Petroleum Refining (2 of 3)

 Desalting & Dehydration
 Pre-Heating (HEN)
 Heating (Furnace)
 Atmospheric Distillation
 Vacuum Distillation
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 Where are we?
 Important units:
 1, 2, 3, 4
 Refining of crude oils or petroleum essentially consists of:
 primary separation processes
 secondary conversion processes.
 The conversion of some of the hydrocarbons into products

having higher quality performance.
 Atmospheric and vacuum distillation of crude oils is the
main primary separation processes producing various
straight run products:
 gasoline, kerosene and diesel
 The first essential task for the crude oil consisting of more
than 100 compounds is to separate its major components
based on boiling point differences.
 This principle is exploited in the crude distillation unit
which involves energy intensive operation.
 Since crude distillation involves the processing of the entire
feed, it remains as the most significant operation in a
refinery.
 It consists of the following important sub-processes:
 Crude desalter
 Furnace
 Pre-flash column
 Crude distillation column supplemented with side
columns.
 Pump around heat exchanger units
 Heat exchanger network (HEN) that facilitates energy
recovery from hot product and reflux streams to heat
the crude oil.
Crude distillation unit (CDU)
Heat exchanger networks (HEN)
 Crude oil comes from the ground, which contains
variety of substances such as:
 Gases
 Water
 Dirt
 Mineral
 Pretreatment of the crude oil is important if the crude

oil is to be transported effectively and to be processed
without causing:
 fouling and corrosion in the subsequent operations
 Distillation, catalytic reforming and secondary

conversion processes.
 Impurities in the crude oil are either oleophobic or oleophilic.
 OLEOPHOBIC IMPURITIES
 Salt, mainly chloride & impurities of Na, K, Ca& Mg
 Sediments such as salt, sand, mud, iron oxide, iron sulphide etc.
 Water present as soluble emulsified and/or finely dispersed water.
 OLEOPHILIC IMPURITIES
 Typically Soluble
 Sulphur compounds
 Organometallic compounds, Ni, V, Fe and As etc
 Naphthenic acids
 Nitrogen compounds.
 Pretreatment of the crude oil removes the oleophobic impurities
 Two main ways:
 Field separation
 Crude desalting
 Field separation is the first step to remove:

 gases, water and dirt that accompany crude oil coming
from the ground
 It is located in the field near the site of the oil
wells.
 The field separator is often no more than a large
vessel, which gives a quieting zone to permit gravity
separation of three phases
 Gases
 Crude oil
 Water (with entrained dirt).
 Poor desalting has the following effects:
 Salts deposit inside the tubes of furnaces and on the
tube bundles of heat ex-changers
 This creates fouling, thus reducing the heat transfer
efficiency
 Corrosion of overhead equipment
 The salts carried with the products act as catalyst
poisons in catalytic cracking units.
 Water washing removes much of the water-soluble
minerals and entrained solids (impurities).
 There are two types of desalting
 Single
 Multistage
 Commercial crudes, salt contents 10-200 ppb

 Refineries aim at 5 ppb or less (1-2 ppb)
 this is not possible through single stage desalting
 hence two-stage desalting is required.
 A high degree of salt removal is desired

 95 – 99% removal of the dissolved salt in the crude oil
 Stages of Desalting:
 Heating
 Mixing
 Settling
 HEATING:
 Crude oil is heated up to 135-140°C in the train of heat exchanger operating in two parallel section.
 MIXING
 Single-stage desalting with water recycle is usually justified if salt content in crude is less than 40 ppb.
 Two-stage desalting involves dehydration followed by desalting.
 Double-stage desalting is better for residuum hydrotreating.
 Fuel oil quality is better.
 Desalting process is two stage process

 Forming emulsion of crude and water
 Demulsification in which emulsion is broken by means of electric field and demulsifying chemicals.
 Desalting carried out by emulsifying the crude
oil and then separating the salt dissolved in
water.
 SETTELING
 Two phases water-oil is separated either by:
 using chemicals to break down the emulsion
 passing high potential electric current.
 By injecting water the salts dissolved in the water
and solution are separated from the crude by
means of electrostatic separating in a large vessel.
 Operating Variables in Desalter
 Crude charge rate
 Temperature & pressure
 Mixing valve pressure drop
 Wash water rate and Temperature
 Wash quality
 Desalting voltage.
 Lower temperature of crude oils will reduce
desalting efficiency:
 Increased viscosity of oil
 Higher temperature reduce desalting efficiency

 greater electrical conductivity of the crude.
 Therefore, the crude oil is heated to about

250°F before it enters the desalter unit.
 Pressure in the vessel must be maintained at a
high value:
 Avoid vaporization of crude oil
 Erratic operation
 Loss of desalting efficiency.
 Typical Desalting Schemes
 Main goal is to pre-heat and set Temperature to the
crude oil
 Typical fuels:
 Fuel oil
 Fuel gas
 This temperature enables over-flash conditions in

the main crude distillation column.
 The preheated crude from the preheater section is further
heated and partially vaporized in the furnace containing tubular
heater.
 The furnace has two zones:
 radiant section
 convection section.
 The radiant zone forms the combustion zone and contains the
burners.
 In convection zone the crude is further heated (inside the tube)
by the hot flue gases from the radiant section.
 Heated and partially vaporized crude from the fired heaters
enters the flash zone of the column and fractionated in the
atmospheric column.
 Over-flash is that the crude is heated to such a
temperature that enables an additional 5 %
vaporization with respect to the residue product.
 The Residue fraction vapors amounting to 5 % of the total
volume of the crude oil are desired.
 Depending upon the quality of the crude, the desired
temperature for the crude oil is about
 T = 600 -700°F.
 T = 310°C - 370°C
5% vap.
 The partially vaporized crude is transferred to the flash
zone of the column located at a point lower down the
column.
 This over-flash has the function of:
 providing liquid wash to the vapours going up the column
from the flash zone
 Improves fractionation on the trays above the flash zone
 This improves the quality of the HGO
 It also reduces the overlap with the bottom products
below the flash zone.
 The overflash provides heat input to the column in
excess to that needed to distill the overhead products.
 This prevents coke deposition on the trays in the wash
zone.
 The furnace outlet temperature is controlled to:
 keep coking inside the furnace tubes
 Avoid coking in the column flash zone to a minimum.
 However, the composition of the crude plays a part in
determining the maximum temperature allowed.
 Paraffinic crude oils cracks more readily than an
aromatic or asphalt-base crude.
 Therefore, the furnace outlet temperature for
paraffinic crude oils is lower than that for other crude
types.
 The crude oil enters the pre-flash column
after leaving the furnace
 The pre-flash tower separates the lighter
fractions of the already heated crude oil.
 The heavier fractions of the crude oil leave
from the bottom section of the pre-flash
tower.
 Both streams:
 Lighter
 Heavier
 Will be fed to the column at various sections
 Pre-flash column enables better refluxes in
the main column
 This is due to the distribution of the
streams effectively between various
processing zones of the crude oil.
 Pre-flash column may or may not be
included i.e., it is optional.
 Typically, this can be avoided and the heated
crude oil from the furnace can be fed to the
main column directly.
 Two heat exchanger networks exist in the
crude distillation unit:
 one before the crude desalter
 one after the crude desalter.
 HEN facilitates energy recovery via:

 hot product naphtha+steam vapor & reflux
streams (HOT)
 heat the crude oil in an indirect heat transfer
mode (COLD)
 Therefore, the design and operation of a heat
exchanger network is very important in the
crude distillation unit.
 NOTE:
 Naphtha heat integrated condenser is a partial
condenser
 All others are heat exchangers without any
phase change streams.
 The heat exchanger networks enable to increase the
crude oil stream temperature to about 200 – 230°C
 This is significantly higher than the crude oil source
temperature (about 20 – 30°C).
 T required for Column T= 310° - 390°C approx
 Crude distillation units without heat exchanger
networks have higher furnace load targets.
 They also cause more pollution due to burning more
fuel oil and fuel gas streams.
 Where are we?
 Crude oil distillation consists of atmospheric and
vacuum distillation.
 The heavier fraction of crude oil obtained from
atmospheric column requires high temperature.
 In order to avoid cracking at higher temperature
the heavier fraction are fractionated under
vacuum.
 Units:
 Atmospheric (ADU)
 Vacuum (VDU)
 Various Processes in atmospheric crude
oil distillation are:
 Preheating of Raw Crude Oil
 Desalting of crude
 Furnace
 Pre-flash*
 Distillation
 Stabilization of Naphtha*
 The distillation section consist of:
 Light Gases / Fuel Gases
 Light straight run naphtha
 A.k.a light gasoline / light naphtha
 Heavy gasolina
 Aviation fueks (jet fuel)
 Kerosene
 light distillate / jet fuel
 Middle distillates
 diesel or light gas oil (LGO)
 Heavy distillates
 atmospheric gas oil (AGO) / heavy gas oil (HGO)
 Crude column bottoms
 atmospheric residue / topped crude.
 CDU Main column is typically 50 m (164 ft) high
 Common Number of Trays:
 30–50 valve trays.
 Crude is fed at a point lower down the column

 It is above what is called the stripping section.
 Heating inside:
 Vapour high flow rate
 Requires large diameter column above the flash zone.
 At the bottom of the stripping section:

 Steam is injected
 It will strip the atmospheric residue of any light hydrocarbon
 Partial pressure of the hydrocarbon vapours in the flash zone
 This lowers the boiling point of the hydrocarbons 
 causes more hydrocarbons to boil and go up the column
 Different HC cuts will be eventually:
 condensed and withdrawn as side streams.
 As the hot vapours from the flash zone rise through the trays
up the column, they are contacted by the colder reflux down
the column.
 In the overhead condenser:
 Vapors are condensed
 Part of the light naphtha is returned to the column as reflux.
 Further reflux is provided by several pump-around streams

along the column.
 Pump-arounds cooling:
 Cold liquid condenses more of the rising vapours
 This provides more reflux to compensate for the
withdrawal of products from the column.
 Heat is removed from the column at higher
temperatures.
 Thermal efficiency of the column is improved and
the required furnace duty is reduced.
 Pumparound streams reduce the vapour flow
rate throughout the column.
 The required column is smaller than what would
otherwise be required if pump-around streams
where not there.
 The drawback of PumpArounds:
 They reduce the fractionation because a more
fractionated liquid is mixed after cooling with a
less fractionated liquid a few trays above.
 The side draw products are usually stripped to
control their initial boiling point.
 The strippers contain several trays
 Stripping is done:
 Steam at the bottom of the stripper
 Steam at the reboiler type side stream strippers.
 The end boiling point is controlled by:

 Flow rate of the side stream product.
 The overhead vapour is condensed at the top of the

tower by:
 heat exchange with the cool crude coming into the unit
 air cooling
 cooling water
 The liquid product is called light straight run naphtha
(LSR)
 Part of this product is returned to the column as an
external reflux.
 Down the column, other products are withdrawn:
 heavy straight run naphtha (HSR), kerosene or jet fuel,
LGO and HGO.
 All of these products are withdrawn above their feed
tray.
 The atmospheric residue is withdrawn from the
bottom of the column.
 The degree of fractionation in a crude unit is determined
by the gap or overlap between two adjacent side stream
products.
 Typical example:
 the gap/overlap of BP range between:
 kerosene and LGO
 Ideal case there would be no overlap between these

products
 The end boiling point of kerosene would be the initial
boiling point of the LGO.
 However, if we compare the ASTM distillation
boiling points, and since ASTM distillation does
not give perfect fractionation:
 the ASTM end point of kerosene is higher than
the initial ASTM boiling point of LGO.
 This is called fractionation overlap.
 Determination of the initial and end point on
the laboratory test is not always possible or
accurate
 The fractionation gap is defined as:
 the difference between the ASTM 5% boiling
point of the product and the 95% point of the
lighter product.
 If:
 positive, we have a gap indicating good fractionation.
 negative difference is called an overlap indication
  light product is still in the heavier product and vice versa.
 By controlling the cut point of any two consecutive

products we can affect the degree of fractionation.
 If:
 positive, we have a gap indicating good
fractionation.
 negative difference is called an overlap
indication
  light product is still in the heavier product
and vice versa.
 By controlling the cut point of any two

consecutive products we can affect the
degree of fractionation.
 The pressure inside the CDU column is controlled by the
back pressure of the overhead reflux drum at about 0.2–
0.34 bar gauge (3–5 psig).
 The top tray pressure is 0.4–0.7 bar gauge (6–10 psig)
higher than the reflux drum.
 The flash zone pressure is usually 0.34–0.54 bar (5–8 psi)
higher than the top tray
 Temperature ranges from 15°C – 30° in the overhead
to 450-550°C in the bottoms
 The overhead temperature must be controlled to be
14–17 °C (25–31°F)
 This is higher than the dew point temperature for the
water at the column overhead pressure so that no
liquid water is condensed in the column.
 This will prevent corrosion due to the hydrogen
chloride dissolved in liquid water (hydrochloric acid).
 The crude flow rate to the CDU determines the capacity of the
whole refinery.
 A crude column is typically designed for 80% loading
 This means that the unit can be operated at 20% throughput more
than the design value.
 The capacity of the column is limited by the vapour flow rate
with a velocity of:
 2.5 and 3.5 ft/s
 0.76 and 1.07 m/s
 The vapour flow rate increases as the vapours rise from

the flash zone to the overhead.
 To keep the vapour velocity within this limits:
 the pumparounds, which are installed at several points along the
column, extract heat from the column.
 This results in condensing the rising vapours and reducing the
vapour velocity.
 To expand crude capacity:
 Add a pre-flash column before the crude heater
 The amounts of the light ends in the crude are now less due to
the pre-flash
 This reduces the vapour loading up the column.
 CDU throughput is increased BUT:
 the furnace duty is not increased
 Crude rate going to the furnace is not affected due to the removal
of the light ends.
 Pre-flash columns are designed for CDU :
 crude oil is light
 Contains a lot of light ends in the naphtha range.
 Naphtha stabilizer, caustic wash and naphtha
splitting section:
 The un-stablished naphtha from the atmospheric
distillation column is pumped to the naphtha
stabilizer section
 This will separate the stabilized overhead vapours
 They will be condensed to recover LPG
 LPG is typically treated in caustic and amine
treating unit.
 The condensates are mostly stabilized naphtha
 It is further separated into:
 Light
 Medium***
 Heavy naphtha.
 Pumps-around units are most essential units in the
crude distillation column.
 They are used to maintain good reflux conditions in
the main column
 This ensures the desired product quality.
 They also control heat distribution:
 as the liquid streams are at higher temperatures and
refluxed within
 Therefore, they are also important units in the
heat exchanger network (HEN)
 The cooled liquid is sent back to a section above.
 Usually two pump arounds (up to 3) are used in
conventional designs.
 The main column consists of 45 trays
 Secondary columns (side strippers) consist of 4
trays each.
 3 side strippers are used to strip:
 light ends from
 kerosene, LGO and HGO products.
 The main column has 2 sections that are

distinguished with respect to a flash zone.
 The flash zone is where the crude oil partially
vaporized is fed to the main column.
 In this Column:
 4 trays below the flash zone
 41 trays above the flash zone.
 The bottom most tray (residue stripping tray) is
numbered as 1
 The top tower tray is numbered as 45
 Trays 1 - 4 process the atmospheric residue

portion (below the flash zone)
 Trays 5 - 10 (6 trays above the flash zone) process
the HGO product portion of the crude.
 From tray 10, HGO:
 draw off product is taken out (as liquid) and enters
the HGO side stripper unit.
 the liquid stream is drawn and sent to tray 12 via a
bottom pump around unit
 This enables cooling of the liquid stream.
 The steam + light ends from the HGO side stripper
enter tray 11 of the main column.
 Trays 13 - 22 (10 trays above the HGO processing
zone) process the LGO product portion of the
crude.
 From tray 22:
 LGO draw off product is taken (as liquid) and sent to
the LGO side stripper unit
 another liquid stream is taken out and sent to tray
24 via a top pump around unit (TPA) that enables
cooling of the liquid stream.
 The steam + light ends from the LGO side stripper
enter tray 23 of the main column.
 Trays 24 - 34 (10 trays above the LGO processing
zone) process the kerosene product portion of the
crude.
 From tray 34:
 the kero draw off stream is taken and sent to the
kerosene side stripper unit.
 The steam + light ends of the kerosene side stripper
enter tray 35.
 Trays 34 - 45 (12 trays above the Kerosene
processing zone) process the naphtha product
portion of the crude.
 Tray 34 is regarded as a tray processing both LGO
as well as naphtha processing zone.
 This is because there is no pump around
associated to the tray 34.
 Where pump around is associated, that tray is
often ignored in counting, as it affects to a large
extent the tray hydraulics and contributes less
towards the separation of the components.
 Also, note that steam enters main column at trays
1, 11, 23, 35
 This steam balances throughout the column are
very important.
 Finally, the cold naphtha stream obtained from
the phase separator is sent back to the main
column as reflux stream.
 Check out this video!
 https://www.youtube.com/watch?v=k-fHuYpEDw8
 The bottom product also called reduced crude oil,
from the atmospheric column is fractionated in the
vacuum column.
 Reduced crude oil is very heavy compared to crude oil
distilling under pressure requires high temperature.
 Distillation under vacuum permits fractionation at
lower temperature
 avoid cracking of the reduced crude oil and coking of the
furnace tube.
 Vacuum is maintained using three-stage steam
ejector.
 PRODUCTS FROM VDU
 Light gasoil
 Heavy gas oil
 light lube distillate
 medium lube distillate
 heavy lube distillate
 vacuum column residue
 OPERATING PRESSURE OF VACUUM COLUMN:

 About 90-95 mm Hg at the top and
 About 135-140 mm Hg at the bottom
 Vacuum towers are much larger in diameter than
atmospheric towers
 usually 12 – 15 meters.
 P = 25 – 40 mm Hg.
 Temperature is kept at around 380 – 420C°.
 A few millimeters decrease in pressure drop

between the vacuum-inducing device and the flash
zone will save operating costs.
 The LVGO and HVGO are eventually subjected to
cracking to yield even lighter products.
 The VDU consists of a main vacuum distillation
column supported with side strippers to produce the
desired products.
 Raw Material:
 ATM. Residue
 Process
 Pre-heating
 Furnace
 Pump-around
 Vacuum
 The reduced crude oil from atmospheric column at about
360°C is heated
 It will be partially vaporized in the furnace.
 The temperature in the flash zone of the tower is
controlled by the furnace coil outlet temperature.
 The pre-heated and partially vapourised reduced crude
enters the flash zone of vacuum column
 The vacuum unit distillates are classified
 light vacuum gas oil (LVGO)
 medium vacuum gas oil (MVGO)
 heavy vacuum gas oil (HVGO)
 In addition a vacuum residue is produced.

 In some refineries the whole atmospheric
residue is hydro-processed before vacuum
distillation.
 The vacuum unit can also be used to
produce lubrication oil grade feed stocks.
 The feed enters the vacuum tower at the lower
part of the column.
 As in the case of atmospheric distillation:
 3–5 vol% overflash is maintained
 This is to provide some fractionation between the

HVGO draw-off tray and the flash zone
 This controls its end-point.
 The two cuts of MVGO and HVGO are necessary to
extract heat from the tower at a more
advantageous level from the HVGO pumparound.
 Vacuum distillation columns are equipped:
 packing for fractionation
 heat exchange zones.
 These reduces the pressure drop in the column

 Bottoms:
 The vapours from the flash zone go through a wash
 Then to fractionation zone where the heavy ends are
condensed with HVGO reflux.
 Top Column:
 Heat exchange
 Fractionation zone
 Sprays of liquid from the pump-around or the internal reflux.
 Vacuum uses ejectors or a combination of ejectors and
liquid ring pumps to achieve low Pressure
 Vapours from the column are sucked into the venturi section
of the nozzle by a stream of medium or low pressure steam.
 The vapour phase at the ejector exit is partially condensed
in an exchanger with cooling water.
 The liquid phase is then sent to the overhead drum.
 The vapour phase goes from the condenser to another
ejector-condenser stage.
 Liquid ring pumps are similar to rotor gas compressors.
 One pump can replace:
 two or three stages of ejectors in vacuum distillation.
 If no use of steam can significantly reduce hydrocarbon-rich aqueous

condensates in a system using ejectors.
 Systems with ejectors are much more flexible and rapid to put into
operation.
 Check out this video
 https://www.youtube.com/watch?v=0yK4Mzv7ei0
 Understand how Ejectors Work

 How do they create vacuum?
 Hydrotreating processes aim at the removal of impurities such as sulfur and nitrogen
from distillate fuels:
 naphtha, kerosene, diesel, gas oils & residues
 This is done by treating the feed with hydrogen gas at elevated temperature and
pressure in the presence of a catalyst
 The principal impurities to be removed are:
 Sulfur
 Nitrogen
 Oxygen
 Olefins
 Metals.
 Sulfur
 mercaptans, sulfides, disulfides, polysulfides, and thiophenes.
 The thiophenes are more difficult to eliminate than most other types of sulfur.
 Nitrogen
 These are transformed into ammonia by reaction with hydrogen.
 Oxygen
 Are eliminated in the form of water after reacting with hydrogen.
 Olefins
 These are easily transformed into stable paraffinic hydrocarbons
 Metals
 Compounds that contain these metals are destroyed and the metals get deposited on the
hydrotreating catalyst.
 Typical streams HT:
 Light/Heavy Napthta
 Kerosene
 Gas Oils/Diesel
 Atm. Residue
 De-sulfurization
 De-nitrification
 Hydrogenation (Saturation)
 Oxygen Removal
 In hydroprocessing, feedstocks are sent to a catalytic
reactor in the presence of hydrogen.
 Depending upon the intensity of the hydroprocessing
operation, the hydroprocessing is termed as:
 Hydrotreating
 Hydrocracking.
 During hydrotreating:
 Sulphur and nitrogen concentration in the final products is
reduced along with the saturation of olefins and aromatics.
 During hydrocracking
 heavier molecules react with hydrogen to generate lighter
hydrocarbons.
 When a change in the molecular weight of the feed is
required, a hydrocracking process is used.
* Hydrocracking is Further Analyzed in FCC Section
 Typical HT Process
 H2 Make-up is added (from Reformer)
 Liquid feed
 Recycle stream
 Pre-heating
HYDROGEN IN
PROCESS PURGE/HYDROGEN IN
 Gas Treating (for H2S) MAKEUP GAS
 Purge Gases NAPHTHA HDS 10%
KEROSENE HDS 15%

 Final Hydrotreated Product
DIESEL HDS 20%
VGO HDS 30%
 The principal types of catalyst used in the HDS service are
 Cobalt
 General service
 Nickel
 Support if Alumina bed + Molybdenum
 This is used especially for denitrification.
 Other Metals
 The neutral support prevents the polymerization of the olefins.
 This catalyst is employed in conjunction with other catalysts for olefinic feeds.
 Hydrogenolysis
 by which C-S, C-N or C-C bonds are cleaved, and hydrogenation of
unsaturated compounds.
 Hydrodesulfurization (HDS)
 as in the case of the HDS of straight-run naphtha, which is used as
reforming feed where sulfur is the main undesirable hetero-atom.
 Hydrodeoxygenation process
 Removal of Oxygen via hydrogenation
 Hydrodemetallization process
 is used for the removal of vanadium and nickel from heavy oils.
 Inorganic sulphur is converted to H2S.
 Organic sulphur compounds:
 mercaptans, sulphides, disulphides, thiophenes
 Are converted to corresponding saturated hydrocarbons along with
the generation of H2S.
 Denitrification reactions also take place during hydrotreating in
which compounds such as:
 Pyrrole, pyridine and quinoline
 Are convered to saturated hydrocarbons.
 Ammonia is generated as a byproduct in the denitrification
reactions.
 The olefins are converted to both:
 cyclic and non-cyclic saturated hydrocarbons.
 Aromatic hydrocarbons such as:

 toluene, naphthalene and tetrahydronaphthalene
 Are converted to corresponding cyclic hydrocarbon compounds
 The removal of vanadium and nickel is usually difficult.

 This is due to the reason that they are held within
asphaltene molecules and intense operating conditions
 Higher T, P
 Molar ratio of hydrogen to hydrocarbon feed
 Typical Process Conditions
 Temperature: 290 – 430°C
 Pressure: 7 – 180 bar
 Higher pressure and temperature are used when

heavier feed stocks are used
 Catalysts
 Cobalt, Molbdenum catalysts are used when
effective sulphur removal is targeted.
 Nickel, molybdenum catalysts are used when
effective nitrogen removal is targeted.
 The hydrotreating reactions are exothermic
 the reactor product needs to be cooled.
 Feed is mixed with recycle hydrogen stream.
 Sent to heat exchange in a furnace for heating the
same.
 Eventually the heated feed mixture is sent to the
hydrotreating packed bed reactor.
 The reactor outlet is cooled and mixed with water.
 Eventually the water mixed reactor stream is
further cooled and sent to a phase separator.
 The phase separator splits the feed stream to three
separate streams:
 a gas phase stream
 an organic stream
 an aqueous stream.
 The aqueous stream is rich in:
 H2S and NH3
 They require sour water processing unit to recover

H2S and NH3.
 This uses amine based absorption technology to
recover H2S
 The hydrotreated product is the organic stream
enters a fractionator to stabilize the hydrotreated
product.
 The stabilizing fractionator produces a gas stream
from the partial condenser:
 H2
 C1-C4
 H2S
 NH3.
 The gas stream emanating from the phase
separator consists of 60 – 90% H2.
 Majority of this stream is recycled using a
compressor to mix with the make-up hydrogen
 It later enter the heat exchanger and furnaces.
 The other part of the gas stream from the phase
separator is purged to mix with the gas
generated from the fractionators
 They will enter the absorption unit for H2S
removal.
 When high sulphur feeds are used, H2S removal is
carried out by placing an additional absorber
unit (with amine as an absorbent)
 This reduces higher concentrations of H2S in the
gas stream.
 Purge stream is allowed to balance off the
additional gas available as another by product
from the process.
 Typical Scheme
 Inlets:
 Feed (non-treated)
 Make-up H2
 Outlets
 Desulfurized product
 Sour Gas is produced
 Purge Gas also
 Secondary:
 Lean Amine/Rich Amine
 Various sections in the naphtha hydro treatment unit are:
 Charge Heater:
 Preheating reactor feedstock to reaction temperature of 340 oC.
 Charge heater has four passes four gas burners.
 Heater tubes are made up of SS-321
 Reaction Section:
 The reactor consists of two catalyst beds.
 Stripping Section:
 Stripping section uses air for stripping the light ends mainly hydrogen sulfide from reactor product,
stripper temperature 14 kg/ cm2 and temp. 172°C
 Stripper Reboiler:
 Stripper reboiler supply heat required for striper
 Operating Variables Naphtha Hydrotreatmernt
 Reactor temperature
 Space velocity
 Hydrogen partial pressure
 H2/HC ratio, feed quality
 Stripper bottom temperature
 The naphtha feed enters the unit through
charge pump
 It is mixed with hydrogen gas coming from a
cat. Reforming (CR) unit or hydrogen plant.
 The feed/hydrogen mix is next heated in
succession through heat exchange with
reactor effluent
 The heated feed/hydrogen mix next enters
the desulfurization reactor at the top.
 The desulfurization reactions take
place over:
 Co-Mo on alumina catalyst contained in
the reactor.
 The reactor effluent contains:
 the desulfurized naphtha
 excess hydrogen
 H2S
 light end elements (C1-C4)
 The reactor effluent is cooled and
partially condensed through
feed/effluent:
 heat exchanger E-101
 Air cooler E-102
 Trim cooler E-103
 Then, it flows into high-pressure

separator V-102.
 The separation between the vapor
and liquid phases occurs in this
separator drum.
 The vapor from this drum contains
 H2S
 Light Ends (C1-C4)
 Excess hydrogen
 The liquid from the flash unit is
preheated
 Stripper bottom in heat exchanger E-105
before charging to the stripper column
V-103
 Here, it is dissolved hydrogen and H2S
contained in the HP separator
 The gross overhead product from V-103
is partially condensed through heat
exchanger E-104
 Gases (mostly H2S) are sent to amine wash
 Liquid is sent to recycle
 The liquid is refluxed back to the column
through pump P-103.
 The column is re-boiled with a fired heater:
 H-102
 The bottom recirculation is provided by P-102.
 The stripper bottom product is cooled by:

 E-105
 E-106
 to 100°F before going out of unit’s battery limits.
 The objective of kerosene hydrotreating is to upgrade
raw kerosene distillate to produce specification
products suitable for marketing as kerosene and jet
fuel.
 Sulfur and mercaptans in the raw kerosene cuts coming
from the crude distillation unit can cause corrosion
problems in aircraft engines and fuel handling and
storage facilities.
 Nitrogen in the raw kerosene feed from some crude
oils can cause color stability problems in the product.
 For aviation turbine fuels (ATF), the ASTM distillation,
flash point, and freeze point of the hydrotreated
kerosene cut has to be rigorously controlled to meet
the stringent requirements.
 This is done by distillation in a series of columns to
remove gases, light ends, and heavy kerosene
fractions.
 The upgrading is achieved by treating hydrogen in the
presence of a catalyst, where sulfur and nitrogen
compounds are converted into hydrogen sulfide and
ammonia.
 Because of the very stringent product
specifications, the ATF product can have only
straight run kerosene or hydrotreated blend
components.
 Another important property of aviation turbine
fuel is its smoke point, which in turn is a
function of the aromatic type hydrocarbons in
the cut.
 Higher aromatic content yields lower smoke point kerosene cuts, which may not meet the
aviation turbine fuel specification.
 Depending on the severity of hydrotreating, the smoke point of the kerosene may be
improved by saturation of aromatics to corresponding naphthenes (see Figure 2-3).
 Kerosene feed from storage is pumped via charge
pump P-101
 It is then preheated in effluent/feed exchanger E-103
 It follow a final heating in fired heater H-101.
 The effluent from H-101 next joins the recycle
 The outlet of H-102 (hydrogen coming from compressor C-101)
is mixed with the effluent of H-101
 It was heated successively in feed/effluent:
 exchanger E-102
 fired heater H-102.
 The heated kerosene feed and hydrogen mix stream next flow
through reactor V-101
 V-101 Reactor is loaded with a Co-Mo or Mo-Ni catalyst.
 Hydro-de-sulfurization and hydro-de-nitrification
reactions take place in the reactor.
 These reactions are exothermic.
 The reactor effluent is cooled in the
effluent/feed exchangers:
 E-102, E-103, and E-104
 This is achieved by exchanging heat with

incoming kerosene feed and hydrogen.
 The effluent is next cooled in air
cooler E-105 before being flashed
 Flashing at V-102
 high pressure
 140°F
 Separation is as follows:
 Gases  H2, H2S, Light Ends
 Liquids  Un-stabilized Kerosene
 The hydrogen-rich gas from the separator is
compressed
 Then it is recycled to the reactor section by centrifugal
compressor C-101.
 Make-up Hydrogen gas is added
 The stream is now recycled to pre-heating in
effluent/hydrogen exchanger E-102.
 It is further heated in fired heater H-102
 Then joins the hydrocarbon feed ready to
be sent to reactor V-101.
 The hydrocarbon liquid from the separator drum is
depressurized into flash drum V-103.
 Split goes:
 The flash gas is sent to the amine unit for H2S removal
before being sent to refinery fuel system.
 The liquid stream continues for stripping
 It is heated in E-104
 The liquid from the flash drum is sent to a
stabilizer column V-105.
 The split goes:
 Top Products  To condenser
 Bottoms  to stabilizer reboiler
 The stabilizer overhead vapor is
partially condensed in air cooler E-106
 It then flows into accumulator V-106.
 The accumulator liquid naphtha is:
 Off gases  Amine treating
 Liquids:
 Returned to the column as reflux (mostly
light kerosene)
 The rest is withdrawn as wild naphtha
(recovery)
 In the bottoms, we get:
 Mostly Kerosene
 Reflux to H-103 Reboiler
 Stabilized product to fractionator V-107
 The stabilizer bottom product is sent to
fractionator column V-107,
 Here, a high flash naphtha cut is taken as
overhead product
 Cooled by Air in E-107
 Stabilized in V-109
 Recycled to V-107
 Off gases  To flare

 Liquid product  High-Flash Naphtha
 Recycle  Light kerosene base stock is
withdrawn from the fractionator as a
sidestream in V-109
 It passes through kerosene side stripper V-108
to adjust its flash point.
 It is cooled in E-111 and E-112 before sending
to storage as  Light Kerosene
 Fractionator bottoms flow to splitter column V-110
 P-106 Reflux to H-104
 P-109  Stabilized Jet fuel / Heavy Kerosene to V-110
 Here, aviation turbine kerosene is withdrawn
as an overhead product
 Cooled by air in E-116
 Stabilized in V-111
 Off gases  To Fuel Gas
 Liquids  Reflux & Aviation Turbine Fuel
 Antioxidant is injected into the ATK product

before it is finally sent to storage.
 The splitter column is heated in a forced
recirculation-type reboiler
 Heat provided by the H-105 fired heater.
 The bottom product is pumped through air

cooler E-114 and water trim cooler E-115
 This is then sent to storage  heavy kerosene.
 This product is used as a blend stock for:
 Diesel
 Fuel oil grades.
 Gas oil hydrodesulfurization is designed to reduce the
sulfur and other impurities (e.g., nitrogen) present in the
raw gas oil cuts.
 The feed to the unit may be:
 straight run diesel cut from the crude distillation unit
 secondary units such as FCCU (light cycle gas oil)
 delayed coker.
 The feed from these secondary units may contain

significant amount of olefinic hydrocarbons
 Must be converted to saturates in the diesel hydrotreating
unit to improve the storage stability of these products.
 The primary improvement in product quality is with
respect to sulfur and conradson carbon.
 The raw diesel cut from most Middle Eastern crudes,
for example, may contain as much as 1–2% sulfur.
 Because of atmospheric pollution concerns
 the sulfur content of saleable diesel grades allowable in
most countries has fallen very rapidly.
 Until a few years ago 1.0% sulfur was acceptable.
 But, because of very rapid increase in the number of
vehicles using diesel worldwide, the pollution level has
risen exponentially.
 Sulfur specifications in most developed countries have
fallen to:
 0.005 wt% or lower.
 The average sulfur decline is often pushed by vehicle

and engine manufacturers aiming at lower particulate
emissions.
 Diesel feed is pumped by charge pump P-101
 They are sent to effluent/feed heat exchangers E-103 and E-101
 It joins the hot recycle hydrogen stream before
entering reactor V-101
 The effluent of the reactor is mostly off gases, light
ends and unstabilized gas oils
 The recycled gas from compressor discharge:
 C-101
 It is heated in effluent/feed heat exchanger:

 E-102
 Next in fired heater H-101 then mixed with

the hydrocarbon feed before going to HDS
reactor V-101.
 In the reactor:
 Catalyst  Co-Mo or Ni-Mo on alumina type
 Hydro-de-sulfurization & Hydro-de-nitrification
reactions take place
 They are converted into hydrogen sulfide and ammonia.
 Hydrodesulfurization reactions are exothermic

 Cool hydrogen quench is added to the interbed areas
to limit the temperature rise in the reactor.
 The reactor effluent is cooled in:
 Effluent/feed heat exchangers:
 E-101
 E-104
 E-102
 E-103
 Air cooler
 E-105
 It is then flashed into high-pressure separator

drum V-102.
 Condensate (Liquid) is injected into the reactor effluent
just before air cooler E-105
 This makes dissolution and removal of ammonium salts
 These were formed as a result of:
 nitrogen in the feed
 the reaction of ammonia with H2S
 These can cause pipe blockages.
Condensate
 The ammonium salt solution is removed from high-pressure
separator drum V-102
 It is then sent to the refinery wastewater system.
 The hydrogen-rich gas from the HP separator:
 mainly hydrogen
 some hydrogen sulfide
 Must be treated  sent to H2S absorber V-107
 Here, H2S is removed by a circulating
diethanolamine (DEA) solution.
To DEA
Make-up hydrogen
 The H2S-free gas is mixed with makeup hydrogen coming

from the hydrogen plant.
 The makeup and recycled hydrogen are compressed by
centrifugal compressor C-101
 Then it goes to the reactor pressure and recycled to
the HDS reactor.
 The gas is:
 heated in effluent/H2 gas heat exchanger E-102 and
fired heater H-101, joins the hydrocarbon feed before
entering the reactor V-101.
 Part of the recycled gas is used as an interbed quench
in the reactor
 The liquid hydrocarbon stream from separator V-102 is
depressurized into flash drum V-103.
 The flash gas is sent for H2S removal before going to
refinery fuel system.
 The bottoms liquid stream from V-103 is preheated in the reactor effluent heat
exchanger E-104 stream before flowing into the stabilizer column V-104.
 Stabilizer column V-104 separates:
 Naphtha Gas  Recovery
 Naphtha Run  Recovery
 Desulfurized Product  Mostly Diesel
 It then is sent to the overhead accumulator
drum V-105.
 This liquid (unstabilized naphtha) is used as
a reflux to the stabilizer column
 Heat is supplied to the stabilizer through
medium-pressure steam.
 The excess is pumped out as naphtha product.
 This stream is cooled in heat exchangers E-110
and E-111 before being sent to storage.
 The stabilizer overhead vapors are condensed in
air-cooled exchanger E-10
 The stabilizer bottoms is the desulfurized diesel
product.
 The residuum produced from the crude unit has:
 high sulfur
 metal (Ni, V, etc.)
 The atmospheric resids from most Crudes have a

sulfur content of 4−5%.
 The purpose of the atmospheric residuum
desulfurization (ARDS) unit is to reduce the sulfur
content to less than 0.5 wt% sulfur
 This meets the quality criteria of products from
downstream units.
 Heavier hydrocarbon hydrotreating is carried out using
guard reactors.
 Guard reactors have catalysts with larger pore size first
and then have decreasing pore size along the reactor
length.
 The guard reactors are followed with conventional
packed bed reactors.
 This is due to:
 Coking formation
 Catalyst Poissoning
 The desulfurized atmospheric resid is used as:
 a blend component for blending low-sulfur fuel
oils
 feed for another processing unit (delayed coker
unit)
 Here, Nickel and Vanadium would stay back on
the surface of the catalyst.
 Except the guard reactors, the remaining flow
sheet for residue hydrotreating remains the
same.
 Live steam is used in the fractionator
 Unstablized naphtha is produced as one of the
products in the residue hydrotreating process.
 The cold resid feed is heated by heat exchange with
ARDS distillate products to 450°F
 The feed is next filtered in continuous backwashing
feed filters.
 The filters remove all particles larger than 25 microns
from the feed.
 The filtered resid flows to a surge drum with
about 10 minutes hold up
 It is then blanketed with fuel gas to prevent
contamination of feed with air.
 The feed is preheated first by exchange of heat with
HP hot separator vapor then in feed heater H-101.
 Condensate-quality water is added to the feed
 at the heater inlet
 this increase the activity and stability of the catalyst.
 Water also prevents the deposit of solid ammonium

salts in the effluent heat exchangers, downstream of
the reactors.
 The heater outlet temperature is about 650°F.
 The temperature is kept below 700°F to prevent
coking of heater tubes.
 Recycled gas plus makeup hydrogen are heated by
exchange with:
 HP warm separator
 HP hot separator
 Recycle gas heater H-102.
 The hot recycled gas is mixed with heated resid
upstream of guard reactor R-102.
 The guard reactor is the first reaction vessel
 contains about 8% of the total catalyst in the unit.
 The function of the guard reactor is to:

 remove sodium and other fouling material from the feed
 This minimizes plugging in the main reactors.
 The reactants leaving the guard chamber are
quenched with cold recycled gas.
 The quenched mixture then flows into the
first main reactor.
 The guard chamber catalyst is the same as in
the main reactors.
 There are three main reactors in series.
 All reactors are the same size
 contain only one bed of catalyst.
 The flow through the reactors is downward.

 Cold recycled gas is injected between reactors
to control inlet temperatures to each succeeding
reactor.
 Scale baskets and liquid distribution trays are
provided in each reactor.
 In addition, layers of size-graded catalyst are
installed in the top of each reactor.
 The graded catalyst allows buildup in the top part
of the bed without building up excessive pressure
drop.
 High pressure separation section:
 The effluent from the last reactor flows to high-
pressure hot separator V-105
 Split of:
 desulfurized liquid product
 recycled gas.
 Vapor from HP hot separator is cooled to 500°F
by heat exchange with recycled gas.
 The cooled, partially condensed HP hot
separator vapors are fed to HP warm separator
V-106.
 The HP warm separator operates at 500°F,
which is well above the dew point of water,
330°F.
 The function of the HP warm separator:
 Remove asphaltenes
 If the asphaltenes are not removed:

 an oil/water emulsion can form when water and
oil condense in the high pressure loop.
 Liquid from the HP warm separator is combined
with liquid from the HP hot separator
 It lets down in pressure through a power
recovery turbine.
 Vapor from the HP warm separator is cooled:
 E-106
 E-106
 The partially condensed HP warm separator
vapor at 105°F feeds HP cold separator V-107.
 The final separation between the liquid and
recycled gas is made in this vessel.
 The condensed water is also removed in this
vessel.
 Water and oil are separated here, although
both the streams are sent to the low-pressure
(LP) cold separator.
 The separation of oil and water:
 HP cold separator
 This avoid emulsification of an oil/water

mixture across the pressure let-down valve in
the line to the low-pressure cold separator.
 Liquids from high-pressure hot and warm
separators after let-down in pressure are fed
to low-pressure hot separator V-108.
 The flashed mixture is separated in this
drum.
 Flashed vapor from the LP hot separator is
partially condensed by heat exchange in E-110
 Then they flow to LP cold separator V-109.
 Then they flow to LP cold separator V-109.
 The liquid from the LP hot separator flows
directly to fractionator feed heater H-103.
 The feeds to LP cold separator V-109 consist of
separated oil and water streams:
 From HP cold separator V-107.
 LP cold separator off-gas is sent to the hydrocarbon

recovery system.
 Water from the LP cold separator is sent to:
 Sour water stripping unit.
 Hydrocarbon liquid from the LP cold separator is
heated in low pressure hot separator (LP-HS) vapor
condenser E-110
 It then flows to the fractionation section of the
column.
 The vapor from the high-pressure cold separator
flows through the recycle gas filter
 Here, the entrained oil and scale are removed to
prevent foaming in the amine system.
 The vapor next flows to H2S scrubber V-110, where
it is in contact with a lean amine solution.
 The rich amine solution goes to amine regeneration
unit.
 The scrubbed recycled gas is sent to recycle gas
compressor C-101, driven by a steam turbine.
 The compressed recycled gas is combined with
make-up hydrogen and split into two streams. Make-up H2
 One stream is heated in the
recycled gas preheater by heat
exchange with HP warm separator
and hot separator off-gases and
finally in recycled gas heater H-102.
 The other stream of recycled gas
from the compressor is utilized to
quench the effluent from each
reactor before entering the next
reactor.
 Three uses are made of process water in the ARDS unit.
 Increase the activity of the catalyst and prevent the
deposit of solids in the reactor effluent cooler.
 Wash recycled gas before and after the amine wash.
 Increase catalyst activity is added to the resid charge
upstream of the charge heater and called injection water.
 The function of the fractionation section is to:
 separate the desulfurized liquid stream
 from hot and cold low-pressure separators
 These are:
 An overhead hydrogen-rich vapor to be processed in
the gas handling plant.
 A stabilized naphtha stream for processing in naphtha
hydrotreater.
 A distillate side cut product with an ASTM end point of
735°F.
 A 680 plus bottom product.
 The fractionator has 26 trays.
 The heated resid feed enters the column on tray 6.
 A small amount of the distillate from the low-pressure cold
separator enters the column on tray 10.
 A stripping steam is introduced below the bottom tray to strip
the material boiling below 6800F from the fractionator bottom.
 Overview
 Process Description
 Where are we?
 Gas Plant!
 Main products
 LPG
 Propane
 Butane (Commercial)
 Olefins
 nC4  Isomerization to iC4
 nC4  Alkylation
 Fuel Gas
Fuel Gas
Sulfur
C3 LPG
C4 LPG
Kerosene
Premium Gasoline
Regular Gasoline
Auto Diesel
Heating Oil
Haring Diesel
Heavy Fuel Oil
Bunker Oil
 Light ends must be processed followed with gas processing and polymerization
processes in the refinery.
 Gas fraction is produced from various units.
 Crude distillation unit
 Catalytic cracking unit
 Catalytic reforming unit
 Hydrocracking unit
 Coking unit
 The light end streams are classified as
 Streams rich in Butane:
 Sold as a mix of LPG.
 Used internally for blending (iC4)
 Alkylation units (nC4)
 Streams rich in Propane.
 Light ends rich in Olefins.
 The objective of gas processing is to
produce:
 Methane
 Ethane.
 The produced ethane and methane is

to serve later for:
 fuel gas
 hydrogen production.
 The gas processing section consists

mainly of two different sections.
 Absorption using Naphtha & Kerosene
 Naphtha rich stream processing
 Absorption using Naphtha and kerosene:
 First, collected gases are compressed to
be fed to an absorption.
 The purpose of naphtha is to absorb
heavier hydrocarbons in the gas fraction.
 These are C3s and C4s in the feed stream.
 To carry out absorption:
 First the gases are cooled and fed to a
phase separator
 This facilitates early separation of lighter
and heavier fractions.
 From the phase separator:
 Gas stream
 Liquid stream.
 The gas stream is fed to an absorber unit

where naphtha is used as a solvent to
absorb the left heavier hydrocarbons in
the gas.
 The gas stream is fed to an absorber unit
where naphtha is used as a solvent to
absorb the left heavier hydrocarbons in
the gas.
 The naphtha rich with hydrocarbons is
fed to the phase separator so as to
stabilize the naphtha stream.
 The gas from the absorber is fed to a
second absorber
 Here, lean oil (such as kerosene) is used
as a solvent to absorb any heavier
hydrocarbons other than the methane
and hydrogen.
 Top Products: Fuel gas
 Bottoms: Rich oil stream.
 Naphtha rich stream processing:
 The liquid product from the phase
separator is fed to a de-ethanizer which
generates ethane rich stream as the top
product.
 This stream is recycled back to the gas
processing unit
 Mixing with the feed and cooling is
present in the phase separator.
 The bottom product from de-ethanizer is:
 Naphtha rich stream
 Butanes
 Propanes
 This stream is subjected to fractionation

using:
 Debutanizer
 Depropanizer
 Deisobutanizer
 Products:
 Propane
 N/iso Butane
 Naphtha.
 LPG – Plant construction
 https://www.youtube.com/watch?v=nuQnBLpM3S0
 Verify the Conditions of the DeButanizer
 https://www.youtube.com/watch?v=par3tAK7VLg
 LPG Tank Filling plant:
 https://www.youtube.com/watch?v=jqaAToQu1kE
 Overview
 The objective of a polymerization unit is to
combine/polymerize the light olefins:
 Propylene
 Butylene
 Into molecules two or three times their original

molecular weight
 C6-C9
 The feed to this process consists of light gaseous

hydrocarbons (C3 and C4) produced by catalytic
cracking, which are highly unsaturated (olefinic)
 The polymer gasoline produced has octane
numbers above 90.
 Typical amounts of polymer gasoline is very small
 It increases the yield of gasoline possible from
gas oil.
 For example:
 the numbers of barrels of polymer gasoline per
barrel of olefin feed is about half those of alkylate
 Note that capital and operating costs are much
lower in polymerization because it operates at
low pressures.
 This makes it convenient when compared to
compared with alkylation.
 The polymerization process was used
extensively in the 1930s and 1940s
 It was replaced to a large extent by the
alkylation process after World War II
 Alkylation units have the advantages of using
isobutane as well as an olefin (expanding the
resulting volume of gasoline) and resulting in a
higher quality product.
 On the other hand, polymer gasoline has more
vapour pressure than the corresponding
alkylation products.
 Note that polymer gasoline product quality is
lower than that obtained from the alkylation unit.
 The end product from polymerization reactor is a
dimer or a trimer of the olefins.
 Dimerization is a form of polymerization that uses
only propylene as its olefin feed.
 The most commonly licensed polymerization process is
the UOP polymerization process, which uses phosphoric
acid as catalyst.
 IFP licenses a Dimersol® process that produces dimers
from propene or butene using a homogeneous aluminum
alkyl catalyst.
 Reaction mechanism comprises of four
basic steps:
 Carbonium ion formation
 Addition reaction
 Regeneration
 Isomerization
 Catalysts used
 Acid catalysts (H2SO4) are used.
 Temperature
 150 – 220oC
 Too high temperatures give tar deposits.
 Pressure
 25 – 100 atms.
 Step 1 - Carbonium ion formation
 Step 2 - Addition reaction
 Step 3 – Regeneration
 Step 4 – Isomerization
 Step 1 - Carbonium ion formation
 Here, olefin reacts with acid catalyst to
yield carbonium ion.
 Step 2 - Additon reaction
 Carbonium ion reacts with olefin to
generate intermediate carbonium ion.
 Step 3 - Regeneration
 The intermediate carbonium ion
converts to the dimer and generates
back the proton on the catalyst surface.
 Step 4 – Isomerization
 Straight chain proton substituted olefins
convert to isomeric carbonium ions.
 Caustic wash:
 C3-C4 olefin feed subjected to caustic
wash to remove H2S and other sulphur
compounds (such as mercaptans).
 These tend to poison the catalyst.
 Water scrubbing
 Eventually water scrubbing is carried out
to remove dissolved impurities and
generate waste water.
 Polymerization reactor
 The reaction mixture is heated,
compressed and fed to a polymerization
reactor.
 The reactor is:
 a shell and tube type design
 The catalyst is placed in the tube
 The reaction takes place inside the tube
 Cooling water is circulated in the shell side
to control the temperature increase due to
the exothermic reaction.
 Fractionation
 Subsequently, the reactor product is fed
to a:
 Depropanizer
 Debutanizer
 This produces propanes, butanes and
polymer gasoline.
 The propane produced is partially
recycled to the reactor and the other
part taken out as a product.
 Butanes are sent to isomerization unit
 The polymeric product is further
stabilization using hydrogenation
stabilizer which converts any freely
available double bonds to single bonds.
 The end product is polymer gasoline.
 Check out this video:
 https://dissolve.com/video/Explanation-polymer-process-
gasoline-refining-royalty-free-stock-video-footage/001-D378-
24-372
 Overview
 Chemistry
 Butanes vs. Naphthas
Fuel Gas
Sulfur
C3 LPG
C4 LPG
Kerosene
Premium Gasoline
Regular Gasoline
Auto Diesel
Heating Oil
Haring Diesel
Heavy Fuel Oil
Bunker Oil
 LSR Naphtha
 C4,C5,C6
 Isomerisation involves
 Isomerisation of Light paraffins
 Isomerisation of nC4to iC4
 Isomerisation of C5-C6 paraffins
 Isomerization reaction is carried out in the
isomerization unit
 Feedstock:
 N-butane (from Butane Splitter)
 nC5, nC6 (light naphtha)
 Products:
 Iso-butane (iC4) make-up (to Alkylation Unit)
 iC5, IC6 (isomerized naphtha)
 Recent pricing trends show isomerisation could be a
significant contributor to octane pool which will
offset the loss from gasoline de-sulfurisation and
aromatic reduction.
 Isomerate as % of gasoline used is:
 USA 8%
 Western Europe 16%
 The octane numbers of the LSR naphtha (C5-82oC) can be improved by the use
of an isomerization process to convert:
 normal paraffins to their isomers
 Isomerization is the process in which:

 light straight chain paraffins of low RON (C⁶, C⁵ and C⁴) are transformed with proper
catalyst into branched chains with the same carbon number and high octane
numbers.
 Typically:
 nC4  iC4
 nC5  iC5
 nC6  iC6
 Octane increases:
 n-pentane RON of 61.7  isopentane RON 92.3
 The unleaded RON of LSR naphtha can be

increased from 70 to about 82–84.
 If the normal components are recycled:
 RON can achieve 87–93
 The highly branched paraffins with 7-10

carbon atoms would be the best to fulfill the
recent requirements of the reformulated
gasoline
 Lightest naphtha feed stock (SRG) with pentanes,
hexanes, and small amounts of heptanes.
 Feed often debutanized —"Debutanized Straight Run".
 Sulfur and nitrogen must be removed since

catalysts employ an ‘acid site’ for activity.
 Merox
 Clay treating
 Hydrotreating
 Common for Straight Run Gasoline and Naphtha to

be hydrotreated as one stream and then
separated.
 Products
 Isoparaffins and cycloparaffins.
 Small amounts of light gasses from
hydrocracking .
 Unconverted feedstock.
 Increased severity increases octane but

also increases yield of light ends.
 Yields depend on feedstock
characteristics and product octane.
 Poor quality feeds might yield 85% or less
liquid product.
 Good feeds might yield 97% liquid product.
 Primary reaction is to convert normal paraffins to isomeric paraffins.
 Olefins may isomerize and shift the position of the double bond.
 1-butene will shift to a mixture of cis-2-butene and trans-2-butene
 Cycloparaffins (naphthenes) may isomerize and break the ring forming an olefin.
 Cyclobutane to butene.
 Isomerisation Catalyst
 Two types of isomerization catalyst:
 Zeolite
 Chlorinated alumina
 Zeolite catalyst requires higher temperatures and provide lower octane

boost
 Chlorinated alumina’s results in highest octane (more sensitive)
 Zeolite catalyst requires higher temperatures and provide lower octane
boost
 Chlorinated alumina’s results highest octane, however, it has higher
sensitivity to feed stock impurities requiring strict feed pretreatment to
eliminate oxygen, water , sulphur and nitrogen containing compounds
 Zeolites are crystallized silico-aluminates that are used to
give an acidic function to the catalyst.
 Metallic particles of platinum are impregnated on the
surface of zeolites and act as hydrogen transfer centres.
 The zeolite catalyst can resist impurities and does not
require feed pretreatment, but it does have lower activity
and thus the reaction must be performed at a higher
temperature of 250 °C (482 °F).
 A comparison of the operating conditions for the alumina
and zeolite
 Vapor phase process
 Hydrogen used to suppress the dehydrogenation and coking.
 High yields and high selectivity to high-octane isomeric forms.
 Provides moderate (but important) contribution to the gasoline pool.
 Catalyst types
 Chloride alumina catalyst.
 Organic chloride deposited on active metal sites.
 High temperature treatment with carbon tetrachloride.
 Chlorides are sensitive to moisture – drying of feed & hydrogen.
 Make-up essential
 Acidic zeolite with noble metal catalyst.
 Platinum catalyst.
 Does not require activation by hydrogen chloride.
 Reactor pressure: 4 – 24 barg
 Reactor temperature: 500 – 525°C
 H2/Hydrocarbon molar ratio: 2 – 3
 Platinum base catalysts are used
 AlCll3 is used as a promoter for the catalyst
 During reaction, part of the AlCl3 gets converted
to HCl
 Therefore, completely dry conditions shall be
maintained to avoid catalyst deactivation and
corrosion.
 Catalytic reaction takes place in the presence of
hydrogen to suppress coke formation
 Light naphtha and hydrogen (make up) are totally
dried and sent to an isomerisation reactor after
pre-heating the feed mixture in a heat exchanger
 Reaction operating conditions
 T = 150 – 200°C & P= 17 – 28 barg
 Typical conversions: 75 – 80 % for pentanes.
 After reaction, AlCl3 is recovered from the product
using condensation or distillation
 The basic principle for AlCl3 recovery is that at the
reactor operating conditions, the AlCll3 is in volatile
conditions and is soluble in hydrocarbons
 After AlCl3 is recovered from the product, it is sent
back to the reactor along with the makeup AlCl3
 Eventually, the product enters a flash drum where
bulkly light ends along with little quantities of
HCl are separated from the liquid product.
 The light ends recovered from the flash drum are
sent to a HCl absorber where HCl is absorbed into
caustic solution to generate the light end gases.
 The light end gases can be further used for other
processes in the refinery.
 The bottom product then enters a HCl stripper
where most of the HCl is stripped from the
isomerisation product rich stream.
 The HCl is recycled back to the reactor to ensure
good catalyst activity.
 Make-up HCl is added to account for losses
 Subsequently, caustic wash is carried out to
remove any trace quantities of HCl
 The isoermized product rich stream is then sent
to a fractionators that separates the isomerized
product from the unreacted feed.
 The unreacted feed from the fractionators is
sent back to the reactor.
 nC4 Isomerization
 Naptha Isomerization
 Naptha Isomerization
 Identify:
 C4 vs. C5/C6
 Isomerization units
 Isomerate
 Identify:
 C4 vs. C5/C6
 Isomerization units
 Isomerate

Petroleum Refining (2 of 3)

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What are the main processes involved in crude oil refining?

What are the main processes involved in crude oil refining?

What are the main steps involved in crude oil distillation?

What are the main steps involved in crude oil distillation?

 Desalting & Dehydration

 The conversion of some of the hydrocarbons into products

 Pretreatment of the crude oil is important if the crude

 Distillation, catalytic reforming and secondary

 Pretreatment of the crude oil removes the oleophobic impurities

 Field separation is the first step to remove:

 Commercial crudes, salt contents 10-200 ppb

 A high degree of salt removal is desired

 Desalting process is two stage process

 Higher temperature reduce desalting efficiency

 Therefore, the crude oil is heated to about

 This temperature enables over-flash conditions in

 Will be fed to the column at various sections

 HEN facilitates energy recovery via:

 Crude is fed at a point lower down the column

 At the bottom of the stripping section:

 Further reflux is provided by several pump-around streams

 The end boiling point is controlled by:

 The overhead vapour is condensed at the top of the

 Ideal case there would be no overlap between these

 By controlling the cut point of any two consecutive

 By controlling the cut point of any two

 The vapour flow rate increases as the vapours rise from

 The main column has 2 sections that are

 Trays 1 - 4 process the atmospheric residue

 OPERATING PRESSURE OF VACUUM COLUMN:

 A few millimeters decrease in pressure drop

 In addition a vacuum residue is produced.

 This is to provide some fractionation between the

 These reduces the pressure drop in the column

 If no use of steam can significantly reduce hydrocarbon-rich aqueous

 Understand how Ejectors Work

 Purge Gases NAPHTHA HDS 10%

KEROSENE HDS 15%

VGO HDS 30%

 Aromatic hydrocarbons such as:

 The removal of vanadium and nickel is usually difficult.

 Higher pressure and temperature are used when

 They require sour water processing unit to recover

 Then, it flows into high-pressure

 The stripper bottom product is cooled by:

 to 100°F before going out of unit’s battery limits.

 This is achieved by exchanging heat with

 Off gases  To flare

 Antioxidant is injected into the ATK product

 The bottom product is pumped through air

 The feed from these secondary units may contain

 The average sulfur decline is often pushed by vehicle

 It is heated in effluent/feed heat exchanger:

 Next in fired heater H-101 then mixed with

 Hydrodesulfurization reactions are exothermic

 It is then flashed into high-pressure separator

 The H2S-free gas is mixed with makeup hydrogen coming

 The atmospheric resids from most Crudes have a

 Water also prevents the deposit of solid ammonium