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SECONDARY PROCESSING :

Thermal conversion process

THERMAL CONVERSION PROCESSES


Thermal Cracking
Visbreaking
Coking
Coke Calcination

THERMAL CRACKING
The processes is which hydrocarbons are decomposed
at elevated temperatures to from material 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 process
are thermal cracking, visbreaking and coking.
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 activity varies with the type of hydrocarbons
and decrease in the following order:
nparaffin > Isoparaffins > cycloparaffins > aromatics >
aromatics / naphthenics > polynuclear aromatics.
Olefins crack to smaller olefins and di-olefins

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. (To avoid this, gasoline or diesel
blend produced from thermal cracking process are
hydrotreated to make them stable usable product).
Since products of thermal cracking have very poor stability
and require further treatment ; Fluid catalytic cracking FCC
finds more favors with refiners.

Simplified 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

Cyclone
Long
Residue
Furnace
Cracked
Residue

Short
Residue
Furnace

F
R
A
C
T
I
O
N
A
T
O
R

Gas oil
Heavy Distillate
+ Recycle

Cracked Residue
F
R
A
C
T
I
O
N
A
T
O
R

Furnace

Gas+ Gasoline
Gas Oil

Cracked Residue

Thermal cracking process

TYPICAL operating conditions and The Yield Patterns in The


SHELL process for Long Residue (Atmospheric Distillation column
bottoms) and Short Residue (Vacuum Distillation column bottoms)
are :
Cracking temperature, 0C
450 500
Furnace outlet pressure, kgf/cm2
(a) For residue
4
(b) For heavy residue
20
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

(Two furnace operation)

(One furnace operation)

C5 1650C

8.5

165 3500C

23.5

12

Separator vessel bottoms (residual oil)

45

Fractionator bottoms (residual oil)

19

82

Products
C1 C4

VISBREAKING
Visbreaking an abbreviation for viscosity breaking or
viscosity lowering is a liquid phase thermal conversion
process to reduce the viscosity of Atmospheric (long
reduce) and Vacuum (short residue) to produce
specification 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)
2. 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.

Coil Visbreaker
Gas

Heater
Gasoline
Reduced
Crude
Charge

Steam
Gas Oil

Tar

Typical operating condition


Equipment

Operating parameter

Furnace
Furnace inlet temp. 0C

Furnace outlet temp. 0C

3400C

470 4900C

Furnace inlet pres; kg/cm 2

22

Furnace outlet pres; kg/cm 2

15

Residence time ; minutes

10

Quench temp; 0C

260

Columns

Fractionate

Stabilizer

Top temp. 0C

138

50

Bottom temp 0C

360

160

Pressure kg/cm 2

5.5

8.5

100

395

Feed temp. 0C
Flash zone temp. 0C

Typical yield pattern


Gas plus loss

Naphtha

Fuel oil (Visbroken


residue)

*If

93*

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
Run length

Yes
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
Waterjet

Delayed Coking
Gas
Accumulator
Naphtha
P/A

Coke Drum

Fractionator

Steam Stripper

Steam

Heater

Light gas oil


Steam

Heavy
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

Gases

13.2

12.0

6.4

Naphtha

11.1

15.7

21.6

Light gas oil

31.4

35.2

46.0

15.5

Coke

44.3

21.6

26.0

Sulfur in coke wt%

0.57

1.2

2.2

Yields

Heavy gas oil

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
&
Boiler

Rotary Kiln

Rotary Cooler

Coke Fines

Calcined
coke

Coke calcination process