MERICAT J: A New Kerosene Treating Technology to Meet Jet

Fuel Specifications
Karl Bussey - Sr. Technical Services Engineer, Merichem
Steven Chachere - Director of Engineering and Projects, ALON Refining
MERICAT J is a new wet treating technology that Merichem has developed for treating
kerosene to meet jet fuel mercaptan specifications. It does not use either hydrogen or
sodium hydroxide (caustic) followed by a catalytic carbon bed. MERICAT Js robust
technology maintains mercaptan treating efficiencies over a wide range of feedstock
qualities. Further, it offers the capability to increase unit capacity using the existing
equipment. This paper reviews the operating experience of the first commercial
MERICAT J installation at Alon USAs Krotz Springs refinery, and describes the
advantages of MERICAT J over other wet treating technologies which include lower
capital investment, reduced operating expenses, and other technical benefits.

Introduction
Jet fuels must meet stringent international specifications because they are used by
airlines world-wide. Regardless of where planes land, airlines need safe, high quality
fuels for re-fueling. Todays jet fuels must meet numerous specifications including
ranges for acidity, aromatics, naphthalenes, distillation range, density, viscosity, flash
point, smoke point, total sulphur, mercaptan sulfur, freeze point, color/appearance,
copper corrosion, water separation index, and thermal stability properties. Many
publications, including ASTM, list the jet fuel specifications and test methods for each jet
fuel grade.
Jet fuel production begins with crude oil distillation which separates the kerosene cut
within a specific boiling range from the whole crude. Some conversion units within the
refinery produce kerosene directly or indirectly. Further treating of the kerosene to meet
jet fuel product specifications varies based on the quality and impurities in the
kerosene.
Kerosene treating processes can be grouped into three categories:
1) No additional processing or minimal cleanup, like clay filtration.

2) Wet treating using caustic (NaOH) solution. Wet treating reduces acids content
and total mercaptan sulphur level to meet corrosion and sulphur tests specifications
without altering other kerosene properties. These processes typically use a NaOH
solution with a catalytic carbon bed to oxidize mercaptans to disulphide oil
(sweetening), followed by water washing, salt tower drying, and clay filtration.
3) Hydrotreating Based on the crude, some kerosene feed stocks will require
hydrotreating to meet specifications. Compared to wet treating processes,
hydrotreating capital costs are likely to be many times higher with operating costs
up to 20 times higher. As hydrotreating can be used to produce jet fuel from almost
any kerosene, it offers more flexibility lowering the total sulfur content in the final
product. Despite some flexibility over wet treating, hydrotreating may alter many
properties of the kerosene while wet treating only reduces the acid and mercaptan
sulfur contents. Of the total jet fuel produced about 45-55% is by hydrotreating and
35-45% by wet treating, with a small percentage falling into a minimal cleanup
category.
MERICAT J falls into a wet treating process category. Unlike other wet treating
processes, MERICAT J uses no NaOH or catalytic carbon bed. Instead, the process uses
Merichems proprietary treating solution JeSOLTM-9 to remove mercaptans from the jet
fuel in a single reactor followed by water washing, salt tower drying and clay filtration.
MERICAT J has many advantages over NaOH treating which are discussed later in this
paper. Prior to further discussion of the MERICAT J process it is valuable to describe the
wet treating process called MERICATTM II that Merichem began licensing in 1986.
Currently, Merichem has more than 40 MERICAT II units operating worldwide. In addition
there are many more wet treating (NaOH) processes operated by owners/operators.

Description of MERICAT II
FIGURE 1 contains a block flow diagram of a Merichem Kerosene Treating Unit (KTU) with
NAPFININGTM, MERICAT II, and AQUAFININGTM. The NAPFINING step reduces strong
acids (mostly naphthenic acids) to meet Total Acid Number (TAN) specifications and
protect the carbon bed in MERICAT II from naphthenic emulsion formations. NAPFINING
uses a dilute NaOH solution with Merichems proprietary contacting technology called
the FIBERFILM Contactor (FFC). Merichems FFC is a patented interfacial contacting
design that has been successfully used in over 800 operating plants worldwide since the
late 1970s. The FFC is an innovative design developed as an improvement to
conventional caustic/hydrocarbon dispersive mixing designs like mix valves. The design

creates a large contacting surface area between the hydrocarbons and the aqueous
treating reagents (E.g. NaOH, water, etc.) without vigorous dispersive mixing that form
emulsions. Merichems FFC reduces NaOH carryover with the hydrocarbon after the
contacting and reduces the size of separation vessels. Please see reference 1 for a more
detailed description of NAPFINING and Merichems FFC.
Upon exiting NAPFINING, the kerosene stream flows to MERICAT II. MERICAT II reduces
mercaptans down to Jet Fuel product specifications, which are typically < 0.003 wt. %
mercaptan sulphur. Mercaptans are a family of organic compounds in which sulphur and
hydrogen atoms (SH) are bonded to a carbon atom that is commonly abbreviated as
RSH. Mercaptans exude a very bad odor, are toxic, and cause corrosion. MERICAT II
consists of two discrete stages. The first stage uses an FFC to contact the kerosene with
caustic and a homogenous catalyst to oxidize lighter mercaptans. In the second stage,
heavier or longer chain mercaptans are treated across a fixed bed of activated carbon.
The two MERICAT II stages first extract mercaptans with a caustic solution to form
sodium mercaptides (NaSR) and then oxide them using injected air. The oxidation
produces disulphides, commonly referred to as DSO (disulphide oil). The overall reaction
is commonly referred to as sweetening. The DSO produced in the process remains
with the kerosene. Although the total sulfur content in the jet product does not change
from the feed kerosene total sulfur, the kerosene has been sweetened after the
mercaptans were removed.
Upon exiting MERICAT II, the treated kerosene passes through a water washing step with
an FFC called AQUAFINING to remove any residual caustic, a salt tower to remove free
water, and a clay filter to remove surfactants, particulates, and other trace
contaminants that may negatively impact jet fuel product specifications.

FIGURE 1: MERICHEM KEROSENE TREATING UNIT WITH MERICAT II

The general mercaptan reactions in MERICAT II are: Extraction: 2RSH + 2NaOH 2NaSR +
2H2O Oxidation: 2NaSR + O2 + H2O + (catalyst) RSSR + 2NaOH Overall Reaction:
2RSH + O2 + (catalyst) RSSR + H2O Where RSH = mercaptan and RSSR = Disulphide
Oil (DSO) Note: In the reactions above, the NaOH is regenerated in the oxidation
reaction to form RSSR and H2O. Also, some kerosene feeds contain H2O that can dilute
the NaOH strength with the H2O formed in the MERICAT II process. Over time, the NaOH
strength lessens until it becomes spent due to reactions with contaminants (E.g. nap
acids, sulfides, carbon dioxide, etc.). Spent NaOH must be replaced.

Description and Benefits of MERICAT J

MERICAT J was developed by Merichem as a new wet treating process for treating
kerosene to meet jet fuel mercaptan specifications. MERICAT J is truly a new step out
process technology that can replace the long used caustic / catalytic carbon bed
processes (which include MERICAT II). It offers many advantages that include lower
capital and operating costs and more robust performance characteristics. MERICAT J is
now proven with the successful operation of the first commercial unit at the ALON USA
Refinery in Krotz Springs, Louisiana. A more complete list of the advantages of MERICAT
J will be given after the process is described in more detail below.
Figure 2 is a block flow diagram of the MERICAT J process for treating kerosene. It should
be noted that the Alon USA Krotz Springs refinery installation is not identical to this
standard Merichem process design. As shown in the figure, MERICAT J replaces MERICAT

II in Merichems KTU process. Downstream of the NAPFINING stage, the kerosene stream
contacts the JeSOL-9 solution and FFC design in the MERICAT J process. The kerosene
then goes directly to the AQUAFINING stage, through the salt tower and clay filter, and
exits the KTU.
Merichems JeSOL-9 solution is a specially formulated treating reagent with higher
activity than the caustic / carbon bed process. Similar classes of reactions occur in the
MERICAT J process as in the MERICAT II process, but at a higher reaction rate. Although
the JeSOL-9 solution is internally regenerated after reacting with mercaptans, some
reactions with contaminants eventually cause the JeSOL-9 solution to gradually become
spent over time. Eventually, the JeSOL-9 solution will become fully spent and require
replacement with fresh JeSOL-9 solution.
Merichem offers a total package service agreement to its MERICAT J licensees. This
service includes supplying all fresh JeSOL-9 and taking back all spent JeSOL-9. As used
by Merichem, the spent JeSOL-9 is not a waste material under the Basel Convention.
This results in the refiner having no waste streams to dispose of in the MERICAT J
process.

FIGURE 2: MERICHEM KEROSENE TREATING UNIT WITH MERICAT J

Advantages of MERICAT J compared to MERICAT II include:
1). Significantly lower capital investment
Merichems evaluations show about 20 - 30% lower capital costs for MERICAT J
compared to a MERICAT II unit having the same design basis. These savings are

realized primarily because the carbon bed vessel is relatively large compared to the
MERICAT J vessel. Since the MERICAT J vessel is significantly smaller than any
vessels required for carbon bed wet caustic treating technologies, operators can
use existing equipment to further reduce capital investment. Additionally, MERICAT J
offers the opportunity to retrofit existing units with carbon beds to higher capacities
using the existing carbon bed vessel.
2). Operating costs are significantly lower
Merichems evaluations show that MERICAT J operates with 30 - 40% lower costs
compared to MERICAT II. These savings are realized by eliminating the carbon bed,
improving on-stream operating time, reducing consumption of JeSOL-9 compared to
NaOH, and lowering catalyst consumption. Another large cost associated with
operating a carbon bed is the cost to downgrade the jet fuel product values into the
diesel pool during routine carbon bed maintenance.
3). Higher Reliability
MERICAT J eliminates the catalytic carbon bed that is susceptible to temporary
fouling and permanent poisoning by certain impurities in the kerosene. In some
cases, the carbon bed is poisoned quickly which may not be recognized until the
carbon bed unit starts producing off specification jet fuel. Operating without a
carbon bed eliminates all of these issues and enables MERICAT J to have a longer
on-stream factor that other carbon based treating units. The ALON operating
MERICAT J has demonstrated on specification jet product that is significantly higher
than many caustic treating units operating with carbon beds.
4). Elimination of Carbon Bed Maintenance
All maintenance activities associated with catalytic carbon beds have been
eliminated. These include recausticization, water-washing, catalyst re-impregnation,
and carbon bed replacement.
5). Elimination of Waste Stream
Since Merichem supplies fresh JeSOL-9 solution and takes back all spent JeSOL-9
solution, a waste stream associated with treating the kerosene has been eliminated
for Merichems licensees. The operator does not have to process a JeSOL-9 waste
stream or any spent carbon material. Merichem assumes title and risk of loss upon
safe loading by the licensee at its facility or upon safe delivery and transfer back to

Merichems plant. All JeSOL-9 materials (fresh and spent) can be shipped by railcar,
tank wagon, or ISO totes depending on the quantity.
6). Revamping for Higher Capacity
MERICAT J offers refiners the opportunity to use existing vessels when they need to
increase capacity of an existing jet fuel wet treating unit. In most cases, Merichem
can retrofit existing carbon bed vessels with the MERICAT J internals to achieve
increased jet fuel capacity.

The ALON Krotz Spring Refinery MERICAT J Unit

ALON started up the MERICAT J unit in December of 2011. With the startup of this unit,
the refinery was able to make jet fuel from lower cost crude slates. In order to reduce
capital and meet an aggressive project schedule, the kerosene treating unit used
equipment for the water washing, salt drying and clay treaters that were already in
place at the refinery.
The Alon MERICAT J unit return on capital employed was greater than 100%, resulting in
a payout of less than 12 months. The kerosene treating unit design included NAPFINING
and MERICAT J technologies. Some of the basic design and normal operating parameters
for Alons MERICAT J unit are shown below in Table 1.

TABLE 1: ALON MERICAT J Primary Design/Operating Parameters

Design Capacity, Kerosene Flow
Normal Operating Capacity, Kerosene
Flow
Normal Operating Temperature

20,000 BPD
13,000 BPD
100 deg F

Normal Operating Pressure

Kerosene Inlet Mercaptan Sulfur, (max)

70 psig
130 ppm-wt.

Jet Fuel Product Mercaptan Sulfur

< 30 ppm-wt.

This MERICAT J unit project was implemented quickly to meet the fast track project
scope using the existing vessels as described earlier. The refinery elected to start the
unit up instead of delaying the project until long lead time parts for the JeSOL-9 water
removal system were delivered.

Soon after startup, Alon confirmed that the kerosene feed to the MERICAT J unit
contained more free water than was originally specified in the design feed basis.
Without the water removal system in place at startup, adequate water balance could
not be maintained and the JeSOL-9 solution was weakened more quickly than expected.
As a result, the JeSOL-9 had to be replaced more often than planned until the water
removal system came on line several months after startup. Despite the higher water
content in the unit, the MERICAT J operated very profitably.
After the water removal system was installed and became operational, the JeSOL-9
replacement frequency returned to predicted levels. A second equipment modification
to mitigate some of the design limits from reusing existing vessels was identified shortly
after startup but was not installed until March 2013. Following installation of both the
water removal system and the equipment modification, unit profitability increased to
new levels that have been maintained to the present.
Chart 1 shows the monthly averaged jet fuel percent on specification mercaptan levels
for the first 24 months of the MERICAT J operation following initial startup. Of the first 17
months of operation prior to May 2013, product mercaptans met specification from 82%
to 97% of the time for 11 months and 100% for 6 months. The equipment modification
was made in March 2013. From May 2013 through March, 2014, product mercaptans
were on specification 100% of the time. The data are a simple average during the
month of each mercaptan measurement taken once per day in the jet fuel product run
down stream.

Chart 2 shows additional mercaptan removal performance on a daily basis over several
months following the equipment modification in March 2013. The kerosene inlet
mercaptan is on the x axis and jet fuel product mercaptan is on the y axis. The
horizontal red line is the mercaptan specification limit of 30 ppm wt. During this time,
the kerosene feed rate averaged 14,080 BPD compared to normal operation design of
13,000 BPD and feed mercaptans exceeded the design basis. During these periods, the
MERICAT J process demonstrated its flexibility by maintaining product specifications
despite the wide range of feed mercaptan levels.

Merichems MERICAT J jet fuel treating technology has been successfully demonstrated
at the Alon Krotz Springs refinery. The process can be designed to treat jet fuel
mercaptans containing up to several hundreds of ppm (wt.). MERICAT J requires lower
capital investment and operates at a lower operating cost than other NaOH treating unit
designs using carbon beds. Additionally, MERICAT J can be used to revamp existing units
quicker and for lower total installed capital by reusing existing vessels. MERICAT J is a
true step out in jet fuel wet treating that has application throughout the world.

References
1) Forero, Patricia and Suarez, Felipe J (Merichem Company), duPont, Abe J (National
Petroleum Refiners of South Africa) Caustic Treatment of Jet Fuel Streams, PTQ Q1
1997.

2) Mohamadbeigy, Kh, Bayat, M., and Forsat, Kh. (Research Institute of Petroleum
Industry, Tehran), Studying on the Jet Fuel Treating Plant for Maximum Efficiency,
Petroleum and Coal 48(3), 36-41, 2006.
3) ASTM D1655, Standard Specifications for Aviation Turbine Fuels, and additional
relevant ASTM specifications and methods.
4) Aviation Fuels Technical Review, by Chevron Corporation, 2006.
5) Internal Merichem Company Reports and Documents.
6) Data and operating information supplied and used with permission by Alon USA Krotz
Springs Refining

Conventional Merox for sweetening jet fuel or kerosene [edit]

The conventional Merox process for the removal of mercaptans (i.e., sweetening) of jet fuel or
kerosene is a one-step process.[3] The mercaptan oxidation reaction takes place in an alkaline
environment as the feedstock jet fuel or kerosene, mixed with compressed air, flows through a fixed
bed of catalyst in a reactor vessel. The catalyst consists of charcoal granules that have been
impregnated with UOP's proprietary catalyst. The oxidation reaction that takes place is:
4 RSH + O2 2RSSR + 2H2O
As is the case with the conventional Merox process for treating LPG, the jet fuel or kerosene
sweetening process also requires that the feedstock be prewashed to remove any H 2S that
would interfere with the sweetening. The reaction that takes place in the batch caustic prewash
vessel is:
H2S + NaOH NaSH + H2O

Flow diagram[edit]
The Merox reactor is a vertical vessel containing a bed of charcoal granules that have been
impregnated with the UOP catalyst. The charcoal granules may be impregnated with the
catalyst in situ or they may be purchased from UOP as pre-impregnated with the catalyst. An
alkaline environment is provided by caustic being pumped into reactor on an intermittent, as
needed basis.[3]
The jet fuel or kerosene feedstock from the top of the caustic prewash vessel is injected with
compressed air and enters the top of the Merox reactor vessel along with any injected
caustic. The mercaptan oxidation reaction takes place as the feedstock percolates
downward over the catalyst. The reactor effluent flows through a caustic settler vessel where
it forms a bottom layer of aqueous caustic solution and an upper layer of water-insoluble
sweetened product.

The caustic solution remains in the caustic settler so that the vessel contains a reservoir for
the supply of caustic that is intermittently pumped into the reactor to maintain the alkaline
environment.
The sweetened product from the caustic settler vessel flows through a water wash vessel to
remove any entrained caustic as well as any other unwanted water-soluble substances,
followed by flowing through a salt bed vessel to remove any entrained water and finally
through a clay filter vessel. The clay filter removes any oil-soluble substances,
organometallic compounds (especially copper) and particulate matter, which might prevent
meeting jet fuel product specifications. The pressure maintained in the reactor is chosen
so that the injected air will completely dissolve in the feedstock at the operating temperature.

Conventional Merox process unit for sweetening jet fuel or kerosene