Alkylation Unit

Alkylation of alkenes (shown here is propene) by isobutane is a major process in refineries. It is

catalysed by strong acids such as HF and sulfuric acid.
In a standard oil refinery process, isobutane is alkylated with low-molecular-weight alkenes
(primarily a mixture of propene and butene) in the presence of a strong acid catalyst, either
sulfuric acid or hydrofluoric acid.[4] In an oil refinery it is referred to as a sulfuric acid alkylation unit
(SAAU) or a hydrofluoric alkylation unit, (HFAU). Refinery workers may simply refer to it as the alky
or alky unit. The catalyst protonates the alkenes (propene, butene) to produce reactive
carbocations, which alkylate isobutane. The reaction is carried out at mild temperatures (0 and 30
C) in a two-phase reaction. Because the reaction is exothermic, cooling is needed: SAAU plants
require lower temperatures so the cooling medium needs to be chilled, for HFAU normal refinery
cooling water will suffice. It is important to keep a high ratio of isobutane to alkene at the point of
reaction to prevent side reactions which produces a lower octane product, so the plants have a
high recycle of isobutane back to feed. The phases separate spontaneously, so the acid phase is
vigorously mixed with the hydrocarbon phase to create sufficient contact surface.
The product is called alkylate and is composed of a mixture of high-octane, branched-chain
paraffinic hydrocarbons (mostly isoheptane and isooctane). Alkylate is a premium gasoline
blending stock because it has exceptional antiknock properties and is clean burning. Alkylate is
also a key component of avgas. The octane number of the alkylate depends mainly upon the kind
of alkenes used and upon operating conditions. For example, isooctane results from combining
butylene with isobutane and has an octane rating of 100 by definition. There are other products in
the alkylate, so the octane rating will vary accordingly.
Since crude oil generally contains only 10 to 40 percent of hydrocarbon constituents in the
gasoline range, refineries use a fluid catalytic cracking process to convert high molecular weight
hydrocarbons into smaller and more volatile compounds, which are then converted into liquid
gasoline-size hydrocarbons. Alkylation processes transform low molecular-weight alkenes and isoparaffin molecules into larger iso-paraffins with a high octane number.
Combining cracking, polymerization, and alkylation can result in a gasoline yield representing 70
percent of the starting crude oil. More advanced processes, such as cyclicization of paraffins and
dehydrogenation of naphthenes forming aromatic hydrocarbons in a catalytic reformer, have also
been developed to increase the octane rating of gasoline. Modern refinery operation can be
shifted to produce almost any fuel type with specified performance criteria from a single crude
feedstock.
Refineries examine whether it makes sense economically to install alkylation units. Alkylation units
are complex, with substantial economy of scale. In addition to a suitable quantity of feedstock, the
price spread between the value of alkylate product and alternate feedstock disposition value must
be large enough to justify the installation. Alternative outlets for refinery alklylation feedstocks

include sales as LPG, blending of C4 streams directly into gasoline and feedstocks for chemical
plants. Local market conditions vary widely between plants. Variation in the RVP specification for
gasoline between countries and between seasons dramatically impacts the amount of butane
streams that can be blended directly into gasoline. The transportation of specific types of LPG
streams can be expensive so local disparities in economic conditions are often not fully mitigated
by cross market movements of alkylation feedstocks.
The availability of a suitable catalyst is also an important factor in deciding whether to build an
alkylation plant. If sulfuric acid is used, significant volumes are needed. Access to a suitable plant is
required for the supply of fresh acid and the disposition of spent acid. If a sulfuric acid plant must
be constructed specifically to support an alkylation unit, such construction will have a significant
impact on both the initial requirements for capital and ongoing costs of operation. Alternatively it
is possible to install a WSA Process unit to regenerate the spent acid. No drying of the gas takes
place. This means that there will be no loss of acid, no acidic waste material and no heat is lost in
process gas reheating. The selective condensation in the WSA condenser ensures that the
regenerated fresh acid will be 98% w/w even with the humid process gas. It is possible to combine
spent acid regeneration with disposal of hydrogen sulfide by using the hydrogen sulfide as a fuel.[5]
The second main catalyst option is hydrofluoric acid. In typical alkylation plants, rates of
consumption for acid are much lower than for sulfuric acid. These plants also produce alkylate
with better octane rating than do sulfuric plants. However, due to its hazardous nature, HF acid is
produced at very few locations and transportation must be managed rigorously.

Alkylation unit
Alkylation unit, is one of the conversion processes used in the petroleum refineries. It is used to
convert isobutane and low-molecular-weight alkenes (primarily a mixture of propene and butene)
in the presence of a strong acid catalyst. The acid can be either sulfuric acid or hydrofluoric acid.
Depending on the acid used as catalyst the unit takes the name of SAAU (Sulphuric Acid Alkylation
Unit) and HFAU (Hydrofluoric Acid Alkylation Unit). Since crude oil generally contains only 10 to 40
percent of hydrocarbon constituents in the gasoline range, refineries use a fluid catalytic cracking
unit (FCCU) process to convert high molecular weight hydrocarbons into smaller and more volatile
compounds, which are then converted into liquid gasoline-size hydrocarbons. Alkylation processes
transform low molecular-weight alkenes and iso-paraffin molecules into larger iso-paraffins with a
high octane number. FCCU is a very common unit in a modern oil refinery, but it is not uncommon
for a refinery not to have an alkylation unit. Indeed, by 2010 there are some countries in the world
without any installed alkylation unit.
The product of the unit is called alkylate and is composed of a mixture of high-octane, branchedchain paraffinic hydrocarbons (mostly isoheptane and isooctane). Alkylate is a premium gasoline
blending stock because it has exceptional antiknock properties and is clean burning. The octane
number of the alkylate depends mainly upon the kind of alkenes used and upon operating
conditions. For example, isooctane results from combining butylene with isobutane and has an
octane rating of 100 by definition. There are other products in the alkylate, so the octane rating
will vary accordingly.
Feeds and process description

The first alkylation units entered in service in 1940. Since around 1,600,000 barrels per day of
capacity have been installed world-wide (capacity installed in 2009),[1] with an equal share of
800,000 barrels per day for SAAU and HFAU technologies. For safety reason SAAU is the prevalent
current technology of choice. Indeed in 1996 around 60% of the installed capacity was based on
HF,[2] but since then this ratio has been reducing.
The availability of a suitable catalyst is also an important factor in deciding whether to build an
alkylation plant. If sulfuric acid is used, significant volumes are needed. Access to a suitable plant is
required for the supply of fresh acid and the disposition of spent acid. If a sulfuric acid plant must
be constructed specifically to support an alkylation unit, such construction will have a significant
impact on both the initial requirements for capital and ongoing costs of operation. Alternatively it
is possible to install a WSA Process unit to regenerate the spent acid. No drying of the gas takes
place. This means that there will be no loss of acid, no acidic waste material and no heat is lost in
process gas reheating. The selective condensation in the WSA condenser ensures that the
regenerated fresh acid will be 98% w/w even with the humid process gas. It is possible to combine
spent acid regeneration with disposal of hydrogen sulfide by using the hydrogen sulfide as a fuel.[3]
The second main catalyst option is hydrofluoric acid. In typical alkylation plants, rates of
consumption for acid are much lower than for sulfuric acid. The small amount of organofluorine
side products are continuously removed from the reactor and the consumed HF is replenished. HF
acid plants can process a wider range of feedstocks with propylenes and butylenes. These plants
also produce alkylate with better octane rating than do sulfuric plants. However, due to its
hazardous nature, HF acid is produced at very few locations and transportation must be managed
rigorously.

The olefin feed to an alkylation unit generally originates from a FCCU and contains butene,
isobutane, and possibly propene and/or amylenes. The olefin feed is also likely to contain diluents

(such as propane, n-butane, and n-pentane), noncondensables (such as ethane and hydrogen) and
contaminants, which are discussed in detail on the following pages. Diluants in principle have no
effect on the reaction of alkylation but occupy a portion of the reactor and can influence the yield
of secondary reactions of polymerisation and of undesired organofluorine side products.
Incondensable are from a chemical perspective similar to diluents but they do not condense at the
pressure and temperature of the process, and therefore they concentrate to a point that must be
vented. Contaminants are compounds that react with and/or dilute the sulfuric acid catalyst. They
increase acid consumption and contribute to produce undesirable reaction products and increase
polymer formation. Common contaminants are water, methanol and ethanol.

The isobutane feed to an alkylation unit can be either low or high purity. Low purity makeup
isobutane feedstock (typically < 70 vol% isobutane) usually originates from the refinery and need
to be processed in the deisobutanizer (DIB). High purity feedstock (> 70 vol% isobutane) normally
originates from an external DIB and is fed directly to the alkylation unit reaction zone. The
isobutane feed does not normally contain any significant level of contaminants.
The catalyst protonates the alkenes (propene, butene) to produce reactive carbocations, which
alkylate isobutane. The reaction is carried out at mild temperatures (0 and 30 C) in a two-phase
reaction. Because the reaction is exothermic, cooling is needed: SAAU plants require lower
temperatures so the cooling medium needs to be chilled, for HFAU normal refinery cooling water
will suffice. It is important to keep a high ratio of isobutane to alkene at the point of reaction to
prevent side reactions which produces a lower octane product, so the plants have a high recycle of
isobutane back to feed. The phases separate spontaneously, so the acid phase is vigorously mixed
with the hydrocarbon phase to create sufficient contact surface.

Economics
Refineries examine whether it makes sense economically to install alkylation units. Alkylation units
are complex, with substantial economy of scale. In addition to a suitable quantity of feedstock, the
price spread between the value of alkylate product and alternate feedstock disposition value must
be large enough to justify the installation. Alternative outlets for refinery alklylation feedstocks
include sales as LPG, blending of C4 streams directly into gasoline and feedstocks for chemical
plants. Local market conditions vary widely between plants. Variation in the RVP specification for
gasoline between countries and between seasons dramatically impacts the amount of butane
streams that can be blended directly into gasoline. The transportation of specific types of LPG
streams can be expensive so local disparities in economic conditions are often not fully mitigated
by cross market movements of alkylation feedstocks.
The common source of the C3 alkenes for the alkylation is made available from the gas recovery
unit processing the effluents of the Fluid catalytic cracking Unit. Isobutane is partly made available
from the Catalytic reforming and from the Atmospheric distillation, although the proportion of the
isobutane produced in a refinery is rarely sufficient to run the unit at full capacity and additional
isobutane needs therefore to be brought to the refinery. The economics of the international and
local market of gasolines dictates the spread that a buyer need to pay for isobutane compared to
stardard commercial butane.
Safety
Alkylation units have two primary process hazards: 1) The unit process large volumes of light
hydrocarbons which are highly flammable and potentially explosive. 2) The acid catalyst is
corrosive and toxic. Both HSAU and HFAU contain similar volumes of hydrocarbon with similar
risks, but the risks associated with each acid are quite different. HF requires much stricter
precautions because of its greater potential for harm (this is due to its lower boiling point and
higher harmful potential). In light of this high risk, the American Petroleum Institute has issued a
Recommended Practice specifically for HF alkylation units (API RP 751). This publication
recommends that access to an HF alkylation unit be strictly limited due to the potential hazards of
HF. No similar, specific safety document is required for sulfuric acid alkylation.
Because of its low boiling point, spent HF is regenerated by fractionation within the HF alkylation
unit. However, fresh HF must still be brought into the refinery to replace the HF consumed. The
unloading and handling of fresh HF must be undertaken with great care since this operation
carries the same risk to the refinery workers and surrounding community from an HF release as
previously discussed. Perhaps the greatest transportation risk related to HF is the potential release
during an accident while transporting fresh acid from the manufacturer to the refinery. Since no
mitigation equipment would be available at an accident site, the consequences could be
catastrophic.
Spent sulfuric acid is regenerated by thermal decomposition outside the battery limits of the
sulfuric acid alkylation unit. This may be accomplished on the refinery site in sulfuric acid
regeneration equipment operated by the refinery or in a commercial sulfuric acid regeneration
plant which serves several refiners. The choice between these two options is site specific and
usually depends on capital versus operating cost considerations and the proximity of the refinery
to an existing commercial regeneration plant. As there is low risk from the sulfuric acid itself, the

choice to regenerate on-site the acid ot elsewhere is based on consideration of economic nature.
Of course, even this relatively minor risk is eliminated with on-site sulfuric acid regeneration
equipment. Most refin
The tanks containing the alkylate produced trough a HFAU needs to be monitored continuously.
Indeed, alkylate produced in such units contains small impurities of HF. If the alkylate enters in
contact with water (for example in the bottom of the tank), the HF can migrate in the water and
cause corrosion of the steel. For this reason the PH of the water from the purge of the tanks used
to storage alkylate need to be monitored periodically.