Kerosene Distillate Hydrotreating

Kerosene Treating Options to meet Jet Fuel Specifications

The major properties kerosene must have to qualify as a jet fuel are energy content, combustion quality,
stability, lubricity, fluidity, volatility, corrosivity, cleanliness, and safety. A summary of specifications for Jet
A, A-1, and B can be found in ASTM D1655.
Kerosene going into the jet fuel pool from hydrotreated or hydrocracked feedstock generally meets these
specifications. Straight run kerosene, however, may or may not. The amount of treatment straight run
kerosene must undergo to meet jet specifications depends on the properties of the crude being
run. Treatment options can run from simple to extensive. A summary of the most common shortcomings
and their remediation is described below:
None (meets all specs): Particulate filtering
High surfactant level: Clay treatment
High naphthenic acid level: Caustic treatment followed by salt drying and clay treatment
High mercaptan level: Caustic oxidation followed by salt drying and clay treatment
High olefin and/or total sulfur level: Mild hydrotreating followed by salt drying
High aromatic level: Heavy hydrotreating followed by salt drying
A brief description of these treatment options follows.
Particulate Filtering
If straight run kerosene meets all of the specifications (a possible but unlikely scenario), then only
particulate filtering needs to be done.
Clay Treatment
Clay treatment is the technology of choice for removing surface active components that can either be
naturally present in crude oil (e.g. naphthenic acid salts) or present due to contamination from other
products carried in common pipelines or containers. The problem with surfactants is their detrimental
effect on the operation of water coalescers.
Attapulgus clay is most often used for this service, and is usually supplied as a sand-like particle between
60 and 90 mesh. In refineries, large percolation columns are used that hold many tons of bulk clay. At
fuel distribution sites, smaller prepackaged cartridge and bag filters are used.
Caustic and/or Oxidation (Wet Treatment)
Caustic treatment is used when the straight run kerosene does not meet acid specifications. The acidic
compounds of most concern are naphthenic acids, which occur naturally in many crudes. A number of
processes have been developed to remove naphthenic acid and H2S, including destruction, adsorption,
and extraction, though the last is the only one that has any significant commercial application. The
Merichem Napfining Process is an extraction process found in many refineries.
Mercaptans are sulfur-containing compounds that are quite corrosive in jet fuel service. They have the
form RSH, where R represents a hydrocarbon group. Mercaptans with R groups higher than C3 are not
extracted to any extent by aqueous caustic solution, but are easily oxidized to disulfides in the presence
of catalysts in a basic solution. Disulfides are considerably less corrosive than mercaptans.
The Merichem Mericat process is commonly found in refineries for H2S and mercaptan removal. UOP
offers a competitive process called the MEROX process. In response to ever-higher costs for disposing
of spent caustic, UOP has developed the Caustic Free Merox process. This process relies on ammonia
instead of NaOH as the base.

Coalescing and Drying

The jet fuel leaving any of these wet processes must also be dried. Water removal is accomplished
through a combination of technologies depending on whether the water is free or dissolved.
Free water is typically removed in a separator (for gross separation) or a filter coalescer (for fine droplet
separation). Dissolved water is typically removed using a salt dryer, which is a vessel containing a bed of
salt particles, usually sodium chloride, though calcium chloride is sometimes used. As the fuel flows
upward through the bed, water in the fuel combines with the salt to form a concentrated brine solution.
Droplets of brine, being much denser than the fuel, collect in a sump at the bottom of the vessel.
Finally, the treated kerosene is passed through a clay treater and particulate filter as before.
Hydrotreating
Hydrotreating is used when the aromatic, olefinic, or total sulfur levels of the straight run kerosene do not
meet requirements. Hydrotreating reduces sulfur and olefin levels, and may reduce aromatic levels. Each
of these compounds is associated with its own set of problems in jet fuel.
Total sulfur is controlled because sulfur oxides formed during combustion can cause corrosion of turbine
metal parts. However, most straight run kerosene easily meets the 3000 ppm limit. (Most jet fuel used
worldwide falls in the 600-800 ppm S range). Constructing and operating a hydrotreater to merely
desulfurize kerosene is generally not economic.
Olefinic compounds are controlled because they present thermal stability problems, as they tend to
polymerize and form gums at higher temperatures. These gums interfere with fuel flow and engine
system control, increase pressure drop across fuel filters, and plug injector nozzles. Jet fuel thermal
stability is assessed using the Jet Fuel Thermal Oxidation Tester (JFTOT).
Olefinic compounds can be catalytically reacted with hydrogen to paraffins under relatively mild conditions
(as low as 300 psig and 500 F). At these conditions 85% or more of the incoming sulfur is converted to
H2S as well. However, nitrogen compounds and aromatics are not typically reacted. Hydrogen
consumption for this kind of unit is typically 50 SCF/BBL or less.
Aromatic compounds are controlled because they present combustion problems. Fuels containing
aromatics tend to form carbonaceous particles as a result of incomplete combustion more than those
without aromatics. This can lead to two types of issues. Burning particles can become incandescent and
result in hot spots that cause metal cracks and premature engine failure. If the particles do not burn
completely, they will build up on turbine blades and stators and plug holes in the combustor walls
designed to let air in. In the boiling point range of kerosene, both mono- and di-aromatic compounds can
be expected. Of these two, di-aromatics (naphthalenes) have the greater tendency for incomplete
combustion. For these reasons, jet fuel is limited to a maximum total aromatic content of 25 vol%. A proxy
test that is correlated to aromatic content is the Smoke Point test. A smoke point of 25mm or greater is
required unless the napthalene content is below 3 vol%, in which case the minimum allowable smoke
point is relaxed to 18 mm.
Aromatic compounds can be catalytically reacted with hydrogen to cyclic paraffins, but the conditions
required are considerably more severe than those to react olefins. The typical reactor conditions are 500
F and a minimum pressure of 600 psig. The operating and capital costs for this type of hydrotreater is
considerably higher than for light hydrotreating. Hydrogen consumption for high severity operation can be
200 SCF/BBL.
In both low and high severity cases the kerosene leaving the reactor must be stripped to remove H2S,
NH3, and light hydrocarbons. Stripping is tyically accomplished in a trayed column using fuel gas,
hydrogen, or most commonly, steam. If steam is used, a coalescer and salt dryer are required as well.
A low pressure unit might be considerably simpler, with once-through hydrogen use, no integral amine
unit, and only a single low temperature separator.

Conclusions
This article briefly summarizes jet fuel specifications, what inherit properties govern the ability of straight
run kerosene to meet these specifications, and what treatment options are typically used to eliminate any
shortcomings. If the correct crude feed is selected and the column is operated properly, it is possible to
create a straight run kerosene that meets jet fuel requirements with almost no downstream processing at
all. However, this severely limits the kinds of crude that can be run. The more processing units that exist
to reduce or transform undesirable components in the straight run kerosene, the wider the range of lower
cost crudes that can be run. However, this flexibility comes at the price of greater capital and operating
cost.