4.

Alkylation

4.3.1 Introduction C7 to C9 highly branched paraffins and is produced

primarily by reacting isobutane with light olefins in
The alkylation reaction is the addition of an alkyl the presence of strong acid catalysts, such as
group to any hydrocarbon. In the petroleum hydrofluoric and sulphuric acid.
industry, however, the term alkylation is used for Due to safety and corrosion problems caused by
the reaction of low molecular weight olefins with a the use of liquid strong acids, a number of companies
light isoparaffin to form a liquid hydrocarbon. The have carried out research to commercialize a solid
alkylation process was commercialized during the alkylation catalyst. In fact, though the process has
second half of the 1930s to convert the light been a reliable and safe producer of a prime high-
hydrocarbons in the Fluid Catalytic Cracking octane gasoline for many decades, in recent years it
(FCC) off-gases into more useful, liquid products. has been the object of environmental concerns and of
During the Second World War, it experienced a research and development efforts.
tremendous growth due to the need for high-octane
aviation fuel. From 1950 to 1970, the world
capacity remained relatively flat due to the 4.3.2 Process chemistry
comparative cost of other gasoline blending and thermodynamics
components. The lead phase-down in many
countries and additional environmental regulations The alkylation unit is traditionally fed with the FCC
after the 1970s increased the demand for alkylate off-gases and is normally installed in refineries
as a blending stock for motor gasoline. equipped with catalyting cracking units. The usual
In addition, the phase-out of MTBE (methyl feedstocks are isobutane and light olefins, mostly C3
tert-butyl ether) in some US states has further and C4; the olefins from cokers (if available) are also
increased the need for high-octane ‘clean’ streams. At sent as feeds to alkylation. Table 1 shows the
the beginning of the millennium, 13% of the US composition of two typical olefinic feedstocks from
gasoline marked was alkylate. In fact, alkylate is a FCC; the alkylation process requires more isobutane
high-octane blend-stock (RON, Research Octane from sources other than cracking. The process
Number, 93-98; MON, Motor Octane Number, 90-95) chemistry is extremely complex due to the large
free of undesirable components such as sulphur, number of possible side reactions. The main product is
benzene and other aromatics. It is mostly made up of a mixture of isoparaffins called alkylate.

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

C
3 1-C
4 2-C
4 i-C
4 C
5 C3 n-C4 i-C4 i-C5 others
C4 cut 6.7 8.2 18.9 6.0 1.1 3.7 10.2 37.4 7.3 0.5
Wide cut 17.7 9.3 18.5 7.3 5.2 7.8 7.8 19.3 6.5 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 reaction proceeds via the carbocation
the olefins. Among isoparaffins, isobutane has been mechanism. The initiation step (step 1) generates the
commonly used, since isopentane is a valuable liquid carbocation (initially C3+ or C4+, depending on feed
hydrocarbon blended directly with commercial composition) by protonation of the olefin. The
gasoline. However, gasoline reformulation has reduced catalytic solvents capable of transferring this proton to
the acceptable vapour pressure, and isopentane has the olefin are strong acids. The more stable tertiary
become an interesting material for propylene alkylation butyl cation is then generated by transfer of a hydride
(Detrick et al., 2004). Some typical reactions of the ion (step 2). The direct formation of a cation from
alkylation process include the following: isobutane at roughly room temperature requires a
solvent system with acidity similar to or higher than
CH3 C CH2  CH3 CH CH3 H2SO4 (Marcilly, 2003). The most diffused
commercial processes have traditionally used HF and
CH3 CH3
H2SO4 (Table 2). The propagation reaction involves the
isobutene isobutane tertiary butyl cation, which reacts with the olefin to
CH3 form a larger cation (step 3), and then generates a new
tertiary butyl cation and the alkylate product (step 4).
CH3 C CH2 CH CH3 This sequence is illustrated below using propylene and
CH3 CH3 isobutene as an example reaction:
2,2,4-trimethylpentane H 
CH2 CH CH3 CH3 CH CH3

CH3
CH3 CH2 CH CH2  CH3 CH CH3 
CH3 CH CH3  HC CH3
CH3
1-butene isobutane CH3

CH3 
CH3 CH2 CH3  CH3 C CH3
CH3 CH2 CH2 CH2 C CH3
CH3
CH3
2,2-dimethylhexane

CH3 CH CH2 CH3 C CH3
CH3
CH3 CH CH2  CH3 CH CH3
CH3
CH3 
CH3 CH CH2 C CH3
propylene isobutane
CH3
CH3
CH3 CH2 CH2 C CH3 CH3 CH3

CH3 CH3 CH CH2 C CH3  HC CH3
2,2-dimethylpentane CH3 CH3

It should be recalled that 2,2,4-trimethylpentane CH3


(isoctane) is one of the two standard hydrocarbons for CH3 CH2 CH2 C CH3 CH3 C CH3
octane number definition, and that its ON (Octane
CH3 CH3
Number) is 100.
The butene isomerization to isobutene An important side reaction of the process is the
(in the alkylation feed) is an important reaction to hydrogen transfer reaction, most pronounced in HF
produce high-octane hydrocarbons from feeds catalyzed processes fed with propylene (the symbol =
containing appreciable quantities of 1-butene. as superscript indicates that there is a double link):
A number of alkylation units processing
C3i-C4 C3i-C4


butenes have an upstream isomerization unit

(Detrick et al., 2004). i-C4i-C4 i-C8 (trimethylpentane)


182 ENCYCLOPAEDIA OF HYDROCARBONS

 ALKYLATION

in a continuous acid phase. Being that olefins are more

Table 2. Typical properties of fresh alkylation acids soluble in acid than the isoalkane, one may expect a
(Marcilly, 2003) high conversion to polymers; this, however, is not in
agreement with industrial practice. An explanation
PROPERTY HF H2SO4 could be that the carbocations formed by the
interaction of the acid with the olefin, which initiate
Molecular weight 20.01 98.08
the reaction chain, are found to a larger extent at the
Boiling temperature (°C) 19.4 290
interface between the two phases, with the carbonium
Melting temperature (°C) 82.8 10.4
ions oriented towards the hydrocarbon phase (Raseev,
Specific weight (d415) 0.99 1.84
2003). The isoalkane in the hydrocarbon phase can
Viscosity (cP) 0.256 (0°C) 33 (15°C)
then interact with the carbonium ion. This opinion is
Hammett acidity (Ho)* 10 11.1
not unanimous, but it allows the alkylation reaction to
* Acidity of the industrial acids during operation. be treated as a homogeneous process where the
reaction rate is proportional to the interfacial area. The
The overall reaction is: rate will then increase with the degree of dispersion
and, therefore, with the decrease in size of the
C3H6  2 i-C4H10 C3H8  hydrocarbon droplets. This is confirmed
propylene isobutane 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
CH3 CH3
mixing and the proper operating conditions, alkylation
 CH3 CH CH2 C CH3 occurs almost instantaneously.
CH3
propane trimethylpentane
4.3.4 Catalysts and reaction
conditions
The octane number of trimethylpentane is sensibly
higher than that of dimethylpentane normally obtained Strong acids: HF and H2SO4
from propylene. However, in this reaction two In order to favour the thermodynamics and to
molecules of isobutane are required to produce only minimize the formation of by-products, the alkylation
one molecule of alkylate. reaction is carried out at the lowest possible
A number of other side reactions may be involved temperature. This is kinetically possible by using large
in the process; the most common include the amounts of strong acid catalysts; the world market has
polymerization and cracking. The polymerization of long been split between H2SO4 and HF (see again Table
olefins results in the production of low-octane, high 2). The acid strength of the two compounds is similar
boiling point components, which are undesirable. This when they carry traces of impurities (Marcilly, 2003).
reaction is minimized by using high isobutane/olefin The catalysts must be used almost pure, since the
ratios and choosing proper reaction conditions. alkylation reaction requires a strong acidity in order to
The heavier polymerization products are known as attain kinetics that are economically acceptable.
Acid Soluble Oils (ASOs) or ‘red oils’ and tend to In general, the HF alkylate has a higher octane
deactivate the catalyst. ASOs are unsaturated number due to the hydrogen transfer reactions;
compounds with more than about 10 carbon atoms per however, the process economics should be analyzed
molecule that can react with H2SO4. while keeping in mind the higher isobutane
Alkylation reactions are higly exothermic (on consumption and the lower catalyst consumption when
average 75-96 kJ/mol); the reaction equilibrium is, using HF. During operation, the acid is contaminated
therefore, shifted to the alkylate formation at low by water and soluble organic matter, which decrease
temperature and high pressure. Moreover, lower the total acidity; in such conditions, the isobutane
temperatures minimize the formation of by-products solubility is higher (e.g. 0.4% by weight in H2SO4 and
due to polymerization and cracking reactions. 3.6% by weight in HF; Marcilly, 2003).
The process temperature depends on the acid type.
The oxidizing properties of H2SO4 suggest a
4.3.3 Process kinetics temperature generally less than 12°C. However, the
acid viscosity increases rapidly by lowering the
The traditional alkylation reaction takes place in a temperature, which restricts the useful temperature
medium in which the hydrocarbon drops are dispersed range between about 2-12°C (5°C being a good

VOLUME II / REFINING AND PETROCHEMICALS 183

PROCESSES TO IMPROVE THE QUALITIES OF DISTILLATES

compromise). HF is not an oxidant and thus the useful yield and quality (Joly, 2001). As already mentioned,
temperature can be in the range of 20-50°C (normally the impurities of the feed greatly affect yield, alkylate
between 30-40°C), which simplifies the reactor formation and acid composition, especially in the case
cooling systems. of H2SO4 catalyst. For HF acid catalyst, consumption
The reaction pressure is fixed at a level capable of is normally less than 1 kg/t since the catalyst is
keeping the reaction media in the liquid phase. In both regenerated by simple distillation.
cases, an excess of isobutane must be used to avoid
olefin polymerization; the excess isobutane is recycled Mitigation of the risk due to acid use: solid catalysts
to the reactor after separation of the alkylate product. Although extensive experience shows that
The reaction medium is composed of two phases: alkylation plants, regardless of acid catalyst choice,
the acid phase (continuous phase) and the hydrocarbon can be operated safely and with low process risks; the
phase (dispersed phase). The reacting hydrocarbons are process acid catalysts have been subject to critical
those solubilized into the acid phase. The acid’s physical attention in the last decades.
characteristics at the process temperature impose a Hydrofluoric acid is very volatile (boiling point:
much more effective stirring in the case of H2SO4. In 19.5°C) and produces dangerous mists in the event of
fact, one of the key differences between HF and H2SO4 an accidental release. Refiners with sulphuric acid
alkylation is the handling of the acid catalyst. alkylation units must ship large quantities of spent
The catalyst activity decreases with time due to acid offsite for regeneration, thus creating potential
dilution, ASO formation and impurity build-up. transportation hazards. Both concentrated acids are
The HF acid can be fractionated to remove water contained in carbon steel and become very corrosive
and ASO. H2SO4 must be removed from the unit when diluted with water.
and regenerated by completely decomposing the The refining industry has developed a number
acid to SO2-SO3 and condensing them back to of mitigation strategies to face these problems:
H2SO4. This regeneration process can be done at water curtain systems, rapid acid dump methods,
the site or, usually, outside of the refinery in remotely operated isolation systems, etc. At the
remote locations. For the above-mentioned same time, catalyst producers and process
reasons, the H2SO4 consumption is normally much licensors have developed, and in some cases
higher than HF consumption, in spite of the fact commercialized, solid-phase acid catalysts.
that HF can form an azeotrope with water Several pilot-size units are operating and a
(the so-called CBM, Constant Boiling Mixture), number of processes have been presented
responsible for acid losses. (Refining processes, 2002, 2004; Meyers, 2004;
Tables 3 and 4 illustrate the influence that both the D’Amico et al., 2006). Solid acid catalysts have
type of acid catalyst and the olefin bear on alkylate long been investigated; these include exchanged

Table 3. Yield and octane number of the product from H2SO4 alkylation process

Type of feed Propylene Butenes Amylenes

Yield (vol C5/vol olefin) 1.45-1.78 1.74 1.57

i-C4 consumption (vol/vol olefins) 1.27-1.32 1.14 1
Catalyst consumption (kg/t C5) 137-171 51-102 102-171
MON 88-90 92-94 88-90
RON 89-92 94-98 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 C
5

Yield (vol C5/vol olefin) 1.76 1.73 1.77 1.78 1.79 1.63
i-C4 consumption (vol/vol olefins) 1.36 1.1 1.14 1.28 1.28 1
MON 92 94.4 97.8 95.9 93.7 91.5
RON 90 91.6 94.6 93.4 90.8 90

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

184 ENCYCLOPAEDIA OF HYDROCARBONS

 ALKYLATION

zeolites, ion-exchange resins such as Amberlyst, to the reactor. There are currently two major
perfluoropolymers with sulphonic acid groups alkylation processes using H2SO4 as catalyst: Stratco
along its backbone (Nafion), superacid solids effluent refrigeration alkylation, and ExxonMobil
(chlorinated alumina, sulphated zirconia) and cascade autorefrigeration process; each uses different
liquid superacids immobilized on solids. approaches for the design of the reaction and
Examples of solid catalysts promoted by strong refrigeration sections.
acids are: alumina (or zeolites)/BF3,
silica/CF3SO3H, silica/SbF5. Most catalysts are Stratco process
proprietary and little information is normally given The Stratco reactor is a horizontal pressure vessel
regarding their composition. Solid catalysts can containing an inner tube bundle, which acts as an
improve safety and production costs, but tend to exchanger to remove the heat of reaction, and a mixing
deactivate rapidly under alkylation conditions due to impeller (Fig. 1). It operates at a pressure of about 3.5
build up of coke and heavy compounds on the to 5.0 bar, sufficient to keep the two phases in the
catalyst surface. Burning off the heavy hydrocarbons liquid state. The acid and hydrocarbon feed come into
through high-temperature oxidation quickly destroys contact and are vigorously stirred by the impeller
the catalyst activity. blades. An emulsion is formed and the reaction takes
To solve the deactivation problem, some place almost instantly; the contact time is very short
companies have developed new reactor types and new and the side reactions are kept to a minimum. The high
generation systems based on the desorption of the recycle rate of the emulsion allows an efficient control
heavy hydrocarbons with the use of a hydrogen stream of the reaction temperature.
(Roeseler, 2004). Another approach proposes the use The general scheme of the process is shown in
of supercritical fluids as the reaction media; as an Fig. 2. The dehydrated olefin feed is mixed with the
example, supercritical CO2 was found to be good at recycle isobutane and cooled in the feed/effluent
dissolving the heavy coke material on the catalysts exchangers; water is removed in the coalescer before
surface (Subramaniam, 2001). entering the reactor. A portion of the emulsion in the
Some companies have proposed special additives contactor reactor is withdrawn from the discharge
that reduce the tendency of HF to form mists. On-site side of the impeller and sent to the acid settler,
sulphuric acid regeneration is available to eliminate which separates the reacted hydrocarbon phase from
the shipment of spent and regenerate acid; although the acid emulsion. The settled acid is returned to the
this technology has been available for half a century, suction side of the impeller. Acid is purged from the
only few refineries operate on-site regeneration. 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
4.3.5 Sulphuric acid alkylation and the isobutene, is sent to the tube bundle in the
processes reactor by reducing the pressure to about 0.4-0.6 bar,
across a back pressure control valve. At this
Sulphuric acid alkylation was the first to be pressure, the lighter components of the effluent
developed, during the decade preceding the Second stream are vaporized, reducing the temperature to
World War. Essentially, the H2SO4 processes consist below 0°C. Additional vaporization occurs in the
in a reaction section where an emulsion of tube bundle as the net effluent stream removes the
hydrocarbons and acid is formed (and the reaction heat of reaction (Graves, 2004). The stream from the
occurs), and in a settling section that separates and tube bundle is sent to the suction trap/flash drum to
recycles the acid. A fractionation section separates the separate the vapour and liquid phase. The liquid
alkylate from the excess isobutane, which is recycled isobutene from the flash drum-side is directly

Fig. 1. Stratco-type
to settler pressure acid hydrocarbon
alkylation reactor.
coolant relief 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
fresh acid
alkylate
isobutane feed spent acid product

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

recycled to the reactor, while the liquid from the zone at the end. A flow scheme of the process is shown
suction trap-side is transferred to the effluent in Fig. 3 (Lerner and Citarella, 1991).
fractionation section after caustic washing or Olefin feed is mixed with recycle isobutane from
passing over a bauxite bed for the elimination of the deisobutanizer, cooled and fed to the reactor. Water
sulphates. Isobutane is recycled back to the reactor condensed at a lower temperature is removed in the
section. The vapour phase from the flash drum is coalescer. The vapours leaving the reactor are routed
compressed, cooled and condensed. Propane is to the refrigerator section where they are compressed,
eliminated in the depropanizer, whose bottoms are condensed and sent to the economizer (an intermediate
recycled to the reactor. pressure flash drum), which reduces the power
requirements of the refrigeration compressor. A
ExxonMobil process slipstream of refrigerant (isobutane) is depropanized
The ExxonMobil cascade process uses the auto- after being caustic and water washed. Propane is
refrigeration system to remove the heat of reaction and separated overhead, while isobutane-rich bottoms are
to maintain the low reaction temperature (4-5°C) returned to the process.
needed for alkylation. The reactor is a horizontal vessel The reactor liquid product is sent to the settler,
containing a number of compartments with mixers in from where the settled acid is recycled back to the
each stage to emulsify the hydrocarbon-acid mixture. reactor. The hydrocarbon portion (containing alkylate,
The reaction is held at low pressure and the heat of excess isobutane and n-butane) is caustic and water
reaction is eliminated by evaporating an isobutane washed to remove any acid components, and is sent to
stream directly fed into one end of the reactor. The acid the deisobutanizer. Overhead from the tower is an
is fed on the same end and moves together with the isobutane-rich stream, which is recycled to the reactor,
isobutane by overflowing from one compartment to the while the bottoms are sent to the debutanizer for the
other. The olefin feed is split and added into each separation of the alkylate product from butane.
compartment. It is not necessary to maintain a high Feed impurities and small amounts of polymerized
pressure in the reactor to prevent vaporization of light olefins that form ASO tend to accumulate in the
hydrocarbons: the pressure varies from about 1.5 bar in recycle acid. Therefore, a spent acid purge is taken
the first stage (richer in isobutane) to about 0.5 bar in from the process to remove these oils and fresh make-
the last stage. Usually, the reactor contains a settling up acid is added to maintain sufficient acid strength.

186 ENCYCLOPAEDIA OF HYDROCARBONS

 ALKYLATION

compressor

water propane

depropanizer
washing
washing
KO drum

caustic

water
economizer

fresh
caustic spent waste
caustic water

deisobutanizer
recycle refrigerant butane
i-C4

debutanizer
waste
coalescer

water washing

washing
caustic

water
reactor
M M M M
settler

olefin feed plus

isobutane recycle
fresh waste
recycle acid caustic water alkylate

make-up spent olefin spent water make-up

acid acid feed caustic isobutane

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

4.3.6 Fluoridic acid alkylation inject the hydrocarbon feed into the acid phase to
processes obtain a good emulsion. Therefore, the HF units
do not have mechanical stirring devices. Water
In 1994, there were 127 HF units and 92 H2SO4 can be used to cool the reactor, given the higher
units in the world refineries (Joly, 2001). In the reaction temperatures. The Conoco-Phillips and
Refining processes handbook (Refining processes, UOP (Universal Oil Products) technologies
2004), the declared licences for the HF units were shared the market at the beginning of the third
160, which almost doubled the declared H2SO4 millennium.
licences. Of course not all the licensed plants
were still working, but the data provide a rough The Conoco-Phillips process
idea of the diffusion of the processes. At normal The original Phillips process is characterized by its
design conditions, an HF alkylation unit requires very simple reactor, similar to that shown in Fig. 4
a higher ratio of isobutane to olefin (I/O) than a (Gary and Handwerk, 1975). Essentially, it is
H2SO4 unit. Both processes fractionate the composed of an acid cooler, a riser reactor and a
isobutane from the reactor effluent stream and settler. Acid circulation is by gravity differential and
recycle it back to the reactor. Due to its higher I/O an acid circulation pump is not necessary. The
ratio, an HF alkylation unit is designed with a residence time in the tubular reactor is in the order of
larger fractionation section. The low HF viscosity half a minute.
and better solubility of isobutane in the acid allow A basic flow scheme of the Phillips process is
simpler reactors to be used: it is sufficient to illustrated in Fig. 5. The more recent version converts

VOLUME II / REFINING AND PETROCHEMICALS 187

PROCESSES TO IMPROVE THE QUALITIES OF DISTILLATES

hydrocarbon product 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.
settler The hydrocarbon phase removed from the top of
the acid settler is a mixture of propane, isobutane,
riser normal butane, and alkylate, along with small amounts
reactor
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
acid  hydrocarbons (20-27°C)

quantities of hydrofluoric acid. The design of the acid

settler-cooler-reactor section is critical to good
acid
conversion in a hydrofluoric acid alkylation unit.

The UOP process

In the UOP HF-alkylation process, a pump
acid provides the inlet pressure into the reactor nozzles,
accumulator
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
hydrocarbon of cooling water. A simplified flow scheme of a
feed typical C4 HF alkylation unit is shown in Fig. 6.
Similar schemes are available for the C3-C4 alkylation
acid cooling units (Detrick et al., 2004).
cooler water
The combined feed enters the shell of the
Fig. 4. Simplified scheme of the Phillips HF reactor. reactor-heat exchanger through several nozzles,
which maintain an even temperature in the reactor.
The effluent from the reactor flows to the settler and
propylene, amylene, butenes and isobutane to motor the acid is recycled to the reactor. The hydrocarbon
fuel using ReVAP (Reduced Volatility Alkylation phase (containing dissolved HF acid) is charged to
Process) alkylation. the iso-stripper. The alkylate and n-butane are
Both the olefin and isobutane feeds are dehydrated recovered from the bottom and as a side stream,
by passing them through a solid bed desiccant. Good respectively. Isobutane is also dotained as a side-cut
dehydration is essential to minimize potential and recycled to the reactor. The overhead, mainly
corrosion of process equipment, which results from consisting of isobutane, propane and acid, is in part
addition of water to hydrofluoric acid. The olefin and charged to the HF stripper. An HF alkylation unit
isobutane feeds are then mixed with hydrofluoric acid fed with C3-C4 olefins is normally equipped with a
at a sufficient pressure to maintain all components in depropanizer, which may be also required with C4
the liquid phase. The reaction mixture is allowed to olefins, if the propane quantity is too high. A small
settle into two liquid phases. The acid is withdrawn slipstream of circulating HF acid is regenerated
from the bottom of the settler and passed through a internally, to keep the purity at the requested level.
cooler to remove the reaction heat; it is then recycled The internal acid regeneration technique has
and mixed with fresh feed. virtually eliminated the need for an acid
A slipstream of acid is withdrawn from the settler regeneration (Detrick et al., 2004). All effluent
and fed by a pump to the acid rerun column to remove streams and process vents, sewer effluents and acid
dissolved water and polymerized hydrocarbons. The regeneration bottoms are treated either with KOH or
overhead product from the rerun column is mostly alumina. The KOH is regenerated on a periodic basis
hydrofluoric acid, which is condensed and returned to by using lime.

188 ENCYCLOPAEDIA OF HYDROCARBONS

 ALKYLATION

acid from
depropanizer section
reactor settler

acid
main recontactor
recycle acid fractionator

acid standpipe
acid acid
reactor make-up tank acid eductor
riser cooling acid
water rerun depropanizer feed
column
acid
cooler steam
mixer
nozzle stripping
i-C 4
ASO

recycle isobutane
steam
butane to
KOH treater
olefin
feed
isobutane from total alkylate to storage
isobutane depropanizer section

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

Risk mitigation in the HF alkylation plants hydrocarbons and solid catalyst, with in situ
In order to reduce aerosol formation in the event of regeneration capability. The liquid-phase operation
an HF release, UOP proposes the Alkad process, to be minimizes abrasion problems. A novel catalyst (HAL-
used with HF alkylation technology. The Alkad 100) was developed with declared good performance
process is a passive mitigation system that will reduce and long stability; it is easily regenerated without a high
aerosol from any leak occurring in the unit. The temperature carbon burn. A simplified flow diagram of
alkylation reactions take place in the presence of a the process is shown in Fig. 7 (Roeseler, 2004).
liquid additive, which form a long chain of associated Reactants and catalyst flow up the reactor riser at a rate
HF molecules; in this form, HF acid loses its tendency of about one foot per second as the reaction occurs. The
to form aerosols when released to the atmosphere. 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
4.3.7 Processes with solid acid and it is contacted with a recycle of cold isobutane
catalysts saturated with hydrogen. Heavy hydrocarbons are
hydrogenated and desorbed from the catalyst. The
Since the 1990s, a number of companies have reactivated catalyst flows down and back into the riser
proposed alkylation processes based on solid catalysts, bottom. A catalyst slipstream is reactivated at a higher
both using fixed-bed or riser reactors. At the moment, temperature in a separate vessel to completely remove
most solid catalyst processes are at the pilot stage and the small quantities of the residual heavy hydrocarbons.
very few commercial units are installed. 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 Other processes
the late 1990s, based on a liquid transport reactor (riser The Topsoe process employs a catalyst system
reactor) to promote fast and good contact between of the supported liquid phase type. The superacid

VOLUME II / REFINING AND PETROCHEMICALS 189

PROCESSES TO IMPROVE THE QUALITIES OF DISTILLATES

HF stripper
isostripper
i-C4 recycle

acid

alumina
recycle

treater
cooling
settler

water

regenerator
acid
olefin
reactor

feed
KOH
treater
KOH KOH
i-C4 treater treater
make-up
ASO and CBM
to neutralization 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 or require post treatment of the reactor effluent or
enables the use of simple fixed-bed reactors. final product.
However, through proper operation of the reactor
system, the liquid nature of the catalyst can be used
to achieve simple maintenance of catalytic activity. 4.3.8 Hazards and corrosion
The AlkyClean process is licensed by ABB Global, problems
Akzo Nobel and Fortum Oil and Gas, and uses a
solid acid catalyst. The reactors are undergoing a Among refinery processes, alkylation plants are
mild liquid-phase regeneration using isobutane and somewhat unique because they use strong
hydrogen. The process does not produce any ASO aggressive acids and contain large volumes of
LPG. A key element of hazard management is
products directed at preventing the release in the first place.
light
Alkylene
ends Extensive experience demonstrates that alkylation
reactor units can be operated safely, and with minimum
LPG process risk to employees or neighbouring
communities (Scott, 1992). The plants are
i-C4/H2 constructed according to standards and with
materials that are specifically designed to make the
catalyst plant as safe as possible.
reactivation alkylate
zone In case of liquid exposure, both acids will
cause serious burns. HF also has the property of
H2
olefin penetrating the tissues and reacting with the
feed calcium and magnesium in the body. In the
hot presence of water, HF forms an azeotrope that
reactivation
vessel contains 36% HF and boils at 109°C. HF is
volatile, and when spilled it forms stable aerosol
clouds. Vapour and aerosol cause serious
isobutane recycle inhalation hazards (lung damage). Both
concentrated acids can be contained in carbon
Fig. 7. Simplified flow diagram of the Alkylene process. steel, but they become very corrosive when diluted

190 ENCYCLOPAEDIA OF HYDROCARBONS

 ALKYLATION

with water. The aggressiveness of both acids varies Quality of the feed
with its concentration, temperature, nature of Impurities increase catalyst consumption. The
contaminants and velocity relative to exposed hydrocarbon feed should be dried and desulphurized,
surfaces. In H2SO4 alkylation, the hydrocarbons especially in HF units. Diolefins cause heavy losses of
are emulsified in concentrate acid and reacted at sulphuric acid.
low temperatures; the acid remains fairly The olefin type in the feed, particularly the ratio of
concentrated, diluting to about 88%. Stainless steel butylene to propylene, affects the product quality and
(304 L or 316 L) should be preferred in areas acid consumption: in propylene alkylation, the octane
where high velocity may be encountered, such as number can be five units lower and acid consumption
pumps, valves and bends (Schillmoller, 1998a). almost double (Parkash, 2003). The olefin type also
Austenitic stainless steels are resistant to influences the heat of reaction, isobutane consumption
anydrous HF, but are unreliable in dilute acid. and alkylate yield.
Alloy 400 (Monel) containing Ni and Cu and
minor amounts of Fe and Mn has been the Acid strength
standard material in alkylation plants for many Acid composition at the equilibrium is an
years and has been used for heat exchangers, important parameter that influences alkylate quality.
columns, reboilers and overhead condensers with There is a minimum acid strength required by the
acid concentrations between 85 and 95%. Alloy process, which varies depending on the acid and
400 is resistant to all concentrations of HF, olefin type and spent acid composition. At lower
including anhydrous, over a wide range of acid concentrations polymerization becomes
temperatures, in the absence of oxygen or predominant. Water lowers the acid catalytic
sulphur dioxide contamination. HF contaminated activity three to five times faster than hydrocarbon
with even small amounts of oxygen can cause diluents (Parkash, 2003). However, some water is
severe pitting and cracking of steel and Monel necessary to ionize the acid. The optimum and
(Schillmoller, 1998b). Special attention should minimum water contents for H2SO4 units are close
be given to the welding, which can be severely to 99% and 90%, respectively. In HF processes, the
corroded if not done properly. HF also attacks all best alkylate quality is produced with a water
materials containing silica (glass, china, etc.), content of about 2.8% (Joly, 2001). The impurities
asbestos and many plastics, except teflon. In present in the feed can be absorbed or react with the
addition to the usual refinery safety procedures, catalyst, causing a decrease in strength and the need
the operators of the ‘acid area’ in the alkylation to increase the acid make-up.
units must follow special ad hoc
procedures. Isobutane/olefin ratio
Isobutane/Olefin (I/O) ratio is the most important
operating parameter: it controls alkylate yields and
4.3.9 Process and operating quality, as well as catalyst consumption.
variables Polymerization occurs in the acid phase and is the
most important reaction competing with the alkylation
The main process variables that influence the yields reaction. During polymerization, two or more olefin
and quality of the alkylate product are: a) quality of molecules react to form a polymer, which causes lower
the feed; b) acid strength and composition; product octane and increased acid consumption. The
c) isobutene/olefin ratio; d) temperature; e) mixing solubility in the acid phase is much higher for olefins
and space velocity. than for isobutane; therefore, a large excess of the
In the case of the liquid catalysts, the properties of latter must be maintained in the reaction zone to
the two acids can explain the differences between the ensure that enough isobutane is absorbed at the acid
related processes and the operating conditions. The interface. The usual I/O ratio ranges from 5 to 8 in
higher viscosity and surface tension of sulphuric acid H2SO4 units and from 10 to 15 in HF processes.
as opposed to hydrofluoric acid make it much more
difficult to obtain a fine dispersion of the hydrocarbon Temperature
in the acid phase. The higher solubility of isobutane in The alkylation process is thermodynamically
HF acid leads to a higher ratio of isobutane to olefins favoured by low temperatures. Reaction temperature
in the acid phase (especially at the interface) with has a greater effect in H2SO4 than in HF processes.
respect to H2SO4 processes; the secondary reactions Reducing the reaction temperature minimizes the
are then reduced and the quality of the alkylate is polymerization rate relative to the alkylation rate,
improved. resulting in a higher octane number and lower acid

VOLUME II / REFINING AND PETROCHEMICALS 191

PROCESSES TO IMPROVE THE QUALITIES OF DISTILLATES

consumption. In the case of H2SO4, temperatures Joly J.F. (2001) Aliphatic alkylation, in: Leprince P. (edited
below 2-4°C are generally avoided because of the very by) Conversion processes, Paris, Technip, 257-289.
high viscosities of the acid phase. Also, very low Lerner H., Citarella V.A. (1991) Improve alkylation
temperatures slow down settling rates and favour acid efficiency, «Hydrocarbon Processing», November, 89.
carryover. The temperature in the reactor depends on Li K.W. et al. (1970) Alkylation of isobutane with light olefins
using sulfuric acid. Operating variables affecting physical
the olefin feed rate, which influences the reaction heat. phenomena only, «Industrial & Engineering Chemistry
Efficient removal of the heat from the reactor is Process Design and Development», 9, 434-440.
essential for all catalytic systems. Marcilly C. (2003) Catalyse acido-basique. Application au
raffinage et à la pétrochemie, Paris, Technip, 2 v.; v. I, 201-
Mixing and space velocity 203.
Increasing mixing produces a better and finer Meyers R.A. (editor in chief) (2004) Handbook of petroleum
dispersion of the hydrocarbon droplets in the refining processes, New York, McGraw-Hill.
emulsion, increasing the surface area, and thus the Parkash S. (2003) Refining processes handbook, Amsterdam,
Elsevier, 128-140.
kinetics and product quality.
Raseev S. (2003) Thermal and catalytic process in petroleum
In the case of liquid acid catalysts, the space refining, New York, Marcel Dekker, 556-585.
velocity can be a measure of the olefin concentration Refining processes handbook 2002 (2002) «Hydrocarbon
in the acid phase and may be defined as follows: Processing», November, 86-90.
olefin space velocity = olefin in the reactor Refining processes handbook 2004 (2004) «Hydrocarbon
Processing», CD.
(m3/h)/acid in the reactor (m3)
Ritter S.K. (2001) Alkylate rising, «Chemical and Engineering
As the olefin space velocity increases, the octane News», 11, 62-67.
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petroleum refining processes, New York, McGraw-Hill,
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Chapter 1.25.
alkylation reaction occurs almost instantaneously.
Schillmoller C.M. (1998a) Select alloys that perform
well in sulfuric acid, «Chemical Engineering Progress», 2,
38.
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192 ENCYCLOPAEDIA OF HYDROCARBONS