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Group 3: Farjanah, Nazurah, Connie, Irfan, Annur Adilia Maisarah

Tutorial: Alkylation

1. Why is Sulphuric acid alkylation run in liquid phase and at low temperatures?

Alkylation is catalysed by a strong acid, either sulphuric (H2SO4) or hydrofluoric (HF). In the
absence of catalysts, alkylation between isobutane and olefin must be run under severe
conditions such as T = 500 deg. C and P=200–400 bars.

In the presence of an acid catalyst, the reaction temperature will be lower than 50 deg. C,
and the pressure will be lower than 30 bars. The major difference in using either acid is that
isobutane is quite insoluble in H2SO4 but reasonably soluble in HF. This requires the use of high
isobutane/olefin ratios to compensate for low solubility in H2SO4.

Higher reaction temperatures intensely favor polymerization reactions that will dilute the acid.
Equipment corrosion will also increase with higher reaction temperatures. Low reaction
temperatures slow the settling rate of the acid from the alkylate

2. What is the role of alkylation in the refinery?


Alkylation is a process to convert olefins such as propylene, butylene, amylene and
isobutane into gasoline range material (alkylates). Common catalyst used in the process is
sulfuric acid or hydrofluoric acid

3. Draw block diagram of alkylation process and explain.


Explanation

•Common catalyst used in alkylation process is either sulphuric acid (with a concentration of 85-
95%) or hydrofluoric acid.

•The presence of catalyst allows the operating conditions to run under lower temperature (50 oC)
and lower pressure (30 bars).

•In the process, high isobutane/olefin ratios must higher to compensate for low solubility of
sulphuric acid. The hydroflouric acid is more soluble compare to the sulphuric acid.

•The process must be run under low temperature to prevent equipment corrosion and
polymerization reaction that will lower the acid concentration.

4. Refer H2SO4/HF process flow diagram and explain the working principle of alkylation
process.
Flow diagram of H2SO4/HF alkylation process:

1. In sulfuric acid, alkylation units, the feeds – propylene, butylene, amylene, and fresh
isobutane – enter the reactor and contact sulfuric acid with a concentration of 85 to 95%.
2. The reactor is divided into zones. Olefins are fed through distributors to each zone, and
sulfuric acid and isobutanes flow over baffles from one zone to the next.
3. The reactor effluent goes to a settler, in which hydrocarbons separate from the acid. The
acid is returned to the reactor.
4. The hydrocarbons are washed with caustic and sent to fractionation. The fractionation
section comprises a depropanizer, a deisobutanizer, and a debutanizer.
5. Alkylate from the deisobutanizer can go directly to motor-fuel blending, or it can be
reprocessed to produce aviation-grade gasoline. Isobutane is recycled.

5. What are the effects of operating variables in alkylation?


The operating condition or variables that influence the quality of alkylation product are the olefin
type, dilution ratio (iC4/iC4=), mixing temperature, impeller speed, space velocity (residence
time), and acid strength.

i. Olefin type
Based on table below, the octane number of alkylates produced from light olefins is given.
Different olefin type and catalyst will give different octane number and acid consumption.
Such as, the presence of propylene or pentene with butane will lower the octane number
and increases acid consumption. And butane with sulphuric acid as catalyst gives the best
octane numbers

Table 1: Effect of type of olefin on alkylate octane number

ii. Isobutane concentration


The iC4/iC4= ratio has an important role regarding the quality of alkylate produced and the
amount of sulphuric acid consumption. High isobutane concentration ([iC4]) prevent olefin
polymerization which results in low quality alkylate and high consumption of sulphuric
acid. Solubility of iC4 ≪ C4=. Thus high concentration of iC4 is required in the mixed
hydrocarbons to compensate for its low solubility. As isobutane increases, alkylate MON
increases and sulphuric acid consumption decreases.

iii. Acid strength


An optimum value of acid strength of 90 wt% H2SO4 is maintained by adding fresh
concentrated acid (98-99 wt%). The spent acid is purged out of the system and usually
regenerated outside the refinery. As the strength of acid decreases, the acid consumption
increases while the octane number decreases. The minimum acid strength required to
operate the system should not be lower than 85 wt%.
iv. Degree of Agitation
When the hydrocarbons (iC4 and C4=) are dispersed in sulphuric acid, the speed of
impeller determines the dispersed phase size (droplet diameter) and hence, the interfacial
contact area. The reaction rate of iC4 and C4= is quite fast, and the reaction is controlled
by mass transfer. Side reactions cause the formation of heavy alkylates as given by the
equation in figure below.

This equation shows that the quality of alkylate produced can be improved by
increasing impeller velocity and iC4 concentration. The rate ratio on the left side of
equation can be maximized by using a low acid hold-up and low olefin space velocity
(SV)o.
v. Space Velocity
The olefin space velocity is defined as below:

The residence time in the reactor is (1/(SV)o) and is defined as the residence time
of the fresh feed and externally recycled isobutane in the reaction mixture. 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 is 5-25 min.

vi. Reaction Temperature


The reaction thermodynamics and kinetics are favoured at low temperatures, as shown
before. Sulphuric acid alkylation units are operated at 5-10°C. Above 10°C, oxidation and
side reactions are promoted, and the deteriorate-alkylate yield and quality while acid
consumption increases. It is impossible to run the reaction below 0°C because acid
viscosity will be too high and agitation becomes difficult. Above 21°C, the polymerization
of olefin will occur, and the octane number of alkylate decreases. For hydrofluoric acid
(HF) alkylation, the reaction temperature is less significant and is between 21-38°C.

6. Compare the hydrofluoric acid process and the sulphuric acid process for alkylation.

Sulphuric Acid alkylation Hydrofluoric Acid alkylation

- The feed are consist of propylene, - Olefins and isobutane are dried and
butylene, amylene, and fresh fed to a reactor, where the alkylation
isobutane reaction takes place over the HF
catalyst.
- Enter the reactor and contact
sulfuric acid with a concentration of
85 to 95%.
- The reactor is divided into zones. -
Olefins are fed through distributors to
each zone, and sulfuric acid and
isobutanes flow over baffles from one
zone to the next.

- The reactor effluent goes to a settler, - The reactor effluent flows to a


in which hydrocarbons separate from settler, where the acid phase
the acid. The acid is returned to the separates from the hydrocarbon
reactor. phase. The acid is drawn off and
recycled.
- The hydrocarbons are washed with - The hydrocarbon phase goes to a
caustic and sent to fractionation. The deisobutanizer (DIB).
fractionation section comprises a
depropanizer, a deisobutanizer, and a
debutanizer.
- Alkylate from the deisobutanizer can - The overhead stream, containing
go directly to motor-fuel blending, or propane, isobutane, and residual HF,
it can be reprocessed to produce goes to a depropanizer (DeC3). The
aviation-grade gasoline. Isobutane is DeC3 overhead goes to an HF
recycled stripper.
- The bottom stream from the
debutanizer goes to product blending
7. Problems: calculate the alkylation reactor volume for a butylene feed of 3000 BPD
with an isobutene/ olefin ratio (I/O)F of 10 centigrade using sulphuric acid

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