Gasoline components

Motor fuel alkylation

Alkylate was found to have excellent aviation gasoline properties.

It was the highest octane fuel component then known, with high motor
octane and excellent lead response.

All of the properties derive from the highly-branched paraffins that

form its composition. Humble Oil built the first commercial H2SO4
alkylation unit in 1938 at Baytown, Texas.3 Alkylation for aviation gasoline
grew rapidly with the Allies war effort. In 1939, six petroleum companies
formed a consortium to pool their alkylation technology and develop both
sulfuric acid and HF acid processes for 100 octane aviation fuel. The first
commercial HF alkylation unit started up in 1942. During the war 60
alkylation units were built for the Allies’ war effort. Half were built with
sulfuric acid as the catalyst and half with HF.

Licensors of motor fuelHFAlkylation processes areUOPLLC and

Phillips. Licensors of H2SO4 alkylation processes are Exxon Mobil and
Stratco Engineering.
 Process chemistry

The reactions taking place in the alkylation reactor are many and relatively
complex. First the olefin reacts with the acid to form an ester; then the ester is
alkylated by a t-butyl carbenium ion chain mechanism.4 The principal overall reactions
are described below.

Primary alkylation reactions

Most of the alkylate product is made by primary alkylation reactions. In these
reactions one mole of olefin reacts with one mole of isobutane to form an isoparaffin
exactly 4 carbon numbers heavier. Example primary alkylation reactions, showing
only the carbon framework and one or two of the principal product isomers, are
shown for each of the principal feed olefins in equations (1.1)–(1.5).
ALKYLATION
cis-Butene-2 + Isobutane → 2,2,4-Trimethylpentane (1.1) (100 RON)
Butene-1 + Isobutane → 2,3-Dimethylhexane (1.2) (71.3 RON)
Butene-1 + Isobutane→2,3,4-Trimethylpentane (1.3) (102.7 RON)
Isobutylene + Isobutane → 2,2,4-Trimethylpentane (1.4) (100 RON)
Propylene + Isobutane→2,3-Dimethylpentane (1.5) (91.1 RON)
2-methylbutene-2 + Isobutane → 2,2,4-Trimethylhexane (1.6) (92 RON)
Feed pretreatment
In the UOP HF alkylation process olefin-rich feeds from the FCC gas plant are
typically deethanized, Merox treated to remove H2S and mercaptans and dried.
Some refiners have also added MTBE or Selective Hydrogenation (SHP) plants
upstream the alkyl.

Reaction
After pretreatment, the olefin feeds are combined with a large excess of recycle
isobutane
to provide an 6–14 isobutane:olefin molar ratio and injected into the circulating
HF acid catalyst at the shell side inlet to the water-cooled reactor. Cooling water
flows through the reactor tubes to remove the highly exothermic heat of reaction
and to maintain reaction conditions at 80–100◦F. The alkylation reaction is very
fast
with 100% olefin conversion. The excess isobutane, alkylate product, non-reactive
hydrocarbons (propane, n-butane) in the feeds and the acid catalyst pass on to
the settler
vessel. The dense acid phase separates from the hydrocarbons rapidly by gravity
and is then pumped back to the reactor. The hydrocarbons containing dissolved
HF
flow off the top of the settler to the isostripper.
Fractionation
It consists of an isostripper, a depropanizer, and an HF Stripper. The
isostripper is a large tower with two sidedraws with the primary function
recycling isobutane to support the high isobutane:olefin molar ratio of the
reactor. The tower typically has two reboilers; the upper reboiler typically
maximizes the use of relatively lowcost low or medium pressure steam and
the lower reboiler uses a heating medium that can give 400–450◦F process
temperatures. Alkylate is drawn off the bottom of the tower, cooled in
exchangers, and sent to product storage. The next product draw up the
tower is the n-butane sidedrawand above that is the isobutane recycle
draw.On mostUOPunits the isobutane draw is located below the feed tray
tominimize HF in the isobutane recycle

The isostripper overhead vapor is a propane-enriched isobutane

stream and HF which is condensed and separated into settling drum. The HF
phase is pumped back to the reactor section. The HF saturated hydrocarbon
phase is charged to the depropanizer.
 The depropanizer and its associated HF stripper
remove propane from the isobutane recycle. The
depropanizer bottoms is returned to the reactors as part of
the recycle isobutane. The depropanizer overhead containing
the propane product and HF are condensed and separated in
the overhead receiver. The acid phase is returned to the
reactor section and the acid-saturated propane is stripped
free of acid in the HF Stripper column. The HF stripper
bottoms is an acid-free propane product which is treated with
hot alumina to remove organic fluorides, cooled and treated
with KOH pellets to remove traces of HF and water.
Acid regeneration
A key advantage of HF alkylation over sulfuric is the ability to recover the acid from
the byproduct polymer, water, and other contaminants. In the UOP HF Alkylation
Process, a small stream of circulating acid is stripped with superheated isobutane in
a small monel tower called the Acid Regenerator. The regenerator overhead is HF
and isobutane that are recycled to the reactor; the regenerator bottoms is polymer
and
the HF–water azeotrope which are neutralized with aqueous KOH. The neutralized
polymer has good fuel value. The amount of polymer produced is generally only 1 to
2 barrels per 1,000 barrels of alkylate product.

KOH regeneration
The UOP process minimizes chemical costs by regenerating the KOH used to treat
products and allwaste and stormwater. ThisKOHregeneration is accomplished using
lime. As the lime is mixed into the KOH, regeneration of the KOH takes place by the
following reaction:
2KF + Ca(OH)2 → 2KOH + CaF2
The calcium fluoride forms a precipitate and can be easily separated from the
regenerated
KOH.
Process variables in HF alkylation

Key variables are reactor temperature, isobutane to olefin molar

ratio, acid strength, and acid to hydrocarbon volume ratio.

Reaction temperature is one of the more important process

variables as it has a significant influence on the octane number of the
product. Almost all HF alkylation reactors are operated below 100◦F. At
higher temperatures a decrease in alkylate octane number will occur.
Above 120◦F polymerization and cracking side reactions become excessive
reducing alkylate quality. In many cases, acid regeneration capacity of the
HF alkylation unit would not be able to maintain proper control of the acid
strength at temperatures above 110◦F. Extremely lowreaction temperatures
may cause incomplete alkylation. Thus reaction temperatures below 80◦F
are typically not used.
 Acid strength is usually kept between 85 and 95 mass% HF.
Maintenance of this strength level results from a balance between the
performance of the unit feed treating systems for sulfur and water removal
and acid regeneration operation. In some cases oxygenate removal
systems or diene removal systems are also used on the feed where there
are known to be high oxygenates (such as downstream of an MTBE unit,
or high diolefins (from severe FCC conditions). The action of the acid on
reactions is a complex phenomenon and is dependent on the type as well
as the amount of diluents.

The fresh acid is supplied by acid manufacturers at 99.0+ wt%

HF. This purity is too high for optimum performance of the HF alkylation
process. As the water content of the circulating acid increases, carbon
steel that is not attacked by anhydrous HF, becomes less resistant to acid
attack.

The acid to hydrocarbon volume ratio used in the reactor of the

UOP process is generally around 1:1. At some point below 0.8–1, excess
polymerization occurs. In the most extreme cases, alkylate production
could stop.
HF feed contaminants

As with many refining processes, the control of

contaminants coming into the unit with the normal feedstocks
is critical to the long and dependable operation of the HF
alkylation unit. Above the recommended maximum levels of
feed stock contaminants, acid consumption, acid regeneration
requirements, and in some cases unit corrosion and product
quality are all measurably affected. Generally all contaminants
are kept as low as possible within the capabilities of the feed
treating systems. The major feed contaminants normally found
in alkylation feeds are water or oxygenates, sulfur compounds,
nitrogen compounds, non-condensibles, and diolefin.
HF alkylation maintenance

Because HF is highly corrosive to most materials, careful control

and maintenance of equipment metallurgy and condition is required.
Carbon steel is the primary material used for vessels and piping and it can
be used only because of a corrosion barrier layer of iron fluoride that forms
on any carbon steel surface exposed to HF. The iron fluoride layer is
tenacious and serves as a barrier against further carbon steel corrosion as
long as the deposit remains undisturbed. Under certain conditions, such as
when wet acid is in the unit, this iron fluoride scale can soften and break off
leading to fouling and corrosion issues. In severe cases this can lead to
considerable unscheduled feed outages as well as clear safety issues.

Most refiners aggressively monitor their equipment’s remaining

corrosion allowance and use regularly scheduled valve and flange
replacement to head off any problems. For maintenance during an FCC
turnaround, the normal time most alkylation turnarounds are maintained,
many refiners choose to dissolve all the iron fluoride scale by using a
chemical cleaning company.
Safe handling

MEA is transported by road or rail tanker in its

concentrated form. It is transferred in the normal way to an
onsite storage bullet, which is blanketed by an inert gas. MEA
is degraded on exposure to air. The use of this, and other
enthanolamines, in the refinery processes is in a dilute form.
This dilution and its onsite storage is very often in a suitably
constructed pit usually in the proximity of the user plant. In
some cases, a cone roof tank may be used for onsite storage.
In all cases, though, the product must be kept free from
exposure to air by inert gas blanketing. The dilution of MEA
for use in the refinery process is between 15 and 20 wt%. The
water for this dilution is usually treated boiler feed water,
which is essentially free of impurities.
Sulfuric acid alkylation
Today there are two processes for H2SO4 alkylation the Cascade
process licensed by Exxon Mobil and MW Kellogg and the Stratco effluent
refrigerated process. Figure 9.1.3 shows the cascade alkylation process.
Sulfuric acid consumption and regeneration

Sulfuric acid alkylation uses about 100 times as much acid as HF alkylation
because H2SO4 cannot be stripped from the conjunct polymer, water, and
contaminants. Sulfuric acid is typically spent at 88–91 wt% H2SO4, below which it is
too weak to carryout alkylation. The spent acid is not a waste. It is regenerated by
burning the organics which reduces the H2SO4 to SO2 and water vapor. The SO2 is
then dried and oxidized to SO3 and scrubbed with water to produce 98.5–99.5%
H2SO4.
For sulfuric alkylation, aside from the direct hazards of contacting the acid,
there are transportation safety issues around the need to ship and regenerate 20–
500 tons of H2SO4 daily. Several refiners have built dedicated acid plants to
regenerate spent acid from the alkylation unit or pipelines to and from an acid
manufacturer.
Acid consumption is generally expressed as the pounds of acid diluted from
99% to 90% by conjunct polymer, water, and other contaminants per gallon or barrel
of alkylate. Consumption can be as low as 16 lbs per barrel alkylate for diene-free,
MTBE raffinates run at ideal process conditions. Acid consumption can exceed 40 lb/
bbl of alkylate when running high levels of isobutylene, pentenes, and propylene at
high temperatures.
H2SO4 contaminants
Dienes

Butadiene and pentadienes are a major contaminants affecting

acid consumption. Dienes and can account for 10–30% of the acid
consumed. Dienes can dilute 5–20 lbs of 99% acid down to 90% per lb of
diene. Some refiners use diolefin selective hydrogenation units (such as
UOP-Huls SHP™) to eliminate this source of acid consumption.

Water and oxygenates

Water can also account for 10–20% of acid consumption. Wet

feeds, wet isobutane recycle, and high reactor temperatures are the main
sources. Oxygenates including acetone from the FCC, methanol and
dimethyl ether from MTBE and TAME units also consume acid. Water and
oxygenates dilute 10 lbs of 99% acid to 90 per lb of contaminant.
Sulfur and nitrogen compounds

Dilute about 20 lbs of 99% acid to 90% per lb of sulfur or nitrogen.

C6+ Dilutes 2 lbs of 99% acid to 90% per lb of contaminant. This can be a
significant contributor to acid consumption when alkylating pentenes.

Ethylene
Dilutes 20 lbs of 99% acid to 90% per lb of contaminant by forming
stable sulfates that stay in the acid.

Ethane and lighter

While inert, light ends increase compressor discharge pressure for

total condensation.
These indirectly increase acid consumptionwhen limited by horsepower by
increasing reactor temperature.
Recent developments

Motor fuel alkylation has recently received a boost from the planned
phase-out of MTBE in gasoline blending formulations. Without MTBE, the best
conventional components for today’s reformulated gasolines are high octane
paraffinic components like alkylate.

While environmental legislation has increased demand for alkylate, its

catalysts H2SO4 and HF came under intense environmental scrutiny in recent
years. While both acids are corrosive and toxic, HF is especially hazardous since it
has the potential to form toxic aerosols, which can travel significant distances
downwind of an accidental release. This scrutiny challenged the petroleum industry
to enhance safety and even to seek new alkylation catalysts.
UOP-Texaco and Mobil-Phillips developed cosolvents called Alkad™ and Revap
™, respectively, to reduce HF aerosoling.

A consortium of refiners and HF manufacturers lead by Amoco developed

HF dispersion models and water spray mitigation with extensive, large-scale testing
to design of release control systems. Together, cosolvents and water spray
mitigation can reduce downwind HF concentrations by over 95% should a release
occur.
 Through the American Petroleum Institute, the industry developed a
comprehensive document for safe operation of HF alkylation units entitled
‘Recommended Practice for Safe Operation of Hydrofluoric Acid Alkylation
Units’, API Recommended Practice 751, first published in June, 1992 and
reissued in February, 1999.

Finally the efforts to find new catalysts for alkylation have yielded
solid catalyst processes such as UOP’s Alkylene™ process that are ready
for commercialization.
Conclusions

Motor fuel alkylation using liquid hydrofluoric or sulfuric acids is

one of the oldest catalytic processes used in refining and petrochemical
operations. The liquid acid processes remain important despite concerns
with safety and environmental properties of the liquid acids. Solid catalyst
alkylation using processes such as Alkylene™ (UOP LLC) are emerging
technology.
Anhydrous hydrofluoric acid

Because of anhydrous hydrofluoric acid’ s (AHFs) highly toxic and

corrosive nature, this item is included to highlight its characteristics and the
safe handling of the acid.
Anhydrous hydrofluoric acid is a colorless, mobile liquid which
boils at 67◦F at atmospheric pressure, and therefore requires pressure
containers. The acid is also hygroscopic therefore its vapor combines with
the moisture of air to form “fumes”. This tendency to fume provides users
with a built-in detector of leaks in AHF storage and transfer equipment. On
the other hand, care is needed to avoid accidental spillage
of water into tanks containing AHF.

AHF vapor, even at very low concentrations in air, has a sharp

penetrating odor that is an effective deterrent to willful overexposure by
operating personnel. Both the vapor and liquid forms of AHF cause
severe and painful burns on contact with the skin, eyes, or mucous
membranes.
 Hydrofluoric acid is very corrosive. It attacks glass, concrete,
and some metals— especially cast iron and alloys which contain silica
(e.g., Bessemer steels). The acid also attacks such organic materials as
leather, natural rubber, and wood, but does not promote their
combustion.

Although AHF is non-flammable, its corrosive action on metals,

particularly in the presence of moisture, can result in hydrogen forming in
containers and piping to create a fire and explosion hazard. Potential
sources of ignition (sparks and flames) should be excluded from areas
around equipment containing hydrofluoric acid.

Despite its corrosive nature, AHF can be handled with relative

safety if the hazards are recognized and the necessary precautions
taken. This item describes certain procedures for the safe handling of
large bulk quantities of AHF.
Safe handling

The safe handling of AHF requires thatwell-designed equipment

be properly operated and maintained by well-trained, adequately
protected, responsible personnel.

Tanks and other containers of AHF should be protected from

heat and the direct rays of the sun. Storage-area temperatures should
preferably remain below 100◦F. If they reach or exceed 125◦F, means for
cooling the containers must be applied. Acid-transfer lines between the
unloading station and the storage tank should tilt toward the latter to
insure free drainage. Relief valves should be installed in those sections
of acid-transfer lineswhere acid may be entrapped between two closed
valves in the line, because expansion of the liquid might create
excessive pressure and rupture the line.

Noopen fires, open lights, or matches should be allowed in or

around acid containers or lines. The possibility of acid acting on metal to
produce hydrogen gas is ever present. Only non-sparking tools and
spark-proof electrical equipment should be used in the AHF storage and
handling areas.
Personal protective equipment
Personal protective equipment is not a substitute for good, safe working
conditions. Its purpose is to protect the wearer in the event of an accident—major or
minor.
The extent of protection needed depends upon the degree of exposure
attending the particular job at hand. Protective equipment should not be worn or
carried beyond the operating area. It should be thoroughly washed with sodium
bicarbonate solution immediately after each use. The minimum protection required
for operating and maintenance personnel includes the following items:
Coveralls with sleeves to the wrists
Face shield or chemical safety goggles
Hard hat
Poly(vinyl chloride)—or neoprene-dipped gauntlets
Poly(vinyl chloride)—or neoprene-soled rubber shoes
When taking acid samples, opening equipment which may contain hydrofluoric acid,
or performing similar hazardous duties, operators should wear the following:
Poly(vinyl chloride) or neoprene overalls
Poly(vinyl chloride) or neoprene boots
Lightweight poly(vinyl chloride) or neoprene gloves under poly(vinyl chloride)—or
neoprene-dipped gauntlets
Unloading and transfer of AHF

AHF is shipped in rail tank cars having capacities ranging from

approximately 5,400 gallons to 25,000 gallons and in road tank trucks of
approximately 5,250 gallons AHF capacity. Compressed dry gas (air,
hydrocarbon, or nitrogen) is the preferred means for transferring bulk
quantities of AHF, but a centrifugal, rotary or positive-pressure pump can be
used if necessary.

The unloading of AHF tank cars or tank trucks, with transfer of the
acid to plant storage, consists of five steps:
(1) Spotting the tank car or tank truck at the unloading station.
(2) Connecting the plant compressed-gas (or vapor) and AHF-unloading
lines to the
proper valves on the carrier tank.
(3) Transferring the AHF from the carrier tank to the storage tank.
(4) Disconnecting the plant compressed-gas (or vapor) and AHF-unloading
lines
from the carrier tank valves.
(5) Releasing the tank car or tank truck for return to the shipper.