CHEMISTRY AND TECHNOLOGY

OF PETROLEUM

By Dr. Dang Saebea

REFINING CHEMISTRY
 INTRODUCTION
 Petroleum refining plays an important role in our
lives.
 Most transportation vehicles are powered by
refined products such as gasoline, diesel, aviation
turbine kerosene (ATK) and fuel oil.
 THE REFINING INDUSTRY IN THREE WAYS

 An increased search for fuel products from non-fossil

sources such as biodiesel and alcohols from vegetable
sources.
 The development of better methods to process tar
sand, coal gasification and synthesis of fuels by new
technology.
 The initiation of long-term plans to look for
renewable energy sources.
REFINING MEANS. . .
1.To a pure state, to remove impurities

2.To improve product

REFINING IS CARRIED OUT IN THREE MAIN STEPS

Step 1 – Separation

Step 2 – Conversion

Step3 - Purification
 REFINING IS CARRIED OUT
Step 1 - Separation
 The oil is separated into its constituents by
distillation, and some of these components (such as
the refinery gas) are further separated with chemical
reactions and by using solvents.
 REFINING IS CARRIED OUT

Step 2 - Conversion
o The various hydrocarbons produced are then
chemically altered to make them more suitable for
their intended purpose.
o For example, naphthas are "reformed" from paraffins
and naphthenes into aromatics.
 REFINING IS CARRIED OUT

Step3 - Purification
o The hydrogen sulfide gas which was extracted from
the refinery gas in Step 1 is converted to sulfur,
which is solid in liquid form to fertiliser
manufacturers.
REFINERY-PETROCHEMICAL INTEGRATION
1. Physical Separation Processes
2.RChemical
EFINERY-Catalytic Conversion
PETROCHEMICAL Processes
INTEGRATION
3. Thermal Chemical Conversion Processes
1.RPhysical
EFINERYSeparation Processes
-PETROCHEMICAL INTEGRATION

Crude Distillation
Crude Distillation
 Crude oils are first desalted and then introduced
with steam to an atmospheric distillation column.

 The atmospheric residue is then introduced to a

vacuum distillation tower operating at about 50
mmHg, where heavier products are obtained.
Atmospheric distillation Vacuum distillation
1.RPhysical
EFINERYSeparation Processes
-PETROCHEMICAL INTEGRATION
Solvent Deasphalting
 This is the only physical process where carbon is rejected from
heavy petroleum fraction such as vacuum residue.
 Propane in liquid form (at moderate pressure) is usually to
dissolve the whole oil, leaving asphaltene to precipitate.
 The deasphalted oil (DAO) has low sulphur and metal
contents since these are removed with asphaltene. This oil is
also called ‘‘Bright Stock’’ and is used as feedstock for lube oil
plant.
 The DAO can also be sent to cracking units to increase light
oil production.

Solvent
deasphalting
process
1.RPhysical
EFINERYSeparation Processes
-PETROCHEMICAL INTEGRATION
Solvent Extraction
 In this process, lube oil stock is treated by a solvent,
such as phenol and furfural, which can dissolve the
aromatic components in one phase (extract) and the
rest of the oil in another phase (raffinate).

 The solvent is removed from both phases and the

raffinate is dewaxed.

Solvent
Extraction
1.RPhysical
EFINERYSeparation Processes
-PETROCHEMICAL INTEGRATION
Solvent Dewaxing
 The raffinate is dissolved in a solvent (methyl ethyl
ketone, MEK) and the solution is gradually chilled,
during which high molecular weight paraffin (wax) is
crystallized, and the remaining solution is filtered.

 The extracted and dewaxed resulting oil is called

‘‘lube oil’’.

 In some modern refineries removal of aromatics and

waxes is carried out by catalytic processes in all ‘‘
hydrogenation process”
2.RChemical
EFINERY-Catalytic Conversion
PETROCHEMICAL Processes
INTEGRATION
Catalytic Reforming
 In this process a special catalyst (platinum metal
supported on silica or silica base alumina) is used to
restructure naphtha fraction (C6–C10) into
aromatics and isoparaffins.

 The produced naphtha reformate has a much higher

octane number than the feed. This reformate is used
in gasoline formulation and as a feedstock for
aromatic production (benzene–toluene–xylene, BTX).
2.RChemical
EFINERY-Catalytic Conversion
PETROCHEMICAL Processes
INTEGRATION
Hydrotreating
 This is one of the major processes for the cleaning of
petroleum fractions from impurities such as sulphur,
nitrogen, oxy-compounds, chloro-compounds,
aromatics, waxes and metals using hydrogen.

 The catalyst is selected to suit the degree of

hydrotreating and type of impurity. Catalysts, such
as cobalt and molybdenum oxides on alumina matrix,
are commonly used.
2.RChemical
EFINERY-Catalytic Conversion
PETROCHEMICAL Processes
INTEGRATION
Catalytic Hydrocracking
 For higher molecular weight fractions such as
atmospheric residues (AR) and vacuum gas oils
(VGOs), cracking in the presence of hydrogen is
required to get light products.

 In this case a dual function catalyst is used. It is

composed of a zeolite catalyst for the cracking
function and rare earth metals supported on
alumina for the hydrogenation function.

 The main products are kerosene, jet fuel, diesel

and fuel oil.
2.RChemical
EFINERY-Catalytic Conversion
PETROCHEMICAL Processes
INTEGRATION
Catalytic Cracking
 Fluid catalytic cracking (FCC) is the main player
for the production of gasoline. The catalyst in this
case is a zeolite base for the cracking function.

 The main feed to FCC is VGO and the product is

gasoline, but some gas oil and refinery gases are
also produced.
2.RChemical
EFINERY-Catalytic Conversion
PETROCHEMICAL Processes
INTEGRATION
Alkylation
 Alkylation is the process in which isobutane reacts
with olefins such as butylene (C4 ) to produce a
gasoline range alkylate.

 The catalyst in this case is either sulphuric acid or

hydrofluoric acid. The hydrocarbons and acid react
in liquid phase.

 Isobutane and olefins are collected mainly from FCC

and delayed coker
2.RChemical
EFINERY-Catalytic Conversion
PETROCHEMICAL Processes
INTEGRATION
Isomerization
 Isomerization of light naphtha is the process in
which low octane number hydrocarbons (C4, C5,
C6) are transformed to a branched product with
the same carbon number. This process produces
high octane number products.

 One main advantage of this process is to separate

hexane (C6) before it enters the reformer, thus
preventing the formation of benzene which
produces carcinogenic products on combustion
with gasoline.

 The main catalyst in this case is a Pt-zeolite

base.
3. Thermal Chemical Conversion Processes
Delayed Coking
 This process is based on the thermal cracking of
vacuum residue by carbon rejection forming coke
and lighter products such as gases, gasoline and
gas oils.

 The vacuum residue is heated in a furnace and

flashed into large drums where coke is deposited
on the walls of these drums, and the rest of the
products are separated by distillation.
Flexicoking
 In this thermal process, most of the coke is
gasified into fuel gas using steam and air.

 The burning of coke by air will provide the heat

required for thermal cracking.

 The products are gases, gasoline and gas oils

with very little coke.
3. Thermal Chemical Conversion Processes
Visbreaking
 This is a mild thermal cracking process used to
break the high viscosity and pour points of
vacuum residue to the level which can be used in
further downstream processes.

 In this case, the residue is either broken in the

furnace coil (coil visbreaking) or soaked in a
reactor for a few minutes (soaker visbreaker).

 The products are gases, gasoline, gas oil and the

unconverted residue.
The End
CRUDE DISTILLATION
 CRUDE DISTILLATION
 Crude distillation unit (CDU) is at the front-end
of the refinery, also known as topping unit, or
atmospheric distillation unit.
 It receives high flow rates hence its size and
operating cost are the largest in the refinery.
 This involves the removal of undesirable
components like sulphur, nitrogen and metal
compounds, and limiting the aromatic contents.
TYPICAL PRODUCTS FROM THE UNIT ARE:
CRUDE OIL DESALTING
o The crude oil contains salt in the form of
dissolved salt in the tiny droplet of water
which forms a water-in oil emulsion.
o This water cannot be separated by gravity
or through mechanical means.
o It is separated through electrostatic water
separation. This process is called
desalting.
CRUDE OIL DESALTING
In the electrostatic desalter, the salty
water droplets are caused to coalesce and
migrate to the aqueous phase by gravity. It
involves mixing the crude with dilution water
(5–6 vol%) through a mixing valve.
POOR DESALTING HAS THE FOLLOWING
EFFECTS:

1. Salts deposit inside the tubes of furnaces and on

the tube bundles of heat exchangers creating
fouling, thus reducing the heat transfer
efficiency;
2. Corrosion of overhead equipment.
3. The salts carried with the products act as
catalyst poisons in catalytic cracking units.
TYPES OF SALTS IN CRUDE OIL
 Salts in the crude oil are mostly in the form of
dissolved salts in fine water droplets emulsified
in the crude oil. The salts can also be present in
the form of salts crystals suspended in the crude
oil.
 These are mostly magnesium, calcium and
sodium chlorides with sodium chloride being the
abundant type.
TYPES OF SALTS IN CRUDE OIL
 These chlorides, except for NaCl, hydrolyze at
high temperatures to hydrogen chloride:
CaCl2  2H 2O  Ca(OH )2  2HCl

MgCl2  2H 2O  Mg (OH )2  2HCl

 Hydrogen chloride dissolves in the overhead

system water, producing hydrochloric acid, an
extremely corrosive acid
DESALTING PROCESS
The process is accomplished through the
following steps:
1. Water washing:
- Water is mixed with the incoming crude oil through
a mixing valve.
- The water dissolves salt crystals and the mixing
distributes the salts into the water, uniformly
producing very tiny droplets.
- Demulsifying agents are added at this stage to aide
in breaking the emulsion by removing the
asphaltenes from the surface of the droplets.
DESALTING PROCESS
2. Heating:
- The crude oil temperature should be in the range of
49-54 ˚C (120–130 F) since the water–oil separation
is affected by the viscosity and density of the oil.
DESALTING PROCESS
3. Coalescence:
- The water droplets are so fine in diameter in the
range of 1–10 mm that they do not settle by gravity.
Coalescence produces larger drops that can be
settled by gravity.
- This is accomplished through an electrostatic
electric field between two electrodes.
- The electric field ionizes the water droplets and
orients them so that they are attracted to each other.
- Agitation is also produced and aides in coalescence.
DESALTING PROCESS
4. Settling: According to Stock’s law the settling
rate of the water droplets after coalescence is
given by
k( H2O  Oil )d 2
Settling rate =
oil

where  is the density

 is the viscosity,
d is the droplet diameter
k is a constant.
DESCRIPTION OF DESALTER

Two electrodes

Simplified flow diagram of an electrostatic desalter

DESCRIPTION OF DESALTER

A primary field of
about 600 V/cm

This field helps

the water droplets
settle faster.

Simplified flow diagram of an electrostatic desalter

DESCRIPTION OF DESALTER

A secondary field of
about 1000 V/cm

The ionization of
the water droplets
and coalescence
takes place here

Simplified flow diagram of an electrostatic desalter

 TWO-STAGE DESALTING

- The desalter of this design achieves 90% salt removal.

However 99% salt removal is possible with two-stage
desalters.
-A second stage is also essential since desalter maintenance
requires a lengthy amount of time to remove the dirt and
sediment which settle at the bottom.
-The crude unit can be operated with a one stage desalter
while the other is cleaned.
DESALTER OPERATING VARIABLES
For an efficient desalter operation, the following
variables are controlled:
 Desalting temperature: The settling rate depends on
the density and viscosity of the crude
T density & viscosity settling rate

Desalting temperature can vary between 50 and 150 ˚C

Washing water ratio: Adding water to the crude oil

helps in salt removal.

Wash water rate Coalescence rate

DESALTER OPERATING VARIABLES
Water level:
- Raising the water level reduces the settling time for the
water droplets in the crude oil

-However, if the water level gets too high and reaches the
lower electrode, it shorts out the desalter.

- it is always better to keep the level constant for stable

operation.
DESALTER OPERATING VARIABLES
Washing water injection point:
-Usually the washing water is injected at the mixing
valve.

- However, if it is feared that salt deposition may

occur in the preheat exchangers, part or all of the
washing water is injected right after the crude feed
pump.
DESALTER OPERATING VARIABLES
Type of washing water:
-Process water in addition of fresh water is used for
desalting. The water should be relatively soft in order to
prevent scaling.

- It should be slightly acidic with a pH in the range of 6.

It should be free from hydrogen sulphide and ammonia
so as to not create more corrosion problems.
ATMOSPHERIC DISTILLATION

330 ˚C

Process flow diagram of an atmospheric

distillation unit
COMPONENT OF ATMOSPHERIC DISTILLATION

Rectifying section

Flash zone

Stripping section
Description OF ATMOSPHERIC DISTILLATION
The vapor from pipestill furnace
discharge as a foaming stream
into distillation tower.

The partially vaporized crude is

transferred to the flash zone.

The vapour goes up the tower to

be fractionated into gas oil that is
called the overhead product .

liquid portion of feed go down to

bottom of tower
Description OF STRIPPING SECTION
 Steam reboilers may take the form of
a steam coil in the bottom of the tower
or a separate vessel.

The bottom product from the tower

enters the rebolier where part is
vaporized by heat from steam coil.

The hot vapor is directed back to the

bottom of the tower and the nonvolatile
leaves the rebolier and passes through a
heat exchanger, where its heat is
transferred to the feed to the tower.
Description OF STRIPPING SECTION

 Steam is also injected into the column

-To strip the atmospheric residue of any light
hydrocarbon.
- To lower the partial pressure of the hydrocarbon
vapours in the flash zone. This has the effect of
lowering the boiling point of the hydrocarbons and
causing more hydrocarbons to boil and go up the
column to be eventually condensed and withdrawn as
side streams.
Description OF RECTIFYING SECTION
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,

the vapours are condensed and
part of the light naphtha is
returned to the column as
reflux.

 Reflux is provided by several

pumparound streams along the
column.
IMPROVEMENT OF DISTILLATION EFFICIENCY WITH
PUMPAROUND

 Vapours Cold liquid condenses Reflux

To compensate for the withdrawal of products from
the column.

 The addition to the heat removal from the condenser.

The thermal efficiency of the column is improved and
the required furnace duty is reduced.
Description OF RECTIFYING SECTION
Liquid collects on each tray to a depth,
and the depth controlled by a dam or weir.
As the liquid spills over the weir into a
channel, which carries the liquid to the tray
below.
IMPORTANT OF STRIPPING AND RECTIFYING
SECTION

 Stripping section
The more volatile component are stripped
from the descending liquid

 Rectifying section
The concentration of the less volatile
component in the vapor is reduced
 Straight-Run Naphtha and Gases

125 ˚C Heavy Naphtha

160 ˚C Kerosene

250 ˚C Gas Oil

Crude Oil
300 ˚C  The Temperature of tray is
progressively cooler from bottom
to top

Residuum
THE EFFICIENT OPERATION OF THE DISTILLATION

Tower requires the rising

vapors to mix with liquid on
each tray.
This is usually achieved by
installing a bubble caps.
The cap forces the vapor to go
below the surface of the liquid
and to bubble up through it.
LIMITING TEMPERATURE OF ATMOSPHERERIC
DISTILLATION

 It is important not to subject the crude oil to temperatures

above 350 °C because the high molecular weight components
in the crude oil will undergo thermal cracking and
form petroleum coke .

 Formation of coke would result in plugging the tubes in

the furnace and the piping from the furnace to the
distillation column as well as in the column itself.

 The constraint imposed by limiting the column inlet crude

oil to a temperature of less than 350 °C yields a residual oil
from the bottom of the atmospheric distillation column.
VACUUM DISTILLATION

 To further distill the residual oil from the

atmospheric distillation column, the
distillation must be performed
at absolute pressures as low as 10 to
50 mmHg so as to limit the operating
temperature to less than 350°C.

 Vacuum distillation is the reduced

temperature requirement at lower
pressures.

 Vacuum distillation increases

the relative volatility of the key
components.
 Vacuum distillation can improve a
separation by:
 Prevention of product degradation or polymer
formation because of reduced pressure leading to
lower tower bottoms temperatures.
 Reduction of product degradation or polymer
formation because of reduced mean residence
time especially in columns using packing rather
than trays.
 Reduction of capital cost because of reduced the
height and diameter.
FRACTIONS OBTAINED BY VACUUM DISTILLATION
used as catalytic cracking stock
Gas Oil or, after suitable treatment, light
lubricating oil
Atmospheric
Residuum

Vacuum Distillation
Light
Medium Lube oil

Heavy

used directly as asphalt or

Residuum, converted to asphalt
Nonvolatile
OPERATION OF CRUDE DISTILLATION UNITS
The factors affect the design and operation of the unit
are explored
1. Fractionation
The degree of fractionation in a crude unit is
determined by the gap or overlap between two adjacent
side stream products.

Example: The gap or overlap in the boiling point range

between kerosene and LGO.
Lighter product: kerosene end boiling point

Heavier product: LGO initial boiling point

In the ideal case there would be no overlap

 However, if we compare the ASTM distillation
boiling points, and since ASTM distillation does not
give perfect fractionation. Since determining 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 heavier product and the 95% point of the lighter
product.
a gap indicating good
fractionation

some of the light

product is still in the
heavier product
2. Overflash
 The partially vaporized crude is transferred to the
flash zone. The furnace outlet temperature should be
enough to vaporize all products withdrawn above the
flash zone plus about 3–5 vol% of the bottom product.

 This overflash has the function of providing liquid

wash to the vapours going up the column from the
flash zone.

 The overflash improve fractionation on the trays

above the flash zone, thereby improving the quality of
the HGO and reducing the overlap with the bottom
products below the flash zone.
3. Column Pressure

 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.

Pflash zone > PTop tray > Preflux drum

4. Overhead Temperature

The overhead temperature must be controlled to

be 14–17 ˚C 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 is to prevent corrosion due to the hydrogen

chloride dissolved in liquid water (hydrochloric acid).
EXAMPLE
If the overhead stream contains 8.5 mol% water
at a pressure of 34.7 psia (2.36 bars), calculate
the overhead temperature for safe operation.
EXAMPLE
If the overhead stream contains 8.5 mol% water
at a pressure of 34.7 psia (2.36 bars), calculate
the overhead temperature for safe operation.

Solution:
The saturation temperature of water at the partial
pressure of water in the overhead vapour.
Water partial pressure = 0.085 x 2.36 =0.2 bars
From the steam tables:
Saturated steam temperature at 0.2 bars = 61 ˚C
Safe overhead operating temperature = 61+17 ˚C
The End