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PETROLEUM COKE HANDLING PROBLEMS

H. W. Nelson

GREAT LAKES CARBON CORPORATION

Carbon Division
New York, N. Y.

INTRODUCTION

Calcined petroleum coke is an i n d u s t r i a l carbon which i s used

a s a raw m a t e r i a l i n t h e Aluminum I n d u s t r y and t h e Graphite Industry.
From t h e time it is f i r s t formed a s a by-product of petroleum r e f i n i n g
u n t i l i t i s f i n a l l y processed i n t o elemen'tal carbon i t is handled many
times. Extreme c a r e m u s t be e x e r c i s e d a t each p o i n t o f handling i n
o r d e r t o p r e s e r v e t h e d e s i r e d p h y s i c a l s t r u c t u r e and maintain the re-
q u i r e d degree o f p u r i t y . This paper reviews t h e steps used i n t h e
carbon i n d u s t r y t o a c h i e v e t h e s e o b j e c t i v e s .

Q u a l i t y Considerations

Calcined petroleum coke is a commodity which m u s t be d e l i v e r e d

t o t h e u l t i m a t e consumer i n a s i z e range which w i l l p e r m i t an adequate
p r o p o r t i o n of coarse p a r t i c l e s . This is necessary i n o r d e r t o m e e t
t h e formulation requirements i n a carbon p a s t e mix. I t must a l s o be
f r e e from contamination.

Formation of Petroleum coke

Raw petroleum coke i s a by-product from r e f i n i n g o f petroleum

r e s i d u a l s . One o f the procedures by which t h i s is accomplished is
known as t h e delayed caking process. This g i v e s a coke w i t h a sponge-
l i k e s t r u c t u r e . O t h e r methods such as t h e f l u i d coking process are
a l s o used b u t the product from t h i s o p e r a t i o n does n o t have t h e s t r u c t -
u r a l p r o p e r t i e s r e q u i r e d f o r u s e i n t h e A l u m i n u m I n d u s t r y or Graphite
E l e c t r o d e Industry.

Figure 1 shows a c r o s s s e c t i o n o f a coke drum and i l l u s t r a t e s

how t h e coke i s formed i n t h e delayed coking o p e r a t i o n . The drum is a
large i n s u l a t e d v e s s e l about 2 0 f e e t i n diameter and 7 0 feet high. The
\
coke i s formed a t the rate o f a b o u t 2 f e e t per hour and proceedes t o
b u i l d up during a . 2 4 hour cycle. The m a t e r i a l a t the bottom is f u l l y
polymerized and develops a porous s t r u c t u r e through which gases and
l i q u i d s can pass. The t o p l a y e r i n t h e cake drum is n o t f u l l y poly-
merized u n t i l it is s u b j e c t e d t o h e a t f o r a prolonged period of time.
A t the very top, s o m e foam occurs. This foam s u b s i d e s d u r i n g t h e
steaming and c o o l i n g c y c l e . I t i s i m p o r t a n t i n f i l l i n g t h e coke
drum t o avoid any c a r r y over o f foam o r p i t c h y m a t e r i a l i n t o t h e
vapor l i n e s . Foam d e p r e s s a n t s a r e used t o minimize t h e amount o f
foam (1). Level i n d i c a t o r s a r e used t o e s t a b l i s h t h e p o s i t i o n o f
t h e l i q u i d o r foam i n t h e drum (2). These are o p e r a t e d by t r a n s -
m i t t i n g a beam from a r a d i o a c t i v e s o u r c e t o an instrument mounted
near t h e t o p o f t h e drum. When t h e l i q u i d r e a c h e s a predetermined
l e v e l t h e feed t o t h e drum i s switched t o an empty drum. A t t h i s
t i m e t h e f u l l drum i s steamed t o remove l i g h t hydrocarbons and
f i n a l l y cooled by i n t r o d u c i n g water a t t h e bottom o f t h e drum.

F a c t o r s a f f e c t i n q S i z i n q o f Coke

The coke i s removed from t h e drum b y means o f high p r e s s u r e

water j e t s which o p e r a t e on t h e p r i n c i p l e used i n h y d r a u l i c mining
o f c o a l ( 3 ) . The p r o c e d u r e used i n c u t t i n g t h e coke from t h e drum
i s extremely i m p o r t a n t . I f it i s n o t c a r r i e d o u t p r o p e r l y t h e
p h y s i c a l s t r u c t u r e o f t h e coke w i l l be d e s t r o y e d and t h e u l t i m a t e
consumer would n o t have enough c o a r s e p a r t i c l e s t o b a l a n c e o u t t h e i r
carbon aggregate f o r m u l a t i o n . The recommended procedure f o r c u t t i n g
t h e coke is i l l u s t r a t e d i n F i g u r e 2 . T h i s series o f diagrams shows
t h e s t e p s which s h o u l d b e taken i n o r d e r t o g e t t h e maximum amount I
of lump coke needed for f u r t h e r p r o c e s s i n g .

The f i r s t s t e p i s t o b o r e a p i l o t h o l e . During t h i s o p e r a t i o n
t h e f i n e c u t t i n g s a r e h e l d i n t h e upper s e c t i o n of t h e drum u n t i l t h e
h o l e i s completely through t h e bottom. A t t h i s t i m e , a l l o f t h e
c e n t e r c u t t i n g s f a l l o u t o f t h e drum t o g e t h e r w i t h t h e water used i n
cutting.

The d r i l l s t e m i s r a i s e d t o t h e t o p and t h e b i t i s changed t o

a c u t t i n g head which has n o z z l e s d i r e c t e d i n a h o r i z o n t a l manner.
I
The p i l o t h o l e is e n l a r g e d so t h a t lumps o f d i s l o d g e d coke can f a l l
f r e e l y through t h e opening. T h i s a v o i d s t h e danger o f a coke b u i l d I
up around t h e d r i l l s t e m which would p r e v e n t t h e r o t a t i o n o f t h e
c u t t ing head.

Once t h e p i l o t h o l e i s e n l a r g e d t h e s t e m i s r a i s e d t o t h e
l e v e l o f t h e coke i n t h e drum. The o p e r a t o r can t e l l by t h e sound
of t h e water h i t t i n g t h e metal w a l l s when t h e t o p i s reached. A t
t h i s t i m e t h e stem i s lowered 3 - 4 f e e t b e l o w the. t o p . I t i s h e l d
i n t h i s p o s i t i o n f o r s e v e r a l minutes u n t i l the coke i s undercut.
Then t h e stem is r a i s e d and lowered r a p i d l y w i t h i n t h i s s e c t i o n u n t i l
t h e coke i s a l l c u t from t h i s l a y e r . T h i s a c t i o n causes t h e coke to
c o l l a p s e from t h e d r u m w a l l s r e s u l t i n g i n l a r g e p i e c e s which fal.1
through t h e p i l o t h o l e . This o p e r a t i o n i s r e p e a t e d u n t i l t h e drum
is completely empty. I n g e n e r a l , t h e decoking o p e r a t i o n r e q u i r e s
about 3 t o 4 h o u r s depending on t h e hardness o f t h e coke. The h a r d e r
 123

t h e coke t h e more t i m e r e q u i r e d .

Lump coke i n t h e s i z e range o f b a s e b a l l s t o f o o t b a l l s can

be handled e a s i l y i n c o n v e n t i o n a l conveying systems. A t t h e c a l -
c i n i n g p l a n t a l l coke is run through a roll c r u s h e r set a t an
opening of 4 inches b e f o r e it i s fed t o t h e k i l n . The tumbling
a c t i o n i n t h e k i l n r e s u l t s i n f u r t h e r d e g r a d a t i o n so t h a t t h e f i n a l
product a l l p a s s e s a 1 inch s c r e e n w i t h approximately 35 t o 40% r e -
t a i n e d on a 6 inch screen.

Procedures t o avoid Contamination

There a r e s e v e r a l systems used i n h a n d l i n g coke a f t e r it i s

discharged from t h e drum. These a r e a s follows:

A. The coker i s mounted over a r a i l r o a d t r a c k so t h a t coke

can be d i s c h a r g e d d i r e c t l y i n t o open hopper c a r s o r gon-
dola cars.

B. A roll c r u s h e r is placed below t h e drum on small t r a c k s .

. This b r e a k s up t h e l a r g e lumps t o a s i z e which w i l l permit
a coke s l u r r y t o b e t r a n s p o r t e d by pumping through a p i p e
line.

C. The coke is d i r e c t e d t o a ramp which l e a d s t o a p i t . The

p i t may or may n o t c o n t a i n water f o r f u r t h e r cooling of
t h e coke.

I n each of t h e ' a b o v e systems it i s n e c e s s a r y t o provide or

t h e recovery o f water used i n c u t t i n g . The areas around t h e coking
u n i t should be paved. Curbs and r e t a i n i n g w a l l s should be provided
t o c o n t a i n any coke s p i l l a g e . The d r a i n a g e around t h e coker must b e
c a r e f u l l y planned t o avoid sand. c l a y and g r a v e l from e n t e r i n g t h e
system. Drainage from r a i n s t o r m s should b e d i r e c t e d away from t h e
coking u n i t .

T r a n s p o r t i n q and Convwinq Coke

The f r e i g h t c a r s used t o t r a n s p o r t t h e coke should be clean.

Any sand. g r a v e l o r i r o n r u s t w i l l contaminate t h e coke. The c a r s
should be c a r e f u l l y i n s p e c t e d b e f o r e loading.

When coke i s unloaded a t t h e c a l c i n i n g p l a n t , i t is e i t h e r

conveyed d i r e c t l y t o a s t o r a g e silo o r t o an outdoor s t o r a g e . When
outdoor s t o r a g e is n e c e s s a r y , it is p r e f e r a b l e t o p r o v i d e paved
a r e a s t o minimize contamination. The a c t i v i t i e s i n t h e surrounding
a r e a can a l s o a f f e c t t h e p u r i t y of t h e coke. For example, unloading
of i r o n o r e i n t h e v i c i n i t y w i l l contaminate t h e coke p i l e under
 124

c e r t a i n wind c o n d i t i o n s .

Magnetic s e p a r a t o r s a r e used a t t h e c a l c i n i n g p l a n t s .
These w i l l remove s c r a p i r o n from g r e e n coke, b u t w i l l n o t remove
i r o n r u s t , s i n c e t h e l a t t e r i s non-magnetic. During c a l c i n i n g any
i r o n o x i d e ( r u s t ) w i l l be reduced t o i r o n which can be removed from
t h e c a l c i n e d petroleum coke w i t h magnets.

Chemical Composition o f Petroleum Coke

Green petroleum coke from t h e delayed coking process i s

e s s e n t i a l l y a hydrocarbon. The chemical composition a s o b t a i n e d
by an u l t i m a t e a n a l y s i s i s given i n Table I. Before it can b e used
a s a carbon a g g r e g a t e i t i s n e c e s s a r y t o c o n v e r t t h e green coke i n t o
e l e m e n t a l carbon by a petrochemical p r o c e s s . This i s c a r r i e d o u t
0
by a p y r o l y t i c t r e a t m e n t a t temperatures around 2300 F. In t h i s
o p e r a t i o n t h e carbon i s n o t developed u n t i l hydrogen is chemically
removed b y thermal decomposition. I n t h e t r a d e t h i s process is re-
f e r r e d to a s c a l c i n a t i o n , b u t it is e s s e n t i a l l y a dehydrogenation
r e a c t i o n which c o n v e r t s a hydrocarbon i n t o e l e m e n t a l carbon as i n -
d i c a t e d i n Table I.

A number o f changes i n basic p r o p e r t i e s and s t r u c t u r e a r e

b r o u g h t about by t h e removal of chemically bound hydrogen from t h e
hydrocarbons i n o r d e r t o produce e l e m e n t a l carbon. Some o f t h e s e
are as follows:

A. The real d e n s i t y of g r e e n petroleum coke i s 1.30. After

calcining t h e r e a l density i s 2.07.

B. G r e e n petroleum coke is an e l e c t r i c a l i n s u l a t o r whereas

elemental carbon ( c a l c i n e d petroleum coke) i s an e l e c t r i c a l
conductor. For example:

E l e c t r i c a l R e s i s t i v i t y of Green Petroleum coke i s 9 x

lo6 ohm-inches.

E l e c t r i c a l R e s i s t i v i t y of Calcined Petroleum coke i s

.03 5 ohm-inches .
C. There a r e corresponding changes i n the X-ray d i f f r a c t i o n
pattern.

While t h e r e a r e profound changes o c c u r r i n g d u r i n g t h e chemical

c o n v e r s i o n of green petroleum coke t o e l e m e n t a l carbon, t h e mineral
m a t t e r a s i n d i c a t e d by t h e a s h c o n t e n t remains e s s e n t i a l l y unchanged.
The composition o f t h e a s h i s important a s t h i s w i l l a f f e c t t h e type
of aluminum metal which can b e produced.
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The m e t a l l i c components which a r e p r e s e n t i n t h e crude o i l

w i l l be c a r r i e d over i n t o t h e coke,. M a t e r i a l s such a s vanadium
and n i c k e l occur i n crude o i l s i n varying amounts depending on t h e
a r e a of o r i g i n . There i s a c t u a l l y very l i t t l e i f any i r o n o r
s i l i c o n i n crude o i l . Iron which is found i n petroleum coke comes
p r i m a r i l y from c o r r o s i o n o f t h e p i p e s and v e s s e l s used t o process
t h e crude o i l . A d d i t i o n a l i r o n f i n d s i t s way i n t o t h e coke i n t h e
form of r u s t from r a i l c a r s and conveying equipment. S i l i c o n can
come from t h e c a t a l y s t used i n r e f i n i n g a l s o from sand o r g r a v e l
contamination.

I r o n and S i l i c o n i n Calcined Petroleum Coke

The i r o n i n c a l c i n e d petroleum coke w i l l normally range

between .01 and .06%. The s i l i c o n c o n t e n t w i l l range between . 0 1
and .OS. Table I1 shows t h e c a r a n a l y s i s o f i r o n and s i l i c o n i n
c a l c i n e d petroleum coke a l l loaded from t h e same s t o r a g e s i l o .
The samples w e r e taken from a conveyor b e l t w i t h an automatic
sampler. In t h i s group o f c a r s , w e f i n d some i n d i v i d u a l cars w i t h
i r o n a s low a s .019% and s i l i c o n a s low a s .010%. T h i s information
i s u s e f u l t o t h e carbon p l a n t s u p e r i n t e n d e n t o f a prebaked p l a n t .
I f h e i s . r e q u i r e d t o supply anodes which are low i n i r o n o r s i l i c o n ,
he .can s e l e c t t h e c a r s from a given shipment and s e g r e g a t e t h e l o w
ash m a t e r i a l i n a s e p a r a t e a r e a o f h i s s t o r a g e shed.

S i n c e t h e i r o n i n c a l c i n e d coke is magnetic, f u r t h e r re-

moval can be accomplished a t t h e consumers' p l a n t by u s i n g magnetic
s e p a r a t o r s . T h i s w i l l be most e f f e c t i v e i f a p p l i e d a f t e r t h e
g r i n d i n g o p e r a t i o n s i n c e i r o n p i c k up does t a k e p l a c e i n equipment
such a s t h e b a l l m i l l .

S e v e r a l aluminum p l a n t s a r e now asking f o r a special grade

o f carbon w i t h v e r y low s i l i c o n . This i s a d i f f i c u l t requirement
t o c o n t r o l a t a n o r d i n a r y c a l c i n i n g p l a n t . However, a s u b s t a n t i a l
improvement can be accomplished by s c r e e n i n g t h e coke and u s i n g t h e
coarse- f r a c t i o n f o r t h e l o w s i l i c o n a p p l i c a t i o n . An example o f the
degree o f improvement which can be achieved by this method i s shown
i n Table 111. The s i l i c o n b e a r i n g material is c o n c e n t r a t e d i n t h e
f i n e s (minus f"). The p l u s f" f r a c t i o n c o n t a i n s o n l y 40% o f the
t o t a l s i l i c o n o r .008%.
 SUMMARY

I n summarizing t h e information j u s t p r e s e n t e d , we f i n d
t h a t a r e a s o n a b l e amount o f c a r e should be e x e r c i s e d a t each s t e p
o f handling petroleum coke. I t i s recongnized t h a t some o f t h e
p h y s i c a l p r o p e r t i e s ( s i z i n g ) o f a c a l c i n e d coke can b e destroyed
i f t h e c u t t i n g o p e r a t i o n i s n o t c a r r i e d o u t properly. . A l s o s o u r c e s
o f contamination should be avoided i n o r d e r t o keep the i r o n and
s i l i c o n c o n t e n t w i t h i n r e q u i r e d l i m i t s . Where a carbon a g g r e g a t e
w i t h low s i l i c o n o r low i r o n is r e q u i r e d a s e l e c t i o n c a n be made
from a given shipment i f t h e m a t e r i a l is d e l i v e r e d i n r a i l c a r s .

. .
References

1. T r a m e l l , W. D., G l a s e r , D., O i l and G a s J o u r n a l p. 65,

June 5 , 1961.

2. Wright, P. G., O i l and G a s Journal p. 93 - 94. Aug. 11, 1958.

3. Maas, R . , Lauterbach, R. E., Petroleum Engineer p. 1 1 0 - 124,

F e b . 1947.
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VAPOR
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Figure 1.
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 TYPICAL ULTIMATE ANALYSIS OF
GREEN PETROLEUM COKE AND CALCINED PETROLEUM COKE

Green Calcined
Petroleum Coke Petroleum Coke
(Polymerized Residual) (Pure Carbon)

CARBON 91-80 98.40

HYDROGEN 3.82 0.14
OXYGEN 1.30 0.02
NITROGEN 0.95 0.22
SULFUR 1.29 1.20
ASH 0.35 0.35
CARBON-HYDROGEN RATIO 24 910

TABLE II

ANALYSIS OF CALCINED COKE SHIPMENTS

CARS LOADED FROM PRODUCT SILO

. ORDER OF LOADING ASH IRON SILICON

CAR NO. % % %

1 .24 .019 .010

2 .21 -021 .012
3 .40 .065 .028
4 .42 .073 .022
5 .34 .043 -025
6 .24 -030 .010
7 -23 .020 .015
8 .33 -035 .025
9 .41 -065 .015
10 .26 .041 .021

TABLE 111

EFFECT OF SCREENING
ON SILICON CONTENT OF
CALCINED PETROLEUM COKE

SIZE % SILICON

Run of Kiln .021

I Plus % Inch Fraction .008

Minus % Inch Fraction .022