PYROLYSIS FURNACE

C. M. Tham
k95tcm@yahoo.com


ABSTRACT

Pyrolysis or steam cracking is the primary process utilized to manufacture olefins from large hydrocarbon
molecules. This gas-phase reaction takes place in metal alloy tubes within a fired furnace. Pyrolysis
proceeds as a series of free radical reactions and the complexity of the mechanisms increases with the
nature of the feedstock. Both rigorous and empirical solution techniques are available. A mathematical
model for design of pyrolysis coil is presented. The effect of residence time, temperature, pressure and
inert on ethylene yield will be discussed briefly.

Coke formation onto the tubular coils continues to be a challenge faced by engineers. Coke deposition
increases fuel consumption, reduces the furnace throughput and causes non-productive outages for
decoking activities. Various coke formation mechanisms will be discussed and a review of recent
developments to mitigate this phenomenon will be presented.

Keywords: Coking, ethylene, furnace, olefins, pyrolysis, steam cracking
1 INTRODUCTION

Olefins manufacturing is the third largest petrochemical sector after ammonia manufacturing and
petroleum refining. Olefins are the building blocks in manufacturing of polymers and elastomers or
converted into derivatives such as aldehydes, alcohols, glycols, etc. Olefins are primarily produced by
steam cracking of large hydrocarbon molecules. This process is also known as pyrolysis.

Pyrolysis is a gas-phase reaction at very high temperature. As the reaction is highly endothermic, it is
carried out in tubular coils within a fired furnace. Many furnace designs are available today, although the
fundamental principles are similar. Commercial technology can be licensed from technology providers
e.g., Kellogg Brown & Root, ABB Lummus, Stone & Webster, Linde, KTI-Technip, etc.

An industrial pyrolysis furnace is a complicated piece of equipment that functions as both a reactor and
high-pressure steam generator. The pyrolysis reactions proceeds in tubular coils made of Cr/Ni alloys.
These coils are hung vertically in a firebox. Depending of furnace design, there may be between 16-128
coils per firebox. Burners are arranged on the walls and on the floor of the firebox for indirect firing. This
section is called the radiant section because the radiant heat is recovered. At the end of the pyrolysis, the
reaction needs to be quenched rapidly to avoid further decomposition of the desired olefins. This is
achieved by either indirect cooling using a quench exchanger or direct cooling by injecting quench oil
into the gas effluent. The heat carried by the flue gas is recovered at the convection section of the furnace.
This section consists of a series of tube banks where the heat is recovered for superheating steam,
preheating the hydrocarbon feed, boiler feed water and dilution steam.

Being the heart of a cracker unit, furnace technology continues to be an active area of research. The large
amount of energy consumed in both the pyrolysis reaction and recovery of the products drives engineers
to continuously improve the energy efficiency of the process. Higher selectivity designs helps to reduce
the size of the recovery section and hence, the capital cost of a steam cracker.


1
2 PROCESS CHEMISTRY

The desired products from the pyrolysis reactions are light olefins, i.e., ethylene, propylene and
butadiene. However, depending on the nature of the feedstock, a wide array of by-products can be
produced as result of pyrolysis. This includes hydrogen, methane, acetylene, butene, benzene, toluene,
xylene and other hydrocarbon structures up to C
12
length. A wide variety of feedstock for pyrolysis can
be employed with ethane and naphtha being the most common. Other feedstocks used are propane,
liquefied petroleum gas (a propane and butane mixture), kerosene, atmospheric gas oil, vacuum gas oil
and wax.

The desired reaction is the decomposition of the hydrocarbon molecule (typically of paraffinic structure)
to its olefinic equivalent. The simplest illustration is decomposition of ethane into an ethylene molecule,
where the overall reaction is:

2 6 2 4 2
C H C H H +
(1)

The mechanism of this reaction however involves a series of free radical reactions as proposed by Rice
and Herzfeld (1934). This can be divided into four steps: initiation, hydrogen abstraction, radical
decomposition and termination.

Initiation
1
k
2 6 3 3
* * C H CH CH + (2)

Hydrogen abstraction
2
k
3 2 6 4 2
* * CH C H CH C H + +
5
*


(3)
3
k
2 6 2 2 5
* H C H H C H + + (4)

Radical decomposition
4
k
2 5 2 4
* * C H C H H +
(5)

Termination
5
k
2
* * H H H + (6)
5
k
3 4
* * H CH CH + (7)
5
k
2 5 2 6
* * H C H C H + (8)
5
k
2 5 3 3 8
* * C H CH C H + (9)
5
k
2 5 2 5 4 10
* * C H C H C H + (10)

In pyrolysis of larger hydrocarbons, the initiation step of splitting the C-C bond can occur in variety of
ways depending on the molecule structure. Addition transient chain reactions can be occurring
simultaneously. In high severity condition (very high reaction temperature), the olefins produced as well
as the species formed in the termination step can proceed for further decomposition.

In pyrolysis of multi-component hydrocarbon mixtures, e.g., naphtha and gas oil, the multiplicity of
reactions that occurred and the largely unknown componential composition, rigorous free radical
mechanism solution is difficult. Techniques of lumping groups of chemical species with similar kinetic
behavior, similar to those utilized in catalytic cracking were developed. These techniques lump the
hydrocarbon into groups of normal paraffin, iso-paraffin, olefin, naphthene and aromatic. Empirical
solutions, e.g. Kivlen (1990), correlates the key components in the product to these lumped groups, as
well as the specific gravity, boiling range, hydrogen content, etc. Modern modeling package, e.g.,


2
SPYRO offers a rigorous solution that combines technique of lumping components and free radical
mechanism.

Two major undesired reactions that occur simultaneously with the desired cracking of alkanes are
dehydrogenation and condensation. Dehydrogenation is the phenomenon where an olefin molecule
further decomposes into a diolefin or the CC group. Examples are formation of acetylene, methyl
acetylene and propadiene:

C H
2 4 2 2 2
C H H + (11)
2 4 3 6 3
H H C H C + (12)

Dehydrogenation results in olefin yield loss. Its products are contaminant to the olefin product. In the
case of acetylene, methyl acetylene and propadiene, they had to be removed downstream using
palladium-based hydrogenation reactors, which are expensive and difficult to operate.

Condensation is a reaction where two or more small molecules combine to form a larger stable structure
such as cyclo-diolefins and aromatic. This secondary reaction occurs in the latter stage of pyrolysis and
the residence time of the reactor is high. In practice, this can be observed when the aromatic
concentration in the pyrolysis gasoline (a by-product) stream and the residual fuel oil (C
9
-C
12
fraction) are
high.

The extreme of dehydrogenation and condensation is coke formation. Coke forms when hydrogen atoms
are removed from the hydrocarbon radicals until the extreme of leaving only a layer of elemental carbon
or coke. Although, aromatic are relatively stable molecules, they can however further react via
condensation to form a chain of its benzene ring structure. These condensation products leave the gas
phase and settle on the inner walls of the radiant coils as a layer of hard coke that is very difficult to
remove. Various mechanism of coke formation will be discussed later in detail.
3 REACTOR PARAMETERS

The pyrolysis coils essentially behaves as a plug flow reactor that receives heat from its surrounding, i.e.,
the radiant heat of the firebox. Much of the early development of furnace technology found inspirations
in the works of Schutt (1959). In industrial pyrolysis of ethane, it was found that the methane yield
increases and the ethylene yield decreases with the approach to the equilibrium of ethane
dehydrogenation reaction. The equilibrium approach can be defined as:

( )( )
( )
2 2 4
2 6
H C H
p C H
y y
P
K y
= (13)

where P = hydrocarbon partial pressure, Pa
K
p
= equilibrium constant for the ethane dehydrogenation reaction at the coil outlet
temperature, Pa
y = mole fraction of constituent in the hydrocarbon mixture of the coil effluent

Based on Schutts data and assumption that every decomposing mole of ethane not converted to ethylene
will yield 2 moles of other pyrolysis products, the molal yield of ethylene per converted mole of ethane
can be represented by the following formula:


3

2 4
2 2
2 2
1.67
1
1 1.2 1
1
p
C H
p
K
P
Y
P K

= +

(14)

where = fractional disappearance of ethane

2 4
C H
Y
= yield of ethylene, moles per mole of ethane converted

The formula shows that higher equilibrium constants and lower partial pressures favor ethylene
formation. Higher equilibrium constants require higher reactor temperatures, which in turn result in
higher reaction velocities and therefore call for shorter residence times to maintain a given conversion
and thus, obtain a higher ethylene yield. This work prompted designers of pyrolysis furnaces to move in
the direction of short residence time, low hydrocarbon pressures and high temperatures for optimum
production of ethylene from any feedstock.

3.1 Residence Time

The bulk residence time, often mentioned in the literature to characterize various furnace designs,
represents the entire length of time that a unit gas spends in the pyrolysis coil.

0
( )
L
B
dl
v l
=

(15)

where L = total coil length
L = distance from the coil inlet, m
v(l) = Gas velocity, ms
-1


B
= bulk residence time, s

However, investigators showed that it is the residence time of the pyrolysis products rather than the bulk
residence time that influences the yield spectrum. Zdonik (1970) proposed an equivalent residence time
based on the decomposition of the n-pentane, one of the more refractory product commonly found in the
pyrolysis of liquid feedstock.

( )
( )
5
0
5
1 B
E
B
K d
K

=


(16)

where
E
= equivalent residence time, s
-1


B
= bulk residence time, s
K
5
= reaction rate of n-pentane, s
-1


All the early pyrolysis cracking furnaces constructed between 1940 and 1960 had horizontal radiant tubes
and residence times in excess of 0.5 seconds. Radiant tube materials were 310 stainless (wrought 25
Chrome 20 Nickel) or Incoloy with internal diameter (ID) larger than 127 mm (5-in). Until mid of 1960s
all furnaces were fired with a very large number of wall burners spaced on about 1,829 mm (6-ft) centers
in the horizontal walls and facing the row of radiant tubes.

In order to reduce the residence time, engineers have designed radiant tubes of smaller diameters, better
metallurgy and burners that are more efficient. Modern cracking furnaces operate in residence time range
between 0.08-0.25 s. Tube diameter has reduced to the range of 25.4 101.6 mm (1-4 in). The smaller
diameter tubes offer a higher surface to volume ratio, which allowed the heat necessary for cracking to
enter the tubes in a much shorter tube length. This enabled the cracking to take place in a much shorter
residence time which gave much better yields of the desired products (mainly ethylene, propylene and
butadiene). Radiant coils are now casted with composition of Cr/Ni in the range of 25/35 to 35/45 and


4
installed vertically to reduce the investment cost. Large wall burners were replaced with smaller but more
efficient floor burners (Bowen, 1992).

Yield in Weight Percent
Residence Time 0.10 s 0.20 s 0.50 s
Methane 15.48 15.78 16.16
Ethylene 34.16 32.16 29.37
Propylene 17.02 17.35 17.78
Butadiene 5.20 5.10 5.00
Benzene 5.89 6.00 5.75
Toluene 2.59 2.65 2.52
Fuel Oil 3.12 3.35 3.61
Table 1: Effect of Residence Time in Cracking of Typical Light Naphtha (Kolmetz, et al, 2002)















4-pass /
W-coil
(0.4 s)
Two-pass /
U-coil
(0.2 0.25 s)
Single-pass
coil
(0.08 - 0.12 s)
Hybrid coil

(0.2 0.4 s)



Figure 1: Types of Coils in Industrial Pyrolysis
3.2 Reaction Temperature

Pyrolysis is a highly endothermic reaction. For a given tube dimension and operating pressure, increase in
reaction temperature drives the reaction to the right to produce smaller hydrocarbon molecules. Over the
last few decades, the operating temperature of pyrolysis furnace has steadily been spread from the region
of 750 850
o
C to close to 900
o
C.

The downside of higher operating temperature is more rapid coking rate and carburization, which
shortens the tube-life. Hence, engineers have continuously worked to developed technology to suppress
coke formation, better metallurgy to sustain the elevated temperatures, as well as, techniques to reduce
carburization. As the initiation step of coking and carburization is the same, i.e., formation of catalytic
coke, recent developments have been collaborative works of both fields of interest.

3.3 Reaction Pressure

Pyrolysis is a gas-phase reaction, which produces more moles of gas molecules for its reaction to the
right. Hence, low operating pressure is favored. Modern furnaces operate under low pressure of 175-240
kPa. Although innovative coil design has reduced coil pressure and contributed better yields, the major
credit goes to improvement in the compressor technology. The coil outlet pressure is indirectly controlled
by the suction pressure of a process gas compressor located downstream.



5
The compression is necessary to achieve the high pressures (~3.5 MPa) for separation of hydrogen and
methane. To achieve lower coil outlet pressure, the required compressor horsepower becomes very large.
This becomes an optimization problem between better yield, processing capacity, capital investment and
energy cost. Fortunately, advancement in turbo machinery designs has provided the economic of scale to
construct high horsepower compressor and allowing the furnaces to operate at low pressures.

3.4 Inert

Dilution steam is an inert that premixed with hydrocarbon feed before feeding to the pyrolysis coils. The
early attempts of industrial pyrolysis were carried out without any dilution steam. It was found that tube
carburization rate becomes very rapid. Dilution steam was added then forth to reduce coking and
carburization. The second function of dilution steam is to lower the hydrocarbon partial pressures. This is
to minimize undesirable secondary reactions and higher ethylene yield as shown by Schutt.

In industrial pyrolysis, the mass ratio of steam to hydrocarbon feed is a controlled parameter in furnace
operations. This ratio varies from 0.3 for ethane feed to 0.6 for gas oil cracking. The general rule of
thumb is that less dilution steam is required for smaller hydrocarbon molecules. In true operations, higher
ratio may be employed if the hydrocarbon feed is less than rated so as the bulk residence time remains
low as desired.

26.0
27.0
28.0
29.0
30.0
31.0
32.0
33.0
34.0
810 830 850 870 890
Coil Outlet Temperature (
o
C)
E
t
h
y
l
e
n
e

Y
i
e
l
d

(
W
t

%
)
200 kPa
220 kPa
240 kPa
26.0
27.0
28.0
29.0
30.0
31.0
32.0
33.0
34.0
35.0
810 830 850 870 890
Coil Outlet Temperature (
o
C)
E
t
h
y
l
e
n
e

Y
i
e
l
d

(
W
t

%
)
S/H 0.6
S/H 0.5
S/H 0.4

Figure 2: Effect of coil out temperature, pressure and steam-to-hydrocarbon ratio to ethylene yield in
naphtha cracking
4 MATHEMATICAL MODEL
4


The steam cracking process can be mathematically described using the following fundamental balance
equations.

Material balance for component -j:
( ) ,
j j
j
i
dw M
r S i j
dz G
=

(17)

where w
j
= mass fraction of component j, kg/kg
z = length along coil, m
M
j
= molecular weight of component j, kg/kmol
G = mass flux, kg/m
2
.s
r
i
= reaction rate, kmol/m
3
.s
S = stoichiometric constant of component j in reaction I


6
Energy balance:
( )
4
Tubeside :
p i i o e
i
dT
G C r H U T T
dz D
= +

(18)
( ) ( ) ( ) ( )
4 4 4 4
1 2
Fireboxside :
o e w e g e g e
U T T C T T C T T U T T = + + (19)

where
p
C
= process gas specific heat, kcal/kg.K
T = process gas bulk temperature, K
H
i
= heat of reaction for reaction i, kcal/kmol
D = inside tube diameter, m
U
o
= overall inside heat transfer coefficient, kcal/s.m
2
.K
comprising - tube wall thermal conductivity
- coke resistance`
- fouling coefficient
- process gas heat transfer` coefficient
- tube inside radiation
` T
e
= outside tube wall temperature, K
T
w
= refractory wall temperature, K
T
g
= flue gas temperature, K
U = flue gas convective heat transfer coefficient, kcal /s.m
2
.K
C
1
= constants containing emissivity factors, kcal /s.m
2
.K
4

C
2
= factors and Stefan-Boltzmann constant

Mechanical energy balance:

2 2
2
2 dP G d fG
dz dz gD g


= (20)

where P = pressure, kgf /m
2

= process gas density, kg/m
3

G = dimensional constant, kg.m /kgf.s
2

f = friction factor

In order to solve these equations, an initial guess of product spectrum, temperature and pressure profile
needs to be made. This initial guess, especially the product spectrum can be made based on past data or
using simple empirical relationships. Then, using iterations and convergence criteria, the equations can be
solved rigorously using high-speed computers.
5 COKE FORMATION

Coke formation is a severe problem in industrial pyrolysis. A progressive fouling of the internal walls of
pyrolysis coil and on surface of quench exchanger takes place during the running time, due to presence of
unsaturated species and depending on the operating conditions. Four main consequences of coking
process can be singled out in cracking furnaces:

The external tube skin temperature continuously rises and can reach its maximum allowable value.
This fact can limit the on-stream time of the unit.
The pressure drop increases with the running time and can influence the process selectivity.
The furnace thermal efficiency is progressively reduced.
The reaction volume progressively declines.



7
5.1 Classification of Coke

Although there are differing schools of thought on coke formation mechanisms, it is generally accepted
that coke is formed through two separate reaction pathways, i.e. catalytic step and pyrolytic step. The two
types of coke are formed during different age of the coil run and hence, exhibit different characteristic.

Catalytic coke is formed by the dehydrogenation of the hydrocarbon with catalysts of metal components
on the surface of the reactor tube. Tiny particles of iron and nickel leave the tube surface as they absorb
carbon (from CH- radicals) on the cooler side of the particle and deposit it on the hotter side. The
deposition is in the form of hollow tubules, which grow in length. This form of carbon has a lot of open
space between tubules and is a good insulator. These cokes are very hard and not easy to remove by
decoking. Catalytic coking is coupled with carburization because the carbon deposit displaces the metal
particles and dissolves into the metal solution under high temperature.


(a) Filamentous coke (b) Coil-type coke
Figure 3: Catalytic Coke (SK Corporation, 2003)

Pyrolytic coke is soft and can be divided into two, gaseous and condensation coke. The gaseous coke is
formed by the dehydrogenation of light olefinic hydrocarbon like acetylene and the condensation coke is
formed by condensation /polymerization /dehydrogenation of heavy aromatic compounds. The decoking
of pyrolytic coke can be easier than that of catalytic coke. Pyrolytic coke has various types and it is very
difficult to define the shape. It is classified into globular, black mirror, fluffy and amorphous type
according to the morphology and classified into gaseous and condensation coke according to the nature of
the hydrocarbon precursor.


Figure 4: Pyrolytic Coke (SK Corporation, 2003)


8
5.2 Coke Formation Mechanism

The primary reactions involved in the formation of coke on the metal surface of radiant tubes and quench
section are as follows:


4 3
* * CH CH H + (21)
CH
3 2
* * CH H + * (22)

2
*
2 2
CH CO 2H H O + + (23)

2 2 2
CO + H O CO H + (24)
C
2 2
*
2
H CH C + (25)

2
CO + CO CO C + (26)

2 2 2
1
2
O H + H O (27)

2
* * H H S + HS
H
(28)

Fresh from a decoke, elements at the internal tube and outlet piping surfaces are in a highly oxidized
state, namely Fe
2
O, MnO, Cr
2
O, NiO, etc. The oxides act as catalytic sites for dehydrogenation. There are
also considerable absorbed O
2
and H
2
O absorbed on these surfaces. Experimental data showed that
equations (22) and (26) are kinetic rate limited while the remaining reactions are at or very near equilibria
at the metal surface.

As the run progresses with time, the O
2
and H
2
O partial pressure at the metal surfaces decrease. The rate
of reduction of the highly oxidized elements at the surface decreases and the coke already formed
provides a diffusion barrier, which inhibits the transport of H
2
O to the surface. As a result, the right side
of reaction (23) is less favored because of lower H
2
O partial pressure. CO production and C
2
H
2
decomposition decreases consequently. The ratio of CO to CO
2
increases per equation (24) and this
favors the carbon reversion reaction.

Ultimately, the H
2
O partial pressure at the metal surface is dominated by the rate of diffusion of H
2
O
through the coke layer. If the operating conditions are held constant, the coking rate will decrease with
time.

5.3 Decoking Methods

Whenever a pyrolysis run is terminated, the furnace needs to be decoked to remove the coke layer on the
tube wall and quench exchanger surface. In modern industrial pyrolysis, decoking is carried out by
feeding a mixture of air and steam into the pyrolysis coils and fire the furnace to a temperature higher
than the normal cracking temperature (~ 880-900
o
C). The primary reaction is the water gas shift reaction,
similar to those in coal gasification.

H C
2 2
O O + C + (29)

In some prior decoking process, hydrogen is admixed with steam before feeding to the coils. An earlier
thought was that addition of hydrogen would promote methanation and drives reaction (29) to the
extreme right. However, in practice this helps very little to hasten the gasification reaction. This method
is no longer in use.


2 4 2
CO + 3H CH + H O (30)

On the contrary, at the quench exchanger surface, high H
2
O partial pressure will actually inhibit the
gasification of coke. Hence, an air/steam mixture is unable to effectively decoke the quench exchangers.


9
Typically, towards the end of decoking the pyrolysis coils, the air/steam ratio is increased to allow more
air into the furnace. This helps to remove the coke on the quench exchanger surface more effectively.
Some modern furnaces exhibit an injection nozzle where air is fed directly to the quench exchangers for
air-only decoke.
6 RECENT DEVELOPMENTS

Modern pyrolysis furnaces have evolved a great way compared to the early furnace designs. Most
industrial furnaces built in the last decade can achieve thermal efficiency up to 98%. High olefins yield
has been achieved with novel coil designs, which offer very short residence time. Efficient burners have
also been designed to operate at low excess air to save fuel but still meet the NO
x
emission limits. The
greatest challenge for engineers today is to improve the on-stream factor by reducing the coke formation
and to extend furnace life between tube replacements. The following are examples of technologies
developed in recent years.

6.1 Chemical Treatment

Sulfur-based compounds e.g. mercaptan, dimethyl sulfide and dimethyl disulfide, have been traditionally
dosed into the pyrolysis coils after a fresh decoke cycle. These sulfur compounds converts the metal
oxide sites on the tube wall surfaces into metal sulfides. Although the primary aim is to reduce
carburization rate, it also reduces catalytic coking.

Sulfur treatment has limitations as the metal sulfides layer tends to be destroyed by flaking or even
liquefied in the case of nickel sulfide. Other chemical additives for the same objective are aqueous salt of
IA and IIA metals, as well as proprietary silicon and phosphorus-based compounds. Each works on the
same principle of forming a layer of diffusion barrier. By forming this barrier, catalytic coke is reduced.
These techniques are not widely used, as they are relatively expensive.

6.2 Tube Coating

Tube coatings practice the same principle of diffusion barrier but the pyrolysis coils are pre-coated during
manufacture instead of online chemical dosing. These are typically glass ceramic coatings onto the tube
walls.

A variant of this technology had a very successful campaign in a Canadian ethylene plant. The on-stream
time was improved from an average 33 days to over 500 days before decoking was required. This
technology has yet to be commercialized.

6.3 Metallurgy

Interesting development in the field of novel tube design has been achieved in recent years. Two fine
examples are the development of cast-finned tube (Tillack et al, 1998) and tube with mixing element
welded on the internal walls (Kubota Corporation, 2003). Both designs aimed to improve the heat and
mass transfer by novel geometry of the tube internals. In the case of cast finned tubes, very short
residence time can be achieved and hence, improving the selectivity for ethylene production. With
regards to tubes with mixing element, due to the superior heat transfer, the tube metal temperature is
lower for a desired gas temperature. This saves fuel, promoting a longer run length and increasing the
tube-life as carburization is reduced.



10

Figure 5: Cast finned tube (Tillack, 1998) Figure 6: Tube with mixing element (Kubota, 2003)
7 CONCLUSIONS

Pyrolysis furnace is an active research area for improved yields, increased capacity and fuel reduction.
Pyrolysis is a series of free radicals reactions utilized in olefins production. High olefin yields are favored
by short residence time, high temperature and low hydrocarbon pressure. Steam is an inert added to
reduce carburization and the hydrocarbon partial pressure. The reaction product spectrum can be
estimated using empirical methods, rigorous solutions or a combination of both. Coke formation is a
challenge to engineers trying to improve the furnace on-stream factor. Several new technologies have
been developed to mitigate the coke formation challenge.
8 REFERENCES

1. Rice, F.O. and Herzfeld, K.F., J. Am. Chem. Soc., 56, 284 (1934).
2. Jacob, S.M., Gross, B., Voltz, S.E., and Weekman, V.W., A.I.Ch.E. J., 22, 701 (1976).
3. Kivlen, J.A., US Patent 4,904,604 (1990).
4. Dente, M., Ranzi, E. and Goossens, A.G., Computer & Chemical Engineering, 3, 61 (1979).
5. van Goethem, M.W.M., Kleinendorst, F.I., van Leeuwen, C. and van Velzen, N., Computer &
Chemical Engineering, 25, 905 (2001).
6. Shutt, H.C., Chem. Eng. Prog., 55(1), 68 (1959).
7. Zdonik, S.B., Hallee, L.P. and Green, E.J., Manufacturing Ethylene, reprinted from The Oil & Gas
Journal, Petroleum Publishing Co., Tulsa, Oklahoma (1970).
8. Bowen, C.P. and Brewer, J.R., US Patent 5,151,158, assigned to Stone & Webster Engineering
9. Corporation (1992).
10. Kolmetz, K, et al., Refining Technology Conference, Dubai, UAE (2002).
11. Bozzano, G., Dente, M, Faravelli, T. and Ranzi, E., Applied Thermal Engineering, 22, 919 (2002).
12. SK Corporation, URL: http://eng.skcorp.com/product/pycoat/technology/ethylene_plant.html, viewed
on 13 February 2003.
13. Kivlen, J.A., Struth, B.W. and Weiss, C.P., US Patent 3,641,190, assigned to Esso Research and
Engineering Company (1972).
14. Kivlen, J.A. and Koszman, I., US Patent 3,557,241, assigned to Esso Research and Engineering
Company (1971).
15. Sliwka, A, US Patent 4,420,343, assigned to BASF Aktiengesellschaft (1983).
16. Gandman, Z, US Patent 6,228,253 B1 (2001).
17. Grossman, D.G., US Patent 6,358,618 B1, assigned to Corning Incorporated (2002).
18. Benum, L., Spring 2002 AIChE National Meeting, New Orleans, LA, USA (2002).
19. Tillack, D.J. and Guthrie, J.E., Nickel Development Institute Technical Series, # 10,071 (1998).
20. Kubota Corporation, URL: http://www.kubota.co.jp/infra/sc-j/mert/mert-e.html, viewed on 26
February 2003.
21. Froment, G.F. and Bischofff, K.B., Chemical Reactor Analysis and Design, 2
nd
Ed., John Wiley &
Sons, Inc (1990).
22. Kivlen, J.A., US Patent 3,579,601, assigned to Esso Research and Engineering Company (1971).
23. Kniel, L., Winter, O. and Stork, K., Ethylene Keystone to the Petrochemical Industry, Marcel
Dekker, Inc (1980).



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