THERMAL CONVERSION PROCESSES

The processes is which higher hydrocarbons are decomposed

at elevated temperatures to hydrocarbons of lower Mol. wt. are
called thermal conversion process.
Any fraction of the crude from Naphtha to Vac. Residue can
be processed thermally.
The most important types of thermal conversion processare :
Thermal Cracking
Visbreaking
Coking
 THERMAL CRACKING

Thermal cracking is used for conversion of residues and higher

Mol. wt. hydrocarbons into more useful products by cracking the
large hydrocarbon molecules into smaller ones at a temp. level of
4500 5000C.
Cracking is the most important process for the commercial
production of gasoline and diesel fuel.
Cracking of petroleum yields light oils (corresponding to
gasoline), middle-range oils used in diesel fuel, residual heavy
oils, a solid carbonaceous product known as coke, and such gases
as methane, ethane, ethylene, propane, propylene, and butylene.
Cracking activity varies with the type of hydrocarbons and
decrease in the following order:
nparaffin > Isoparaffins > cycloparaffins > aromatics
 Important variables in thermal cracking are
Temp.; pressure and residence time.

Cracking reactions begin to occur at Temp. of 315

3700C.
Pressure determines the phase in which the cracking
reactions take place.
Thermal cracking conversion increases with temp. and
residence time.
Under very severe thermal cracking conditions, there is
tendency for coke formation.
Cracking also generates double bonded hydrocarbons
(olefins). Side reactions like condensation and polymerization
reactions also occur leading to gum formation and tar-like
polymerization products.
Thermal Cracking Process :

Simple Thermal cracking process produces gas,

naphtha, middle distillates and thermal tar from almost all
variety of charge stocks from distillates to the heaviest
crude and residual oils.

The feed is heated to cracking temp. 4500 5000C and

the cracked products containing gas and Full Boiling
Range distillates enters the fractionators after passing
through an intermediates separator vessel.
 Gas+ gasoline

F Gas oil
Cyclone R
A Heavy Distillate
C + Recycle
Long T
I
Residue O
N
Furnace A Furnace
T
O
Cracked R

Residue
Cracked Residue
Gas+ Gasoline
F
R Gas Oil
A
C
T
Short I
Residue O
N
A
Furnace T
O
R
Cracked Residue
Thermal cracking process
 TYPICAL operating conditions:
Cracking temperature, 0C 450 500
Furnace outlet pressure, kgf/cm2
(a)For residue 4

Typical Yield Pattern

The yield of fractions in the Shell process for long residue and short
residue

Yield, wt. % on feed

Long residue Short residue
Products
(Two furnace operation) (One furnace operation)

C1 C4 4 2
C5 1650C 8.5 4
165 3500C 23.5 12
Separator vessel bottoms (residual 45 -
oil)
 VISBREAKING

Visbreaking an abbreviation for viscosity breaking or

viscosity lowering is a liquid phase thermal conversion
process to reduce the viscosity of fuel oil.
Small quantities of LPG and a fair amount of naphtha are
also produced.

Visbreaking is a mild thermal cracking process and

help in reducing the viscosities and pour point of long
and short residues. Refinery production of heavy oils can
be reduced by 30% using visbreaking. Visbreaking also
produces gas, gas oil stock and gasoline which go for
further processing.
 The principal reaction which occur during The Visbreaking
are :
Cracking of the side chains attached to cycloparaffins
and aromatic rings.
Cracking of resins to light hydrocarbons (primarily olefins)
Some cracking of naphthene rings under higher temp.
of operations (5000C)

. types of Visbreaking operations :

Conventional Visbreaking (Furnace or coil cracking)

Soaker Visbreaking
Conventional Visbreaking

Also known as coil cracking

The process uses Furnace outlet temp. of 475-5000C and
reaction time from one to three minutes.
This process produces minimum of Naphtha and a
maximum of fuel oil from long and short residues and
other heavier feed stocks.
Gas, Naphtha and light gas oils are recovered from the
top section of the fractionators. Gas and Naphtha can be
further processed in a gas concentration unit for the
recovery of LPG.
 Gas

Coil Visbreaker

Heater

Gasoline
educed
rude Steam
harge Gas Oil
stripper
fractionator
470-
4900c
Tar
 Typical yield pattern

Gas plus loss 3

Naphtha 4

Fuel oil (Visbroken 93*

residue)

*If diesel production is to be maximized, a second

cracking furnace is added to the stream and the heavy
fraction boiling between 350 5000C, obtained by distilling
the visboken residue under vacuum is recycled to second
furnace for further cracking.
Run lengths of 3 6 minutes are common for coil
visbreakers.
 Soaker Visbreaking :
In this process a soaker drum is added between the
furnace and the fractionator. This drum provide large
residence time for the feedstock. The cracking reactions
take place in soaking drum. Since higher residence time
allows improved conversion at lower temps. ; Soaker
Visbreaking Technology is more energy efficient and
provides higher run lengths as coking reactions in the
furnace coil are significantly reduced. Run lengths to 6-18
months for Soaker Visbreaker.
Other advantages of Soaker Visbreaking are :
Lower capital cost (10/15% lower)
Smaller furnace ; less waste Heat Recovery equipment
Less pressure drop through furnace
Lower fuel consumption (15% less fuel : 0.2% on feed)
Better and more selective yields.
 Gas
Soaker Visbreaker

Naphtha

Steam Steam
Gas Oil

Soaker
Drum
Tar

Heater

Residual
Stock
 Typical operating condition
Equipment Operating parameter
Soaker Drum
Pre. 5 15 bar (g)
Temp. 4400C
Vapour Cracking minimum

Liquid Cracking Yes

Run length 300 days

Yield Pattern
Product Yield; % of feed
Gas 1.7
Naphtha (80-2000C) 3.1
Light gas oil (200-3500C) 13.2
Heavy gas oil (350-5200C) 27.0
Residue (5200C+) 55.0
 Visbreaking is an effective and cost effective way
to produce more valuable products from heavy
residues. Earlier, it used to reduce the viscosity and/
or pour point of a fuel oil but now it is employed to
obtain Cat. Cracker feed and to reduce fuel oil
production.
 COKING
Coking is the most widely practiced means of reducing
the C H ratio of residual oils, Of the 2 main process
delayed coking and fluid coking more than 90% capacity is
in delayed coking units.
Delayed coking is a thermal cracking process in which a
hydrocarbon feedstock, mainly residue is converted to lighter
and more valuable products and coke.
Main advantage of the process is that it can take residual
stocks from a wide variety of process unit in a Refinery
Coking Furnace and the coke drums are the key elements in
the process. Cracking is initiated in the furnace tubes where
short residence time is allowed. Coking of the feed material
is delayed until it reaches large coking drums with larger
retention time; downstream of the coking heater.
Three types of coke structures can be produced shot,
sponge or needle coke.
Decoking Delayed Coking
Waterjet
Gas
Accumulator
Naphtha
Coke Drum P/A

Fractionator Steam Stripper

Steam

Heater Light gas oil

Heavy
Steam
gas oil
Steam Gen.

Feed
Condensate
Drum
Coke
 Process Description

Delayed coking is a semi continuous process in which

the heated charge is transferred to large coking drums
which allow the long residence time needed to allow the
cracking reactions to proceed to completion feed to
these units is normally heavy atmospheric residues,
although heavy catalytic cycle oils and cracked tars may
also be used.

Feedstock gets pre heated by exchange of heat from

outgoing products and is partially vaporized in a specially
designed coking furnace. Mild cracking takes place in
the furnace where thermal cracking temps; of 4850 to
5050C are reached.
 From the furnace, the liquid-vapor mixture goes to the
coking drum (operating in batch-1 coking, the other
decoking). The vapors under-go cracking as they pass
through the coke drum.

The cracked products go to fractionate where cracked

gas, Naphtha, Kerosene and gas oils are separated. The
petroleum coke is formed in the drum due to high
residence time of cracking in the drum.

The feed stream is regularly switched between the

operating drum and drum under decoking. Decoking is
done using high pressure water jets. This generally fallows
a 12-16 hr. cycle.
 decoking operation

Following procedure is used to remove the coke :

(i) The coke deposit is cooled with water.

(ii) One of the heads of the coking drums is removed
to permit the drilling of a hole through centre of the
deposit.
(iii) A hydraulic cutting device, which uses multiple
high pressure water jets, is inserted into the hole and
the wet coke is removed from the drum.
(iv) After the removal of coke from the coke drum, it is
flushed with water and is readied for reuse.
 Typical operating conditions
Furnace outlet temp. 4800 5150C
Coke Drum Pressure 1.7 Kg/cm2g
Fractionator top temp. 1500C
Fractionator Bottom temp. 3500C
Fractionator Pres. 1.4 3.4 Bar
Typical yield from delayed coker
Feed
0
API 7.4 12.0 12.5
Sulfur wt% 2.76 1.6 0.6
CCR wt % 19.6 9.6 14.8
Yields
Gases 13.2 12.0 6.4
Naphtha 11.1 15.7 21.6
Light gas oil 31.4 35.2 46.0
Heavy gas oil - 15.5 -
Coke 44.3 21.6 26.0
Sulfur in coke wt% 0.57 1.2 2.2
 Fluid Coking
Fluid coking is a continuous process that uses the
fluidized solids technique to convert residue including
vacuum pitches to more valuable products.
Fluid coking uses 2 vessels a Reactor and a
Burner. Both the reactor vessel and the burner vessel
contain fluidized beds with coke particles circulating
between the two vessel by fluidized solids technique.
Coke particles are circulated to transfer heat to the
reactor. The residuum is cooled by distributing it as a
thin film of liquid on the outside of the hot-coke
particles.
The vapor products pass through cyclones that
remove most of the entrained coke.
 COKE CALCINATION PROCESS
Petroleum coke is produced as delayed sponge
coke, delayed needle coke, fluid coke.
Calcination of raw petroleum coke (green coke) is
needed to transform it into useable material.
Calcined coke is mostly used by the Aluminum
Industry in the manufacture of anodes for Alumina
Reduction, Calcined needle coke is used to
manufacture. Graphite products and prebaked graphite
electrodes for use in electro metallurgical furnaces.
Process Description
Calcination of green coke is essentially a high temp.
treatment involving drying, devolatilization and
dehydrogenation by which the C/H ratio of the feed is
increased from about 20 to 1000. It may be carried out in a
rotary kiln.
To Stock
Steam
Green Coke

Fuel Gas
Incinerator Rotary Kiln
&
Boiler

Rotary Cooler

Coke Fines Calcined

coke

Coke calcination process