Petroleum Refining Technology

(CHE F422)
 Coking

• Coking is a high severity thermal cracking process for

conversion of heavy, low grade residues.
• Reduced crudes, vacuum residues, tars, pitches etc are
converted into more valuable lighter products and
coke
• With short residence time in furnace tubes, the coking
of feed material is thereby delayed until it reaches coke
drum (Delayed coking)
Types of Coking

• Delayed coking
• Fluid coking
• Flexi-coking

Common objective: To maximize the yield of distillate products in a refinery by rejecting large
quantities of carbon in the residue as solid coke, known as petroleum coke.
 Coking
• Feed: ADU/VDU bottom

• T: ~460 to 510°C & fed to

• P: 1.2−4 kg/cm2(g)

• 4-8 drums are common,

drum dia 6-10m & height
30-40m
 Delayed coking

• Feed: Vcuum residue

feed & heavy coker 415-450 °C
gas oil recycle
• Steam to heater
• Heated feed to coke
drum
• Insulated coke drum
• 16-18 h

• Long residence time

475-515 °C
10-30 psi

Note: All of the heat necessary for coking is provided in the heater, whereas
coking takes place in the coke drum; hence, the process is called “delayed
coking.”
• To maintain continuous operation two or
more drums are used where one drum is on
stream and the other drum is emptied
• Temperature in the coke drum ranges from
415 to 450 oC and the pressure varies
from 1.5 kg/cm2 to 3.5 kg/cm2.
• The coke removal from the coke drums is
achieved through drilling a central hole
using high pressure water jets ( 200-250 kg
/cm2)
 Operating Variables
• Heater outlet temperature, Pressure, Recycle ratio, & Cycle time
• Variable selection: characterization factor, asphaltene content, and Conradson
Carbon Residue (CCR )
• To minimize coking in heater & maximize liquid product yield
• Typical recycle ratio: 3-5%: to control the endpoint of the coker heavy gas oil
• Temperature ( 485-505 oC)
• As temperature increases, at constant recycle ratio and pressure,
coke yield decreases
• At very high temperatures coke produced will be very hard
• At too low temperatures, soft coke with a high VCM is produced
• Pressure
• At constant temperature and recycle ratio, increase in pressure
• increases coke and gas yield. For coke yield to be minimum the lowest
pressures must be used
 Cycle time of coke drums

Operation Time ( Hours)

Coking 24
Decoking 24
Switch Drums 0.5
Steam , Cool 6.0
Drain , Unhead & Decoke 7.0
Reheat, Warm up 9.0
Spare Time, Contingency 1.5

Coke drums with lower cycle time of 16 hrs to 24 hrs are also in operation
 Kinds of coke
Delayed coking of VDR:
• High density Shot coke
• 5 mm diameter spherical particles.
• Faces difficulties to remove from drum
• Problem in grinding
• Uses in TiO2 production
• Porous Sponge coke
• Porous, irregular shaped lumps. Used
as solid fuel
• Manufacturing anodes for aluminium
production. If metal & sulfur content
are very low
• Needle coke
• produced mostly from coking of a highly aromatic FCC
decant oil
• low coefficient of thermal expansion, a low puffing
tendency during graphitization
 Typical Coke End Uses
Application Coke type State End Use
Carbon Source Sponge Calcined Aluminum Electrodes
TiO2 Pigments
Carbon raiser
Sponge Green Silicon carbide
Foundries
Coke Ovens
Needle Calcined
Electrodes , Synthetic
graphite
Fuel use Sponge Green Lump Space heating
Sponge Green Industrial boilers
Shot Green Utilities
Fluid Green Cogeneration
Flexicoke Green Lime
Cement
Delayed Coking Process- Products & Yields
Typical yields of products from RCO feed

PRODUCT YIELD, wt %

Gas 10-12
Naphtha 8-10
Kero I+II 25-30
(140-300oC)
Gas oil 18-20
(300-360/370oC)
Residual fuel oil 5-6
Coke 15-18
 Delayed Coking Process-
Products & Yields ..contd.

PRODUCTS YIELD PATTERN (Typical )

( Ex Panipat DCU )
Design Actual
Fuel Gas 3.71 3.72
LPG 2.8 3.09
Lt Naphtha 6.48 6.56
Hy Naphtha 1.94 5.36
LCGO 28.78 23.34
HCGO 24.76 25.43
CFO 1.42 1.22
Coke 28.82 31.28
H2S + Misc. 1.29 -
 Operating Variables

Operating variables ( Temperature, Pressure and Recycle ratio )

determine product yields and quality:
Temperature ( 485-505 oC)
• As temperature increases, at constant recycle ratio and pressure,
coke yield decreases
• At very high temperatures coke produced will be very hard
• At too low temperatures, soft coke with a high VCM is produced
Pressure
• At constant temperature and recycle ratio, increase in pressure
increases coke and gas yield
For coke yield to be minimum the lowest pressures must be used
 Sponge Coke

•Sponge Coke is porous, irregular shaped

lumps
•Depending upon level of impunities it finds
use as fuel or as Anode grade coke.
 Needle Coke

Hard & dense mass of highly crystalline

structure with carbon threads oriented in single
direction & high degree of graphitization

Important properties
•
Low Co-efficient of Thermal Expansion (CTE) – to
prevent splintering due to thermal stress on
electrode tip ( Most Important property)
•
Low sulfur content - to avoid puffing during
graphitization at ~ 2800oC
•High real density – to provide mechanical strength
Low ash content – to avoid any void when
graphitized
 Typical Properties for Sponge Coke

Green Coke Coke calcined

Component as produced at 1300 °C
Fixed carbon, wt % 86 − 92 99.5
Sulphur, wt % <2.5 <2.5
Volatile matter, wt % 8-14 0.5
Moisture, wt % 6-14 0.1
Ash, wt % 0.25 0.4
Iron 0.01 0.02
Nickel 0.02 0.03
Silicon 0.02 0.02
Vanadium 0.02 0.03
 Typical properties of Sponge & Needle Cokes

Property Sponge Needle

(Calcined) (Calcined)

Sulphur, wt % 2.5 1.0

Ash , wt % 0.50 0,15

“V”, ppm 200 10

“Ni”, ppm 200 20-40

“Si”,ppm 0.02 0.04

 Typical properties of Sponge & Needle
Cokes.. Contd.

Property Sponge Needle

(Calcined) (Calcined)
Volatile Matter, wt% -
Resitivity, micro-ohm 980 965

Real Density, g/cc 2.06 2.12

Bulk Density, g/cc 0.80 0.88

-7 -7
CTE per degree C 20 X 10 5x10
o
( 30-100 C)