Alkylation process, Feedstocks, reactions, products, catalysts

and effect of process variables.

Catalytic Alkylation

[1-7]

Catalytic alkylation process is used in refineries to upgrade light

olefins (produced from catalytic crackers as well as from cokers viz
breakers) and isobutene into a highly branched paraffins. In
petrochemical industry it is used to produce alkylate benzenes and
other petrochemical products.
The alkylation reaction involves the addition of photon H +( supplied
by an acid catalyst),to the double bond of an olefin to form
carbonium ion. This ion then adds to another olefin molecule to
form a new carbonium ion which abstracts a hydride ion, H -, and
from isobutene to become a paraffin. At the same time new
carbonium ion is produced to continue the reaction.
STEP 1: Addition of proton H+(supplied by Acid catalyst to
propagate double bond of olefin)
Carbonium ion Formation

[5-12]

STEP 2: Addition of this ion to another olefin.

STEP 3: Abstraction of Hydride ion H- from olefin.

Alkylation process are conducted by Lewis acids like sulphuric acid,

hydrofluoric acid, aluminium chloride (obsolete). Highly exothermic
reaction HP = - ( 630 to 700 Btu/lb for isobutane alkylation).
Side Reactions

Feed Stocks
i-butane, Propenes, butenes.(olefins and isobutenes are alkylation

feed
stocks)
o
T
=
10-20 C
for
H SO alkylation.
Low temperature required for H SO because at higher temperature
tar formation occurs due to oxidation-reduction reactions.
Acid strength 88-90% .High Acid concentration for alkylation
reaction.Weaker acid gives polymerization reaction.
For HF, temperature is higher T ~ 38 oC .Liquid phase reaction in
both cases.
2

Process for H2SO4 alkylation:

[5-12]

Fig:7.2 Sulphur Acid Alkylation Processes

Process has been applied to isobutanes and butenes.
Important features:
Absorption of olefinic HC occurs hundred times faster as fast as the

absorption of paraffins and sent to the stabilizer hence in order to

maintain proper concentration of the two HC in the acid. It is
necessary to recycle large access of saturated HCs through the
system. Higher the ratio of paraffin to olefin in the feedstock,
greater the yield, higher O/W and smaller the acid consumption.
Operating Variables:

Acid concentration is kept high because of strong acid catalyst

alkylation reaction where as acid catalyst polymerization reaction
occurs.
Cascade Refrigeration Process

Fig:7.3 Cascade Refrigeration Process

Uses of multistage reactors with mixers at each stage is to emulsify
the hydrocarbon and mixture of olefin in split in parallel in various
reactions occurs whereas i-butane in series feed to the system. This

increases i-butane to olefin ratio. Refrigeration by vaporization of a

portion of hydrocarbon in each reaction is necessary.
H F alkylation:
Highly successful
isobutene.

process

for

combining

isobutane

and

No refrigeration.
Feed is dried.
Special material of construction is required (monel) because HF is
very
much
corrosive.
HF process is favorable for small plant but for large plant
H SO catalytic process is used.
2

Process Variables (Alkylation):

(for both process) Major Variables are:- Reaction T, Acid strength, Ibutane concentration, olefin space velocity.
Reaction Temperature:

Low
T
increases
octane
number
&
reduces
H SO acid
requirements.Unfortunately low T also requires higher refrigeration
investment & operating cost. Miixing is difficult.
High T ---> acid attacks the olefins significant sensitive to temp.
HF alkylation ---> less sensitive to temperature. Increase in T from
30Co to 100oC.
2

Isobutane Recycle Rate:

High isobutane recycle rate increases the octane number and lowers
acid requirements. However high isobutane rate also increases the
investment required for deisobutanizer and increase the operating
cost of the tower because of the higher steam requirements.
Space Velocity:
velocity of olefin/h / velocity of acid in reactor.Low space velocity
increases octane number and lowers acid requirements.High space
velocity increases formation of acid sulphates which are corrosive to
downstream fractionation facilities.
Spent acid strength:
High spent acid strength tends to increases octane No, but also
increases make up acid requirements. Low spent acid strength
tends to decrease make up acid requirements, it increases risk of
acid runaway.93-95% acid by weight, 1-2% water remainder, Hc
diluents. Some water is initially added to the acid which promotes
the proton transfer for alkylation reaction. Lowering olefin space
velocity reduces the amount of High boiling hydrocarbon produced,
increases the product octane and lowers acid consumption.
Contact Time:
Residence time of (fresh feed + external recycled i-butane in the
reactor.)
5-25
minute-->HF
alkylation
5-40 minute-->H SO alkylation
2

Isobutane concentration:

Excess of i-butane/olefin ratio desirable. It increases the octane

number. Catalytic consumption is less.
Miixing:
i-butane
solubility
in
H SO --> 0.1%
by
weight
i-butane
solubility
in
HF-->3%
by
weight
solubility of i-butane in acid is very small (sparingly soluble) Olefins
relatively soluble in acids. So proper mixing is required otherwise
polymerization will take place instead of alkylation.
2

I --->
isobutane
(I/O) --->
(value
of
(SV ) ---> olefin space velocity
E

in
reactor
isobutane/olefin)

effluent.
in
feed.

F
=
Higher the 'F' better is the Quality product.

10-40

Alkylation of benzene:
With ethylene -----> gives ethylbenzene Starting material for
styrene
production
cat
AlCl
CH =
CH +
HCl
----->
CH CH Cl
HCl is used as promoter for Aluminium Chloride and lowers its
consumption.
3

Exothermic
reaction
H
=
110
Dehydration
of
ethylbenzene
gives
Cat
Fe CO with
metallic
oxide
or
o
T
=
600C
Addition of K CO reduces coke on catalyst.
2

KJ/mol
styrene.
ZnO
630oC

Cumene:By alkylation of propylene with benzene yields

Isopropylbenzene.
Cumene is used for production of phenol and methyl styrene.

Alkylation and polymerization

[1-2,7-12]

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 so araffins Although this
reaction is simply the reverse of cracking, where as that of paraffin
hydrocarbons are chemically inert and belived to be delayed in its
discovery until 1935. Although alkylation can take place at high
temperatures and pressures without catalysts, the only processes of
commercial importance involve low temperature alkylation
conducted in the presence of either sulfuric or hydrofluoric acid. The
reactions occurring in both processes are complex and the product
has a rather wide boiling range. By proper choice of operating
conditions, most of the product can be made to fall within the
gasoline boiling range with motor octane numbers from 88 to 94
and research octane numbers from 94 to 99.
Alkylation of olefins was developed to improve the octane of

aviation gasoline.Catalyst: aluminum chloride

FCC significantly increased the production of light ends. High
concentration of the C2, C4, & C5 isomers, both olefinic &
paraffinic which led to development of both catalytic
polymerization and alkylation.Processes are used to make
gasoline components from materials that are too light to
otherwise be in gasoline.
Alkylation forms a longer chain highly branched isoparaffin by
reacting an alkyl group ( isobutane) with a light olefin
( butylene). This process produces high-octane gasoline.
Polymerization is the formation of very short chains product is
nearly all olefinic high research octane but moderate motor
octane number. Sulfuric acid, hydrogen fluoride, and aluminum
chloride are the main catalysts used commercially. Sulfuric
acid is used with propylene and higher- boiling feeds, but not
with ethylene because it reacts to form ethyl hydrogen
sulphate and a suitable catalyst contains a minimum of 85%
acidity. The acid is pumped through the reactor and forms an
air emulsion with reactants. The emulsion is maintained at
50% acid. The rate of deactivation varies with the feed and
iso-butane change rate. Butene feedstocks cause less acid
consumption than propylene feeds. Aluminum chloride is not
widely used as an alkylation catalyst , but when employed
hydrogen chloride is used as a promoter and water is injected
to activate the catalyst .
The form of catalyst is an aluminum chloridehydrocarbon
complex, and the aluminum chloride concentration is 63% to
84%. The advantage of hydrogen fluoride is that it is more
readily separated and recovered from the resulting product.
The usual concentration is 85% to 92% titratable acid, with
about 1.5% water.
Sulfuric Acid Alkylation

 A consortium of major refiners and contractors developed

process with sulfuric acid as the catalyst.
Sulfuric acid alkylation required access to acid regeneration on
a large scale.
Most sulfuric acid alkylation plants were located on deep
water for barge transport of spent acid to regeneration at
acid plants & return of fresh acid.
HF Acid Alkylation
Phillips Petroleum & UOP developed process using hydrofluoric
acid as a catalyst.
HF could be readily regenerated in alkylation plant
facilities.
No need to transport catalyst in large quantities for
regeneration.
HF alkylate in general was not quite as high quality as sulfuric
acid alkylate.
Feedstocks
Olefinic stream from the catalytic cracker.
Butylene is the preferred olefin since it produces the
highest octane number & yields.
Isobutane & isopentane can be reacted with the olefinIsopentane not usually used since it is a good gasoline
blend stock.

 High octane number & low vapor pressure.

Catalytic cracker feed contains significant sulfur.
Treating unit often precedes alkylation unit.
Products
Alkylate desirable component for high performance automotive
fuels.
Very high octane index (R+M)/2 of 95.
Low vapor pressure.
Vapor pressure is adjusted for final boiling point.
IBP adjusted for addition of normal butane.
Low sulfur levels.
Essentially no olefins, benzene or aromatics.
Contributes large volume to the gasoline pool (19% vol).
Catalytic cracker (34% vol).
Reformer (28% vol).
Isomerization unit (15% vol).
Process Chemistry
Propylene, butylene, & pentenes are olefins used butylene
preferred.

 High octane isooctane alkylate produced.

Lower reactant consumption.
Alkylation reactions have complex mechanisms & it may
produce many different varieties.

Alkyaltion and Polymerisation Reaction

[5-15]

Formation of tert-butyl carbonium ion:

Operating Variables & Their Effects

Capacity is expressed in terms of alkylate product, not feed
capacity.
Most important variables are type of olefin (Propylene,
butylene, or pentene), Isobutane concentration, Olefin
injection & mixing, Reaction temperature, and Catalyst type
and strength.The critical measures for success is based on the
Alkylate octane number, volume olefin and isobutane
consumed per volume of alkylate produce, degree of
undesirable side reactions, and acid consumption.
These effects are briefly discussed below:

 Type of Olefin
Butylene is preferred.
Produces the highest isooctane levels.
Resulting Research Octane Numbers of 93-95 (with
isobutane).
RON and MON are about equal for alkylation.
Amounts of butylene
produced is the lowest.

consumed

per

alkylate

Side reactions are limited.

Propylene is worse.
Octane numbers are low (89-92 RON).
Propylene and acid consumption are high.
Pentene results are mixed.
Side reactions are frequent
Isobutane concentration.
Excess isobutane required normal volume ratio of
isobutane to olefin in the feed is 6-10.
Limited isobutane solubility in acid phase.
Olefins need to be surrounded by isobutane exposed
to acid if not, olefins will polymerize instead of
alkylate.
Newer plants have multi injection and vigorous mixing

systems.
Effect of isobutane is expressed
concentration in the reaction zone

in

terms

of

Isobutane to olefin ratios maintained at 10,000 to 1.

Isobutane/Olefin Injection and Mixing.
More important in sulfuric acid systems.
Acid viscosity at operating temperatures.
Provide optimal reaction conditions for the very fast
reaction.
Inject olefin feedstock in incremental fashion to
increase isobutane/olefin ratios
Newer plants designed for multi-injection locations
into an agitated emulsion to disperse olefin as
rapidly as possible.
Systems with single point injection can easily have an
overload of olefin in the emulsion.
Leads to lower quality & higher acid consumption
from esterification reactions.
Reaction Temperature
Most noticeable variable in both reaction systems.
Increasing temperature reduces octane number.
HF systems run at 35oC.

 Sulfuric acid systems run at 7oC.

Often employ auto refrigeration of the reactant
mass to provide coolant for the reactors.
Acid Type and Strength
HF acid strength is not an important variable in the range
of 80% to 95%.
Sulfuric acid strength is somewhat a function of the
diluent.
Water lowers acid activity 3 to 5 times as fast as
hydrocarbon diluents.
Acid is considered "spent" at around 88% sulfuric
acid.
Sulfuric vs HF Acid Alkylation

[1-2,5-19]

Principal difference is operating temperature.

Sulfuric acid alkylation refrigeration required
HF alkylation
temperatures.

can

operate

at

cooling

water

Sulfuric acid alkylation is dominant process.

Sulfuric acid plants require extensive recuperation of the
spent acidgenerally done off site.
Larger coastal refiners tend to have sulfuric acid
alkylation plants with barge or short haul transportation
to acid regeneration facilities.

 HF plants generally smaller and catalyst regeneration is

done inplant with a small acid makeup.
Urban community concerns to hazards of HF escape.
Table:7.1
Operating conditions in Alkylation
Variables

H2SO4

HF

Iso butane concentration

(Vol.%)

40-80

30-80

Total HC contact time (s)

12001800

5001200

Temperature(oC)

2-16

16-46

Acid(Concentration wt.%)

88-95

80-95

Acid in emulsion (vol.%)

40-60

25-80