Delayed Coking Process

Research Institute of Petroleum

Processing(RIPP)

Shen Haiping

Mar. 2004

WHAT IS DELAYED COKING

Delayed coking is a thermal cracking process

to upgrade and convert petroleum residuum
into liquid and gas product streams leaving
behind a solid concentrated carbon material,
petroleum coke. A fired heater with
horizontal tubes is used in the process to
reach thermal cracking temperatures of 485
to 505oC. With short residence time in the
furnace tubes, coking of the feed material is
thereby delayed until it reaches large
coking drums downstream of the heater.

Delayed Cokings
Advantages
Low investment and operating
cost

Wide feedstock sources and

process flexibility
Deep conversion from low value
feeds into high value naphtha,
LCGO and HCGO

Simplified Process of DC
Coke Drums

Fractionator

Gas

Naphtha
LCGO
Furnace
Coke

HCGO

Feedstock

Typical Delayed Coking Process Flow Diagram

MODERN DELAYED COKING PROCESS

The delayed coker is the only main process in a

modern petroleum refinery that is a batchcontinuous process.The flow through the tube
furnace is continuous. The feed stream is
switched between two drums. One drum is online filling with coke while the other drum is
decoked and warmed up. The overhead vapors
from the coke drums flow to a fractionator,
usually called a combination tower. This
fractionator tower has a reservoir in the bottom
where the fresh feed is combined with
condensed product vapors (recycle) to make up
the feed to the coker heater.

1.4 mm tons/a
delayed coking unit

Central Control Room

Petroleum Coke

Petroleum coke is the

solid carbonaceous
material produced
from petroleum
during thermal
processing. It is often
characterized as
having a high carbon
content (95wt%+)
and a honeycomb
type of appearance.

Petroleum Coke

Three physical structures of petroleum

coke: shot, sponge, or needle coke can
be produced by delayed coking. These
physical structures and chemical
properties of the petroleum coke
determine the end use of the material
which can be burned as fuel, calcined
for use in the aluminum, chemical, or
steel industries, or gasified to produce
steam, electricity, or gas feedstocks for
the petrochemicals industry.

Delayed Coker Feed

The delayed coker is integrated with

the rest of the refinery. Delayed
coker feed originates from the crude
oil supplied to the refinery.
Therefore, brief descriptions of each
of the processing steps preceding
the delayed coking unit are provided
as following.

A basic

refinery

flow diagram

Crude Oil Desalting

Crude oil contains around 0.2% water in

which is mixed soluble salts such as
sodium chloride and other metals which
are on the edge of the sphere of water. In
desalting, crude oil is washed with around
5% water to remove the salts and dirt from
the crude oil . The water, being heavier
than the oil, drops out of the bottom, and
the cleaned oil flows overhead with around
0.1% water.

Atmospheric
Distillation

The desalted crude oil is heated in a

tube furnace to over 385oC (725oF),
just below the temperature that
cracking of the oil can occur, then
flashed into a distillation column.
The primary products are straight
run gasoline, kerosene, jet fuel,
diesel, atmospheric gas oil (AGO)
and atmospheric reduced crude.

Vacuum Distillation

The atmospheric reduced crude (ARC) is

then heated to around 395C (743F) and
flashed into a vacuum distillation column
that is operated at low pressures, 10 mm
Hg absolute desired but more common 25
to 100 mm Hg absolute. The desired aim is
to lift the maximum amount of oil boiling
below 565C into heavy vacuum gas oil
(HVGO) reducing the production of vacuum
reduced crude (VRC), the main feedstock to
the delayed coker.

Vacuum Distillation
The HVGO and the AGO are the principal
feedstocks to a fluid catalytic cracking unit
(FCCU) for the production of gasoline and
diesel. Improving vacuum distillation is
one of the best methods for increasing gas
oil yield in a refinery while at the same
time reducing the amount of vacuum
reduced crude (coker feed). This enables
higher refinery throughput rates to be
achieved.

VRC Processing
Options

Delayed Coking
Visbreaking - Primary function is to reduce viscosity
of the oil with some production of heavy gas oil.
Resid FCC - Residuum Fluid Catalytic Cracking,
metals deactivate catalyst, must use passivating
chemicals to reduce unwanted reactions
Resid Hydrocracking - Feed is contacted with a
catalyst and hydrogen at high temperature and
pressure to remove sulfur, nitrogen, and some
aromatic compounds with some conversion to lighter
liquid products.
Propane Deasphalting / Bright Stock - Solvent
extraction of heavy lubrication oils

Heavy Oil Processing

Capacity (mm tons/a)
USA

Japan

Europe Others

Total

Visbreaking

670

110

10825

8240

19845

Coking

9275

315

3135

6090

18815

Deasphalting

1300

80

65

520

1965

Fixed Bed HT

2505

2900

735

4065

10205

Ebullated Bed HT

545

125

125

915

1710

Residue FCC

3150

1250

1070

3680

9150

Properties of Sudan Fula-North 3

Crude and Atmospheric Residue1
Item

AR

Crude

0.9496

0.9431

80oC

651.6

280.0

100oC

241.9

Flash Point(Open Cup), oC

263

171

Conradson Carbon,wt%

8.80

7.38

TAN, mgKOH/g

10.3

10.9

-5

0.42

0.37

Density(20oC), g/cm3
Kinematic Viscosity,
mm2/s

Solidification Point, oC
Ash, wt%

Properties of Sudan FulaNorth 3 Atmospheric

Elemental Analysis wt%
CResidue and Crude-2
86.41
86.49
H
S
N
Hydrocarbon Compositionwt%
Saturates
Aromatics
Resins
Asphaltenes

12.01
0.17
0.31
28.1
32.9
38.8
0.2

12.12
0.15
0.28
15.8
0.2

Properties of Sudan FulaNorth 3 Atmospheric

Residue
and
Metal Analysis
mg/kg Crude-3
Ni
V
Na
Al
Fe
Cu
Ca
Distillation
IBP
5%
10%
30%

17.5
0.7
70.3
5.4
97.8
0.2
1474

15.7
0.6
66.3
4.0
50.4
0.2
1250

384
422
444
533(29.5%)

237
329
389

Density
Density is also expressed as the API
gravity. API=141.5/(sp gr at 60/60F)-131.5
Density usually ranges from 0.9(25API) to
over 1.0(10API). It is mainly influenced by
the chemical composition of petroleum, but
quantative correlation is difficult to
establish. Nevertheless, it is generally
recognized that increased amounts of
aromatic compounds result in an increase in
density, whereas an increase in saturated
compounds results in a decrease in density.

Viscosity
Viscosity is the force in dynes required to move a
plane of 1 cm2 at a distance of 1 cm from another
plane of 1 cm2 area through a distance of 1 cm in
1 s. Its unit is the Poise. Kinematic viscosity is the
viscosity in centipoises divided by the specific
gravity, and the unit is the stokes(cm2/s). The
changes in viscosity with temperature, pressure,
and rate of shear are pertinent not only in
lubrication but also for such engineering concepts
as heat transfer. The effect of temperature on
viscosity is generally represented by the equation

Loglog(n+C) = A+BlogT

Flash Point

The flash point of petroleum is the

temperature to which the product must be
heated under specified conditions to give off
sufficient vapor to form a mixture with air
that can be ignited momentarily by a
specific flame. From the viewpoint of safety,
flash points are of most significance at or
slightly above the maximum temperatures
(30 to 60oC) that may be encountered in
storage, transportation, and use. For
product with flash point below 40 oC special
precautions are necessary for safe handling.

Carbon Residue

The amount of carbon residue was the nonvolatile

compounds left after evaporation and pyrolysis of an
oil. The residue is not composed entirely of carbon,
but is a coke which can be further changed by
pyrolysis. The carbon residue is correlated with
hydrogen content and coke yield.

H/C(atomic ratio)=171-0.0115CR(conradson)

Coke%(wt)=1.6*CCR
Gas(C4-)%(wt)=4.07+0.224*CCR

Total Acid Number

The acidic constituents are defined as total

acid number. The acidic components in crude
oil typically include naphthenic acid, other
carboxylic acid, inorganic acid, phenols,
mercaptans, and so on. Naphthenic acid and
other organic acid are generally referred as
petroleum acid, over 90% of which is
naphthenic acid, so naphthenic acid is a
generic term used to identify a mixture of
organic acids present in petroleum feedstocks.
the acidic crude with high TAN over 1mgKOH/g
is corrosive to refinery equipments.

Solidification Point

The melting point of petroleum

product tends to increase
qualitatively with the molecular
weight and with symmetry of the
molecule. They are useful for
identification of oils or when
planning the storage of oil supplies,
as low temperatures may cause
handling difficulties with some oils.

Ash

Ash content is one of the most

important properties of the
petroleum coke. Any ash-forming
materials present in the feedstock
will deposited in the coke, so the
ash content is the coke is directly
correlated with the ash content in
feedstock.

Elemental (Ultimate)
Analysis
The analysis of petroleum for the percent by

weight of carbon, hydrogen, nitrogen,

oxygen, and sulfur is perhaps the first method
used to examine the general nature of a
feedstock and evaluate it. Although atomic
ratio can be used in a comparison of
feedstocks, there is no guarantee that a
particular feedstock will behave as predicted
from these data. The sulfur content and the
API had the greatest influence on determining
the value of petroleum as a feedstock. The
majority of sulfur concentrates in the residue.

Hydrocarbon Fractions
Feedstock
n-Heptane
Asphaltene

Deasphaltened oil
Alumina

Polar Aromatics
(Resins)
Naphthene Aromatics
(Aromatics)

Saturates

Metal Content

Metals affect many upgrading processes

and cause particular problems because
they poison catalysts used for sulfur and
nitrogen removal as well as other
processes such as catalytic cracking. Even
minute amounts of iron, copper, nickel, and
vanadium in the charging stocks for
catalytic cracking affect the activity of the
catalyst and result in increased gas and
coke formation and reduced yields od
gasoline. The ash residue left after
combusting a feedstock is due to the
presence of these metallic constituents.

Distillation

Petroleum can be subdivided by

distillation into a variety of fractions of
different cut points. In fact distillation is
the method by which petroleum
feedstocks are determined to be suitable
for various refinery options. In each
homologous series of hydrocarbons, the
boiling points increase with molecular
weight. The branched paraffin iosmers
have lower boiling points than the
corresponding n-alkanes.

Crude Oil

Crude oil contains three different fractions. The Oil is the

hydrocarbon: paraffinic, naphthenic, and aromatic which
also contain sulfur and nitrogen. The second part of the
crude oil, the resins, coat the asphaltene fraction so that it
can be peptized into the crude oil. The resins are a brown,
sticky hydrocarbon which contain nitrogen, oxygen, and
sulfur, are soluble in n-pentane but insoluble in propane,
and have molecular weights greater than 3000. The
asphaltenes contain the chelated metals, vanadium, nickel,
and possibly some calcium along with sulfur, oxygen, and
nitrogen. During crude oil distillation, the asphaltenes are
not volatilized and remain in the vacuum reduced crude
along with most of the resin fraction. With higher
temperatures and lower pressures, the hydrocarbon part of
the coke could be reduced but not the resin and asphaltene
fraction. The amount of coke produced in a delayed coker is
always more than the carbon residue percentage by a
factor of about 1.6.

HISTORY OF
THE DELAYED COKING PROCESS

Petroleum coke was first made by the

pioneer oil refineries in Pennsylvania in
the 1860's.These primitive refineries
boiled oil in small, iron stills to recover
kerosene, a valuable and much needed
luminescent. The stills were heated by
wood or coal fires. After the distillation
was completed, the workmen dug out
the coke and tar before next run.

In the 1920's the tube furnace with

distillation columns (bubble cap
distillation trays patented by Koch) were
being built with the bottoms from the
distillation column going to wrought iron
stills in which the total outside of the
horizontal still was in direct contact with
the flue gases. This produced the
maximum amount of heavy gas oil.
Operators assigned as decokers used
picks, shovels, and wheelbarrows and had
rags wrapped around their heads to
protect against heat.

The coke that was produced in the

horizontal stills had a high density,
low volatile matter (VM) content of
around 8 wt%, and less than 1 wt%
moisture. One problem was that ash
content was high, around 1 wt%
compared to under 0.2 wt% in most
modern delayed cokers. This was due
to the lack of desalting and washing
of the crude oils processed at that
time.

The first delayed coker was built by

Standard Oil at Whiting, Indiana in 1929.
The development of hydraulic decoking
came in the late 1930's. Standard Oil of
Indiana had patents on the original
cutting nozzles used by Pacific Pump. A
very similar nozzle is currently used in
the new compact combination coke
cutting unit. A pilot hole is drilled down
through the coke in the drum and then
the coke is cut out with a drilling bit with
horizontal water nozzles.

The number of cokers built before

1955 was small, with a surge in
delayed coker construction
between 1955 to 1975 at 6% per
year and an 11% growth rate
during the 1965 to 1970 period.
The growth of delayed cokers was
in step with the growth of fluid
catalytic cracking and rapid
decline in thermal cracking.

A fluid coker, similar to a fluid

catalytic cracker except that fluid
coke is circulated instead of
catalyst, was first built in 1954.
Five more fluid cokers were built in
the late fifties, and one in 1970.
Today there are only 6 fluid
cokers/flexicokers.

Thermal Cracking
Reactions
The term cracking usually applies to
decomposition induced by elevated
temperature(>350oC) , whereby the
higher molecular weight constituents
of petroleum are converted to lower
molecular weight products. Cracking
reactions involve carbon-carbon
bond rupture and thermodynamically
favored at high temperatures.

The Decomposition of large

molecules into small
molecules(primary reactions)
CH3CH2CH2CH3

CH4 + CH3CH=CH2

Some of the primary products

interact to form higher molecular
weight materials(secondary
reactions)

CH2=CH2 +CH2=CH2

CH3CH2CH=CH3

RCH=CH2+RCH=CH2
Tar, heavy oil, coke, etc
Polymerization

Free radical chain

reactions
CH3CH2CH2CH3
CH3 + CH3CH2CH2CH3
CH3CH CH2CH3
CH3CH2 +CH3

CH3CH2CH2 + CH3
CH4 + CH3CH CH2CH3
CH2=CH2+CH3CH2
CH3CH2CH3

A free radical is an atom or group of atoms

possessing an unparired electron. One of
the significant features of hydrocarbon free
radicals is their resistance to isomerization,
such as , migration of an alkyl groups. So
thermal cracking does not produce any
degree of branching in the feedstock.

CH3CHCH2CH3

C(CH3)3

Cycloparaffins(naphthenes) react
differently to their noncyclic
counterparts and are somewhat more
stable. For example, cyclohexane
produces hydrogen, ethylene, butdiene,
and benzene. CH =CH + CH =CHCH=CH +H
2

ethlyene

+ H2

butadiene

The aromatic rig is considered to be

fairly stable at moderate cracking
temperatures (350 to 500oC).
Alkylated aromatics, like the alkylated
naphthenes, are more prone to
dealkylation than to ring destruction:

CH2CH2CH2CH2R

CH2CH3+CH2=CHR

CH3+CH2=CHCH2R

Comparison of Thermal
cracking and Catalytic
Cracking
Catalytic cracking
Thermal Cracking
nParaffins

C2-C6 branched
aliphatics. Few normal aolefins C4+

Much C1-C2 fragments.

C4+ normal a-olefins,
unbranched

IsoHigher cracking rate

paraffins than n by tertiary carbon

Rate increasing little by

tertiary carbon

Alkylaromatic
s

Much higher rate than n,

entire alkyal cracked.

Lower cracking rate than

n, leave 1 or 2 carbon
with ring

All
olefins

Hydrogen transfer, crack

at much higher rate

Minor hydrogen transfer,

crack at same rate.

Product Distribution of DC(wt%)

Recycle Ratio

0.50

0.30

Gas

7.19

6.44

C 5-C 6

1.64

1.42

Naphtha

15.40

13.84

LCGO

35.78

31.59

HCGO

22.58

30.44

Coke

17.41

16.27

Total

100.00

100.00

Properties of Naphtha
Item
3
Density(20 )g/cm
Total Acid Number mgKOH/g
Induction Period min
S mg/kg
N mg/kg
Cl mg/kg
Bromine Number gBr/100ml
Hydrocarbon Compo sition wt%
Normal Paraffins
Isoparaffins
Naphthenes
Olefins
Aromatics

DC
0.7332
0.24
669
244
114
2.3
45.8

DC
0.7378
0.27
782
248
120
2.3
48.1

SR
0.7655
0.54
>1000
63
5
1.3

29.58
15.50
8.20
37.15
9.57

28.60
15.00
8.27
38.79
9.34

11.01
45.05
33.16
0.08
10.70

Properties of LGO(180-350)
Item
3
Density(20)g/cm
Refractive Index(20)
Solidification Point
Total Acid NumbermgKOH/g
Aniline Point
Copper Corrosion50 3h
10% Conradson Carbonwt%
S mg/kg
N mg/kg
Bromine NumbergBr/100ml
Calculated Cetane Index

DC
0.8322
1.4656
-25
0.17
61.8
2b
0.06
600
651
24.8
51.6

DC
0.8345
1.4666
-19
0.18
63.4
2b
0.04
543
676
24.1
52.3

SR
0.8964
1.4947
<-50
0.93
57.3
1a
0.08
729
115
1.8
38.3

Properties of HCGO
Recycle Ratio
Density(20 ) g/cm 3
Solidification Point
Basic Nitrogen mg/kg
Total Acid Number mgKOH/g
Flash Point(Open Cup)
Conradson Carbon wt%
Ash wt%
Elemental Analysis wt%
C
H
S
N

0.50

0.30

0.8983
20
1005
<0.05
195
0.27
0.004

0.9034
24
995
<0.05
207
0.38
0.002

86.79
12.21
0.16
0.29

86.94
12.19
0.16
0.28

Properties of Green Coke

Real Density g/cm 3
Volatile Matter wt%
Sulfur wt%
Ash wt%
Metal Analysis mg/kg
Ni
V
Na
Al
Fe
Cu
Ca

2.101
8.8
0.41
3.33

2.099
8.0
0.40
3.43

99.9
3.4
470
26.1
471
0.5
8665

111
4.1
494
28.7
519
0.6
9753

Gas Composition
Composition
H2
CH4
C2H6
C2H4
C3H8
C3H6
C4H10
C4H8
C4H6
Hydrogen Sulphide
Average Molecular Weight

v%
8.51
45.63
17.03
3.01
10.02
5.76
5.52
4.14
0.06
0.32
25.90

wt%
0.66
28.18
19.73
3.25
17.02
9.33
12.35
8.94
0.12
0.42
25.90

v%
7.75
45.84
17.72
2.94
10.37
5.60
5.54
3.85
0.05
0.34
26.05

wt%
0.60
28.16
20.41
3.16
17.52
9.02
12.32
8.27
0.10
0.44
26.05

Bromine Number

The number of grams of bromine

absorbed by 100 g of oil,which
indicates the percentage of double
bond.

Aniline Point

Aniline point was defined as the

minimum temperature at which equal
parts of 2 liquids are miscible. For oils
of a given type it increases slightly
with molecular weight; for those of a
given molecular weight it increases
rapidly with increasing paraffinic
character. It was used for rough
estimation of aromatic and naphthene
content.

Operating Variables

Three operating control variables

in a delayed coker govern the
product quality and yieldsfor a
given feedstock. These variables
are heater outlet temperature,
coke drum pressure, and the ratio
of recycle to fresh feed.

Temperature

At constant pressure and recycle, the coke

yield decreases as the drum temperature is
increased. Part of the heavy hydrocarbon,
at lower temperature remains in the drum
to be converted to coke, is flashed of at the
higher temperature. However there is only
a narrow range over which the temperature
can be adjusted. Because delayed coking is
an endothermic reaction, the heater outlet
temperature is the control point for
adjusting the coking reaction temperature.

Temperature

In actual practice, if the temperature is too

low, the coking reaction does not proceed far
enough, resulting in the formation pitch or high
VCM coke. Above a specific temperature, the
coke formed will be excessively hard and
difficult to remove from the drum with the
hydraulic decoking equipment. In addition, at
higher temperature the possibility of
prematurely coking the heater tubes and/or
the transfer line in creases. Controlling VCM
translates to lost liquid product. Current
practice is to target fuel coke VCM contents of
8~10wt%.

Pressure

A decrease in pressure has the effect of

vaporizing more of the heavy hydrocarbon
liquid the would otherwise be trapped in the
coke drum and converted to coke and light
hydrocarbons. The strong economic
incentives for producing maximum liquid in
cokers where the feedstock produces fuel
grade drive the operation to the lowest
possible coke drum pressure. These types of
cokers are currently being designed to
operate with coke drum pressures of
1.055kg/cm2g

Recycle Ratio

Recycle ratio has the same

general effect as pressure on
coker product distribution, i.e., as
recycle is increased the coke and
gas yields increase while the
pentane and heavier liquid yield
decreases. In practice, recycle is
used primarily to control the end
point of the coker gas oil.

Recycle Ratio

The same economics that are forcing coker

operations to lower operating pressures
are at work on recycle ratios. In general,
refiners operate at as low a recycle ratio as
product quality and until operations permit.
Operations below 5%recycle are common
and many new designs incorporate ultra
low recycle coking technologyif down
stream conversion facilities can accept the
higher endpoint, metal content, and carbon
residue of the heavy gas oil product.

Delayed Coking Cycle

Drum Cycle
Hours
Hours
Steam to Fractionator
0.5
0.5
Steam to Blow Down
0.5
3.5
Depressure, Water Quench
4.5
4.0
Drain
2.0
2.0
Unhead Top and Bottom
0.5
1.0
Cutting Coke
3.0
3.0
Rehead / Steam Test / Purge
1.0
2.0
Drum Warm-Up (Vapor Heat)
4.0
8.0
-----------------------------------------------------------Total Time
16.0
24.0

Drum Warm-Up (Vapor Heat)

To prepare the cold empty coke drum to be

put back on-line to receive the hot feed,
hot vapors from the on-line drum are
circulated into the cold empty drum. The
hot 415oC (780oF) vapors condense in the
cold drum, heating the drum to a target
temperature of around 340oC (650oF).
While the drum is heating, the condensed
vapors are continuously drained out of the
drum.

On-line Filling
After the cold drum has been vapor heated for a few
hours, hot oil from the tube furnace at about 485oC is
switched into the drum. Most of the hot vapors
condense on the colder walls of the drum. The drum
walls are heated up by the condensing vapors, the
liquid at the bottom of the drum starts to heat up to
coking temperatures. A main channel is formed
similar to the trunk of a tree. As time goes on the
liquid pool above the coke decreases and the liquid
turns to a more viscous type tar. The liquid pools in
the quiescent zones slowly turn to solid coke.

Steam-Stripping / Hot
Spots.
Steam must be flowing before the switch and immediately after

the switch; otherwise, the yet unconverted liquid feed on top of

the coke bed will run down the channels which will coke or
solidify and plug the channels. The plugging of the channels
causes problems in cooling the coke since sections of the coke
bed will be isolated from the steam and cooling water by the
plugged channels. This is the cause for hot spots and steam
eruptions when cutting the coke. Cold water from the cutting
nozzle hits the exposed hot coke which results in a steam
explosion. This is particularly hazardous when the pilot hole is
being cut, since the drum is filled with a large quantity of hot
water. A steam explosion during pilot hole cutting can cause the
hot water to erupt out of the top of the drum and has caused
fatalities in the past.

Steam-Stripping / Hot Spots.

Steam stripping also serves to transfer heat from the

hot bottom section of the coke bed to the unconverted
liquid present at the top of the coke drum. Adequate
steam stripping increases the amount of recovered gas
oil yield while at the same time reduces the amount of
volatile matter and pitch left in the top section of the
coke drum. After the steam has been flowing up
through the coke bed for about thirty minutes with the
vapors going to the fractionator, the vapor line is
vented to blowdown system.

Water Cooling / Drum

Bulging.

The rate of cooling water injection is critical.

Increasing the flow of water too rapidly can
case harden the main channels up through
the coker without cooling all of the coke radially
across the coke bed. The coke has low porosity
(the porosity comes from the thermal cracking)
which then allows the water to flow away from
the main channels in the coke drum. If the rate
of water is too high, the high pressure causes
the water to flow up the outside of the coke bed
cooling the wall of the coke drum.