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