from
FCC; the alkylation process requires more isobutane
from sources other than cracking. The process
chemistry is extremely complex due to the large
number of possible side reactions. The main product is
a mixture of isoparaffins called alkylate.

Table 1. Typical olefin feeds from FCC units (weight %)

C4 cut
Wide cut

C
3

1-C
4

2-C
4

i-C
4

C
5

C3

n-C4

i-C4

i-C5

others

6.7
17.7

8.2
9.3

18.9
18.5

6.0
7.3

1.1
5.2

3.7
7.8

10.2
7.8

37.4
19.3

7.3
6.5

0.5
0.6

The symbol  as superscript indicates that there is a double link.

VOLUME II / REFINING AND PETROCHEMICALS

181

PROCESSES TO IMPROVE THE QUALITIES OF DISTILLATES

Isoparaffins with tertiary carbon atoms react with


the olefins. Among isoparaffins, isobutane has been
commonly used, since isopentane is a valuable liquid
hydrocarbon blended directly with commercial
gasoline. However, gasoline reformulation has reduced
the acceptable vapour pressure, and isopentane has
become an interesting material for propylene alkylation
(Detrick et al., 2004). Some typical reactions of the
alkylation process include the following:
CH3

CH2  CH3

CH

CH3

CH3

CH3
isobutene

isobutane
CH3
CH3

CH2

CH3

CH

CH3

CH3

The reaction proceeds via the carbocation


mechanism. The initiation step (step 1) generates the
carbocation (initially C3+ or C4+, depending on feed
composition) by protonation of the olefin. The
catalytic solvents capable of transferring this proton to
the olefin are strong acids. The more stable tertiary
butyl cation is then generated by transfer of a hydride
ion (step 2). The direct formation of a cation from
isobutane at roughly room temperature requires a
solvent system with acidity similar to or higher than
H2SO4 (Marcilly, 2003). The most diffused
commercial processes have traditionally used HF and
H2SO4 (Table 2). The propagation reaction involves the
tertiary butyl cation, which reacts with the olefin to
form a larger cation (step 3), and then generates a new
tertiary butyl cation and the alkylate product (step 4).
This sequence is illustrated below using propylene and
isobutene as an example reaction:
H

2,2,4-trimethylpentane

CH3

CH2

CH

CH2  CH3

CH

CH

CH3


CH

CH3

CH3
1-butene

CH2

CH3

CH3  HC

CH2

CH2

CH3

CH3

isobutane

CH2

CH3

CH3

CH3
CH3


CH

CH3

CH3

CH3

CH3  CH3

CH2

2,2-dimethylhexane
CH3

CH

CH2  CH3

CH

CH2 CH3

CH


C

CH3

CH3

CH3

CH3
propylene

CH3

isobutane


CH

CH3
CH2

CH2

CH2

CH3

CH3

CH3

CH3


CH

CH2

2,2-dimethylpentane

It should be recalled that 2,2,4-trimethylpentane


(isoctane) is one of the two standard hydrocarbons for
octane number definition, and that its ON (Octane
Number) is 100.
The butene isomerization to isobutene
(in the alkylation feed) is an important reaction to
produce high-octane hydrocarbons from feeds
containing appreciable quantities of 1-butene.
A number of alkylation units processing
butenes have an upstream isomerization unit
(Detrick et al., 2004).

182

CH3

CH3

CH3
CH3

CH3

CH3

CH3

CH3


C

CH3
CH3  HC

CH3

CH3

CH3
CH3

CH3

CH2

CH2

CH3 CH3


C

CH3

CH3

CH3

An important side reaction of the process is the


hydrogen transfer reaction, most pronounced in HF
catalyzed processes fed with propylene (the symbol =
as superscript indicates that there is a double link):
C3i-C4 C3i-C4


i-C4i-C4 i-C8 (trimethylpentane)




ENCYCLOPAEDIA OF HYDROCARBONS

ALKYLATION

Table 2. Typical properties of fresh alkylation acids

(Marcilly, 2003)
PROPERTY

HF

H2SO4

Molecular weight
Boiling temperature (C)
Melting temperature (C)
Specific weight (d415)
Viscosity (cP)
Hammett acidity (Ho)*

20.01
19.4
82.8
0.99
0.256 (0C)
10

98.08
290
10.4
1.84
33 (15C)
11.1

* Acidity of the industrial acids during operation.

The overall reaction is:


C3H6  2 i-C4H10
propylene

C3H8 

isobutane
CH3
 CH3

CH

CH3
CH2

CH3

in a continuous acid phase. Being that olefins are more


soluble in acid than the isoalkane, one may expect a
high conversion to polymers; this, however, is not in
agreement with industrial practice. An explanation
could be that the carbocations formed by the
interaction of the acid with the olefin, which initiate
the reaction chain, are found to a larger extent at the
interface between the two phases, with the carbonium
ions oriented towards the hydrocarbon phase (Raseev,
2003). The isoalkane in the hydrocarbon phase can
then interact with the carbonium ion. This opinion is
not unanimous, but it allows the alkylation reaction to
be treated as a homogeneous process where the
reaction rate is proportional to the interfacial area. The
rate will then increase with the degree of dispersion
and, therefore, with the decrease in size of the
hydrocarbon droplets. This is confirmed
experimentally: in fact, the octane number and,
generally, the alkylate quality increase by intensifying
the mixing in the reactor (Li et al., 1970). With good
mixing and the proper operating conditions, alkylation
occurs almost instantaneously.

CH3
propane

trimethylpentane

The octane number of trimethylpentane is sensibly


higher than that of dimethylpentane normally obtained
from propylene. However, in this reaction two
molecules of isobutane are required to produce only
one molecule of alkylate.
A number of other side reactions may be involved
in the process; the most common include the
polymerization and cracking. The polymerization of
olefins results in the production of low-octane, high
boiling point components, which are undesirable. This
reaction is minimized by using high isobutane/olefin
ratios and choosing proper reaction conditions.
The heavier polymerization products are known as
Acid Soluble Oils (ASOs) or red oils and tend to
deactivate the catalyst. ASOs are unsaturated
compounds with more than about 10 carbon atoms per
molecule that can react with H2SO4.
Alkylation reactions are higly exothermic (on
average 75-96 kJ/mol); the reaction equilibrium is,
therefore, shifted to the alkylate formation at low
temperature and high pressure. Moreover, lower
temperatures minimize the formation of by-products
due to polymerization and cracking reactions.

4.3.3 Process kinetics


The traditional alkylation reaction takes place in a
medium in which the hydrocarbon drops are dispersed

VOLUME II / REFINING AND PETROCHEMICALS

4.3.4 Catalysts and reaction


conditions
Strong acids: HF and H2SO4

In order to favour the thermodynamics and to


minimize the formation of by-products, the alkylation
reaction is carried out at the lowest possible
temperature. This is kinetically possible by using large
amounts of strong acid catalysts; the world market has
long been split between H2SO4 and HF (see again Table
2). The acid strength of the two compounds is similar
when they carry traces of impurities (Marcilly, 2003).
The catalysts must be used almost pure, since the
alkylation reaction requires a strong acidity in order to
attain kinetics that are economically acceptable.
In general, the HF alkylate has a higher octane
number due to the hydrogen transfer reactions;
however, the process economics should be analyzed
while keeping in mind the higher isobutane
consumption and the lower catalyst consumption when
using HF. During operation, the acid is contaminated
by water and soluble organic matter, which decrease
the total acidity; in such conditions, the isobutane
solubility is higher (e.g. 0.4% by weight in H2SO4 and
3.6% by weight in HF; Marcilly, 2003).
The process temperature depends on the acid type.
The oxidizing properties of H2SO4 suggest a
temperature generally less than 12C. However, the
acid viscosity increases rapidly by lowering the
temperature, which restricts the useful temperature
range between about 2-12C (5C being a good

183

PROCESSES TO IMPROVE THE QUALITIES OF DISTILLATES

compromise). HF is not an oxidant and thus the useful


temperature can be in the range of 20-50C (normally
between 30-40C), which simplifies the reactor
cooling systems.
The reaction pressure is fixed at a level capable of
keeping the reaction media in the liquid phase. In both
cases, an excess of isobutane must be used to avoid
olefin polymerization; the excess isobutane is recycled
to the reactor after separation of the alkylate product.
The reaction medium is composed of two phases:
the acid phase (continuous phase) and the hydrocarbon
phase (dispersed phase). The reacting hydrocarbons are
those solubilized into the acid phase. The acids physical
characteristics at the process temperature impose a
much more effective stirring in the case of H2SO4. In
fact, one of the key differences between HF and H2SO4
alkylation is the handling of the acid catalyst.
The catalyst activity decreases with time due to
dilution, ASO formation and impurity build-up.
The HF acid can be fractionated to remove water
and ASO. H2SO4 must be removed from the unit
and regenerated by completely decomposing the
acid to SO2-SO3 and condensing them back to
H2SO4. This regeneration process can be done at
the site or, usually, outside of the refinery in
remote locations. For the above-mentioned
reasons, the H2SO4 consumption is normally much
higher than HF consumption, in spite of the fact
that HF can form an azeotrope with water
(the so-called CBM, Constant Boiling Mixture),
responsible for acid losses.
Tables 3 and 4 illustrate the influence that both the
type of acid catalyst and the olefin bear on alkylate

yield and quality (Joly, 2001). As already mentioned,


the impurities of the feed greatly affect yield, alkylate
formation and acid composition, especially in the case
of H2SO4 catalyst. For HF acid catalyst, consumption
is normally less than 1 kg/t since the catalyst is
regenerated by simple distillation.
Mitigation of the risk due to acid use: solid catalysts

Although extensive experience shows that


alkylation plants, regardless of acid catalyst choice,
can be operated safely and with low process risks; the
process acid catalysts have been subject to critical
attention in the last decades.
Hydrofluoric acid is very volatile (boiling point:
19.5C) and produces dangerous mists in the event of
an accidental release. Refiners with sulphuric acid
alkylation units must ship large quantities of spent
acid offsite for regeneration, thus creating potential
transportation hazards. Both concentrated acids are
contained in carbon steel and become very corrosive
when diluted with water.
The refining industry has developed a number
of mitigation strategies to face these problems:
water curtain systems, rapid acid dump methods,
remotely operated isolation systems, etc. At the
same time, catalyst producers and process
licensors have developed, and in some cases
commercialized, solid-phase acid catalysts.
Several pilot-size units are operating and a
number of processes have been presented
(Refining processes, 2002, 2004; Meyers, 2004;
DAmico et al., 2006). Solid acid catalysts have
long been investigated; these include exchanged

Table 3. Yield and octane number of the product from H2SO4 alkylation process
Type of feed
Yield (vol C5/vol olefin)
i-C4 consumption (vol/vol olefins)
Catalyst consumption (kg/t C5)
MON
RON

Propylene

Butenes

Amylenes

1.45-1.78
1.27-1.32
137-171
88-90
89-92

1.74
1.14
51-102
92-94
94-98

1.57
1
102-171
88-90
90-92

Table 4. Yield and octane number of the product from HF alkylation process
Type of feed

C
3

1-C
4

2-C
4

i-C
4


C
3 C4

Yield (vol C5/vol olefin)


i-C4 consumption (vol/vol olefins)
MON
RON

1.76
1.36
92
90

1.73
1.1
94.4
91.6

1.77
1.14
97.8
94.6

1.78
1.28
95.9
93.4

1.79
1.28
93.7
90.8

C
5
1.63
1
91.5
90

The symbol  as superscript indicates that there is a double link.

184

ENCYCLOPAEDIA OF HYDROCARBONS

ALKYLATION

zeolites, ion-exchange resins such as Amberlyst,


perfluoropolymers with sulphonic acid groups
along its backbone (Nafion), superacid solids
(chlorinated alumina, sulphated zirconia) and
liquid superacids immobilized on solids.
Examples of solid catalysts promoted by strong
acids are: alumina (or zeolites)/BF3,
silica/CF3SO3H, silica/SbF5. Most catalysts are
proprietary and little information is normally given
regarding their composition. Solid catalysts can
improve safety and production costs, but tend to
deactivate rapidly under alkylation conditions due to
build up of coke and heavy compounds on the
catalyst surface. Burning off the heavy hydrocarbons
through high-temperature oxidation quickly destroys
the catalyst activity.
To solve the deactivation problem, some
companies have developed new reactor types and new
generation systems based on the desorption of the
heavy hydrocarbons with the use of a hydrogen stream
(Roeseler, 2004). Another approach proposes the use
of supercritical fluids as the reaction media; as an
example, supercritical CO2 was found to be good at
dissolving the heavy coke material on the catalysts
surface (Subramaniam, 2001).
Some companies have proposed special additives
that reduce the tendency of HF to form mists. On-site
sulphuric acid regeneration is available to eliminate
the shipment of spent and regenerate acid; although
this technology has been available for half a century,
only few refineries operate on-site regeneration.

4.3.5 Sulphuric acid alkylation


processes
Sulphuric acid alkylation was the first to be
developed, during the decade preceding the Second
World War. Essentially, the H2SO4 processes consist
in a reaction section where an emulsion of
hydrocarbons and acid is formed (and the reaction
occurs), and in a settling section that separates and
recycles the acid. A fractionation section separates the
alkylate from the excess isobutane, which is recycled
Fig. 1. Stratco-type

alkylation reactor.

to settler
coolant

to the reactor. There are currently two major


alkylation processes using H2SO4 as catalyst: Stratco
effluent refrigeration alkylation, and ExxonMobil
cascade autorefrigeration process; each uses different
approaches for the design of the reaction and
refrigeration sections.
Stratco process

The Stratco reactor is a horizontal pressure vessel


containing an inner tube bundle, which acts as an
exchanger to remove the heat of reaction, and a mixing
impeller (Fig. 1). It operates at a pressure of about 3.5
to 5.0 bar, sufficient to keep the two phases in the
liquid state. The acid and hydrocarbon feed come into
contact and are vigorously stirred by the impeller
blades. An emulsion is formed and the reaction takes
place almost instantly; the contact time is very short
and the side reactions are kept to a minimum. The high
recycle rate of the emulsion allows an efficient control
of the reaction temperature.
The general scheme of the process is shown in
Fig. 2. The dehydrated olefin feed is mixed with the
recycle isobutane and cooled in the feed/effluent
exchangers; water is removed in the coalescer before
entering the reactor. A portion of the emulsion in the
contactor reactor is withdrawn from the discharge
side of the impeller and sent to the acid settler,
which separates the reacted hydrocarbon phase from
the acid emulsion. The settled acid is returned to the
suction side of the impeller. Acid is purged from the
unit, usually on a continuous basis, and fresh acid is
introduced so that the acid strength is kept high. The
hydrocarbon phase, containing the alkylate product
and the isobutene, is sent to the tube bundle in the
reactor by reducing the pressure to about 0.4-0.6 bar,
across a back pressure control valve. At this
pressure, the lighter components of the effluent
stream are vaporized, reducing the temperature to
below 0C. Additional vaporization occurs in the
tube bundle as the net effluent stream removes the
heat of reaction (Graves, 2004). The stream from the
tube bundle is sent to the suction trap/flash drum to
separate the vapour and liquid phase. The liquid
isobutene from the flash drum-side is directly

pressure
relief

acid

hydrocarbon
feed
driver

drain
coolant

VOLUME II / REFINING AND PETROCHEMICALS

185

PROCESSES TO IMPROVE THE QUALITIES OF DISTILLATES

n-butane product
compressor
accumulator
economizer

i-C4
propane
product

olefin feed
isobutane feed

fresh acid
spent acid

alkylate
product

Fig. 2. Simplified flow diagram of the H2SO4 Stratco process.

recycled to the reactor, while the liquid from the


suction trap-side is transferred to the effluent
fractionation section after caustic washing or
passing over a bauxite bed for the elimination of
sulphates. Isobutane is recycled back to the reactor
section. The vapour phase from the flash drum is
compressed, cooled and condensed. Propane is
eliminated in the depropanizer, whose bottoms are
recycled to the reactor.
ExxonMobil process

The ExxonMobil cascade process uses the autorefrigeration system to remove the heat of reaction and
to maintain the low reaction temperature (4-5C)
needed for alkylation. The reactor is a horizontal vessel
containing a number of compartments with mixers in
each stage to emulsify the hydrocarbon-acid mixture.
The reaction is held at low pressure and the heat of
reaction is eliminated by evaporating an isobutane
stream directly fed into one end of the reactor. The acid
is fed on the same end and moves together with the
isobutane by overflowing from one compartment to the
other. The olefin feed is split and added into each
compartment. It is not necessary to maintain a high
pressure in the reactor to prevent vaporization of light
hydrocarbons: the pressure varies from about 1.5 bar in
the first stage (richer in isobutane) to about 0.5 bar in
the last stage. Usually, the reactor contains a settling

186

zone at the end. A flow scheme of the process is shown


in Fig. 3 (Lerner and Citarella, 1991).
Olefin feed is mixed with recycle isobutane from
the deisobutanizer, cooled and fed to the reactor. Water
condensed at a lower temperature is removed in the
coalescer. The vapours leaving the reactor are routed
to the refrigerator section where they are compressed,
condensed and sent to the economizer (an intermediate
pressure flash drum), which reduces the power
requirements of the refrigeration compressor. A
slipstream of refrigerant (isobutane) is depropanized
after being caustic and water washed. Propane is
separated overhead, while isobutane-rich bottoms are
returned to the process.
The reactor liquid product is sent to the settler,
from where the settled acid is recycled back to the
reactor. The hydrocarbon portion (containing alkylate,
excess isobutane and n-butane) is caustic and water
washed to remove any acid components, and is sent to
the deisobutanizer. Overhead from the tower is an
isobutane-rich stream, which is recycled to the reactor,
while the bottoms are sent to the debutanizer for the
separation of the alkylate product from butane.
Feed impurities and small amounts of polymerized
olefins that form ASO tend to accumulate in the
recycle acid. Therefore, a spent acid purge is taken
from the process to remove these oils and fresh makeup acid is added to maintain sufficient acid strength.

ENCYCLOPAEDIA OF HYDROCARBONS

ALKYLATION

compressor

spent
caustic

depropanizer

propane

waste
water

reactor
M
M

water
washing

waste
water

butane

debutanizer

i-C4

caustic
washing

coalescer

recycle refrigerant

deisobutanizer

fresh
caustic

water
washing

caustic
washing

economizer

KO drum

water

settler

olefin feed plus


isobutane recycle
fresh
caustic

recycle acid
make-up
acid

spent
acid

olefin
feed

spent water
caustic

waste
water

alkylate

make-up
isobutane

Fig. 3. Flow diagram of the H2SO4 ExxonMobil process.

4.3.6 Fluoridic acid alkylation


processes
In 1994, there were 127 HF units and 92 H2SO4
units in the world refineries (Joly, 2001). In the
Refining processes handbook (Refining processes,
2004), the declared licences for the HF units were
160, which almost doubled the declared H2SO4
licences. Of course not all the licensed plants
were still working, but the data provide a rough
idea of the diffusion of the processes. At normal
design conditions, an HF alkylation unit requires
a higher ratio of isobutane to olefin (I/O) than a
H2SO4 unit. Both processes fractionate the
isobutane from the reactor effluent stream and
recycle it back to the reactor. Due to its higher I/O
ratio, an HF alkylation unit is designed with a
larger fractionation section. The low HF viscosity
and better solubility of isobutane in the acid allow
simpler reactors to be used: it is sufficient to

VOLUME II / REFINING AND PETROCHEMICALS

inject the hydrocarbon feed into the acid phase to


obtain a good emulsion. Therefore, the HF units
do not have mechanical stirring devices. Water
can be used to cool the reactor, given the higher
reaction temperatures. The Conoco-Phillips and
UOP (Universal Oil Products) technologies
shared the market at the beginning of the third
millennium.
The Conoco-Phillips process

The original Phillips process is characterized by its


very simple reactor, similar to that shown in Fig. 4
(Gary and Handwerk, 1975). Essentially, it is
composed of an acid cooler, a riser reactor and a
settler. Acid circulation is by gravity differential and
an acid circulation pump is not necessary. The
residence time in the tubular reactor is in the order of
half a minute.
A basic flow scheme of the Phillips process is
illustrated in Fig. 5. The more recent version converts

187

PROCESSES TO IMPROVE THE QUALITIES OF DISTILLATES

hydrocarbon product

settler

acid  hydrocarbons (20-27C)

riser
reactor

acid

The UOP process


acid
accumulator

hydrocarbon
feed
acid
cooler

cooling
water

Fig. 4. Simplified scheme of the Phillips HF reactor.

propylene, amylene, butenes and isobutane to motor


fuel using ReVAP (Reduced Volatility Alkylation
Process) alkylation.
Both the olefin and isobutane feeds are dehydrated
by passing them through a solid bed desiccant. Good
dehydration is essential to minimize potential
corrosion of process equipment, which results from
addition of water to hydrofluoric acid. The olefin and
isobutane feeds are then mixed with hydrofluoric acid
at a sufficient pressure to maintain all components in
the liquid phase. The reaction mixture is allowed to
settle into two liquid phases. The acid is withdrawn
from the bottom of the settler and passed through a
cooler to remove the reaction heat; it is then recycled
and mixed with fresh feed.
A slipstream of acid is withdrawn from the settler
and fed by a pump to the acid rerun column to remove
dissolved water and polymerized hydrocarbons. The
overhead product from the rerun column is mostly
hydrofluoric acid, which is condensed and returned to

188

the system. The bottom product from the rerun column


is a mixture of ASO and HF-water azeotrope. These
components are separated in a settler (not shown in the
flow diagram). The ASO is used for fuel and the
HF-water mixture is neutralized with lime or caustic.
This rerun operation is added to maintain the activity
of the hydrofluoric acid catalyst.
The hydrocarbon phase removed from the top of
the acid settler is a mixture of propane, isobutane,
normal butane, and alkylate, along with small amounts
of hydrofluoric acid. These components are separated
by fractionation and the isobutane is recycled to the
reactor. Propane and normal butane products are
passed through caustic treaters to remove trace
quantities of hydrofluoric acid. The design of the acid
settler-cooler-reactor section is critical to good
conversion in a hydrofluoric acid alkylation unit.

In the UOP HF-alkylation process, a pump


provides the inlet pressure into the reactor nozzles,
which allow the hydrocarbon phase to be dispersed in
the acid continuous phase. The dried olefin and
isobutene are fed at different reactor heights, while the
acid is fed at the reactor bottom. The mixing between
hydrocarbons and acid phases is improved by the
pumping design. The reactor heat is removed by means
of cooling water. A simplified flow scheme of a
typical C4 HF alkylation unit is shown in Fig. 6.
Similar schemes are available for the C3-C4 alkylation
units (Detrick et al., 2004).
The combined feed enters the shell of the
reactor-heat exchanger through several nozzles,
which maintain an even temperature in the reactor.
The effluent from the reactor flows to the settler and
the acid is recycled to the reactor. The hydrocarbon
phase (containing dissolved HF acid) is charged to
the iso-stripper. The alkylate and n-butane are
recovered from the bottom and as a side stream,
respectively. Isobutane is also dotained as a side-cut
and recycled to the reactor. The overhead, mainly
consisting of isobutane, propane and acid, is in part
charged to the HF stripper. An HF alkylation unit
fed with C3-C4 olefins is normally equipped with a
depropanizer, which may be also required with C4
olefins, if the propane quantity is too high. A small
slipstream of circulating HF acid is regenerated
internally, to keep the purity at the requested level.
The internal acid regeneration technique has
virtually eliminated the need for an acid
regeneration (Detrick et al., 2004). All effluent
streams and process vents, sewer effluents and acid
regeneration bottoms are treated either with KOH or
alumina. The KOH is regenerated on a periodic basis
by using lime.

ENCYCLOPAEDIA OF HYDROCARBONS

ALKYLATION

acid from
depropanizer section
reactor settler
main
fractionator

recycle acid

acid
recontactor

acid standpipe
reactor
riser

acid
make-up
cooling
water

acid
tank

acid eductor

acid
rerun
column

acid
cooler

depropanizer feed

steam

mixer
nozzle

stripping
i-C 4
ASO

recycle isobutane
steam
butane to
KOH treater
olefin
feed
isobutane

isobutane from
depropanizer section

total alkylate to storage

Fig. 5. Typical scheme of the Phillips HF process.

Risk mitigation in the HF alkylation plants

In order to reduce aerosol formation in the event of


an HF release, UOP proposes the Alkad process, to be
used with HF alkylation technology. The Alkad
process is a passive mitigation system that will reduce
aerosol from any leak occurring in the unit. The
alkylation reactions take place in the presence of a
liquid additive, which form a long chain of associated
HF molecules; in this form, HF acid loses its tendency
to form aerosols when released to the atmosphere.

4.3.7 Processes with solid acid


catalysts
Since the 1990s, a number of companies have
proposed alkylation processes based on solid catalysts,
both using fixed-bed or riser reactors. At the moment,
most solid catalyst processes are at the pilot stage and
very few commercial units are installed.

hydrocarbons and solid catalyst, with in situ


regeneration capability. The liquid-phase operation
minimizes abrasion problems. A novel catalyst (HAL100) was developed with declared good performance
and long stability; it is easily regenerated without a high
temperature carbon burn. A simplified flow diagram of
the process is shown in Fig. 7 (Roeseler, 2004).
Reactants and catalyst flow up the reactor riser at a rate
of about one foot per second as the reaction occurs. The
catalyst is quickly separated from the hydrocarbon at
the top of the riser and falls by gravity into the
reactivation zone. The catalyst flows slowly downward
and it is contacted with a recycle of cold isobutane
saturated with hydrogen. Heavy hydrocarbons are
hydrogenated and desorbed from the catalyst. The
reactivated catalyst flows down and back into the riser
bottom. A catalyst slipstream is reactivated at a higher
temperature in a separate vessel to completely remove
the small quantities of the residual heavy hydrocarbons.
Alkylate from the reactor is sent to a fractionation
section similar to those of the liquid acid processes.

The Alkylene process

The UOP Alkylene process was developed during


the late 1990s, based on a liquid transport reactor (riser
reactor) to promote fast and good contact between

VOLUME II / REFINING AND PETROCHEMICALS

Other processes

The Topsoe process employs a catalyst system


of the supported liquid phase type. The superacid

189

acid
regenerator

alumina
treater

acid
recycle

reactor

olefin
feed

cooling
water

settler

i-C4 recycle

isostripper

HF stripper

PROCESSES TO IMPROVE THE QUALITIES OF DISTILLATES

KOH
treater

i-C4
make-up

KOH
treater

ASO and CBM


to neutralization

KOH
treater

to depropanizer
alkylate

n-butane

Fig. 6. Typical scheme of a UOP HF-alkylation unit fed with C4 cuts (Detrick et al., 2004).

liquid is adsorbed on a porous solid support. This


enables the use of simple fixed-bed reactors.
However, through proper operation of the reactor
system, the liquid nature of the catalyst can be used
to achieve simple maintenance of catalytic activity.
The AlkyClean process is licensed by ABB Global,
Akzo Nobel and Fortum Oil and Gas, and uses a
solid acid catalyst. The reactors are undergoing a
mild liquid-phase regeneration using isobutane and
hydrogen. The process does not produce any ASO
products

light
ends

Alkylene
reactor

LPG

i-C4/H2
catalyst
reactivation
zone
olefin
feed

alkylate

H2
hot
reactivation
vessel

isobutane recycle

Fig. 7. Simplified flow diagram of the Alkylene process.

190

or require post treatment of the reactor effluent or


final product.

4.3.8 Hazards and corrosion


problems
Among refinery processes, alkylation plants are
somewhat unique because they use strong
aggressive acids and contain large volumes of
LPG. A key element of hazard management is
directed at preventing the release in the first place.
Extensive experience demonstrates that alkylation
units can be operated safely, and with minimum
process risk to employees or neighbouring
communities (Scott, 1992). The plants are
constructed according to standards and with
materials that are specifically designed to make the
plant as safe as possible.
In case of liquid exposure, both acids will
cause serious burns. HF also has the property of
penetrating the tissues and reacting with the
calcium and magnesium in the body. In the
presence of water, HF forms an azeotrope that
contains 36% HF and boils at 109C. HF is
volatile, and when spilled it forms stable aerosol
clouds. Vapour and aerosol cause serious
inhalation hazards (lung damage). Both
concentrated acids can be contained in carbon
steel, but they become very corrosive when diluted

ENCYCLOPAEDIA OF HYDROCARBONS

ALKYLATION

with water. The aggressiveness of both acids varies


with its concentration, temperature, nature of
contaminants and velocity relative to exposed
surfaces. In H2SO4 alkylation, the hydrocarbons
are emulsified in concentrate acid and reacted at
low temperatures; the acid remains fairly
concentrated, diluting to about 88%. Stainless steel
(304 L or 316 L) should be preferred in areas
where high velocity may be encountered, such as
pumps, valves and bends (Schillmoller, 1998a).
Austenitic stainless steels are resistant to
anydrous HF, but are unreliable in dilute acid.
Alloy 400 (Monel) containing Ni and Cu and
minor amounts of Fe and Mn has been the
standard material in alkylation plants for many
years and has been used for heat exchangers,
columns, reboilers and overhead condensers with
acid concentrations between 85 and 95%. Alloy
400 is resistant to all concentrations of HF,
including anhydrous, over a wide range of
temperatures, in the absence of oxygen or
sulphur dioxide contamination. HF contaminated
with even small amounts of oxygen can cause
severe pitting and cracking of steel and Monel
(Schillmoller, 1998b). Special attention should
be given to the welding, which can be severely
corroded if not done properly. HF also attacks all
materials containing silica (glass, china, etc.),
asbestos and many plastics, except teflon. In
addition to the usual refinery safety procedures,
the operators of the acid area in the alkylation
units must follow special ad hoc
procedures.

4.3.9 Process and operating


variables
The main process variables that influence the yields
and quality of the alkylate product are: a) quality of
the feed; b) acid strength and composition;
c) isobutene/olefin ratio; d) temperature; e) mixing
and space velocity.
In the case of the liquid catalysts, the properties of
the two acids can explain the differences between the
related processes and the operating conditions. The
higher viscosity and surface tension of sulphuric acid
as opposed to hydrofluoric acid make it much more
difficult to obtain a fine dispersion of the hydrocarbon
in the acid phase. The higher solubility of isobutane in
HF acid leads to a higher ratio of isobutane to olefins
in the acid phase (especially at the interface) with
respect to H2SO4 processes; the secondary reactions
are then reduced and the quality of the alkylate is
improved.

VOLUME II / REFINING AND PETROCHEMICALS

Quality of the feed

Impurities increase catalyst consumption. The


hydrocarbon feed should be dried and desulphurized,
especially in HF units. Diolefins cause heavy losses of
sulphuric acid.
The olefin type in the feed, particularly the ratio of
butylene to propylene, affects the product quality and
acid consumption: in propylene alkylation, the octane
number can be five units lower and acid consumption
almost double (Parkash, 2003). The olefin type also
influences the heat of reaction, isobutane consumption
and alkylate yield.
Acid strength

Acid composition at the equilibrium is an


important parameter that influences alkylate quality.
There is a minimum acid strength required by the
process, which varies depending on the acid and
olefin type and spent acid composition. At lower
acid concentrations polymerization becomes
predominant. Water lowers the acid catalytic
activity three to five times faster than hydrocarbon
diluents (Parkash, 2003). However, some water is
necessary to ionize the acid. The optimum and
minimum water contents for H2SO4 units are close
to 99% and 90%, respectively. In HF processes, the
best alkylate quality is produced with a water
content of about 2.8% (Joly, 2001). The impurities
present in the feed can be absorbed or react with the
catalyst, causing a decrease in strength and the need
to increase the acid make-up.
Isobutane/olefin ratio

Isobutane/Olefin (I/O) ratio is the most important


operating parameter: it controls alkylate yields and
quality, as well as catalyst consumption.
Polymerization occurs in the acid phase and is the
most important reaction competing with the alkylation
reaction. During polymerization, two or more olefin
molecules react to form a polymer, which causes lower
product octane and increased acid consumption. The
solubility in the acid phase is much higher for olefins
than for isobutane; therefore, a large excess of the
latter must be maintained in the reaction zone to
ensure that enough isobutane is absorbed at the acid
interface. The usual I/O ratio ranges from 5 to 8 in
H2SO4 units and from 10 to 15 in HF processes.
Temperature

The alkylation process is thermodynamically


favoured by low temperatures. Reaction temperature
has a greater effect in H2SO4 than in HF processes.
Reducing the reaction temperature minimizes the
polymerization rate relative to the alkylation rate,
resulting in a higher octane number and lower acid

191

PROCESSES TO IMPROVE THE QUALITIES OF DISTILLATES

consumption. In the case of H2SO4, temperatures


below 2-4C are generally avoided because of the very
high viscosities of the acid phase. Also, very low
temperatures slow down settling rates and favour acid
carryover. The temperature in the reactor depends on
the olefin feed rate, which influences the reaction heat.
Efficient removal of the heat from the reactor is
essential for all catalytic systems.
Mixing and space velocity

Increasing mixing produces a better and finer


dispersion of the hydrocarbon droplets in the
emulsion, increasing the surface area, and thus the
kinetics and product quality.
In the case of liquid acid catalysts, the space
velocity can be a measure of the olefin concentration
in the acid phase and may be defined as follows:
olefin space velocity = olefin in the reactor
(m3/h)/acid in the reactor (m3)
As the olefin space velocity increases, the octane
number tends to decrease and the acid consumption
increases. In general, the residence time of the
reactants is not a limiting parameter because the
alkylation reaction occurs almost instantaneously.

References
DAMICO V. et al. (2006) Consider new methods to dedottleneck
clean alkylate production, Hydrocarbon Processing,
February, 65-70.
Detrick K.A. et al. (2004) UOP HF alkylation technology,
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refining processes, New York, McGraw-Hill, Chapter 1.33.
Gary J.H., Handwerk G.E. (1975) Petroleum refining.
Technology and economics, New York, Marcel Dekker, 152.
Graves D.C. (2004) Stratco effluent refrigerated H2SO4
alkylation process, in: Meyers R.A. (editor in chief)
Handbook of petroleum refining processes, New York,
McGraw-Hill, Chapter 1.11.

192

Joly J.F. (2001) Aliphatic alkylation, in: Leprince P. (edited


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Ritter S.K. (2001) Alkylate rising, Chemical and Engineering
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Roeseler C. (2004) UOP alkylene process for motor fuel
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Chapter 1.25.
Schillmoller C.M. (1998a) Select alloys that perform
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Carlo Giavarini
Dipartimento di Ingegneria Chimica, dei Materiali,
delle Materie Prime e Metallurgia
Universit degli Studi di Roma La Sapienza
Roma, Italy

ENCYCLOPAEDIA OF HYDROCARBONS