NAPHTA HYDROTREATING UNIT

INTRODUCTION:
Purpose of the naptha hydrotreater is to produce clean hydro treated feed stocks to feed the isomerization
unit and platforming unit.NHT unit reduces the level of contaminants such as S, N , H2O, halogens,diolefoins,olefins,arsenic,mercury and other metals to very low level so as not to affect the downstream unit
performance
PROCESS FLOW DIAGRAM:

PROCESS DESCRIPTION:
Straight run naphtha from atmospheric distillation column is sent to naphtha hydro treating unit. In NHT
straight run naphtha is sent to the surge drum where water present in the feed is routed to OWS. Naphtha is
sent to reactor section by the charge pumps. Naphtha from charged pumps is combined with hydrogen rich
recycle gas from the recycle gas compressor. The combined feed is heated in the charge heater before going
to NHT reactor. In the reactor sulphur, nitrogen and other contaminants from the feed gets removed in a
down flow catalyst bed. Reactor effluent passes through the product condenser to condense the naphtha
vapours to low enough temperature to recover the naphtha and enters the separator. Separator ensures
separation of liquid naphtha, sour water and hydrogen rich recycle gas. Separator is provided with water boot

to collect the water injected for salt removal. Sour water is routed to sour water stripper unit under a level
controller. The hydrogen rich gas is recycled via recycle compressor suction drum and recycle compressor to
upstream of the combined feed exchanger. Hydrocarbon liquid from the separator under level controller and
any entrained liquid from recycle gas compressor suction drum are combined and routed to the stripping
section through stripper feed bottom exchanger where it is pre heated.
In the stripper hydrocarbon liquid is re-boiled in the re-boiler with high pressure steam. Stripper strips off
H2S, any water traces light hydrocarbons and any dissolved hydrogen in the hydrocarbon. The over head
vapor from the stripper passes through an air fan cooler and enters the stripper receiver. Light hydrocarbons
collected in the stripper receiver are returned to the stripper as reflux by the stripper reflux pump. Normally
no net over head liquid product is drawn although a line is provided to allow draining of accumulated light
hydrocarbon liquid over a period of time. Stripper bottom liquid is cooled in the stripper feed bottom
exchanger and then passes to splitter column.

Splitter splits the hydro treated naphtha to light naphtha which is NIU unit feed and heavy naphtha which is
feed to platforming unit. A re-boiler heater is provided for necessary heat of vaporization. Splitter over head
vapours leaving from the top of the naphtha splitter under pressure control are cooled in over head condenser
and passes to splitter over head receiver. Part of the over head liquid is drawn as over head product (LN) and
the remaining liquid is pumped back to the splitter as reflux. Splitter bottom liquid splits into two streams
one stream to splitter re-boiler and the second stream is cooled in the stripper feed splitter bottom exchanger

and routed to salt water cooler to drop the HN temperature to atmospheric temperature before routing to
storage.
PROCESS CHEMISTRY:
Introduction:
Naphtha like other petroleum fractions contains varying amount of naturally occurring contaminants
including organic sulphur nitrogen and metal compounds. These contaminants are removed by hydro treating
process which is a proprietary, fixed bed, catalytic hydrogenation method developed by UOP to upgrade the
quality of light kerosene with a negligible effect on the boiling range of light naphtha product. Hydro
treating is designed primarily to remove sulphur and nitrogen. In addition, the process does an excellent job
of saturating olefins and aromatics compound and removing other contaminants such as oxygenates halides
and organometallic compounds.
Hydro treating of naphtha is carried out at elevated temperatures and pressures in a hydrogen
atmosphere to make it suitable for CCR. Catalysts of naphtha hydrotreater are formulated by compositing
varying amount of nickel and cobalt with molybdenum oxide on an alumina base. Design of the unit is based
on feed quality. Desired product property, ease of operation, desired cycle length, operating flexibility and
operating cost. The following chemical steps and/or reactions occur during hydro treating of naphtha.
Sulphur removal
Naphtha feed stock to the unit contains simple mercaptans, sulphides and disulphides. These compounds are
easily converted to H2S. However, feed stocks containing hetero atomic aromatic molecules are more
difficult to process. Desulphurization of these compounds proceeds by initial ring opening and sulphur
removal followed by saturation of the resulting olefins. Benzothiophene is considered fifteen times more
difficult to process compared to di ethyl sulphide. Desulphurization reaction takes place with sulphur
removal followed by olefin saturation. At high conversion level, desulphurization reaction follows first order
kinetics.

Mercaptan

C-C-C-C-SH

H2

C-C-C-C

H2S

Sulphide
C-C-S-C-C

2 H2

2 C-C

H2S

2 C-C

2H2S

Disulphide
C-C-S-S-C-C

3 H2

Cyclic Sulphide

Thiophenic

NITROGEN REMOVAL:
Denitrogenation is generally more difficult than desulphurization. Side reactions may yield nitrogen
compounds more difficult to hydrogenate than the original reactant. Nitrogen removal follows closely first
order kinetics. Both increasing temperature and increasing hydrogen pressure enhance the removal of total
nitrogen. The reaction mechanism steps are different compared to desulphurization. The Denitrogenation of
pyridine proceeds by aromatic ring saturation, ring hydrogenolysis, and finally Denitrogenation. Saturation
of heterocyclic nitrogen containing rings is also hindered by large attached groups shown below:
Pyridine

Quinolone

Pyrrole

OXYGEN REMOVAL:
Organically combined oxygen is removed by hydrogenation of the carbon-hydroxyl bond forming water and
the corresponding hydrocarbon.

OLEFIN SATURATION:
Olefin saturation reactions proceeds very rapidly and have a high heat of reaction than other
hydrotreatingreactions.
Linear olefin:
C-C=C-C-C-C

H2

C-C-C-C-C-C (and isomers)

AROMATIC SATURATION: Aromatic saturation reactions are the most difficult. The reactions are
influenced by process conditions and are often equilibrium limited. Unit design parameters would consider
the desired degree of saturation for each specific unit. The saturation reaction is very exothermic.

METALS REMOVAL:

Organic metals native to most crude oils are nickel and vanadium. Iron can be found concentrated at the top
of the catalyst beds as iron sulphides that are corrosion products. Sodium, calcium and magnesium are due to
contact of the feed with salt, water and additives.
Lead may also deposit on the hydro treating catalyst from reprocessing leaded gasoline through the crude
unit. Lead has a large effect on the catalyst activity. Arsenic occurs naturally in certain crude oil and is
observed in all crude oil fractions. It is even more severe poison than lead.
Improper use of additives to protect fractionator overhead system from corrosion and to control foaming
,accounts for the presence of phosphorous and silicon. Metal removal is essentially complete above
temperature of 315oC to a metals loading of 2-3 wt. % of the total catalyst. Above this level, the catalyst
begins to approach equilibrium saturation and metals breakthrough.
The total metals retention of the catalyst system can be increased by using a guard reactor or a guard bed of
catalyst specifically designed for demetallisation. Some demetallisation catalysts may retain as much as 100
wt. % metals based on fresh catalyst weight. Such catalysts typically have a lower activity for
desulphurization and Denitrogenation.
HALIDES REMOVAL:
Organic halides, such as chloride and bromides, present in naphtha are decomposed in the reactor. The
inorganic ammonium halide salts that are produced when the reactants are cooled are then dissolved by
injecting water into the reactor effluent or leave with the stripper off-gas. Decomposition of organic halides
is considered difficult with a maximum removal of approximately 90%.

HCl +

NH3

NH4Cl