Alkylation Process

PGS.TS. Trương Hữu Trì

 CONTENTS

1 Objectives, feedstocks and products

2 Reactions, Mechanisms

3 Catalysts

4 Operating conditions

5 Process technology

6 Future trends
2
 Alkylation process
Location of Alkylation units in an oil refinery

NSRP
 Process objective

 Alkylation is the transfer of alkyl group from one molecule to another.

 The addition of an alkyl group to any compound is an alkylation
reaction but in petroleum refining terminology the term alkylation is
used for the reaction of low molecular weight olefins with an isoparaffin
to form higher molecular weight isoparaffins.
 In oil refineries, alkylation process refers to a particular alkylation of iso
butane with olefins it is a major aspect of up grating of petroleum.
 To combine light olefins (propylene and butylene) with isobutane to
form a high octane gasoline (alkylate).
 Process objective

 The Akylation Unit designed to maximize the production of high octane

alkylate suitable for gasoline blending and to recover unreacted butanes
for blending into LPG;
 Alkylation occurs in the presence of a highly acidic catalyst
(hydroflouric acid or sulfuric acid);
 Depending on the acid used as catalyst the unit takes the name of SAAU
(Sulphuric Acid Alkylation Unit) or HFAU (Hydrofluoric Acid
Alkylation Unit).
 Role of the process in gasoline production
 The growing demand for higher quality gasoline has also brought new
constraints on fuel lead content.
 Recently, the United States has decided to prohibit lead entirely and
with the Clean Air Act. to limit the concentration in gasoline of certain
other components considered to be toxic.
 Gasoline reformulation is necessary and the requirements to be met are
essentially as follows:
• total elimination of lead;
• reduction in the benzene content: less than 1%vol;
• reduction in the aromatics content: 25%vol maximum;
• maximum olefin content: close to 10% vol;
• oxygen content: greater than 2% wt;
• vapor pressure: ranging from 0.46 to 0.56 bar
Role of the process in gasoline production

Properties of the main motor fuel components

 Role of the process in gasoline production
 Gasoline pool composition of a typical refinery (United States)
 Role of the process in gasoline production
 Average gasoline pool composition (Western Europe).
 Feedstock

 Olefins (ranging from C4-C5) and isobutane;

 Olefins feed originates from FCC unit;
 Isobutane feed obtains from Isomerization process.
 Feed composition varies depending on the refinery.
 The refiner may have to process basically three types of olefinic
feeds:
• C4 Cuts
• C3 + C4 Cuts
• C4 Cuts Containing C5
 Feedstock
C4 Cuts
The typical
composition of
a C4 cut from
FCC

Representative
composition of
an olefinic C4
cut coming from
FCC and having
been used in an
MTBE
production unit
 Feedstock

C3 + C4 Cuts
A large number of HF alkylation units convert feeds containing
butenes and propylene

Composition of an olefinic C3, C4 cut coming from FCC

and used as feed in an HF alkylation unit
 Feedstock
C4 Cuts Containing C5
 Reformulation may induce refiners to eliminate certain low-
molecular-weight compounds from motor fuels, particularly C5
oletins (amylenes). The compounds then become available for use as
alkylation feeds and allow a vapor pressure gain in comparison with
the initial olefins.
 A representative composition of a C5 cut from FCC that can be used
in alkylation after mixing with the C4 cut.
 In comparison with the C4 cut from FCC, the diolefin content of the
C5 cut is much higher: 1%wt instead of 0.3%. The amylene content in
alkylation feeds generally ranges between 5 and 15%wt.
 Feedstock

C4 Cuts
Containing C5

Composition of a typical C5 cut from FCC

Feedstock
 Feedstock
Feed pretreatment
• The principal effect of the impurities in alkylation unit feeds is
increased catalyst consumption.
• To a lesser extent, alkylate octane number also drops and its end point
rises

Effect on acid consumption of the type of impurities in sulfuric

acid alkylation unit feeds
 Feedstock
Effect of diolefins
 The diolefins in the C4 cut cause a loss of sulfuric acid equal to
around 10 times their weight.
 Selective hydrogenation is of only little economic interest for sulfuric
acid alkylation. However, it is more attractive for HF alkylation if it is
carried out in conditions where there are both hydrogenation of
butadiene and double bond shirt by position isomerization (butene-l
to butene-2) simultaneously.
 It has been shown that the alkylate end point (C4 cut from FCC) is
lowered from 200 to 175oC approximately.
 Additionally, there is also a very signiflcant octane number gain: the
RON goes from 93 to 96 and the MON from 91.5to 93,5.
 Feedstock
Effect of water
 Generally speaking, H2SO4 alkylation unit feeds are not dried.
 Acid and caustic treatment of the hydrocarbon phase before the
fractionation section means that an isobutane fraction saturated in
water coming from the top of the main fractionation column is
recycled to the reactor.
 HF unit feeds are dried and the residual water content is then very
low (less than 20ppm).
 Feedstock
Effect of oxygenated compounds (Alcohools, Ethers)

 The presence of oxygenated compounds in alkylation feeds is

the consequence of ether production upstream of the alkylation
unit.
 Their effect on acid consumption is still in adequately
understood.
 Products

 The product streams leaving an alkylation unit are:

 LPG grade propane liquid;
 Normal butane liquid;
 C5+ alkylate;
 Tar.
 Products

 The primary products of the isobutane alkylation reaction by olefins

 Products

Composition of
industrial
alkylates
resulting from
isobutane
alkylation by
olefinic C4 cuts
in the presence
of H2S04 and
HF catalysts
 Products

Composition of
industrial
alkylates
resulting from
isobutane
alkylation by
olefinic C4 cuts
in the presence
of H2S04 and
HF catalysts
(cont.)
 CONTENTS

1 Objectives, Feedstocks and Products

2 Reactions, Mechanisms

3 Catalysts

4 Operating Conditions

5 Process technology

6 Future Trends
24
 Reactions

Primary
alkylation
reactions:
The principal
reactions are
the combination
of olefins with
isoparaffins
 Reactions

Primary
alkylation
reactions:
The principal
reactions are
the combination
of olefins with
isoparaffins
 Reactions

Complex
alkylation
reactions
 Reactions

Complex
alkylation
reactions
 Mechanisms

 The complete process by which isobutane reacts with an olefin

is extremely complex due to the large number or possible side
reactions.
 The mechanism of isobutane alkylation by an olefin in the
presence of HF and H2SO4 catalysts is of the cationic type (acid
catalysis) where the reaction intermediates are carbocations.
 This set of reactions gives rise to two families of compounds: a
complex mixture of isoparaffins called “lakylate", and polymers
soluble in the acids called "red oils".
 Mechanisms
Main Reaction
The olefin, butene-lor butene-2 for example, is protonated by an add (HF
or H2SO4 to form a secondary carbocation.
(1)
(2)

The n-C4+X- species are in equilibrium with a mixture of butene-l and

butene-2 at thermodynamic equilibrium, where butene-2 is the most
prevalent by far:
(3)
n-C4+X- can also react with isobutane, by means of a hydride (R-H)
transfer reaction to give rise to normal butane and a tertiobutyl cation:
(4)

This reaction is often called the initiation step

 Mechanisms
Main Reaction
When a high i-C4+X- concentration is reached, the butene-2 in
equilibrium with n-C4+X- (reaction 3) reacts with the i-C4+X- carbocations
to give 223 TMP
(5)

Equilibrium reaction 3 is therefore shifted to the right. If the rate of

reaction 5 is much higher than that of reactions 1 and 2, then the olefin is
directly added onto the i-C4+X- cations without the n-C4+X- intermediate.
In this case the nature of the i-C8+X- isomer produced depends on the
nature of the butene (223 TMP or 22 DMH):
(6)
(7)

When H2SO4 is the catalyst, most of the butene-l is isomerized into 2-C4=
(reaction 3) before addition onto i-C4+X-.
When HF is the catalyst, this isomerization is incomplete.
 Mechanisms
Main Reaction
Desorption of TMP+X- and DMH+X- generally follows skeletal
isomerization reactions by rearrangement of -H or -CH3 groups. The
resulting C8 cut contains the isomers: 224, 234, 233and 223 TMP and 23,
24, 25, and 34 DMH.

Desorption takes place by a hydride (R-H) transfer reaction

(8)
(9)
The i-C4+X- carbocations are therefore regenerated.

 The mechanism described here is now widely accepted for isobutane

alkylation by n-butanes.
 Alkylation by propylene, by isobutene and by amylenes is more
complex, since side reactions are at the origin of at least 30% of the
compounds present in the alkylates.
 Mechanisms
Side Reaction
These are the reactions that cause the light C5-C7 and heavy C9-C14
fractions to be produced. The main one are as follows
 Mechanisms
Red Oil Production Mechanisms
These are reactions that involve olefinic compounds where isobutane has
practically no function

Consecutive hydrogen transfer reactions lead to the formation of highly

unsaturated polymers, which are soluble in the HF and H2SO4 catalysts
and cause catalyst deactivation.
In the presence of H2SO4 acid, paraffin and olefin oxidation reactions.
also cause the production of red oils, water and SO2.
 CONTENTS

1 Objectives, Feedstocks and Products

2 Reactions, Mechanisms

3 Catalysts

4 Operating Conditions

5 Process technology

6 Future Trends
35
 Catalysts

 Isobutane alkylation by olefins can be carried out without

catalyst in severe conditions: temperature approximately 500oC
and pressures ranging from 200 to 400 bar.
 In the presence of acid catalysts, the reaction occurs at low
ternperature (lower than 50°C) and pressure (lower than 30 bar).
 Only two catalysts are used industrially in alkylate production
plants: liquid HF and H2SO4 acids.
 Concentrated sulfuric and hydrofluoric acids are the only
catalysts used commercially today for the production of high
octane alkylate gasoline.
Catalysts

Main physicochemical
characteristics of HF
and H2SO4 catalysts

 The characteristics presented in table above are valid for fresh acids (i.e. not
containing any dissolved organic species (polymers)).
 The characteristics of acids operating in alkylation units, or "equilibrium"
acids, are not very well known and can depend on the type of unit. For
example, an “equilibrium” sulfuric acid contains around 1.5to 3%wt water
and 7 to 8.5% wt organic matter ("red oils").
 Isobutane's solubility in "equilibrium" acids is much greater than its measured
solubility in fresh ones: 0.4% wt for H2SO4 and greater than 3.6%wt for HF.
 Catalysts

 The desirable reactions are the formation of C8 carbonium ions

and the subsequent formation of alkylate.
 The main undesirable reaction is polymerization of olefins.
 Only strong acids can catalyze the alkylation reaction but
weaker acids can cause polymerization to take place. Therefore,
the acid strengths must be kept above 88% by weight H2SO4 or
HF in order to prevent excessive polymerization.
 Sulfuric acid containing free SO3 also causes undesired side
reactions and concentrations greater than 99.3% H2SO4 are not
generally used.
 Catalysts
 Alkylation product properties/yields
 Catalysts
Comparison of Processes
Catalysts
 CONTENTS

1 Objectives, Feedstocks and Products

2 Reactions, Mechanisms

3 Catalysts

4 Operating Conditions

5 Process technology

6 Future Trends
42
 Operating Conditions
 Aliphatic alkylation processes are all operated in conditions
such that the feed oletins are completely converted.
 The operating parameters discussed below influence only
alkylate quality and catalyst consumption.
 There are three main operating variables that allow the
alkylation unit to be optimized in terms of product quality
(octane number) and catalyst consumption for a given feed:
• catalyst composition (water and red oil content);
• reaction temperature;
• isobutane/olefin molar ratio.
 The stirring power in H2SO4 units can also be considered as an
operating parameter. However, its effect on performance is not
very well known (very little literature available).
 Operating Conditions
Catalyst Composition
 The composition of the equilibrium catalyst in alkylation units is one
of the key parameters that governs alkylate quality.
 Sulfuric acid strength must be kept close to 90% wt, so the refiner
adds fresh acid containing 98-99.5%wt continuously (or batch-wise)
and draws off spent acid with a concentration of about 90%wt (purge).
 To limit oxidation reactions that cause formation of part of the red
oils, the fresh acid must not contain any free SO3.
 Operating Conditions
Catalyst Composition
The influence on alkylate quality of the water and red oil content of the
equilibrium sulfuric acid is known in the figure below.

Optimum
catalyst
composition
corresponds to
water content
of
approximately
1%wt and red
oil content
ranging from 4
to 8%wt.
 Operating Conditions
Catalyst Composition
 The water content of the HF catalyst is an important parameter.
 A low value, i.e, 1%wt, is favorable for isobutane alkylation by an
olefinic C3-C4 cut.
 In contrast, overly high water content, i.e. higher than 10% wt, leads
to isopropyl fluoride formation at the expense of alkylate production.
 The best alkylatequality corresponds to water content of
approximately 2.8% wt.
 Operating Conditions
Reaction Temperature
 The alkylation reaction is thermodynamically promoted at low
temperature.
 The alkylate's RON increases by one point with each 11oC drop in
reaction temperature.
 In practice, H2S04 alkylation units operate at temperatures ranging
from 0 to +10oC. Above +10oC, oxidation reactions become too
prevalent, and it is impossible to operate at less than 0oC because the
acid's viscosity becomes very high.
 Trials have been carried out with a two-stage operating protocol. In the
first step, butyl sulfates are produced and then transferred to a second
reactor containing sulfuric acid and excess isobutane.
 Controlled decomposition of the butyl sulfates then leads to alkylate
productlon.
 Operating Conditions
Reaction Temperature
The influence of reaction temperature on the RON is these
particular conditions is given in table below

Effect of reaction temperature on alkylate yield and RON.

Catalyst: H2SO4
Yield: weight of alkyfate/weight of butene converted
 Operating Conditions
Reaction Temperature
 HF units are quite different, since HF is not an oxidizer.
 The reaction temperature here ranges between +10 and +40oC.
The effect of reaction temperature on the alkylate's RON is
illustrated by figure below

HF alkylation. Influence
of reaction temperature
on RON. Feed: C4 cut
from FCC
 Operating Conditions

Reaction temperature
 Reactor temperature has a greater effect in sulfuric acid process than
using HF;

 Typical value of sulfuric acid ranges 4-13oC, HF ranges 16-52oC;

 If too low, increase acid viscosity and hinder good mixing of reactant.
If too high side reaction set in.
 Operating Conditions
Isobutane/Olefin Ratio
 That is the most important operating parameter for it controls
catalyst consumtion, reaction yield and alkylate quality.
 It is necessary to use a large amount of excess isobutane with respect
to the olefins to limit olefin polymerization side reactions which
form heavy compounds and red oils.
 The isobutane/olefin molar ratio governs the isobutane concentration
in the reactor.
 Isobutane concentration is generally expressed in term of
isobutane/olefin ratio. It varies from 5/1 – 15/1;

 The higher the ratio the better the octane number.

 Operating Conditions
Isobutane/Olefin Ratio

H2S04 alkylation.

Influence of isobutane concenmuion in the reactor on the alkylate's MON

 Operating Conditions
Isobutane/Olefin Ratio
H2S04 alkylation.

lnfluence of isobutane concemnuion in the readOron

sulfuric acid consumption
 Operating Conditions
Isobutane/Olefin Ratio
HF alkylation.

Effect of the isobutane/oletin molar ratio on alkylate MON, RON

 Operating Conditions
Isobutane/Olefin Ratio
HF alkylation.

Effect of the isobutene/ofefin molar ratio on acid consumption

Operating Conditions
Operating Conditions
 Operating Conditions
Olefin space velocity
 Olefin space velocity is defined as the volume of olefin charged per
hour divided by the volume of acid in the reactor. Typical value ranges
from 0.1 – 0.3 1/h;
 The lower the ratio the higher the octane number.
 Lowering the olefin space velocity reduces the amount of
highboiling hydrocarbons produced, increases the product octane, and
lowers acid consumption.
 Olefin space velocity is one way of expressing reaction time; another
is by using contact time. Contact time is defined as the residence time
of the fresh feed and externally recycled isobutane in the reactor.
 Contact time for hydrofluoric acid alkylation ranges from 5 to 25
minutes and for sulfuric acid alkylation from 5 to 40 minutes.
 CONTENTS

1 Objectives, Feedstocks and Products

2 Reactions, Mechanisms

3 Catalysts

4 Operating Conditions

5 Process technology

6 Future Trends
59
 Process technology
Sulfuric Acid Alkylation Processes

 The major alkylation processes using sulfuric acid as a catalyst are the
autorefrigeration process;

 The reaction is held at a pressure of approximately 10 psig (69 kPag)

in order to maintain the temperature at about 40°F (5°C);

 The gases vaporized to remove the heats of reaction and mixing

energy are compressed and liquefied;

 The acid-hydrocarbon emulsion from the last reactor stage is

separated into acid and hydrocarbon phases in a settler.
 Process technology
Sulfuric Acid Alkylation Processes
 There are two major alkylation processes using sulfuric acid as
the catalyst: the Stratco and the Exxon/Kellogg.
 The two processes have the following points in common:
• a reaction zone where an emulsion of acid and hydrocarbons is
formed and the reaction occurs;
• a settling zone for the two phases, acid and hydrocarbons, with the
acid recycled to the reactor and the hydrocarbons routed to the
separation zone;
• an isobutane/n-butane/alkylate separation zone, with the isobutane
recyeled to the reaction zone inlet.
 Process technology
Sulfuric Acid Alkylation: Stratco Process
 Process technology
Sulfuric Acid Alkylation: Stratco Process
 This process is often called "effluent refrigeration process".
 The Stratco reactor allows contact time between the feed and the
catalyst to be kept to a minimum, thereby minimizingthe extent of the
side reactions that lead to formation of red oils.
 A very high internal recycle rate of the emulsion permits proper
dilution of the olefin in the reaction volume and control of the
emulsion temperature with an accuracy of 1oC.
 The reactor is horizontal, and the two phases are stirred by a turbine.
The reaction takes place almost instantly when the two phases, acid
and hydrocarbons come into contact while passing through the turbine
blades.
 The heat of reaction is eliminated by a tube bundle inside the reactor.
 Process technology
Sulfuric Acid Alkylation: Stratco Process

Alkylation reactor developed by Stratco (sulfuricacid alkylation)

 Process technology
Sulfuric Acid Alkylation: Stratco Process

Contactor reactor and acid settler arragement

 Process technology
Sulfuric Acid Alkylation: Stratco Process

 The Strateo reactor has a volume of approximately 34 m3. Its

output is 0.39 to 0.44 m3 of alkylate/m3 of reactor.h-1.
 The acid/hydrocarbon volume ratio is slightly greater than 1.
 The pressure in the reactor is sufficient to keep the two phases
in the liquid state.
 Process technology
Sulfuric Acid Alkylation:
Exxon/Kellolg Process (Cascade Autorefrieration Process)
 The Exxon process uses an evaporator reactor in the form of a
horizontal vessel divided into several adjacent compartments
equipped with agitators.
 The heat of reaction is eliminated from the reactor by evaporation of
an isobutene stream brought directly into one end of the reactor.
 Sulfuric acid is let in on the same end and moves by overflowing
from one compartment to the next.
 The feed-isobutane mixture is divided up into several aliquot
portions that are let in to each of the compartments at the same time.
 The last third of the reactor usually contains one or two settling
zones
 Process technology
Sulfuric Acid Alkylation: Exxon/Kellolg Process

Diagram of the H2SO4 alkylation reactor developed by Exxon

 Process technology
Sulfuric Acid Alkylation: Exxon/Kellolg Process

Diagram of the H2SO4 alkylation reactor developed by Exxon

 Process technology
Sulfuric Acid Alkylation: Exxon/Kellolg Process

Simplified flow scheme of the Exxon alkylation process

 Process technology
Sulfuric Acid Alkylation: Exxon/Kellolg Process
 The temperature of the various stages is controlled by isobutane
evaporation.
 Since the olefin reaction rate is very fast, the gas phase contains no
olefms. The various stages work at pressures chosen so that the
temperature remains within the +2 to +12oC range.
 Since the isobutane content is the highest in the first stage, the
pressure will also be the highest.(1.4-1.75 bar). The pressure in the
last stage is the lowest (0.35-0.84 bar).
 The residence time in the settling zone is some 30 to 50 minutes.
Almost all of the acid in the settling zone is recycled to the inlet of
the reactor's first stage.
 The output of the Exxon/Kellogg reactor is from 0.15 to 0.18 m3 of
alkylate/m3 of reactor.h-1.
 The acid/hydrocarbon volume ratio is slightly greater than 1.
 Process technology
Sulfuric Acid Alkylation Processes

Compared with the Stratco process, the evaporator reactor provides

two advantages:
 direct vaporization of isobutane in the reactor makes exchanger
tubes unnecessary;
 by avoiding fluid transportation and loss of frigories, in-situ
evaporation of isobutane allows operation at lower reaction
temperatures than with the Strateo.
 Process technology
Sulfuric Acid Alkylation Processes performance
Yield and Catalyst Consumption
Process technology

Sulfuric Acid
Alkylation
Processes
performance

Alkylate
Composition
and Quality
Process technology

Influence of the amylene

content in the olefinic feed
on RON and MON

Influence of the amylene content

in the olefinic feed on sulfuric
acid consumption
 Process technology
Sulfuric Acid Regeneration
 Sulfuric acid alkylation processes produce large amounts of acid
sludge (90% wt of H2SO4).
 It is complex and costly to reprocess because the sulfuric acid can
not be separated physically from the red oils. It must therefore be
destroyed, and sulfuric acid is then made up from the SO2 produced
when H2SO4 is reduced by red oils.
 The simplified sulfuric acid reprocessing scheme is as follows:
• the acid and organic oils are decomposed by air into SO2, H20.
CO2 and N2;
• SO2 is converted into SO3;
• SO3 is absorbed by water to be transformed into H2SO4 with a
titer of over 98.5% wt.
 These operations are very often carried out outside the refinery.
 Process technology
HF Alkylation Processes
 Two HF alkylation processes share the market: the Phillips and the
UOP version.
 HF and H2SO4 processes differ in that HF processes do not have
mechanical stirring systems such as turbines.
 The low viscosity of HF and great solubility of isobutane in the acid
allow simpler technologies to be used: the emulsion between the two
phases is effected by injecting the hydrocarbon feed into a continuous
HF phase through nozzles at the bottom of a tubular reactor.
 The resulting emulsion circulates from bottom to top in the reactor,
and separation is then done by settling, the same as for the H2SO4
process.
 Reaction temperatures of approximately 30oC allow water to be
utilized to cool the reactor.
 Process technology
HF Alkylation: Phillips Process

Simplified diagram of the Phillips HF alkylation process

 Process technology
HF Alkylation: Phillips Process
 The mixture of fresh feed and recycled isobutane is injected into an
HF acid circulation loop.
 From the top of the reaction zone, the emulsion is introduced into a
settling zone.
 The residence time in the tubular reactor is 20 to 40 seconds. Reactor
output is from 4 to 7 m3 of alkylate/m3 of reactor.h-1 depending on the
acid/hydrocarbon volume ratio (between 1 and 4).
 The acid phase is recycled to the reactor inlet after going through a
water-cooled exchanger.
 Asmall proportion of the HF acid is drawn off and sent to the
regeneration zone (separation of HF from water + tars). The HF acid
condensed at the top of the regeneration column is recycled to the
reactor-settler, The hydrocarbon phase is routed to the main
fractionation column. The propane withdrawn at the top of the
fractionation column contains HF.
 HF and propane are separated in a stripper.
 Process technology
Hydrofluoric acid processes: Phillips hydrofluoric acid.
 Process technology

Hydrofluoric acid process:

 The reaction mixture is allowed to settle into two liquid layers.

 The acid has a higher density than the hydrocarbon mixture and is
withdrawn from the bottom of the settler and passed through a cooler
to remove the heat gained from the exothermic reaction.

 The acid removed is re-distillated and the polymerization products

removed as a thick, dark “acid soluble oil”.

 The concentrated HF is recycled and the net consumption is about 0.3

lb per barrel of alkylate produced.
 Process technology

Hydrofluoric acid processes

Phillips HF reactor.
Process technology

HF Alkylation:
UOP Process

Simplified diagram
(butene feed) of the UOP
HF alkylation process
 Process technology
HF Alkylation: UOP Process
 The reactor is vertical and acts as a heat exchanger. Nozzles allow the
hydrocarbon phase to be dispersed in the acid, which is the continuous phase
of the emulsion, the sameas in the Phillips process. The hydrocarbon feed is
let in at different reactor heights, and HF is let in at the bottom of the reactor.
The heat of reaction is eliminated by means of cooling water. Reactor output
is approximately 2 m3 alkylate/m3 of reactor.h-1.
 The acid and hydrocarbons are separated in a settler. The hydrocarbon phase
is fractionated and the isobutane is recycled to the reactor inlet.
 An HF stripper is used to separate HFfrom the propane + isobutane mixture
coming off the top of the fractionation column. If the feed contains C3,
propane and isobutane are separated in a depropanizer. The propane is then
alumina treated to remove any trace of fluorine. The alkylate recovered at the
bottom of the fractionation column is treated with potassium hydroxide.
 Several reactors can be used depending on the unit's capadty, and in this case
they are in series.
 Process technology
HF Processes performance
Alkylate Yield and Quality
 Process technology
HF Processes performance
Alkylate composition
 Process technology
Spent Acid Regeneration
 The HF acid purged from the unit, with a concentration of about 90%
wt, is regenerated continuously on the refinery site by distillation. For
example, for an a1kylate production capacity equal to 58 000 t/year,
the tar purge from the bottom of the HF regeneration column is
approximately 265 t/year.
 The corresponding HF consumption is 0.82 kg/t of alkylate.
 The regeneration column treats 16m3 of acid a day.
 CONTENTS

1 Objectives, Feedstocks and Products

2 Reactions, Mechanisms

3 Catalysts

4 Operating conditions

5 Process technology

6 Future trends
88
 Future Trends

A lot of research has been done both to decrease sulfuric acid

consumption and to develop different processes using - solid acid catalysts

Two Step Process

 In the first step of the process, n-butyl sulfates are formed from
sulfuric acid and n-butenes in a stoichiometric ratio and at a
temperature lower than 0oC.
 In a second reactor, these esters react in the presence of free sulfuric
acid and an additional amount of isobutane to produce the alkylate.
 These two steps yield good quality alkylates: more than 90%wt
trimethylpentanes with RON values as high as 98-100.
 The best alkylate quality is achieved when the temperature in the
second reactor ranges between -15 and -20'C.
 Future Trends
Solid Acid Catalysts
In order to replace liquid acids by a solid as alkylation reaction
catalysts, several solids have been studied in depth: exchanged zeolites,
ion-exchange resins (Amberlyst, Nafion), superacid solids (chlorinated
alumina, sulfated zirconia). superacids adsorbed on solids (HF-
SbF5/Al203, BF3/zeolites. oxides or resins).

Influence of the type of solid acid catalyst in isobutane alkylation by butane-2