2.5.

Alkylation
Alkylation is any reaction in which an alkyl group is added to a compound; in petroleum
reIining, it normally means reaction oI an oleIin with an i-paraIIin to produce a larger i-paraIIin.
2.5.1Mechanism of Reaction
A number oI theories have been advanced to explain catalytic alkylation. Probably the
most popular is one involving carbonium ions. Carbonium ions result Irom unions oI oleIins with
protons Iurnished by the acid catalyst:

Carbonium ions react with I-butane to Iorm i-butyl carbonium ions:



i-Butyl carbonium ions combine with oleIins to Iorm larger carbonium ions:


The larger carbonium ions react with isobutane to yield i-paraIIins:



Thus, the i-butyl carbonium ion is regenerated, and a chain reaction commences. The reaction
intermediates the larger carbonium ions isomerize readily to other skeletal structures. This
phenomenon explains the mixtures oI isomers usually Iound in alkylation products.

2.5.2 Alkylation Objectives

Alkylation processes combine light oleIins (primarily propylene and butylene) with
isobutane in the presence oI a highly acidic catalyst, either sulIuric acid or hydroIluoric acid. The
product (alkylate) contains a mixture oI high-octane, branched-chain paraIIinic hydrocarbons.
Figure 1 illustrates the reaction between isobutane and trans-2-butene. Alkylate is a highly
desirable gasoline blend stock because, in addition to its high octane, it has a low vapor pressure.
The octane oI the product depends on the operating condition and the kinds oI oleIins used.

The major alkylation processes using sulIuric acid as a catalyst are the Cascade SulIuric
acid alkylation (auto reIrigeration process) and the eIIluent reIrigeration process(Stratco).

2.5.3 Process Flow: Sulfuric Acid Alkylation
2.5.3.1 Cascade Sulfuric Acid Alkylation
This is a low-temperature process (Figure.2) employing concentrated sulIuric acid
catalyst to react oleIins with iso -butane to pro duce high-octane aviation or mo tor Iuel blending
stock. The oleIin Ieed is split into equal streams and charged to the individual reaction zones oI
the cascade reactor. Iso-butane-rich recycle and reIrigerant streams are introduced in the Iront oI
the reactor and passed through the reaction zones. The oleIin is contacted with the iso-butane and
acid in the reaction zones, which operate at 28C to 78C (358F to 458F) and 5 to 15 psi, aIter
which vapors are withdrawn Irom the top oI the reactor, compressed, and condensed. Part oI this
stream is sent to a de-propanizer to control propane concentration in the unit. De-propanizer
bottoms and the remainder oI the stream are combined and returned to the reactor. Spent acid is
withdrawn Irom the bottom oI the settling zone; hydrocarbons spill over a baIIle into a special
withdrawal section and are hot-water washed with caustic addition Ior pH control beIore being

successively de-propanized, de-iso-butanized, and de-butanized. Alkylate can then be taken

directly to motor Iuel blending or be rerun to produce aviation grade blending stock. Isobutane is
recycled.


2.5.3.2 1he Effluent Process


The eIIluent reIrigeration process (Stratco) uses a single-stage reactor in which the
temperature is maintained by cooling coils (Fig.3). The reactor contains an impeller that
emulsiIies the acidhydrocarbon mixture and recirculates it in the reactor. Average residence

time in the reactor is on the order oI 20 to 25 minutes. Emulsion removed Irom the reactor is sent
to a settler Ior phase separation. The acid is recirculated and the pressure oI the hydrocarbon
phase is lowered to Ilash vaporize a portion oI the stream and reduce the liquid temperature to
about 30F . The cold liquid is used as coolant in the reactor tube bundle. The Ilashed gases are
compressed and liqueIied, then sent to the depropanizer where LPG grade propane and recycle
isobutane are separated. The hydrocarbon liquid Irom the reactor tube bundle is separated into
isobutane, n-butane, and alkylate streams in the deisobutanizer column. The isobutane is
recycled and n-butane and alkylate are product streams.
A separate distillation column can be used to separate the n-butane Irom the mixture or it
can be removed as a sidestream Irom the deisobutanizing column. The choice is a matter oI
economics because including a separate column to remove the n-butane increases the capital and
operating costs. Separating nbutane as a sidestream Irom the deisobutanizing can be restricted
because the pentane content is usually too high to meet butane sales speciIications. The
sidestream n-butane can be used Ior gasoline blending.

2.5.4.Hydrofluoric Acid Processes
There are two commercial alkylation processes using hydroIluoric acid as the catalyst.
They are designed and licensed by Phillips Petroleum Company and UOP. The basic Ilow
scheme is the same Ior both the Phillips and the UOP processes.
2.5.4.1.Process Flow: HF Alkylation
Figure 4 shows a process schematic Ior hydroIluoric acid (HF) alkylation. OleIins and
isobutane are dried and Ied to a reactor, where the alkylation reaction takes place over the HF
catalyst. The reactor eIIluent Ilows to a settler, where the acid phase separates Irom the
hydrocarbon phase. The acid is drawn oII and recycled. The hydrocarbon phase goes to a
deisobutanizer (DIB). The overhead stream, containing propane, isobutane, and residual HF,
goes to a depropanizer (DeC3). The DeC3 overhead goes to an HF stripper. It is then treated with
caustic and sent to storage. Isobutane Irom the DIB main Iractionator is recycled. The bottom
stream Irom the debutanizer goes to product blending.

This process (Figure 4.) uses regenerable hydroIluoric acid as a catalyst to unite oleIins
with iso-butane to produce high-octane blending stock. The dried charge is intimately contacted
in the reactor with acid at 208C to 1408C (708F to 1008F) and a high (15:1) iso-butane-oleIin
ratio. The mixture is separated in a settler and acid is returned to the reactor, but an acid side
stream must be continuously regenerated to 88 purity by Iractionation to remove acid soluble
oils. The hydrocarbon Iraction Irom the settler is de-iso-butanized, and alkylate is run to storage.
2.5.4.2.Phillips

#eactor systems designed by Phillips usually have been similar to that illustrated in
Figure 5. Acid circulation in this system is by gravity diIIerential and thus a relatively expensive
acid circulation pump is not necessary. In portions oI the process system where it is possible to
have HFwater mixtures, the process equipment is Iabricated Irom Monel metal or Monel-clad
steel. The other parts oI the system are carbon steel. Special precautions are taken to protect
maintenance and operating personnel Irom injury by accidental contact with acid. These
precautions include special seals on acid-containing equipment such as pumps and valve stems;
rubber saIety jackets, pants, gloves, and boots which must be worn by personnel entering an acid
area; saIety eyeglasses; caustic tubs Ior washing all hand tools; saIety showers; special acid drain
systems; and many others. CareIul attention to engineering design details and extensive operator
training combined with the above precautions are necessary to provide saIe operations Ior
hydroIluoric acid alkylation units.

2.5.5.Comparison Of Processes
Advocates oI the hydroIluoric acid process argue that both capital and total operating costs are
less than those oI sulIuric acid processes Ior the Iollowing reasons:
1. Smaller and simpler reactor designs are Ieasible.
2. Cooling water can be used instead oI reIrigeration.
3. Smaller settling devices are needed Ior emulsions.
4. Essentially complete regeneration oI the hydroIluoric acid catalyst occurs.
Hence, hydroIluoric acid consumption and costs are very low.
5.Disposal oI spent acid is not necessary.
6. There is increased Ilexibility oI operation relative to temperature, external
ratio oI isobutane to oleIin, etc.
7. There is decreased need Ior turbulence or agitation when acid and hydrocarbon
streams are combined.
Advocates oI sulIuric acid processes counter the above arguments Ior hydroIluoric acid
processes with the Iollowing:
1. Additional equipment is needed Ior the hydroIluoric acid process to recover or
neutralize the hydroIluoric acid in various streams. Such equipment includes
the hydroIluoric acid stripper tower, hydroIluoric acid regeneration tower, and

neutralization Iacilities Ior the several product streams. With sulIuric acid, the
entire eIIluent hydrocarbon stream is neutralized.

2.Equipment is required to dry the Ieed streams to a Iew ppm water in
hydroIluoric acid processes. Drying is beneIicial but typically not required in
sulIuric acid processes. Normally only Ieed coalesers are used to remove the Iree
water that drops out oI the chilled Ieed.
3. Additional equipment at increased cost is required Ior saIety in a hydroIluoric
acid unit. In some hydroIluoric acid plants, a closed cooling water system is
required as a saIety measure in the event oI hydroIluoric acid leakage into the
system. Maintenance costs and the amount oI saIety equipment in hydroIluoric
acid processes are greater.
4. Capital costs Ior hydroIluoric acid processes are slightly more than sulIuric
acid processes when the cost oI hydroIluoric acid mitigation equipment is
included.
5. Isobutane in hydroIluoric acid processes is not Iully used Ior production oI
alkylate, since selI-alkylation occurs to a higher extent when hydroIluoric acid is
used as a catalyst.
6. There are greater limitations on obtaining alkylates with high octane numbers
with hydroIluoric acid processes. This is particularly true iI isobutylene is
removed Irom the Ieed by an upstream MTBE or ETBE unit.
7. SaIety and environmental restrictions limit the use oI hydroIluoric systems in
highly populated areas .