Desulfurization

Desulphurization Units

1. Hydrotreater
2. Mercaptane Oxidizer (Merox)
3. Atmospheric Residue Desulphuriser (ARDS)

1. Hydrotreating
Hydrotreating is a mild catalytic process (moderate temperature and pressure)

Objectives

1. Reduce objectionable materials like sulfur and nitrogen, oxygen, halides, and trace
metals content

2. Saturate olefins and (gum-forming unstable) diolefins

3. Hydrogenate aromatic rings into paraffins (to reduce aromatic content and meet
environmental regulations)
4. Does not change the BP of the feed
5. There are about 30 hydrotreating processes available for licensing
6. Most of them have essentially the same process flow

Feed and Products

Feeds and Products
The feed ranges from Naphtha to reduced crude (residue).
The heavier the feed the more severe the process is (higher T & P)

Process Hydrotreating
The process is basically the same for all except naphtha
The oil feed is mixed with hydrogen-rich gas consisting of both recycle and fresh makeup hydrogen
It is then preheated, utilizing hot streams within the unit and a fired heater, to the
reactor inlet temperature of 500 800 F depending on the feedstock
Reactor inlet temperature for Kerosene: SOR-624F / EOR-700F
Reactor inlet temperature Gasoil: SOR-626F / EOR-698F
The feed mixture enters the top of a fixed-bed reactor
SOR : Start of Run; EOR: End of Run
The lowest temperature at which plant is commissioned to yield desired product quality for example sulfur of 0.5 ppm is
called SOR When the catalyst deactivation is reached to the extent that it has to be regenerated to get specified product
quality we say that it has achieved EOR
Cycle length=EOR - SOR
Ultimate life is the period from SOR to catalyst replacement.

Process Hydrotreating Contd...

In the presence of the metal-oxide catalyst, the hydrogen reacts with the objectionable
materials in the oil to produce hydrogen sulfide (H2S), ammonia (NH3), saturated
hydrocarbons, and free metals
Metals remain on the surface of the catalyst and other products leave the reactor with
the oil-hydrogen stream
reactor outlet cooled (by heating the feed) before separating the oil from the H2-rich gas
H2-rich gas is recycled and supplemented with fresh make-up H2 before it is mixed with
the fresh feed again
Some gas is purged continuously from recycle gas section to H2 recovery unit maintain
the required hydrogen purity and partial pressure in the reactor
Desulfurized oil is stripped of any remaining hydrogen sulfide (and light ends to adjust
the flash point) in a steam stripper
Small quantity of wild naphtha is produced from the top of the stripper and is sent to
the Naphtha HTU (via CDU fractionator or ARDS stabilizer) for recovery as product
The stripped oil is fed to a vacuum dryer (operating at 80 mmHg, using a two-stage
steam jet ejector system) where moisture is removed
The treated final product from the dryer bottom is cooled then sent to storage

Process Kerosene Hydrotreating

Product is Aviation Turbine Kerosene (ATK) or illuminating Kerosene (IK)
The major improvements for the product quality will be with respect to smoke point (23
to 25) sulfur and olefin to (0.05 wt% max)
The reaction pressure is 668 psig & H2 consumption 235 SCF/B feed
The hydrogen requirements of the reaction are jointly met by ARDS purge gas and
high purity hydrogen make up gas
A two-bed reactor with quench gas is provided

Process Naphtha Hydrotreating

Naphtha Hydrotreater -designed to meet the requirements for blending into
Petrochemical Naphtha pool or into Motor Gasoline pool
Major improvements for the product quality will be in the olefins content, nitrogen
content & sulfur content
Reaction pressure is 415 psig
Hydrogen consumption is about 415 SCF/BBL
The Coker Naphtha is first mixed with make-up H2 gas, heated up and sent to the first
reactor where a liquid phase hydrogenation reaction is carried out to take care of the
diolefins and gums in Coker naphtha (which would otherwise cause severe fouling
problems in vapor phase naphtha hydrotreating reaction)
The feed (saturated naphtha) from ARDS (after heating up against 2nd reactor effluent)
is then combined with first reactor effluent and recycle gas and vaporized totally in a
heater before sending to the second reactor

Process Naphtha Hydrotreating contd...

Hydrotreating reactions are completed in the second reactor which has 2 types of
catalysts
Distillation section consist of a naphtha stabilizer to achieve required RVP & H2S
content on finished product
Reboiler heat comes from second reactor effluent

Process Diesel Hydrotreating

Major improvements for the product quality are with respect to sulfur content and
reduction of Conradson carbon (from 0.22 % to 0.05 wt%)
The reaction pressure is 668 psig and H2 consumption about 277 SCF/B feed
The hydrogen requirements of the reaction are jointly met by ARDS purge gas and
high purity hydrogen make up gas
A two bed reactor with quench gas is provided
The diesel product is cooled and sent through a coalescer to storage.

Hydrotreating Catalyst
Hydrotreating catalysts:
Cobalt and molybdenum oxides on silica alumina base (CoMo)
Nickel oxide
Nickel thiomolybdate
Tungsten and nickel sulfides
Vanadium oxide
Desulfurization CoMo catalysts are more common because:
High selectivity
Easy to regenerate
Resistant to poisons
Denitrification (denitrification)
requires the more efficient Nickel-molybdenum (NiMo) catalyst on silica alumina
base.
For middle distillates, 10% nickel-tungsten catalyst is added to NiMo catalyst to
treat high nitrogen concentration
Both CoMo and NiMo catalysts can remove sulfur and nitrogen. However, CoMo is
more selective for sulfur removal and NiMo is more selective to nitrogen removal

Hydrotreating Catalyst contd...

Usually both desulfurization and denitrification are necessary and a nickelcobaltmolybdenum (NiCoMo) catalyst over silica alumina base is used
Since nitrogen is more difficult to remove than sulfur from HC, any treatment which
reduces excess nitrogen to a satisfactory level also removes excess sulfur
NiMo catalyst has a higher hydrogenation activity than CoMo catalyst (at the same T&P)
which results in a greater saturation of aromatic rings
Hydrotreating gasoil (400-1050 F) requires larger pore-size catalyst (than naphtha for
example) to overcome diffusion restrictions at both SOR and EOR conditions
Pores that are larger than necessary are not desirable because it decreases the
catalyst surface area
Pores that are smaller than necessary are not desirable because of diffusion
restrictions
Highest activity is maintained if pore volume is concentrated in a very narrow
range of pore diameters
Catalyst consumption varies from 1 to 7 PTB of feed depending on operation severity
(T&P) and feed (API & S, N, halides, and metal content).

Hydrotreating Catalyst contd...

Catalyst Activation
Hydrotreating catalyst requires activation by converting the hydrogenation metals
from the oxide form to the sulfide form every time a new catalyst is added or unit is shut
down for maintenance (catalyst is exposed to air)
Nickel containing catalysts require activation by presulfiding with carbon disulfide,
mercaptans, or dimethyl sulfide before bringing up to reaction temperature
Some refineries activate cobalt-moly catalysts by injecting the sulfiding chemical into
the oil feed during startup
If the feed is high in sulfur then the feed is enough for the sulfiding operation
The sulfiding reaction is highly exothermic and care must be taken to prevent
excessive reactor temperature during activation

Reactions
1)

Reactions contd...

Reactions contd...
Smaller compounds are desulfurized more easily than larger ones
Difficulty of sulfur removal increases in the order; paraffins, naphthenes, then
aromatics
Nitrogen removal requires more severe conditions (T&P) than sulfur removal
Hydrogen consumption;
Desulfurization 70 scf/bbl feed (per % S removed)
Denitrification 230 scf/bbl feed (per % N removed)
Deoxygenation 180 scf/bbl feed (per % O removed)
Olefin/Aromatic saturation use stoichiometry
Cracking V. high H2 required (if operations are severe enough)

Process Variables
Increasing T and H2 partial pressure increases S and N removal, and hydrogen
consumption
Excessive T increases coke formation (and should be avoided)
Increasing pressure increases hydrogen saturation and reduces coke formation

Liquid Hourly Space Velocity (LHSV)

= Total volumetric flow rate to reactor / total catalyst volume
Unit : hr-1

2. Mercaptane Oxidation (Merox)

Two major types in many refineries
Merox Mercaptans Extraction Process (gases, C3, C4, LPG, Naphtha)
Merox Sweetening Process (Kerosene/Jet Fuel)
The overall oxidation reaction that takes place in converting mercaptans to
disulfides is:
4 R-SH + O2 2R-S-S-R + 2H2O
(mercaptans)
(disulfides)
The Merox catalyst is either a liquid or impregnated charcoal granules
Merox Mercaptans Extraction process achieve the following objectives
1. Improve the odor of the naphtha
2. Reduce mercaptans sulfur (to pass doctor test*)
The units are based on UOPs licensed conventional Fixed Bed Sweetening
MEROX process
Merox process is usually more economical than using a catalytic
hydrodesulfurization process
*A qualitative test for the presence of hydrogen sulfide or mercaptans in gasoline, jet fuel, kerosene and similar
petroleum products.

Merox (Extraction) Process

Merox (Extraction) Process

Merox unit Simplified Process Flow

Merox (Extraction) Process

The unit treats light naphtha produced in the coker unit (along with some of the
coker heavy naphtha)
The coker naphtha entering the unit passes through a guard caustic scrubber which
insures complete removal of H2S (if present) from the naphtha
The naphtha is then mixed with a controlled quantity of air in a mixer before entering
the Merox reactor
The merox reactor contains a bed of specially selected activated charcoal
impregnated with merox catalyst and wetted with caustic solution
While the naphtha air mixture passes through the reactor, the mercaptans in the
naphtha are converted to disulfides
Caustic circulation pump provides intermittent circulation of caustic from the settler to
wet the catalyst bed
The frequency of caustic circulation depends on the stock being treated and activity of
the catalyst
The naphtha effluent from the reactor is sent to a caustic settler to separate the entrained
caustic
The naphtha then passes through a sand filter (to reduce alkalinity and caustic haze)
before sending to storage

Merox (Sweetening) - Process Flow

Merox (Sweetening) - Process Flow

Conventional Merox for sweetening jet fuel or kerosene Process

Merox (Sweetening) Process

Feedstock jet fuel or kerosene is first prewashed in a batch caustic prewash vessel to
remove any H2S that would interfere with the sweetening.
The following reaction takes place:
H2S + NaOH NaSH + H2O
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 pressure maintained in the reactor is chosen so that the injected air will
completely dissolve in the feedstock at the operating temperature
The Merox reactor is a vertical vessel containing a fixed bed of charcoal granules that
have been impregnated with the UOP proprietary catalyst
The mercaptan oxidation reaction takes place in an alkaline environment provided by
caustic being pumped into the reactor on an intermittent (as needed) basis
The oxidation reaction that takes place is:
4 R-SH + O2 2R-S-S-R + 2H2O

Merox (Sweetening) Process contd...

Mercaptan oxidation reaction takes place as the feedstock percolates downward
over the catalyst
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
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
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
Water-washed product flows through a salt bed vessel to remove any entrained water
The salt filtered product flows through a clay filter vessel to remove any oil-soluble
substances, organometallic compounds (especially copper) and particulate matter, to
meet jet fuel product specifications

3. ARDS

ARDS -Objectives
ARDS is a fixed bed catalytic process for hydrotreating a variety of feedstocks (heavy
oils like atmospheric residue and some vacuum residues)
Objectives
In the reaction section: To reduce the sulfur content of CDU atmospheric residue
from 4.5 to 0.5-0.7 wt% and metal content from 88 to 21 ppmw in addition to nitrogen
and residual carbon in the presence of hydrogen for meeting quality criteria of the
feed/products to the downstream processing units
In the fractionation section: To obtain lighter (more valuable) products such as
LPG and Naphtha, in addition to middle distillate and low-sulfur fuel oil which are
excellent feedstocks for other process units like fluid catalytic crackers (FCC),
hydrocrackers (HCR), and vacuum unit and delayed coker
Commercial Name Unicracking/HDS Process
Licensor Jointly licensed by Unocal* and UOP

*Unocal processes have been licensed for use in over 260 units in 35 countries worldwide

ARDS Feedstock Guidelines

Because of problems related to flow and product instability, feeds with very high viscosities
(e.g., Heavy Iranian vacuum residue) are difficult to upgrade with fixedbed residue hydrotreating
processes. However, if diluent such as light or heavy cycle oil are added, even feedstocks such as
these can be handled successfully
Restrictions on a typical ARDS unit feed specifications

ARDS Product Properties

ARDS units are designed to meet a given refiners particular process objectives
Typically, an ARDS unit can achieve:
> 95% removal of sulfur & metals
> 70% removal of carbon residue
> 60% removal of nitrogen & 60% conversion of Vacuum Residue

Yield pattern of products from the ARDS unit

ARDS Process Flow

ARDS Process
ARD unit reaction section is generally divided into two parallel reactor trains
Fractionation section is a single train common for both reactor trains
(a) Reactor
The reactor section has two parallel trains (i.e. the feed is split between the 2
trains)
Each train consists of a guard reactor (chamber) and 3 more reactors in series,
and has independent recycle gas scrubbing facilities (MEA)
The feed is pumped to over 2000 psi pressure by charge pumps (each train has
its own pumps)
The feed charge is preheated by the hot effluent residue and further heated in a
charge heater to the reaction temperature
The feed is mixed with the recycle hydrogen which has been preheated in a
separate (recycle-gas) heater.

ARDS Process contd...

The feed enters a guard chamber (a small reactor that contains a relatively small
quantity of ARDS catalyst) to remove particulate matter and residual salt from the
feed to protect the other three following reactors
The catalyst in the reactors is chosen such that demetallization is achieved in the
first two reactors and the desulfurization is achieved in the third and fourth reactors
A substantial fraction of the VR feed (1050+ F material) is converted into gas oil
The hydrogen consumption is about 610 - 670 scf/bbl of feed
The reactor effluent (two phase) is separated to liquid and vapor in a HPHS
(High Pressure Hot Separator) The pressure is 1740 psig at SOR and 1720 psig
at EOR
The vapor is cooled to 500 F and sent to HPWS (High Pressure Warm Separator)
where the high MW HCs (which condensate because of cooling) are removed
because they might cause emulsions in the HPCS (High Pressure Cold Separator)
where water will be condensed
The liquid from HPWS is mixed with the liquid from the HPHS and sent to LPHS
(low pressure hot separator)

ARDS Process contd...

In the HPCS the three phase mixture comprising sour water (containing ammonium
sulfide), hydrocarbon liquid, and H2 gas is separated
The sour water is sent to the sour water treating unit
The hydrocarbon liquid is sent to the low pressure cold separator No.1 (LPCS1)
where the dissolved gases are flashed off and sent to the hydrogen production
(HP) unit after treatment (in ammonia removal scrubber) and the liquid is sent to
the fractionator section
The gas (H2-rich) is washed with water to remove traces of ammonia then it is
contacted with ADIP (di-isopropanolamine) solution in recycle gas ADIP
scrubber to remove H2S
Part of the recycle H2-rich gas is purged (to increase the purity of the recycle gas)
and sent to the Hydrogen Production (HP) unit
The rest is compressed and mixed with make-up hydrogen and returned to the
reactors
Most of the hydrogen gas is preheated before mixing with the oil feed to the guard
chamber. However, part of cold recycle hydrogen is sent directly to the reactor to
maintain nearly constant temperature by quenching

ARDS Process contd...

(b) Fractionator Section:
Dissolved vapors released in the LPHS are cooled then separated in the LPCS2 into
gas, HC liquid, and water
HC liquid is fed separately to the fractionator
Gas (rich in H2) is sent after ammonia removal to either HP or H2S Removal
(HSR) unit
Water is sent to SWT unit
Liquids from the LPHS of both trains are sent to the flash zone of the fractionator
after preheat in the main heater
The fractionator is similar to a conventional crude unit distillation column
Naphtha produced from the fractionator overhead is sent to a debutanizer to
control its IBP, flash point, and RVP by removing C4 and lighter gases. Both
debutanizer top (LPG) and bottom (naphtha) products are sent to storage
Distillate is drawn as a side stream from the fractionator to a steam side stripper to
adjust its IBP then sent to storage
The fuel oil (fractionator bottoms) is sent to storage after cooling

ARDS Process contd...

(C) Catalyst
There are catalysts for demetallization, desulfurization, denitrification, and
conversion of residual oils
A clients objectives determine which combination of catalysts is best for a
particular plant
To convert a high-metals residue into low-sulfur fuel oil, a bed of demetallization
catalyst might be used followed by a bed of desulfurization catalyst
To achieve substantial conversion and denitrification, the above catalysts might be
followed by a hydrotreating or mild hydrocracking catalyst
Desulfurization catalyst life cycle ranges from one to two years
Demetallization catalysts must be reclaimed or disposed of once or twice per year
Desulfurization catalyst can be regenerated if protected by a demetallization
catalyst

Queries?

Merox (Extraction) - Process Flow

Merox for Coker Naphtha treatment

Condenser
Steam Ejector
Water

Reflux pump

Condensate drum
Dryer

Stripper
HP Steam

Recycle
condensate

Wild Naphtha to CDU

Recycle gas
compressor
Make-up H2
compressor

Water

Product cooler
Kerosene product

Product pump Fin Cooler

STPR Feed
Btm Exch.

HP separator
Water

Feed
preheater

Surge drum

Feed/Rxt
Feed Exch.
Heater

Reactor

Feed
Feed pump

Process flow diagram (PFD) for kerosene HTU

Process Flow Naphtha Hydrotreating

Heater

Purge gas to HR

Stabilizer

Naphtha from ARDS

Purge gas to
gas recovery

HX

2nd Reactor
Satd. Feed Pumps
Water
Naphtha
from
Coker

Sour water
HX
HX
Naphtha to storage

H2 take-up

1st Reactor

HX

ARDS Process Flow

Make-up Hydrogen
Compressor

Rec. Gas compressor

Recycle gas heater
Main Reactors

Purge gas

Charge heater
Condensate
tank

Residue feed

Rec. Gas ADIP Scrubber

To Fractionator

Guard reactor

Off gas
Tempered water
Ammonia Removal Column

Low Pr.
cold Sep.
Low Pr. Hot Sep.

Debutanizer
Dist.
Stripper

Naphtha
Distillate
LSFO

Frac. Feed Heater

Fractionator