ALKYLATION PROCESS

Introduction
◦ The alkylation process combines light iso-paraffins, most commonly isobutane, with C3–
C4 olefins, to produce a mixture of higher molecular weight iso-paraffins (i.e., alkylate) as
a high-octane number blending component for the gasoline pool.
◦ The alkylation process was developed in the 1930s and 1940s to initially produce high-
octane aviation gasoline, but later it became important for producing motor gasoline
because the spark ignition engines have become more powerful with higher compression
ratios that require fuel with higher octane numbers.
◦ With the recent restrictions on benzene and the total aromatic hydrocarbon contents of
gasoline by environmental regulations, alkylation has gained favor as an octane number
booster over catalytic reforming.
◦ Alkylate does not contain any olefinic or aromatic hydrocarbons.
Introduction
◦ Alkylation is the process of producing gasoline range material (alkylates) from olefins
such as propylene (C=3) butylenes (C=4) amylene (C=5) and isobutane.
◦ Iso-butane and C3–C4 olefins are produced as by-products from FCC and other
catalytic and thermal conversion processes in a refinery.
Introduction
◦ Alkylation reactions without a catalyst severe conditions: T = 500 ºC and P = 20–40 Mpa
◦ Using a strong acid catalyst T < 50 ºC and P < 3 Mpa.
◦ The alkylation process consists of running the hydrocarbons in liquid form at low
temperature with a high isobutane to olefin ratio.
Introduction
◦ Alkylation reactions are catalyzed by strong acids (i.e., sulfuric acid [H2SO4] and hydrofluoric
acid [HF]) to take place more selectively at low temperatures of 70°F (21.1 °C) for H2SO4 and
100°F(37 °C) for HF.
◦ By careful selection of the operating conditions, a high proportion of products can fall in the
gasoline boiling range with motor octane numbers (MONs) of 88–94 and RONs of 94–99.
◦ Early commercial units used H2SO4, but more recently, HF alkylation has been used more
commonly in petroleum refineries.
◦ HF can be more easily regenerated than H2SO4 in the alkylation process, and HF alkylation is
less sensitive to temperature fluctuations than H2SO4 alkylation.
◦ In both processes, the volume of acid used is approximately equal to the volume of liquid
hydrocarbon feed.
◦ Important operating variables include acid strength, reaction temperature, iso-
butane/olefin ratio, olefin type, and space velocity.
◦ The reactions are run at sufficiently high pressures to keep the hydrocarbons and the acid in the
liquid phase. Good mixing of acid with hydrocarbons is essential for high conversions.
Principal alkylation
reactions
◦ Some examples of desired alkylation
reactions (combination of iso-
paraffins with olefins) to produce
alkylate are as shown in the figures.
◦ There are many undesirable reaction
also take place such as Secondary
reactions include polymerization,
isomerization, and cracking.
◦ Primary alkylation reactions
Acid catalyzed alkylation reactions
◦ These occur through ionic chain reactions initiated by donation of a proton from the
acid catalyst to an olefin to produce a carbocation that reacts with iso-butane to form a
tert-butyl cation.
◦ Subsequent propagation reactions involve the reactions of a tert-butyl cation with olefins
to form larger iso-paraffin cations that lead to final products through reactions with iso-
butane to form a new tert-butyl cation to sustain the chain reaction.
◦ The alkylation reaction is highly exothermic; therefore, cooling the reactor contents
during alkylation is important.
Alkylation
Process description
Feed Pretreatment
Typical alkylation unit location in refinery • Feeds to the alkylation unit are dried and treated
to remove impurities and contaminants such as
diolefins, oxygenates, nitrogen, and sulfur.***

Olefin-rich feeds from the FCC gas plant are typically:

I. de-ethanized,
II. treated with amine and caustic extraction (UOP
MeroxTM process)
➢ to remove H2S and mercaptans,
III. dried
IV. Selective hydrogenation process units:
➢ to saturate dienes (diolefin)
➢ reducing the amount of conjunct
polymer formed
➢ reduce acid consumption
***These contaminants cause: ➢ isomerizes the 1-butene to 2-butene.
➢ higher acid consumption, V. Add ORU (oxygenate removal units)
➢ higher acid-soluble oil formation, and ➢ to remove acetone, ethers, and alcohols.
➢ lower acid strength in liquid acid technologies
Alkylation
Process description
EFFECT OF OPERATING CONDITIONS
The process conditions that influence the quality of alkylate product and acid
consumption rate are:
olefin type
dilution ratio (iC4/iC=4)
mixing temperature
impeller speed
space velocity (or residence time)
acid strength
Olefin Type
◦ The presence of propylene or pentene with butane will lower the
octane number and increase the acid consumption.
◦ Butene in sulphuric acid as a catalyst gives the best octane numbers.
◦ The presence of propylene with butene increases acid consumption and
lowers the alkylate octane number.
◦ In the case of a C=3/iC=5 feed mixture, the trend is interesting since sulphuric
acid consumption decreases. However, the octane number also decreases.
◦ At lower acid consumption, it is better to separate the C=3/iC=5 mixture
from C=4 and let it react with iC4 in a separate reactor
Olefin Type
Isobutane concentration
◦ The iC4/C=4 (isobutane to olefin) ratio has an important role regarding the quality of alkylate produced
and the amount of sulphuric acid consumption.
◦ The iC4/C=4 ratio is kept in industrial operation between 5:1 and 15:1 as the external isobutane to
olefin (I/O) ratio.
◦ Inside a reactor with high circulation, this ratio becomes 100–1000:1.
1. High isobutane concentration ([iC4]) prevents olefin polymerization which results in
low quality alkylate and high sulphuric acid consumption.
2. Solubility of iC4 << C=4. Thus, a high concentration of iC4 is required in the mixed
hydrocarbons to compensate for its low solubility.
3. The conversion to alkylate increases as (iC4/C=4 ) is increased.
4. The rate of alkylate formation increases while the rate of formation of undesirable
heavy alkylates decreases as iC4 increases.
5. As isobutane increases, alkylate MON increases and sulphuric acid consumption
decreases.
Acid strength
◦ Acid strength is the measure of the ability of the acid to lose its H^+ ion.
◦ An optimum value of acid strength of 90 wt% H2SO4 is maintained by adding
fresh concentrated acid (98–99 wt%).
◦ As the strength of the acid decreases, the acid consumption increases with the
octane number decreases.
◦ Although water lowers the acid activity, 1–2 wt% water is added to ionize the
acid.
◦ The acid strength decreases because of the formation of gums and other
products resulting from the reaction with other impurities.
Degree of agitation
◦ When the hydrocarbons (iC4 and C=4 ) are dispersed in sulphuric acid the speed of the
impeller determines the dispersed phase size (droplet diameter) and hence, the interfacial
contact area.
◦ The reaction rate of iC4 and C=4 is quite fast, and the reaction is controlled by mass transfer
Space velocity
◦ Since the alkylation reaction is very fast, the residence time is not a limiting parameter.
◦ However, as the space velocity increases, the octane number tends to decrease while
acid consumption tends to increase.
◦ Residence time for sulphuric acid is usually from 5 to 40 min, and for hydrofluoric acid,
it is 5–25 min.
Reaction temperature
◦ The reaction thermodynamics and kinetics are favoured at low temperatures.
◦ Sulphuric acid alkylation units are operated at 5–10 ºC.
◦ Above 10 ºC, oxidation and side reactions are promoted, and the deteriorate-alkylate
yield and quality while acid consumption increases.
◦ Above 21 ºC, the polymerization of olefin will occur, and the octane number of alkylate
decrease.
◦ For HF alkylation, the reaction temperature is less significant and is between 21 and 38
ºC.
UOP HF Alkylation Process
◦ The following Figure shows a flow diagram for a UOP HF alkylation process. Olefin and iso-butane feed
streams are dried to remove water before they are mixed with the iso-butane recycle stream.
◦ The mixture is fed to the reactor, where it is highly dispersed into an incoming stream of acid catalyst.
◦ Conversion of reactants to high-quality alkylate takes place quickly, and the mixture flows up to the settling
zone.
◦ In the settler, the catalyst is separated out as a bottom phase and flows, by gravity, through the catalyst
cooler and returns to the reactor.
◦ The hydrocarbon phase from the settler, which contains propane, recycled iso-butane, normal butane, and
alkylate, is charged to the main fractionator.
◦ High-purity propane is sent overhead to pass through the HF- propane stripper, de-fluorinator, and
potassium hydroxide (KOH) treater before it is recovered.
◦ Recycled iso-butane is drawn from the side of the fractionator and returned to the entrance of the reactor
after it is mixed with the dried olefin and isobutane feed.
◦ The n-butane product is taken from the side of the fractionators condensed and KOH- treated before
recovery.
◦ The alkylate product is obtained from the bottom of the fractionator. The HF catalyst is regenerated onsite
in the regeneration section, where heavy oils (tars) are removed from the catalyst.
 Alkylation
Process description HF Alkylation
UOP AlkyPlusTM process for propylene and butene alkylation
Reaction after feed pretreatment
5
The alkylation reaction is very fast with
100 % olefin conversion.
3
1- molar ratio of isobutane/olefin = 6:1-14:1
1
2. Cooling water flows through the reactor tubes
➢ To ,maintain reactor temp.: (80-100ºF) 2
3. Reactor effluent: “the excess isobutane,
alkylate product, nonreactive hydrocarbons 4
(propane, n-butane), and the acid catalyst”
➢ pass to the settler vessel.

4. The dense acid phase separates from the

hydrocarbons rapidly by gravity

5. The hydrocarbons containing dissolved HF

flow
➢ to the isostripper
 Alkylation
Process description HF Alkylation
Fractionation UOP AlkyPlusTM process for propylene and butene alkylation
3
Consists of an isostripper (main fractionator), a
depropanizer, and an HF stripper (8). 5
➢ generates a very large isobutane recycle
stream (6), and
➢ produces n-butane (9) and
➢ alkylate product streams (10).
1
7. Overhead vapor: propane-enriched
7
isobutane stream that contains HF,

isobutane
2
➢ stream is condensed and separated in a
settling drum.
a. The heavier HF phase is returned to the 4
reactor section.
b. The hydrocarbon phase is charged to the 6
9
depropanizer.
• The depropanizer bottom stream is returned
to the reactors as part of the recycle 8
isobutane.
• The depropanizer overhead contains n-butane
propane product and vaporized HF. 10
cooled in exchangers and sent
to product storage.
 Alkylation
Process description HF Alkylation
Fractionation UOP AlkyPlusTM process for propylene and butene alkylation
3
• The depropanizer overhead vapor is
condensed and the two liquid phases are 5
separated in the overhead receiver.
• The heavier acid phase is returned to the
reactor section, and the acid-saturated
hydrocarbon phase is fed to the HF stripper
(8) column 1
➢ HF is stripped overhead and joins the 7

isobutane
depropanizer overhead vapor where the 2
HF can be recovered.
4
11. The HF stripper bottoms is an acid-free
propane product
6
➢ is treated with hot alumina 9
➢ to remove organic fluorides,
➢ cooled, and treated over a bed of
granular KOH
8
➢ to remove traces of HF and water.
11
n-butane
10
 Alkylation
Process description HF Alkylation
Process Variables in HF Alkylation
Reaction
Reaction temperature:
temperature:
• Almost all HF alkylation reactors are operated below 110ºF.
➢ At higher temperatures, a decrease in alkylate ON will occur and increases RVP and acid
consumption

➢ Above 120ºF polymerization and cracking side reactions become excessive,

➢ reducing alkylate quality, and
➢ acid regeneration capacity of the HF alkylation unit would not be able to maintain proper control
of the acid strength.

Isobutane to olefin ratio:

Isobutane to olefin ratio:
➢ As the isobutane to olefin ratio is increased,
➢ increase primary alkylation reactions and hydride transfer reactions
➢ while reducing polymer formation, cracking, and competitive reactions,
➢ resulting in increased yield and octane and reduced acid consumption.
 Alkylation
Process description HF Alkylation
Process Variables in HF Alkylation
Pressure:
• does not have an effect on the process
• it is kept high enough to prevent the vaporization of hydrocarbon and acid in the reactor section.
Acid strength:

• kept between 85 and 95 mass% HF.

➢ The fresh acid is supplied by acid manufacturers at 99.97+ wt% HF.

➢ The water content of the acid is typically controlled between 0.5 and 1.5 wt%.
➢ Water levels below 0.5 wt% cause a reduction in octane.
➢ Water levels above 1.5 % lead to higher corrosion rates.

Acid-to-hydrocarbon volume ratio:

• Generally, 1:1 or higher.

➢ At some point, below 0.8:1.0, excess polymerization occurs.
➢ alkylate production could stop.
◦ The hydrofluoric acid processes have no mechanical stirring as in
the sulphuric acid processes.
◦ The low viscosity of HF and the high solubility of isobutane in the
acid allow for a simpler design.
◦ The emulsion is obtained by injecting the hydrocarbon feed into
the continuous HF phase through nozzles at the bottom of a
tubular reactor.
◦ Reaction temperature is about 20-30 ºC, allowing for the use of
water as a coolant to the reactor.
◦ The major licensor of the HF alkylation processes is UOP, whereas
ExxonMobil and Stratford Engineering Corporation license H2SO4
alkylation processes.
◦ In Sulphuric Acid Alkylation Process, reactor cooling done by
either the auto-refrigeration process (Exxon) the evaporation of
iC4 and C=4 induces cooling of the emulsion in the reactor, or by
the effluent refrigeration process (Stratford) a refrigeration unit
provides cooling to the reactor.
◦ Transporting and working with concentrated acids pose
safety risks.
◦ In particular, HF tends to form a vapor cloud that is difficult
to disperse.
◦ HF is a very hazardous material for humans because it can
penetrate and damage tissue and bone.
◦ A newly designed alkylation process by UOP uses a solid
catalyst.
◦ Advantages of this new process over traditional HF
alkylation processes (liquid acid technology) include no acid
transportation, no acid spills, no corrosion, and reduced
maintenance cost.
◦ Efforts to develop alternative processes that use solid acid
catalysts instead of concentrated HF and H2SO4 for
alkylation are underway.
◦ Solid Catalyst such as: metal halides, chlorided alumina;
boron trifluoride supported on silica, beta zeolite, triflic acid
supported on silica.
SOLID CATALYST ALKYLATION
◦ The overall process scheme is similar to the liquid acid base process scheme,
except for the regeneration section, which is necessary for solid acid catalysts
because of rapid deactivation.
 Alkylation
Recent Developments
Solid Catalyst Alkylation (SCA) - UOP AlkyleneTM process
• UOP developed the Alkylene process during the late 1990s.
• UOP catalyst: HAL-100
➢ has high alkylation activity and long catalyst stability and easily regenerates without a high temperature carbon burn.
➢ Selectivity of the HAL-100 is excellent, and product quality is comparable to that of the product obtained from liquid
acid technologies.

➢ In the UOP AlkyleneTM process:

❑ The catalyst is fluidized and moves through a riser reactor.
❑ The catalyst is then separated from the product at the top
of the reactor
❑ The catalyst is reactivated by a simple hydrogenation
of the heavier alkylate on the catalyst
➢ The reactivation process is highly effective, restoring
the activity of the catalyst to nearly 100% of fresh.
❑ Alkylate from the reactor is sent to a fractionation section,
which is similar to fractionation sections in liquid acid
process flow schemes.
UOP AlkyleneTM process