Naphtha Hydrotreating

• Heavy naphtha hydrotreating is usually used to remove the

impurities so that the hydrotreated naphtha can be
introduced to the catalytic reformer.
• The expensive platinum based catalyst used in the reformer is
sensitive to poisoning by such impurities. A schematic flow
diagram for the naphtha hydrotreating process is shown in
Figure 7.6.
• The naphtha reformer consists of a feed heater, reactor, high
and low pressure separators, recycle compressor and treated
naphtha fractionator. A hydrogen sulphide scrubber might be
placed between the high and low pressure separators. Some
of the recycled gas is purged to lower the concentration of
light hydrocarbon (C1–C4).
• A catalyst of Co–Mo on alumina is used.
Naphtha Hydrotreating process
 Middle Distillates Hydrotreating
• Middle distillate is mainly composed of saturated paraffins and also some
aromatics which include simple compounds with up to three aromatic
rings.
• Kerosene, jet fuel oil and diesel fuel are all derived from middle distillate
fractions. Typical kerosene feed and product properties are given in Table
7.4.
• The typical overall yield balance for a kerosene hydrodesulphurization
(HDS) unit is given in Table 7.5 (Parakash, 2003). Diesel hydrotreating is
shown here as an example of this class in Figure 7.7. The feed stream is
combined with recycled hydrogen and make-up hydrogen and heated in a
fired heater.
• The reactor effluent is separated in a high pressure separator into a liquid
and recycled hydrogen. The liquid is then flashed into the low pressure
separator, producing a gas which is sent to the C3 and C4 recovery unit
and a liquid which is sent to a fractionator which produce gases, naphtha
and hydrotreated diesel. A hydrogen sulphide scrubber and a gas purging
are usually used to improve the quality of recycled hydrogen.
Diesel fuel hydrotreating unit
 Atmospheric Residue Desulphurization

• Atmospheric residue can be desulphurized

using the process shown in Figure 7.8. Middle
East atmospheric residue has a sulphur content
of 4–5 wt% and metals (Ni + V) of 70- 90 wppm.
The purpose of this process is to remove most
of the metals and reduce sulphur content in the
product to less than 0.5 wt%.
Atmosphere residue desulphurization
process
 Atmosphere residue desulphurization

• The feed is introduced into the heater where steam is injected (to
prevent coking) to a temperature below 371 C (700 F). The heated
recycled hydrogen is mixed with feed and together, they are introduced
into a guard reactor which contains a hydrogenation catalyst similar to
that in the main reactor but usually cheaper. The catalyst should have
wide pores to avoid plugging due to metal deposition. In the reactor,
organo-metalic compounds are hydrogenated and metal is deposited.
• Salts from crude desalters are also removed here. Due to the fast
deactivation of this catalyst, usually two reactors are used and the
catalyst is changed in one of them while the other reactor is still online.
The catalyst in the guard reactor contains 8% of the total catalyst used
in the process.
• Desulphurization, denitrification and hydrodemetallization reactions
require severe conditions. Three to four reactors are usually used with
different combinations of catalysts to achieve desired objectives. In
some units there is a provision for online catalyst replacement in the
guard reactor
• The stream leaving the guard reactor is quenched with cold recycle
hydrogen and introduced to the first of the three fixed bed reactors.
The main reactions of hydrodemetallization, hydrodesulphurization,
denitrogenation and aromatic hydrogenation take place in the
reactors.
• The flow diagram also contains high and low pressure separators,
recycled hydrogen stream with online amine treatment and purge.
The liquid stream from the separators are send to a fractionator to
produce naphtha, diesel and low sulphur fuel oil (LSFO).
• The ARDS unit reactor temperature is increased at the end of the run
(EOR) to burn off any deposited carbon; where thermal cracking
occurs at these temperatures. It is possible to use the same unit as a
hydrocracker by switching the catalyst to a bifunctional type in which
hydrotreating and hydrocracking take place as explained under
hydrocracking. Typical ARDS feed and products properties are given
in Table 7.6, and typical ARDS yields are given in Table 7.7 (Parakash,
2003).
Operating Conditions of Hydrotreating
• The operating conditions of the hydrotreating processes include pressure,
• temperature, catalyst loading, feed flow rate and hydrogen partial pressure.
• The hydrogen partial pressure must be greater than the hydrocarbon partial
• pressure. High pressure and high hydrogen flow rate (make-up and recycle)
• would insure that. Increasing hydrogen partial pressure improves the
• removal of sulphur and nitrogen compounds and reduces coke formation
• (Heinrich and Kasztelan, 2001).
• Higher temperatures will increase the reaction rate constant and improve
• the kinetics. However, excessive temperatures will lead to thermal cracking
• and coke formation. The space velocity is the reverse of reactor residence time
• (y). High space velocity results in low conversion, low hydrogen consumption
• and low coke formation. The range of operating conditions for
• hydrotreating of different feed fractions is given in Table 7.9.
Process parameters for hydrotreating
different feedstocks