Alkylation

In petroleum terminology, the term alkylation is used for the reaction of low molecular weight
olefins with an isoparaffin to form higher molecular-weight isoparaffins. The need for high-octane
aviation fuels during World War II acted as a stimulus to the development of the alkylation process
for production of isoparaffinic gasolines of high octane number.

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 process using sulfuric acid as a catalyst is much more sensitive to temperature than the
hydrofluoric acid process. With sulfuric acid, it is necessary to carry out the reactions at 40 to 70°F
(5 to 21°C) or lower, to minimize oxidation reduction reactions that result in the formation of tars
and the evolution of sulfur dioxide.

Alkylation Reactions

In alkylation processes using hydrofluoric or sulfuric acids as catalysts, only isoparaffins with
tertiary carbon atoms, such as isobutane or isopentane, react with the olefins. In practice, only
isobutane is used because isopentane has a sufficiently high octane number and low vapor pressure
to allow it to be effectively blended directly into finished gasolines. The principal reactions that
occur in alkylation are the combinations of olefins with isoparaffins as follows:
Another significant reaction in propylene alkylation is the combination of propylene with
isobutane to form propane plus isobutylene. The isobutylene then reacts with more isobutane to
form 2,2,4-trimethylpentane (isooctane). The first step involving the formation of propane is
referred to as a hydrogen transfer reaction. Research on catalyst modifiers is being conducted to
promote this step because it produces a higher octane alkylate than is obtained by formation of
isoheptanes.

The one most widely accepted involves the formation of carbonium ions by transfer of protons
from the acid catalyst to olefin molecules, followed by combination with isobutene to produce
tertiary-butyl cations. The tertiary-butyl ion reacts with 2-butene to form C8 carbonium ions
capable of reacting with isobutane to form C8 paraffins and tertiary-butyl ions. These tertiary-butyl
ions then react with other 2-butene molecules to continue the chain. Figure 1. illustrates the above
sequence using sulfuric acid, 2-butene, and isobubbbtane as the example reaction.

Alkylation Products

In addition to the alkylate stream, the products leaving the alkylation unit include the propane
and normal butane that enter with the saturated and unsaturated feed streams, as well as a small
quantity of tar produced by polymerization reactions.

The product streams leaving an alkylation unit are

1. LPG-grade propane liquid

2. Normal butane liquid

3. C5+ alkylate

4. Tar
Catalysts

Concentrated sulfuric and hydrofluoric acids are the only catalysts used commercially today for
the production of high-octane alkylate gasoline

Hydrofluoric Acid Processes

The basic flow scheme for hydrofluoric acid alkylation processes is shown in Figure 2. Both the
olefin and isobutane feeds are dehydrated by passing the feedstocks through a solid bed desiccant
unit. Good dehydration is essential to minimize potential corrosion of process equipment, which
results from addition of water to hydrofluoric acid After dehydration, the olefin and isobutane
feeds are mixed with hydrofluoric acid at sufficient pressure to maintain all components in the
liquid phase. 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 is then recycled
and mixed with more fresh feed, thus completing the acid circuit. A small slip stream of acid is
withdrawn from the settler and fed to an acid rerun column to remove dissolved water and
polymerized hydrocarbons. The acid rerun column contains about five trays and operates at 150
psig (1034 kPa).

The overhead product from the rerun column is clear hydrofluoric acid, which is condensed and
returned to the system. The bottom product from the rerun column is a mixture of tar and an HF-
water azeotrope. These components are separated in a tar settler (not shown on the flow diagram).
The tar is used for fuel, and the HF-water mixture is neutralized with lime or caustic. This rerun
operation is necessary to maintain the activity of the hydrofluoric acid catalyst.

The hydrocarbon layer removed from the top of the acid settler is a mixture of propane, isobutane,
normal butane, and alkylate along with small amounts of hydrofluoric acid. These components are
separated by fractionation, and the isobutane is recycled to the feed. Propane and normal butane
products are passed through caustic treaters to remove trace quantities and hydrofluoric acid.

Special precautions are taken to protect maintenance and operating personnel from injury by
accidental contact with acid. These precautions include special seals on acid-containing equipment
such as pumps and valve stems; rubber safety jackets, pants, gloves, and boots that must be worn
by personnel entering an acid area; safety eyeglasses; caustic tubs for washing all hand tools; safety
showers; special acid drain systems; and many others.
Sulfuric Acid Alkylation Processes

The major alkylation processes using sulfuric acid as a catalyst are the autorefrigeration process.
The process flow diagram for the autorefrigeration process is shown in Figure 3.

The autorefrigeration process uses a multistage cascade reactor with mixers in each stage to
emulsify the hydrocarbon-acid mixture. Olefin feed or a mixture of olefin feed and isobutane feed
is introduced into the mixing compartments, and enough mixing energy is introduced to obtain
sufficient contacting of the acid catalyst with the hydrocarbon reactants to obtain good reaction
selectivity. 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. A portion of this liquid is vaporized in an economizer to cool the olefin hydrocarbon
feed before it is sent to the reactor. The vapors are returned for recompression. The remainder of
the liquefied hydrocarbon is sent to a depropanizer column for removal of the excess propane that
accumulates in the system. The liquid isobutane from the bottom of the depropanizer is pumped
to the first stage of the reactor.

The acid-hydrocarbon emulsion from the last reactor stage is separated into acid and hydrocarbon
phases in a settler. The acid is removed from the system for reclamation, and the hydrocarbon
phase is pumped through a caustic wash followed by a water wash (or a fresh acid wash followed
by either caustic or alkaline water washes) to eliminate trace amounts of acid and then sent to a
deisobutanizer. The deisobutanizer separates the hydrocarbon feed stream into isobutane (which
is returned to the reactor), n-butane, and alkylate product.

The reactor contains an impeller that emulsifies the acid-hydrocarbon mixture and recirculates in
the reactor. The average residence time in the reactor is on the order of 20 to 25 min.

Emulsion removed from the reactor is sent to a settler for phase separation. The acid is recirculated,
and the pressure of the hydrocarbon phase is lowered to flash vaporize a portion of the stream and
reduce the liquid temperature to about 30°F (−1°C). The cold liquid is used as a coolant in the
reactor tube bundle. The flashed gases are compressed and liquefied, then sent to the depropanizer,
where LPG-grade propane and recycle isobutane are separated.
The hydrocarbon liquid from 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 from the
mixture, or it can be removed as a sidestream from the deisobutanizing column.

Comparison of Processes

If the refinery is at a distance from either sulfuric acid suppliers or purchasers of spent sulfuric
acid, the cost of transportation of fresh acid or the costnof disposing of the large quantities of spent
acid can render the use of sulfuric acid economically unattractive. Only a small amount of makeup
hydrofluoric acid is required for the HF process, as facilities are provided to regenerate the spent
hydrofluoric acid. As a result, the cost of transporting hydrofluoric acid from a remote supplier is
not a major cost. Albright, in a series of articles on alkylation processes, summarized the
comparison of the processes. The following discussion highlights the main issues.

Advocates of the hydrofluoric acid process argue that both capital and total operating costs are less
than those of sulfuric acid processes for the following reasons:

1. Smaller and simpler reactor designs are feasible.

2. Cooling water can be used instead of refrigeration.

3. Smaller settling devices are needed for emulsions.

4. Essentially complete regeneration of the hydrofluoric acid catalyst occurs. Hence, hydrofluoric
acid consumption and costs are very low. Disposal of spent acid is not necessary.

5. There is increased flexibility of operation relative to temperature, the external ratio of isobutane
to olefin, and so on.

6. There is decreased need for turbulence or agitation when acid and hydrocarbon streams are
combined.

Advocates of sulfuric acid processes counter the above arguments for hydrofluoric acid processes
with the following:

1. Additional equipment is needed for the hydrofluoric acid process to recover or neutralize the
hydrofluoric acid in various streams. Such equipment includes the hydrofluoric acid stripper tower,
hydrofluoric acid regeneration tower, and neutralization facilities for the several product streams.
With sulfuric acid, the entire effluent hydrocarbon stream is neutralized.

2. Equipment is required to dry the feed streams to a few ppm water in hydrofluoric acid processes.
Drying is beneficial but not required in sulfuric acid processes. Normally, only feed coalescers are
used to remove the free water that drops out of the chilled feed.

3. Additional equipment at increased cost is required for safety in a hydrofluoric acid unit. In some
hydrofluoric acid plan ts, a closed cooling water system is required as a safety measure in the event
of hydrofluoric acid leakage into the system. Maintenance costs and the amount of safety
equipment in hydrofluoric acid processes are greater.

4. Capital costs for hydrofluoric acid processes are slightly more than sulfuric acid processes when
the cost of hydrofluoric acid mitigation equipment is included.

5. Isobutane in hydrofluoric acid processes is not fully used for production of alkylate, because
self-alkylation occurs to a higher extent when hydrofluoric acid is used as a catalyst.

6. There are greater limitations on obtaining alkylates with high octane numbers with hydrofluoric
acid processes. This is particularly true if isobutylene is removed from the feed by an upstream
MTBE or ETBE unit.

7. Safety and environmental restrictions limit the use of hydrofluoric systems in highly populated
areas.