Delayed-Coking Process Update

11
Delayed-Coking Process Update

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Robert DeBiase, John D. Elliott, and ThomasE.Hartnett
Foster Wheeler Energy Corporation, 110 South Orange Avenue, Livingston, NJ 07039
Publication Date: April 14, 1986 | doi: 10.1021/bk-1986-0303.ch011
Important recent trends and new developments have

contributed to profitable, reliable, and safe operation
of delayed cokers. A typical delayed coker consists of
four sections: coking, fractionation, coker blowdown,
and coke dewatering and handling. The main types of
coke dewatering and handling systems are described as
pit, pad, railcar, and dewatering bin. General coke
types, feedstock considerations, pretreatment and
process variables are reviewed with emphasis on recent
trends towards minimizing production of fuel grade coke
from heavy feedstocks. Typical uses of petroleum coke
are discussed, including those for fuel grade coke.
Trends and developments on the design of modern delayed

cokers include improved heater design, larger coke
drums designed for longer life at short operating
cycles, extended range hydraulic decoking systems,
enclosed blowdown systems and improved energy
efficiency. Older delayed cokers can be revamped in a
number of ways to increase capacity and improve the
yield of desirable products.
Delayed c o k i n g i s a p r o c e s s i n g t e c h n o l o g y t h a t has been i n use f o r

o v e r f i v e decades. D u r i n g t h i s time, i t has come i n t o widespread
use as an economic means f o r u p g r a d i n g heavy c r u d e s , r e s i d u e s , t a r s
and decant o i l s t o produce gas, g a s o l i n e , gas o i l and coke. It is
seen as an a t t r a c t i v e r e s i d u e u p g r a d i n g p r o c e s s because o f i t s
moderate c a p i t a l investment and i t s a b i l i t y as a s i n g l e u n i t , t o
p r o c e s s a wide v a r i e t y o f f e e d s t o c k s . As more and more d e l a y e d
c o k e r s are b u i l t , new t e c h n o l o g y i s b e i n g developed t o c r e a t e a
more p r o f i t a b l e , r e l i a b l e and s a f e o p e r a t i o n . T h i s paper w i l l
b r i e f l y r e v i e w the b a s i c a s p e c t s o f d e l a y e d c o k i n g and d i s c u s s -
r e c e n t t r e n d s and new developments.
In d e l a y e d c o k i n g , a r e s i d u a l f e e d s t o c k i s charged t o a
f u r n a c e where i t i s r a p i d l y heated and t h e r m a l l y decomposed. The
h e a t e r e f f l u e n t then e n t e r s a coke drum where the r e a c t i o n i s
0097-6156/86/0303-0155$06.00/0
© 1986 American Chemical Society
In Petroleum-Derived Carbons; Bacha, J., et al.;

ACS Symposium Series; American Chemical Society: Washington, DC, 1986.
156 PETROLEUM-DERIVED CARBONS
completed and p e t r o l e u m coke and overhead vapors are formed. The

process mechanism for delayed coking is as follows (1_) :
(1) Partial vaporization and m i l d cracking of the feed as
it passes through the furnace.
(2) Cracking of the vapor as it passes through the drum.
(3) Successive c r a c k i n g and p o l y m e r i z a t i o n of the heavy
liquid trapped in the drum u n t i l it is converted to
vapor and coke.
The coke produced is mostly elemental carbon and is used in
applications described below. The gaseous and liquid products are
valuable feedstocks for downstream processing or sometimes used as
products.
Unit Description
A typical delayed coker unit consists of coking, fractionation and

blowdown sections, along with coke handling facilities. Coker gas

is either processed in a dedicated vapor recovery unit or may be
sent for processing, together with other gases, to a centralized
vapor recovery unit.
Coking Section. Figure 1 is a simplified process flow diagram of

typical coking and fractionation sections. The major equipment
included in the coking section are the coker heater, the coke
drums and the hydraulic decoking equipment. The feedstock enters
either hot from an upstream processing unit or cold from storage.
It is often preheated within the delayed coker unit. The feed is
charged to the bottom of the fractionator which is used for feed
surge. In the bottom of the fractionator the feed combines with
the condensed recycle. The resulting heater charge is pumped to
the coker heater where it is r a p i d l y heated to the desired coking
temperature before flowing to the coke drum where the coking
reaction is completed. The coke remains in the drum and the over-
head vapors are directed to the fractionation section. A minimum
of two coke drums are required, one drum i s in coking service
while the other drum is being decoked. After steaming and cooling
of the coke, the upper and lower flanges of the coke drum are
removed. Next, a pilot hole is bored through the coke using high
pressure water and a hydraulic boring tool. The coke is then cut
out with a hydraulic cutting tool. The coke falls from the drum
to the dewatering facilities for separation of the coke from the
water.
Fractionation Section. A typical fractionation section includes

the coker fractionator and attendant heat exchange equipment, the
light gas oil side stream stripper and the overhead system. The
coke drum o v e r h e a d vapors enter the fractionator under shed trays
which are located below conventional wash trays. Hot induced gas
oil reflux is pumped to the wash trays to condense recycle and to
wash the product vapors. The light and heavy gas o i l products are
condensed as sidestream products. The light gas oil product is
usually steam stripped in a sidestream stripper. The overhead
vapors from the fractionator are partially condensed and the gas
and gasoline products are directed to the vapor recovery unit.

11. DEBIASE ET AL. Delayed-Coking Process update 157
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A portion of the condensed gasoline is pumped b a c k to the tower as

reflux. The sour water collected in the overhead drum i s sent to
battery limits for treating.
Coker Blowdown System. Figure 2 shows a typical coker blowdown

system. This system is utilized for both pollution control and
for increased recovery of hydrocarbons. After a drum i s switched
from coking to decoking service, the coke is steamed out and then
cooled by water injection. During this time, the hydrocarbons
stripped from the coke are directed, together with the resultant
steam, to the blowdown system. The steam and h y d r o c a r b o n from the
steamout and cooling cycle operations flow to the coker blowdown
drum where the heavy hydrocarbons are condensed by a circulating

gas oil stream. These heavy hydrocarbons are pumped b a c k to the
coker fractionator. Steam leaves the top of the coker blowdown
drum and is condensed in the blowdown condenser along with a small
amount of o i l . The o i l and water are separated in the blowdown

settling drum, with the water going to offsite treating facilities
or to the decoking water tank, while the oil goes to slop for
dewatering and recovery. The remaining vapors from the blowdown
settling d r u m may be compressed and sent back to the coker
fractionator overhead drum o r treated and sent to the fuel gas
system. Alternatively, these vapors c a n be flared or recovered by
a flare gas recovery compressor.
Coke Dewatering and Handling System. When a coke drum i s being

emptied, coke and water must be collected and separated. To
accomplish this, the facilities commonly used today include pit
dewatering, pad dewatering, dewatering bin, and d i r e c t railcar
loading. A short description of each follows.
In pit dewatering, the coke and water drop from the coke drum,
through a chute, into a large pit which provides several days of
storage. Water d r a i n s through the coke into a maze where any
remaining coke fines settle to the bottom. Coke is removed from
the coke pit with an o v e r h e a d crane. The large storage capacity of
the pit makes it especially suited for units with four or more coke
drums. Foster Wheeler has implemented this approach i n many of the
recently built delayed cokers. A typical pit dewatering system is
depicted in Figure 3.
Pad type dewatering is similar to pit dewatering. The major
difference is that the coke and water drop onto a grade level pad.
Traditionally, water drains through coke packed ports in the pad
wall and is then c l a r i f i e d of remaining fines in a settling maze.
A new coke fines filtering system has been developed by Foster
Wheeler which removes coke fines from the decoking water by use of
coke filled baskets. Coke is removed from the pad w i t h a front-end
loader. Pad d e w a t e r i n g offers a lower capital investment and
simpler operation than pit dewatering. The drawbacks of pad
dewatering are that the coke storage capacity is limited by plot
area. A typical pad d e w a t e r i n g operation is illustrated in
Figure 4.
Direct railcar loading allows the coke to drop d i r e c t l y from
the coke drum i n t o a railcar. Coke and m a j o r i t y of fines remain
in the railcar. Water d r a i n s from the railcar to a sump and is

11. DEBIASE ET AL. Delayed-Coking Process Update 159

then pumped to a clarifier. This system offers the lowest capital

investment, but requires extra time to decoke the coke drum to
allow for r a i l c a r movement. It is usually limited to units with
small coke drums. A direct railcar loading system is shown in
Figure 5.
A dewatering bin system is one i n which the coke and water
fall from the coke drum i n t o a crusher and then, either by gravity
or by s l u r r y pump, are directed to a dewatering bin. In a gravity
flow system, an innovation developed by Foster Wheeler, the coke
drum and c r u s h e r are mounted on top of the dewatering bin. In a
slurry system the crushed coke is pumped from a sump located
directly below the coke drum and crusher to the dewatering bin.
The dewatering bin is a large vertical drum where the coke and
water are separated by gravity. The coke is allowed to settle and
the water is drained from the drum and d i r e c t e d to a water tank for
clarification. When dewatering is complete, the coke is discharged
from the dewatering bin. Foster Wheeler has developed totally

enclosed systems which are especially desirable in areas with
strict environmental regulations. The main drawback of the
dewatering bin is that it requires the largest capital investment
of all dewatering facilities. Of the two systems, gravity and
slurry, gravity flow is the more expensive. However, the slurry
system requires a substantial amount of water circulated to
transport the coke. The slurry flow and g r a v i t y flow systems are
depicted in Figures 6 and 7, respectively.
Types of Petroleum Coke
The three main types of coke that are produced in a delayed coker
are typically categorized as needle coke, sponge coke and shot coke.
Needle coke is a premium grade coke, which is considered a
specialty coke and is produced from specific aromatic feedstocks.
The regular grades of coke are sponge coke and shot coke. A short
description of each type of coke follows.
Needle Coke. Usually produced from highly aromatic thermal tar,

pyrolysis tar or decanted oil stocks. This coke is typically
characterized by a fibrous texture with long, unidirectional
"needles" of coke. This form of coke is a premium p r o d u c t , which
is sold to the carbon industry for use in the manufacture of large
graphite electrodes.
Sponge Coke. This type of coke is considered a form of regular

coke and is produced from high resin - asphaltene feeds. It
contains small pores with no interconnections. Sponge coke can
vary from light "honeycomb" varieties to heavy isotropic types.
Sponge coke with low sulfur and ash contents is generally sold as
anode coke to be used in the aluminum industry. High s u l f u r , high
metals coke is frequently sold as low value fuel grade coke.
Shot Coke. Another form, generally undesirable, of regular coke is

formed as small spheres often held together in a matrix of sponge
coke or in large spheres of shot coke alone. The formation is
highly dependent upon feedstocks such as Maya, West T e x a s Sour and

RAILROAD
HOPPER CAR
Figure 3. P i t Type Coke Handling System.
Figure 4. Pad Type Dewatering System.
Figure 5. Direct Rail Car Loading.

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Figure 7. G r a v i t y Flow Dewatering B i n System

some C a l i f o r n i a r e s i d u e s , s h a l e o i l and g i l s o n i t e . Operating

c o n d i t i o n s such as temperature, p r e s s u r e and r e c y c l e a l s o a f f e c t
s h o t coke f o r m a t i o n .
Feedstocks
As crudes become h e a v i e r w i t h h i g h e r l e v e l s o f s u l f u r and m e t a l s ,

i t becomes more d i f f i c u l t t o produce a c c e p t a b l e m a r k e t a b l e coke
q u a l i t y w h i l e maximizing d e s i r a b l e l i q u i d product y i e l d . This
mandates t h a t r e f i n e r s and d e s i g n e r s s c r u t i n i z e p h y s i c a l p r o p e r t i e s ,
upstream p r o c e s s i n g and downstream requirements when s e l e c t i n g a
feedstock.
The p h y s i c a l p r o p e r t i e s o f a c e r t a i n f e e d s t o c k t h a t determine
the y i e l d s and p r o d u c t q u a l i t i e s i n c l u d e g r a v i t y , c h a r a c t e r i z a t i o n
f a c t o r , carbon r e s i d u e , s u l f u r c o n t e n t and m e t a l s c o n t e n t . The
l a s t t h r e e p r o p e r t i e s a r e o f s p e c i f i c importance.
Carbon Residue. The carbon r e s i d u e i s one f a c t o r used t o determine

coke y i e l d as a percentage o f f r e s h f e e d , and i s d e f i n e d as t h e
carbon r e s i d u e r e m a i n i n g a f t e r e v a p o r a t i o n and p y r o l y s i s o f t h e
f e e d s t o c k i n a s p e c i f i e d procedure. A l l other operating conditions
b e i n g t h e same, as t h e carbon r e s i d u e i s i n c r e a s e d , more coke w i l l
be produced. I n r e c e n t y e a r s , as t h e q u a l i t y o f crudes has
d i m i n i s h e d , t h e carbon r e s i d u e o f vacuum r e s i d u e f e e d s t o c k s has
i n c r e a s e d from t y p i c a l v a l u e s o f 10 t o 20 weight % t o 20 t o 30
w e i g h t % and more.
S u l f u r Content. Another i m p o r t a n t f e e d s t o c k p h y s i c a l p r o p e r t y
r e l a t e d t o d e l a y e d c o k i n g i s t h e s u l f u r c o n t e n t . The s u l f u r
p r e s e n t i n t h e f e e d s t o c k tends t o c o n c e n t r a t e i n t h e coke, where
the s u l f u r l e v e l i s u s u a l l y e q u a l t o o r h i g h e r than t h a t o f t h e
f e e d s t o c k . S u l f u r l e v e l s as h i g h as 4 weight % i n today's
f e e d s t o c k s can cause u n a c c e p t a b l y h i g h l e v e l s o f s u l f u r i n t h e
coke p r o d u c t . The r e s u l t i n g coke may n o t be a c c e p t a b l e f o r
m e t a l l u r g i c a l use and may be a problem when burned as f u e l .
M e t a l s Content. When p r o d u c i n g coke f o r e l e c t r o d e o r anode u s e ,

f e e d s t o c k m e t a l s c o n t e n t must be reviewed r e l a t i v e t o coke p r o d u c t
s p e c i f i c a t i o n s . As i n t h e case o f s u l f u r , m e t a l s tend t o
c o n c e n t r a t e i n t h e coke.
The most common upstream p r o c e s s i n g methods f o r p r o d u c i n g
r e g u l a r coke f e e d s t o c k s a r e atmospheric and vacuum d i s t i l l a t i o n .
Another upstream f e e d s t o c k p r e p a r a t i o n p r o c e s s i s v i s b r e a k i n g .
Other a l t e r n a t i v e s i n c l u d e c h a r g i n g heavy crude o i l o r a s p h a l t
from a s o l v e n t d e a s p h a l t e r . Charging whole crude w i l l a l l o w t h e
c o k e r f r a c t i o n a t o r t o o p e r a t e as both a crude u n i t , by d i s t i l l i n g
o f f t h e l i g h t e r p o r t i o n o f t h e crude, and a d e l a y e d c o k e r by c o k i n g
and c r a c k i n g t h e h e a v i e r r e s i d u a l f r a c t i o n . However, c h a r g i n g whole
crude i s g e n e r a l l y l i m i t e d t o heavy crudes w i t h m i n i m a l d i s t i l l a t e .
Examples o f r e g u l a r grade coke f e e d s t o c k and p r o d u c t y i e l d s a r e
given l a t e r .
When p r o d u c i n g needle coke, t h e r e f i n e r must be more s e l e c t i v e
i n d e t e r m i n i n g i f a f e e d s t o c k i s s u i t a b l e . Needle coke has a
h i g h l y c r y s t a l l i n e s t r u c t u r e which must be produced from an

aromatic feedstock with low sulfur and m e t a l s content. Needle coke

that meets stringent specifications commands a premium p r i c e for
use in manufacturing graphite electrodes. In general, feedstocks
which are to be used for needle coke production should be tested in
a pilot plant to assure product quality.
Because of the increased sulfur and impurity levels in crudes
currently being processed, refiners in recent years have been
considering residue desulfurization units upstream of the delayed
coker. In addition to the reduction in sulfur content, residue
desulfurization units also lower the metals and carbon residue
contents. Due to the reduction in the carbon residue, the liquid
product yield is increased and the coke yield reduced. In addition,
the coke produced from a desulfurized residue may b e suitable for

use as anode grade coke. Table I shows the yields and product
properties after coking Medium A r a b i a n vacuum residue, with and
without upstream residue desulfurization.
Process Variables
Three operating control variables in a delayed coker dictate the

product quality and yields for a given feedstock. These variables
are the heater outlet temperature, coke drum p r e s s u r e and the ratio
of recycle to fresh feed.
At constant pressure and recycle ratio, the liquid product
yield increases with an increase in temperature. This is often a
desired effect, but there is only a narrow range over which the
temperature can be adjusted. As the temperature is increased, the
tendency of the heater and transfer line to coke increases, causing
shorter run-lengths. Above a certain temperature, the coke formed
can be excessively hard and d i f f i c u l t to remove from the drum with
existing hydraulic cutting equipment. Operating the heater at too
low an o u t l e t temperature can cause difficulties as well. If the
temperature is too low, then the volatile combustible material
(VCM) of the coke will be excessively high or, possibly a soft tar
or pitch could be produced. Modern u n i t s are designed so that an
8 to 12 weight % VCM c o k e is produced.
A decrease in pressure has the effect of v a p o r i z i n g more heavy
hydrocarbons. As the production of desirable liquid hydrocarbons
is increased at low pressures, the coke yield is correspondingly
decreased. Thus, most modern delayed cokers have been designed to
operate at a low coke drum pressure.
The effect of recycle ratio on coke production is analogous to
the effect of pressure. As the recycle ratio is decreased, the
production of liquid products is increased. Reduction of recycle
also lowers the fuel usage in the furnace because of lowered
throughput. Recycle is often reduced to the minimum rate which
s t i l l produces acceptable product qualities.
Regular Grade Coke Operation - Typical Yields and Product Qualities
Illustrated in Table I are the estimated yields and product

qualities of several representative delayed coker feedstocks. The
yields were established from generalized correlations using typical
operating conditions for the operation noted.

TABLE I. Estimated Yields and Product Properties for Regular Grade Coke Production
>
m
Venezuelan m
Visbreaker Medium Desulfurized H
North
Feed Venezuelan Tar Arabian Medium Arabian African
TBP Cut Point, °F 950+ 1,000+ 1,000+ 1,000+

Gravity, °API 2.6 1.5 7.0 17.0 15.2
Con. Carbon, Wt% 23.3 28.5 21.0 6.5 16.7
Sulfur, Wt% 4.4 4.0 4.8 0.5 0.7
Operation -Maximum Liquid Yield-

I
Anode Coke
Products
I'
Dry Gas, C -, Wt% 8.8 9.1 8.5 6.8 7.7
4
Naphtha, C -380°F, Wt% 14.0 13.6 14.0 13.1 19.9
Gravity, °API 55.0 55.5 58.9 58.6 62.1
Sulfur, Wt% 1.1 0.9 0.6 0.1 0.1
Gas O i l , 380°F+, Wt% 44.7 40.2 46.5 67.5 46.0

Gravity, °API 23.9 23.6 25.7 28.9 34.9

Sulfur, Wt% 2.7 2.0 2.9 0.3 0.5
Coke, Wt% 32.5 37.1 31.0 12.6 26.4

Sulfur, Wt% 5.7 5.2 6.5 1.2 1.2

Needle Coke O p e r a t i o n - T y p i c a l Y i e l d s and P r o d u c t Qualities
Table I I shows e s t i m a t e d y i e l d s and p r o d u c t q u a l i t i e s f o r t h r e e

t y p i c a l needle coker f e e d s t o c k s . The f e e d s t o c k s a r e c o n s i d e r e d
d e s i r a b l e needle c o k e r f e e d s t o c k s because o f t h e i r h i g h d e n s i t y ,
low s u l f u r c o n t e n t and h i g h l y a r o m a t i c n a t u r e . Note t h e h i g h
p r o d u c t i o n o f coke, t h e r e s u l t o f h i g h p r e s s u r e and h i g h r e c y c l e
r a t i s , w h i c h i s t y p i c a l i n needle coke p r o d u c t i o n .
Table I I . E s t i m a t e d Y i e l d s and P r o d u c t P r o p e r t i e s
For Needle Coke P r o d u c t i o n
Pyrolysis Decanted
Feed Thermal T a r Tar Oil
G r a v i t y , °API 2.4 -3.9 -0.7

S u l f u r , Wt% 1.0 0.5 0.5
Products
Dry Gas, C -, Wt% 14.4 10.3 9.8
C -380°F, Wt% 16.7 3.5 8.4
G r a v i t y , °API 54.9 41.7 59.8
S u l f u r , Wt% 0.04 0.09 0.01
Gas O i l , 380°F+, Wt% 15.7 31.2 41.6
G r a v i t y , °API 23.3 11.5 16.9
S u l f u r , Wt% 0.7 0.2 0.3
Coke, Wt% 53.2 55.0 40.2
S u l f u r , Wt% 1.0 0.6 0.6
Uses o f Petroleum Coke
Petroleum coke i s e s s e n t i a l l y pure carbon and can be u t i l i z e d

wherever one would use a s i m i l a r carbon p r o d u c t . I t may be used as
a f u e l s u b s t i t u t e f o r c o a l and can sometimes be used as a f e e d s t o c k
f o r a p p l i c a t i o n s such as p a r t i a l o x i d a t i o n . Depending on i t s
p r o p e r t i e s , p e t r o l e u m coke has f o u r b a s i c u s e s : f u e l , f e e d s t o c k f o r
downstream p r o c e s s i n g , m e t a l l u r g i c a l a p p l i c a t i o n s , and f o r s p e c i a l t y
g r a p h i t e and carbon p r o d u c t s .
As a f u e l , t h e most common uses o f petroleum coke a r e i n f i r i n g
cement k i l n s and steam g e n e r a t o r s . I n t h e cement i n d u s t r y , p e t r o -
leum coke i s s u i t a b l e as f u e l i n k i l n s because o f i t s low a s h
c o n t e n t , h i g h h e a t i n g v a l u e and t h e p r o c e s s ' s h i g h s u l f u r a l l o w a n c e s .
As much as 50% coke can be burned i n c o m b i n a t i o n w i t h b i t u m i n o u s
c o a l o r 75% coke when burned i n c o m b i n a t i o n w i t h o i l and/or g a s .
The o n l y l i m i t a t i o n on coke f o r cement k i l n f i r i n g may be i t s m e t a l s
c o n t e n t . F o r steam g e n e r a t i o n , two o p t i o n s a r e a v a i l a b l e . The most
common i s t h e b u r n i n g o f p e t r o l e u m coke i n p u l v e r i z e d f u e l b o i l e r s .
T h i s u t i l i z a t i o n o f t e n r e q u i r e s t h a t downstream e n v i r o n m e n t a l
p r o c e s s i n g o f t h e f l u e gas be employed. Another method r e c e n t l y
developed by F o s t e r Wheeler f o r u s i n g h i g h s u l f u r petroleum coke as
f u e l f o r steam g e n e r a t i o n i s b u r n i n g low q u a l i t y coke i n a s u l f u r
c a p t u r e f l u i d i z e d bed b o i l e r . The f l u e gas meets e n v i r o n m e n t a l

s t a n d a r d s f o r NOx and SOx. The o n l y e n v i r o n m e n t a l c o n s i d e r a t i o n i s

the removal o f a s h from t h e f l u e gas i n a baghouse and removal o f
the spent l i m e s t o n e . F l u i d i z e d bed b o i l e r s can be d e s i g n e d t o burn
petroleum coke a l o n g w i t h t h e o p t i o n o f b u r n i n g h i g h s u l f u r c o a l o r
heavy f u e l o i l . (2_)
A p o t e n t i a l l y a t t r a c t i v e use f o r low q u a l i t y , r e g u l a r grade
coke i s t o g a s i f y i t t o produce ammonia s y n t h e s i s gas, f u e l gas, o r
hydrogen. F o s t e r Wheeler has i n v e s t i g a t e d p r o m i s i n g schemes f o r a i r
p a r t i a l o x i d a t i o n (APO), where t h e coke i s p a r t i a l l y combusted w i t h
a i r a t e l e v a t e d p r e s s u r e t o generate a gas c o n s i s t i n g e s s e n t i a l l y o f
hydrogen, carbon o x i d e s , hydrogen s u l f i d e and n i t r o g e n . A f t e r s h i f t
c o n v e r s i o n , hydrogen s u l f i d e and carbon d i o x i d e a r e removed by

s c r u b b i n g . S u l f u r may be r e c o v e r e d e i t h e r as s u l f u r i c a c i d o r
e l e m e n t a l s u l f u r . Depending on the d e s i r e d end p r o d u c t , n i t r o g e n
may be p a r t i a l l y removed by c r y o g e n i c s e p a r a t i o n and f u r t h e r
removed by p r e s s u r e swing a d s o r p t i o n (PSA). R e s i d u a l carbon

monoxide i s removed by methanation o r by PSA.
One o f t h e l a r g e s t uses o f petroleum coke i s f o r anodes
employed i n t h e p r o d u c t i o n o f aluminum. T h i s usage demands a
somewhat premium f e e d s t o c k t o produce sponge coke t h a t i s low i n
m e t a l and s u l f u r c o n t e n t i n o r d e r t o meet p r o d u c t q u a l i t y s p e c i f i -
c a t i o n s . A f t e r p r o d u c t i o n i n a d e l a y e d coker, anode q u a l i t y coke
must be c a l c i n e d t o remove VCM and m o i s t u r e .
A s p e c i a l i z e d a p p l i c a t i o n o f p e t r o l e u m coke i s the p r o d u c t i o n
o f e l e c t r o d e s f o r the s t e e l i n d u s t r y . F o r t h i s a p p l i c a t i o n , i t i s
n e c e s s a r y t o use needle coke because i t s low c o e f f i c i e n t o f t h e r m a l
expansion and low r e s i s t i v i t y . The needle coke must have low
s u l f u r and low metals c o n t e n t . A f t e r p r o d u c t i o n i n a d e l a y e d c o k e r ,
needle coke i s crushed and c a l c i n e d i n p r e p a r a t i o n f o r e l e c t r o d e
production.
By 1980, s p e c i a l a p p l i c a t i o n s accounted f o r a p p r o x i m a t e l y 11%
o f t h e t o t a l coke p r o d u c t i o n i n t h e U n i t e d S t a t e s . These uses
i n c l u d e t i t a n i u m pigments, carbon r a i s e r s and s y n t h e t i c g r a p h i t e
(3_). A s p e c i a l t y use o f green coke i s as a h i g h p u r i t y r e a c t a n t i n
the p r o d u c t i o n o f c a l c i u m and s i l i c o n c a r b i d e . (4_)
Coke C a l c i n i n g
When petroleum coke i s u t i l i z e d f o r anode and e l e c t r o d e p r o d u c t i o n

and some s p e c i a l t y a p p l i c a t i o n s , i t i s n e c e s s a r y t o c a l c i n e i t t o
remove m o i s t u r e and hydrocarbon VCM. P r o d u c t q u a l i t i e s , a l o n g w i t h
p r o d u c t i o n r a t e , a r e based on f e e d s t o c k c o m p o s i t i o n , k i l n tempera-
t u r e p r o f i l e , k i l n r e s i d e n c e time and c o o l i n g p r o c e d u r e s . The two
methods a v a i l a b l e f o r c a l c i n i n g coke c o m m e r c i a l l y a r e t h e r o t a r y
k i l n (5^) shown i n F i g u r e 8 and the r o t a r y h e a r t h (€0 shown i n
F i g u r e 9.
In t h e r o t a r y k i l n p r o c e s s , coke i s f e d t o a r o t a t i n g
c y l i n d r i c a l f u r n a c e s l o p e d s l i g h t l y toward t h e d i s c h a r g e end. Coke
f l o w s down t h e k i l n c o u n t e r c u r r e n t t o t h e h o t gas f l o w . M o i s t u r e
i s l i b e r a t e d from t h e coke i n the f e e d zone, then t h e coke passes
through t h e combustion zone where VCM i s l i b e r a t e d . As coke l e a v e s
the k i l n , i t i s d i s c h a r g e d t o a c o o l e r where i t i s quenched w i t h
water and then c o o l e d w i t h ambient a i r . Recent d e s i g n s have
i n c o r p o r a t e d energy e f f i c i e n t f e a t u r e s such as a i r p r e h e a t and steam

STACK
AIR IN
BURNER
C A L C I N E D COKE
TO Q U E N C H I N G
AND C O O L I N G
F i g u r e 8. T y p i c a l Rotary K i l n C a l c i n e r .
STACK r— R O O F
/ B U R N E R S "7
GREEN COKE
FEED IN STATIONARY
MR ' AIR /
RABBLES
ni. AIR IN
ϋ ϋ ϋ ϋ ΰ ΰ
ROTATING CIRCULAR
TABLE
C A L C I N E D COKE
TO Q U E N C H I N G
AND C O O L I N G
F i g u r e 9. T y p i c a l R o t a r y Hearth Furnace.

generation facilities as w e l l as designs i n which the liberated

hydrocarbons are used as a f u e l i n the combustion zone.
In the p r o p r i e t a r y rotary h e a r t h method of calcining coke,
green coke is fed to the perimeter of the rotating circular table
and gently moved toward the center of the hearth in a circular
path by s t a t i o n a r y rabbles. A combustion zone above t h e coke b e d ,
formed by l i b e r a t e d volatiles, supplies the heat necessary for
calcination. A rotating hearth furnace can also be e q u i p p e d with
energy efficient features, such as steam generation and a i r preheat.
Design Features and C o n s i d e r a t i o n s

Through the years, delayed coking has evolved from a "black a r t "
to a high technology refining process. Both major and minor pieces
of equipment have been examined and updated a s new technology
becomes available, thus assuring a safe, economical and r e l i a b l e
design. Today's designs must combine versatility and state-of-the

art technology with low o p e r a t i n g and c a p i t a l investment costs.
To increase heater run lengths with today's heavier crudes
while improving heater efficiency, i t h a s become necessary to
improve t r a d i t i o n a l coker heater design. Most of the recent
improvements instituted by Foster Wheeler have resulted in a more
conservative heater design, g i v i n g more flexibility to the refiner
to later increase capacity, optimize operating c o n d i t i o n s and
increase run lengths. Fire boxes have been designed with more
liberal dimensions a n d more space between tubes, which reduces the
ratio o f peak to average heat flux. Injection steam i s used to
regulate the o i l v e l o c i t y through the heater coil thereby preventing
coking i n the tubes. Heaters are designed with each parallel coil
havings i t s own s e t o f b u r n e r s and independent flow and temperature
control. These features permit run lengths that range between 9
to 12 m o n t h s and longer i n normal o p e r a t i o n . {1)
Of t h e new d e v e l o p m e n t s that have been i n c o r p o r a t e d in coke
drum d e s i g n , t h e most notable is size. The f i r s t coke drums used
were 10 f e e t i n diameter. With today's improved m e t a l l u r g y and
increased hydraulic cutting capacity, Foster Wheeler has been able
to employ coke drums u p t o 27 feet i n diameter a n d 110 f e e t in
length. (1_) Another development by F o s t e r Wheeler has been to
determine the effect of shortened decoking cycles on coke drum life
by computer analysis. Results indicate that by m o n i t o r i n g and
controlling stress on a drum d u r i n g rapid heating and c o o l i n g , coke
drum life c a n be extended.
Decoking equipment and coke handling f a c i l i t i e s have undergone
significant changes since the advent of delayed coking. Decoking
equipment has evolved from m e c h a n i c a l d e v i c e s employed with the
early small diameter drums to the use of high pressure water,
delivered through flexible hoses with the a b i l i t y t o c u t coke from
27 foot diameter drums. Coke i s dewatered by one o f the systems
described previously. Steam, o i l and water removed while cooling
coke i n t h e drum a r e no l o n g e r directed t o a blowdown pond o r
settling pool, but are sent t o an e n c l o s e d blowdown system where the
oil, gas and water are separated and r e c y c l e d .
As w i t h most refinery units, the delayed coker has been updated
to be as energy efficient as p o s s i b l e . Modern c o k e r h e a t e r s now

incorporate boiler feedwater preheat, steam generation or air

preheat to raise the heater efficiency. Heaters are no longer
designed for operation with 20% excess air but for as little as
5-10% excess air. In addition to the improvements in heater
design, cokers have had feed preheat, steam generation, and heat
integration with other units added where possible.
Revamps and Retrofits
Refiners with existing delayed cokers often have the option to

expand their units at a lower incremental cost than adding new
units. F o r most revamps the main concern is whether the
fractionation section has sufficient capacity. Methods of

increasing fractionator capacity while lowering operating pressure
include using packed beds in the fractionator and full port valves
in the vapor lines. Adding upper pumparounds to reduce condenser
overhead duty and p r e s s u r e drop has also proved helpful. The

least expensive option for increasing fractionator capacity is to
increase the operating pressure. This is accomplished at the
expense of lower liquid yield.
Once it has been determined that the capacity of the
fractionator section is adequate for the new load, the capacity of
the coke drums may b e increased. The easiest way to do this is
to shorten the coke drum c y c l e . Refiners have been able to shorten
cycles to less than 16 hours with minimum c a p i t a l investment. If
it is not possible to substantially decrease the length of the
coking cycle, another alternative successfully employed by
Foster Wheeler is to add another coke drum. This will allow cycles
for each drum t o be shortened to 12 hours or less and s t i l l allow
adequate decoking time. These methods for increasing the coke
capacity are also applicable when processing heavier feedstocks that
produce more coke. In this case, the fractionation section will
often handle the distillate production without any modification.
Another option open to refiners is to retrofit an existing
heavy o i l unit such as a visbreaker into delayed coking service.
Other than the coking section, the visbreaker is very similar to
a delayed coker. If plot area permits, a coking section may be
added and the heater modified.
Summary
Since its inception, the basic process of delayed coking has

remained basically unchanged, but the feedstocks, process equipment
and operating philosophy have changed substantially. Delayed
coking has evolved to process a wide range of today's heavy, high
sulfur feedstocks, while s t i l l producing acceptable product yields
and qualities. Processing equipment has been updated to provide
more on-stream time and a more energy efficient operation. In years
to come, delayed coking is expected to continue to remain an
important residual upgrading process.

Literature Cited
1. DeBiase, R., and E l l i o t t , J . D., Oil and Gas Journal, 16, 81
(1982).
2. Nagy, R.L., Broeker, R. G., and Gamble, R. L . , "Firing Delayed
Coke in a Fluidized Bed Steam Boiler", paper presented at the
1983 NPRA Annual Meeting, San Francisco, CA, March 20-22 (1983).
3. Fasullo, P.Α., Matson, J., and Tarrillion, T., Oil and Gas
Journal, 44, 76 (1982).
4. Guthrie, V . B . , Ed., Petroleum Products Handbook, McGraw-Hill
Book Company, New York, 1960; Chapter 14.
5. Kennedy Van Saun Corporation's Technical Brochure No.
COK 1/82(2).
6. Allred, V.D., "Rotary Hearth Calcining of Petroleum Coke",
paper presented at the 100th National Meeting of the American
Institute of Metallurgical Engineers, New York, NY, March 1-4
(1971).
RECEIVED February 23, 1985


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11

Delayed-Coking Process Update

Robert DeBiase, John D. Elliott, and ThomasE.Hartnett

Important recent trends and new developments have

Trends and developments on the design of modern delayed

Delayed c o k i n g i s a p r o c e s s i n g t e c h n o l o g y t h a t has been i n use f o r

In Petroleum-Derived Carbons; Bacha, J., et al.;

completed and p e t r o l e u m coke and overhead vapors are formed. The

A typical delayed coker unit consists of coking, fractionation and

blowdown sections, along with coke handling facilities. Coker gas

Coking Section. Figure 1 is a simplified process flow diagram of

Fractionation Section. A typical fractionation section includes

In Petroleum-Derived Carbons; Bacha, J., et al.;

In Petroleum-Derived Carbons; Bacha, J., et al.;

A portion of the condensed gasoline is pumped b a c k to the tower as

Coker Blowdown System. Figure 2 shows a typical coker blowdown

drum where the heavy hydrocarbons are condensed by a circulating

amount of o i l . The o i l and water are separated in the blowdown

Coke Dewatering and Handling System. When a coke drum i s being

In Petroleum-Derived Carbons; Bacha, J., et al.;

In Petroleum-Derived Carbons; Bacha, J., et al.;

then pumped to a clarifier. This system offers the lowest capital

from the dewatering bin. Foster Wheeler has developed totally

Types of Petroleum Coke

Needle Coke. Usually produced from highly aromatic thermal tar,

Sponge Coke. This type of coke is considered a form of regular

Shot Coke. Another form, generally undesirable, of regular coke is

In Petroleum-Derived Carbons; Bacha, J., et al.;

Figure 3. P i t Type Coke Handling System.

Figure 4. Pad Type Dewatering System.

Figure 5. Direct Rail Car Loading.

In Petroleum-Derived Carbons; Bacha, J., et al.;

Figure 6. Slurry Dewatering B i n System.

Figure 7. G r a v i t y Flow Dewatering B i n System

In Petroleum-Derived Carbons; Bacha, J., et al.;

some C a l i f o r n i a r e s i d u e s , s h a l e o i l and g i l s o n i t e . Operating

As crudes become h e a v i e r w i t h h i g h e r l e v e l s o f s u l f u r and m e t a l s ,

Carbon Residue. The carbon r e s i d u e i s one f a c t o r used t o determine

M e t a l s Content. When p r o d u c i n g coke f o r e l e c t r o d e o r anode u s e ,

In Petroleum-Derived Carbons; Bacha, J., et al.;

aromatic feedstock with low sulfur and m e t a l s content. Needle coke

the coke produced from a desulfurized residue may b e suitable for

Three operating control variables in a delayed coker dictate the

Regular Grade Coke Operation - Typical Yields and Product Qualities

Illustrated in Table I are the estimated yields and product

In Petroleum-Derived Carbons; Bacha, J., et al.;

TBP Cut Point, °F 950+ 1,000+ 1,000+ 1,000+

Operation -Maximum Liquid Yield-

Gas O i l , 380°F+, Wt% 44.7 40.2 46.5 67.5 46.0

In Petroleum-Derived Carbons; Bacha, J., et al.;

Coke, Wt% 32.5 37.1 31.0 12.6 26.4

ACS Symposium Series; American Chemical Society: Washington, DC, 1986.

Needle Coke O p e r a t i o n - T y p i c a l Y i e l d s and P r o d u c t Qualities

Table I I shows e s t i m a t e d y i e l d s and p r o d u c t q u a l i t i e s f o r t h r e e

G r a v i t y , °API 2.4 -3.9 -0.7

Uses o f Petroleum Coke

Petroleum coke i s e s s e n t i a l l y pure carbon and can be u t i l i z e d

In Petroleum-Derived Carbons; Bacha, J., et al.;