Lecture 6

Fractionation of petroleum
Crudes contain salts and moisture in varying proportions, water occurs as emulsions
when crude is naphthenic.
Crude has to be dehydrated to remove the salts, removal is effective in the form of
brine.
Chlorides of calcium and magnesium help in overhead corrosion when mixed with
the steam.
Any crude that contains more than 5kg of total salts expressed in terms of sodium
chloride per thousand barrels may be regarded as salty crude.
Dehydration may be done at two stages, initially at the mine itself and at the
refinery
The following methods are used for dehydration of crude
1. Chemical treatment
2. Gravity settling
3. Centrifugal separation
4. Electric desalting
At the mining itself crude is processed either by setting or by adding the chemicals some
times both are used.
Crudes possessing emulsifying characteristics require emulsifying agents such as sodium
hydroxide, soda ash, salts of fatty acids and petroleum sulfonates, hasten the process of
agglomeration.
They are allowed to stand at 75-80oC and pressure of 15Kg/cm2in huge tanks.
Good separation into hydrocarbon and aqueous phase results when crude is allowed to
stand for 48 hours.
Continuous separation is not possible because of large amount of crude, high floor space
and cost of the equipment. Centrifugal separation is not feasible because of less capacity
and high energy requirements. Hence electric desalting is the feasible method for desalting
the crude.
Other treatments that can be given to waxy crude are solvent addition and chemical
additives.
Electric desalting

 This method helps in simultaneous removal of salt and moisture content from the
feed
 The principle used for this separation is under the application of potential, all the
polar molecules orient.
 A potential of 20,000 to 30,000 volts is applied between the electrodes through
which crude is passed.
 Water present in the form of emulsion agglomerates into a stream entrapping salts
in the process
 Brine collected at the bottom of the tank and crude floats at the top.
 Temperature and pressure are kept at 90oC and 5 to 6 Kg/cm2 and power
consumption is less than 0.01 KWh per barrel.
 HIGH VOLTAGE
SYSTEM

HEAT EXCHAGER
CRUDE
Pumping of crudes
Property that determines energy required for the pumping of crude is pour point.
Indian crudes are generally waxy in nature with less sulfur content, where as the
crude from middle east contains high sulfur content and very low pour points.
If the temperature falls down during transportation, the viscosity of the crude
increases and inhibits transportation. Processing of this kind of crudes is essential
before transportation.
At a definite rate of heating and cooling modifies the crystal structure and the
response to retain this kind of properties for pumping is taken advantage of.
First heating is done up to 95oC and cooling is done in two stages, first cooling goes
down to 65oC and gradual cooling up to 15oC at a rate of 0.5oC per minute.
Solvents that improve the flow properties can be considered as flow improvers.
This solvents change the crystal structure and retard the growth of crystal, they are
added after the preliminary desalting of crude. After the stabilization, which lasts of
40hrs, are ready for transportation and this solvents retain their properties for a
month.
Indigenous additives like Flowcell, SWAT 104, 105 and 106, they depress the pour
points by 5.
Heating of crude
Initially direct heating was used before sending them to them to the refineries.
Non uniformity and excessive heating could not be abated with direct heating.
Pipe still heaters are used for heating of crude which has radiant and convective
section separately.
Recent advancements in in pipe still heaters have brought the heat transfer in
radiant section as high as 70%
Considerations for designing radiant section
Heat Duty
Different heat transfer rates are necessary for different types of operation. They are
specified either on the basis of projected area of the tube or outside surface area of
the tube.
Air fuel ratio
Fuel rich in hydrogen gives better radiating characteristics due to the formation of
water vapor after combustion.
Excess air fuel ratio generally increases maximum attainable temperature, they also
increase heat transfer.
Tube spacing
Tubes are placed one above the other and more than two rows are not opted due
to the following reasons
1. Cost of the structure shoots up
2. Maintenance cost increases
3. Third row absorbs only 8% of heat transfer but first and second row absorbs
more than 90% of heat transfer.
Over burned tubes
Some of the tubes receive more heat from both radiation and convection.
Such overheating causes problem like coke formation. This kind of tubes are
generally used for super heating.
Cross over temperature
Modern furnaces extract 60 to 70% of net heat available .
Convective zone is above the radiant section and passage leading from the radiant
zone to the convective zone is called duct and the opening of this is generally 1/3 of
the width of the furnace.
Combustion volume
Air fuel ratio determines the volume for combustion.
For moderate heating rates furnace volume of 1CC is required for 11.7×104KJ of
heat release for one hour.
Design of furnace is based on Hottle and Wilson method
Radiant heat absorption is given as

1
R  100
G Q
 Ac
1
S
Where R= % heat absorbed in radiant section
G= air fuel ratio and
α=factor to convert exposed surface to cold surface.
Q=heat in KJ/hr for S=14200 area in m2
Ac= area of walls having tubes in front it

Lobo and Evans method gives a good procedure for checking the furnace performance.
Monard’s empirical relation for convective heat transfer coefficient is given by
2.845  G 0.667  T 0.3
hc 
D 0.33
Where G= mass flow rate
T=temperature in K
D= out side dia of tubes in cm
Lobo- Evans Method
It incorporates all the factors that influence radiation.
This methods consists of following steps
α factor is evaluated
Area of the walls that carry tubes is evaluated
Tube skin temperature is evaluated by assuming adiabatic flame temperature is equal to
the bridge wall temperature.
Flame emissivity is related to the partial pressure of radiant gases and mean radiant
beam length(L)
For rectangular type of furnace where length: breadth: height dimensions are in the
ratio 1:1:1 to 1:2:4 then L=1/3(volume of furnace)0.333 . Effective refractive area is the
total wall area less than the effective surface αAc
Exchange factor is calculated in terms of flame emissivity and ratio of AR/ αAc
Rate of heat absorption is given by RQ/ (αAc Q)
Checking with that of the from literature the gas temperature should not differ more
than ±54oC
Distillation of crude
It is a technique used for the separation of soluble liquid mixtures into individual
components.
Crude being a mixture of hydrocarbons has a boiling range of -160 to 1000oC
Several fractions of crude taken from the distillation unit are called as cuts. These
later are further processed as per the requirements.
The basis for the refinery distillation completely vests on TBP tests. Fractionation is
generally conducted in two stages, one in Atmospheric Distillation Unit(ADU) and the
other is in Vacuum Distillation Unit.
They differ from conventional practice that they doesn’t contain reboiler and this has
been over come by heating the feed to the maximum permissible temperature only
once and allowed to flash in the towers.
When the crude contains good amount of soluble gases or if the crude has to be
transported, preflashing or topping in the column is employed
Distillation or flash is conducted in two series, doesn’t exceeds more than two and the
arrangements are done in the following methods
1. Top tray reflux
2. Pump back reflux
3. Pump around reflux towers

Top tray reflux is conventional way distilling the crude, which creates always a build of
vapour necessitating large towers and hence the reflux is of poor quality, no economic
utilization of heat input and hence quality of fractions cannot be sacrificed.
Pump back reflux
In this arrangements reflux is provided in regular intervals and hence every plate acts as
true fractionators, tower is uniformly loaded, less tower diameters hence most of the
refineries use this method.
Pump around reflux
In this arrangement reflux from lower plate is taken cooled and fed into the new column
at higher section by 2 to 3 plates
This creates problem of non uniform mixing and to overcome this designers have
considered all plates in this zone as single plates and this reflects in the height of the
tower.
In distillation the cuts doesn’t exceed more than eight and side stream strippers are
used to ensure the quality of the cuts.
Atmospheric Distillation Unit
All types of conventional trays like bubble-cap trays, ballast trays, sieve trays, valve
trays are generally used.
Usual dimensions and operating conditions data are given below for an atmospheric
column
Tower diameter 5 to 8 metres
Number of plates 25 to 40
Maximum allowed pressure drop per plate 0.015 Kg/cm2
Allowed pressure drop between flash zone to top 0.5 to 0.55 Kg/cm2
of tower

Pressure drop from furnace outlet to flash zone 0.3 to 0.4 Kg/cm2
Pressure at the top of the tower 1.2 to 1.4Kg/cm2
Light naptha to heavy naphtha 6 to 8 plates
Heavy naphtha to light distillate 5 to 6 plates
Light to middle distillate 4 to 6 plates
Middle distillate to gas oil 3 to 4 plates
Flash zone to first draw 3 plates
Flash zone to bottoms 3 plates
Tower top temperature 110oC
Steam rate per barrel 4 to 5Kgs
Reflux ratio for light fractions 2 to 3
Reflux ratio for heavier fractions 1.5 to 2.5
Vacuum distillation unit
Reduced crude from the bottoms of ADU is further distilled under reduced pressure
to get the remaining fractions
The bottoms of vacuum distillation is known as Goudron or residuum.
Design is more empirical than ADU, major altercations are difficult, side cut doesn’t
go beyond four and more costlier than ADU
Steam require does entirely depend on vacuum maintained
Plate that gives low pressure is generally preferred
The crude with high emulsion are operated in vacuum distillation operating under
10-11 mm of Hg. These are highly costlier and are not generally preferred.
Most of the towers operated under a vacuum of 30- 40 mm of Hg
 Temperature of reduced crude in flash 350-400oC
zone
Pressure in flash zone 30-40 mm of Hg
Pressure for long residuum 40-60 mm of Hg
Top pressure 12 to 15 mm of Hg
Temperature at top 225 to 250oC
Trays between two draws 3 to 4
Steam rate 0.3 to 5 Kg per barrel
Over flash 2%

Vacuum Distillation Unit is crude specific and the most important products of this
unit are cracking stocks, fuel oils, lube oils and bitumen
All these products are free detrimental compounds like sulfur, which poisons
catalyst in cracking and hydro cracking units
Over head corrosion in distillation units
Corrosion in distillation units are mainly because of sulfur and chloride ions.
Inefficient desalting techniques prior to the distillation.
Less concentration of sulfur provides protective coating over the surface but high
concentration leads to severe corrosion problems.
Chlorides are mainly because of hydrolysable calcium and magnesium ions.
This can be prevented by adding ammonia into the column but high concentration
leads to the formation of crystals ammonium chloride.
Instead of using ammonium which in turn aggravates corrosion problems, organic
amine are used, they are more basic and have no side effects
Topping operation
Blending of gasoline
Blending is an important operation in the refinery, a physical process in which accurately
measured components are mixed thoroughly to form homogenous mixture.
There are two effective ways of blending are batch and continuous blending.
Line blending
This is widely used technique in blending in the refineries. All the compounds in fixed
proportions are travelled in a long pipe line and acts a mixer to form homogenous
mixture of blending compound.
Gasoline blending
Different gasoline like Alkylated gasoline and cracked gasoline are blended with
different additives to improve the efficiency of gasoline.
The important properties that are critical during blending are vapor pressure and octane
number.
Schematic diagram for blending of gasoline