Simulation of GTL Process in Slurry Bubble Column Reactor

A Thesis
Submitted To The
Department of Chemical Engineering of the University of
Technology in a Partial Fulfillment of the Requirements for the
Degree of Master of Science in Chemical Engineering

By
Ali Adel Nader
B.Sc. in Chemical Engineering 2004

Supervised by
Dr. Khalid A. Sukkar

November / 2008

Ministry of Higher Education &
Scientific Research
University of Technology
Chemical Engineering Department

Simulation of Gas-to-Liquid (GTL)
Process in Slurry Bubble Column Reactor

/

) 2004 (

/ 2008

) 32 (

CERTIFICATION OF THE SUPERVISOR
I certify that this thesis was prepared under my supervision in
a partial fulfillment of the requirements for the degree of Master of
Science in Chemical Engineering at the Department of Chemical
Engineering of the University of Technology

In view of the available recommendation, I forward this thesis
for debate by the Examining Committee.

Signature:
Supervisor
Date: / / 2008

Signature:

Head of Post Graduate Committee
Chemical Engineering Department
Date: / / 2008

CERTIFICATION
We certify that we have read this thesis and as an Examining
Committee examined the student (Ali Adel Nader) in its content and
that in our opinion, it meets the standard of a thesis for the degree of
Master of Science in Chemical Engineering.

Signature:
Name: Dr. Khalid A. Sukkar
(Supervisor)
Date: / / 2008

Signature: Signature:
Name: Dr. Jamal Manee Ali Name: Dr. Wadood T. Mohamed
(Member) (Member)
Date: / / 2008 Date: / / 2008

Signature:
Name:. Dr. Balasim Ahmed Abid
(Chairman)
Date: / / 2008

Approved by the Head of the Chemical Engineering Department

Signature:
Name: Dr. Jamal Manee Ali
Head of Chemical Engineering Department
Date: / / 2008

CERTIFICATION
I certify that this thesis entitled (Simulation of Gas to Liquid
(GTL) Process in Slurry Bubble Column Reactor) was prepared
under my linguistic supervision. It was amended to meet the style of
English Language.

Signature:
Asst Prof. Eyad Shamseldeen
University of Technology
Date: / / 2008

Dedication

To My Family With Love
And Appreciation

Ali

ACKNOWLEDGMENTS

Praise be to Allah Who gave me ability to achieve this
research.

I wish to express my sincere gratitude, and appreciation to
my supervisor Dr. Khalid A. Sukkar for his kind supervision
and useful advice during the work on the research.

My deep thanks go Dr. Jamal Manee Ali the Head of
Chemical Engineering Department, for his encouragement and
providing facilities throughout this work.

I would also like to express my acknowledgment to the
staff of Chemical Engineering Department of the University
of Technology. Also great thanks are due, to the staff of the
Central Library in the University.

To all who helped me in one way or another, I wish to
express my thanks.

And finally my special thanks go to my family for their
support and encouragement.

Ali

I
Abstract

II

ABSTRACT

Gas-to-liquid (GTL) is one of the new processes that are becoming
increasingly important in petroleum industry. This process enables conversion of the
natural gas into very low sulfur content quality middle distillate. The heart of this
process is the slurry bubble column reactor. In the present study a simulation is
developed to describe mass transfer, heat transfer and reaction kinetics in this
reactor.

The model is simulated through derivation of three differential equations to
describe the transport processes that are present in slurry bubble column reactor:

-Mass balance in gas phase
0 (
1
1 1
2
2
) X - Y - St
d
Y d
) Y * (
*) (
-
d
Y d
B

g
OG
=
+
+

-Mass balance in liquid phase
0 exp
1
)
2
2
= + X /) ( C Da ) X - Y ( St
d
X d
B

P (Z) P( L
OL

-Heat balance
0 exp 1 -
1
) ( 2
2
X C /) ( Be Da ) ( - St
d
d
Pe
P p H
= +

The differential equations are solved numerically using finite difference
method. The solution is carried out by designing a numerical simulation program in
Fortran language. The simulator is systematically used to predict the effects of
reactor geometry, superficial gas velocity, catalyst concentration, operation pressure
and inlet HR
2
R/CO ratio on the performance of an industrial scale slurry bubble column
reactor. Two types of catalysts were tested in present model, Cobalt and Iron
Abstract

III

catalysts. The results indicate that, the Cobalt catalyst shows higher conversion rate
of (90%) than that of Iron catalyst (78%). Therefore, the Cobalt catalyst is better for
the Fischer-Tropsch synthesis than Iron catalyst. For both types of catalysts, the
model results show high distribution of solid catalyst along the reactor height. Also,
it was found that the favorable HR
2
R/CO ratio for Cobalt catalyst is about 2, while, for
Iron catalyst it is in the range of 1.5 to 1.7.

On the other hand, the relation between superficial gas velocity and heat
transfer coefficient in slurry bubble column reactor was studied in model
formulation. The results indicate that the heat transfer coefficient increases with
increasing superficial gas velocity and catalyst concentration.

The predictions of the derived model agree well with the experimental and
theoretical data of the literature with an error of 6 % - 9 %.

Contents

I V
UCONTENTS
UPage No.
Acknowledgment .......................................................................................... I
Abstract ........................................................................................................ II
Contents ...................................................................................................... IV
Nomenclature ............................................................................................ VIII
Greek Symbols ............................................................................................ XI
Chapter One: I ntroduction
1.1 Introduction ............................................................................................. 1
1.2 The Aims of this Work ............................................................................ 5
Chapter Two: Literature Survey
2.1 Scope ........................................................................................................ 6
2.2 History of Fischer Tropsch Synthesis FTS .............................................. 7
2.3 Gas to Liquid (GTL) Technology ............................................................ 9
2.3.1 Synthesis Gas Manufacturing ....................................................... 11
2.3.2 Fischer-Tropsch Synthesis (FTS) ................................................. 13
2.3.3 Product Upgrading and Separation ............................................. 16
2.4 Fischer-Tropsch Reactors ...................................................................... 18
2.5 Slurry Bubble Column Reactor ............................................................. 22
2.6 Fischer-Tropsch Catalysts ..................................................................... 25
2.7 Hydrodynamic of Slurry Bubble Columns ............................................ 29
Contents

V
2.7.1 Flow Regime Analysis ................................................................ 29
2.7.2 Gas Hold-Up (ER
g
R) ........................................................................ 31
2.7.3 Operation Pressure ...................................................................... 34
2.7.4 Solid Suspension ......................................................................... 35
2.8 Transport Processes in SBCR ................................................................ 35
2.8.1 Mass Transfer .............................................................................. 35
2.8.2 Heat Transfer ............................................................................... 39
2.9 Fischer Tropsch Mechanism .................................................................. 44
2.9.1 Carbene Mechanism .................................................................... 44
2.9.2 CO-insertion mechanism ............................................................. 45
2.9.3 Parallel mechanism ..................................................................... 46
2.10 Modeling and Simulations ................................................................... 47
Chapter Three: Mathematical Model
3.1 Introduction ........................................................................................... 51
3.2 Reactor Model and Assumptions ........................................................... 52
3.3 Formation of Model Equation ............................................................... 54
3.3.1 Mass Balance for Hydrogen in Gas Phase ................................... 54
3.3.2 Mass Balance for Hydrogen in Liquid Phase ............................... 55
3.3.3 Energy Balance for Hydrogen ....................................................... 57
3.4 Development of Model Equation .......................................................... 58
3.5: Numerical Formulation using (Finite Difference Method) .................. 68
3.5.1 Solution of Mass Balance Equation .............................................. 68
3.5.2 Solution of Energy Balance ........................................................... 71
Contents

VI
3.5.3 Boundary Condition Solution ........................................................ 73
3.6 Parameter Estimation ............................................................................. 74

Chapter Four: Results and Discussion
4.1 Introduction ........................................................................................... 78
4.2 Hydrogen Profile in Liquid and Gas Phase ........................................... 79
4.3 Catalyst Distribution Along the SBCR ................................................. 81
4.4 Temperature Distribution Along the SBCR .......................................... 83
4.5 Superficial Gas Velocity Profile Along The SBCR .............................. 85
4.6 Heat Transfer Coefficient ...................................................................... 87
4.6.1 Effect of Superficial Gas Velocity ............................................... 88
4.6.2 Effect of Catalyst Concentration .................................................. 88
4.7 Syntheses Gas Conversion .................................................................... 91
4.7.1 Effect of Superficial Gas Velocity and Catalyst Concentration .. 91
4.7.2 Effect of Reactor Height .............................................................. 94
4.7.3 Effect of Operating Pressure ....................................................... 95
4.7.4 Effect of Reactor Diameter .......................................................... 97
4.7.5 Effect of inlet ratio ...................................................................... 99
4.8 The Validity of the Present Model ...................................................... 102
4.8.1 Synthesis Gas Conversion .......................................................... 103
4.8.2 Heat Transfer Coefficient .......................................................... 104
4.8.3 Hydrogen Profile in the Gas Phase ............................................ 105
4.8.4 Hydrogen Profile in the Liquid Phase ........................................ 106
Contents

VI I
Chapter Five: Conclusions and Recommendations
5.1 Conclusions ......................................................................................... 107
5.2 Recommendations .............................................................................. 109
References .............................................................................................. 110
Appendix A .......................................................................................... A-1
Appendix B ........................................................................................... B-1
Nomenclature

VI I I
UNOMENCLATURE
Symbol Definition Units
A Across section area of reactor (mP
2
P)
AR
P
Liquid- solid cross section area
a
gasliquid specific interfacial area per unit expanded bed volume

(mP
2
P/ mP
3
P)
aR
H

specific heat transfer area referred to the total reactor volume

(mP
2
P/ mP
3
P)
aR
P
Liquid- solid specific interfacial area (mP
2
P/ mP
3
P)
Be
Dimension less group defined by eq

T He
y P
)
Cp
H -
( Be
w
o R
=

(-)
BR
OC

Bodenstein number of catalyst particles
C
CS
OC
E
L U
B =

(-)
BR
OG

Bodenstein number for gas phase
g g
go
E D
L u
B
OG
=

(-)
BR
OL

Bodenstein number for liquid phase

L L
go
E D
L u
B
OL
=

(-)
CR
g
Concentration in gas phase (mol/mP
3
P)
CR
H
R /CR
H.L
Concentration of hydrogen in the liquid phase (mol/ mP
3
P)
CR
H*
Equilibrium concentration of hydrogen in the liquid phase (mol /mP
3
P)
CR
H.P
Hydrogen concentration at catalyst surface (mol/ mP
3
P)
CR
P
Particles concentration (mol /mP
3
P)
Cp Heat capacity of the liquid-solid suspension (J/ kg K)
L
Cp
Heat capacity of liquid (J/ kg K)
P
Cp
Heat capacity of catalyst (J/ kg K)
Da
Damkohler number

go

L f
u
L E K
Da =

(-)
g
D
Gas phase dispersion coefficient (mP
2
P/ s)
L
D

Liquid phase dispersion coefficient (mP
2
P /s)
H L
D
.

Diffusivity of hydrogen (mP
2
P/s)
P
d
Catalyst particle diameter (m)
Dr

Reactor diameter (m)
Nomenclature

I X
E Specific energy dissipation rate. mP
2
P/ sP
3

A
E
Activation energy (J/ mol)

C
E
Axial dispersion coefficient of the catalyst Particles (mP
2
P /s)
g
E
Gas holdup (-)
L
E
Liquid holdup (-)
Fr
Froude number
g Dr / u Fr
g
=

(-)
g Gravitation constant (m/ sP
2
P)
He Henry coefficient
(Kpa/mP
3
PMol)
h Heat transfer coefficient (W/mP
2
P K )
R
H

Heat of reaction for the overall conversion
of synthesis gas to hydrocarbons
(J/ mol)
I
Molar ratio of hydrogen to carbon
Monoxide at the reactor inlet
(-)
K
Reaction rate constant for hydrogen consumption rate referred to
wt % (Fe or Co) in slurry
(1/ s)
ax
K Effective heat conductivity of suspension (W/m K)
f
K

Frequency factor for hydrogen consumption rate referred to wt %
(Fe or Co) in slurry
(1/s)
0 K
f

Frequency factor for
f
K

(1/s)
H
K

Reaction rate constant for hydrogen consumption rate (1/s)
L
K
Liquid side mass transfer coefficient (m/ s)
P
K

Liquid - solid mass transfer coefficient (m/ s)
L Reactor length (m)
N Mole flow rate (mole/ s)
P Total pressure (Pa)
Pe
Peclet number for heat
ax L
go
K E
L Cp u
Pe =

(-)
R Universal gas constant (J /mol K)
2
H CO
R
+

Synthesis gas consumption rate (-)
2
H
R

Hydrogen reaction rate (-)
Nomenclature

X
H
St

Stanton number for heat transfer
Cp u
L h a
St
go
H
H
=

(-)
g
St

Stanton number in gas phase
go
w
H L g
u He
L T R
a) (K St

=

(-)
L
St

Stanton number in liquid phase
go
H L L
u
L
a) (K St =

(-)
T Temperature K
TR
w
Cooling wall temperature K
g
u
gas velocity (m/ s)
g
U

Superficial gas velocity (-)
go
u

Inlet gas velocity (m / s)
CS
U

Settling velocity of catalyst particle in swarm (m/ s)
U Usage ratio of hydrogen to carbon monoxide (-)
V Volume of reactor (mP
3
P)
g
V

Volumetric gas flow rate (mP
3
P/ s)
P
V
Volume fraction of catalyst in suspension (-)
P
W

Concentration of catalyst in suspension wt% (-)
x Axial coordinate (-)
X
Dimensionless hydrogen concentration in liquid phase (-)
H
X

Conversion of hydrogen (-)
2
H CO
X
+

Conversion of synthesis gas (-)
y
Hydrogen mole fraction in gas phase (-)
Y
Dimensionless hydrogen concentration y /
o
y
(-)
o
y
Inlet hydrogen mole fraction (-)
Nomenclature

XI

UGREEK SYMBOLS
Symbol Definition Units
Dimensionless axial coordinate (-)
Contraction factor eq. (3.137) (-)
*
Modified contraction factor eq.(3.47) (-)

Arrhenius number (-)

P

Liquid solid mass transfer effectiveness factor
(-)

Heat conductivity of suspension ( W/m K )
L

Heat conductivity of liquid ( W / m K )
P
Heat conductivity of catalyst ( W/ m K )

Viscosity of suspension
(kg /m s)
L

Viscosity of liquid
(kg /m s)

Density of suspension
(kg/ mP
3
P)
L

Density of liquid
(kg /mP
3
P)
P

Density of particle
(kg /mP
3
P)
Dimensionless temperature T/TR
w

(-)

Symbol Definition
CFB Circulation fluidized bed
FFB

Fixed fluidized bed
FTS Fischer-Tropsch Synthesis
GTL Gas To Liquid
LAS Linear Alkyl Benzene Sulphonate
SMDS Shell Middle DistillateSynthesis
SMR Steam Methane Reforming
TFB Tubular fixed bed

Chapter One I ntroduction

1
CHAPTER ONE
INTRODUCTION
1.1
GTL is the technology using natural gas to make a clean, versatile
liquid fuel. This is a complementary rather than competitive technology for
the exploitation of stranded natural gas. In the present world of energy
scenario, the supply of oil and other natural resources is limited and not
uniformly distributed [ Dry, 2002; Tiefeng et al.2007].
I ntroduction

Natural gas is available in large quantities and the reserve is not used
to the same extent as crude oil. Although it does have some drawbacks
compared to other fuels, mainly issues dealing with its volume, it promises to
be an increasingly important energy source in the years to come. It is
important to mention here that methane is the principal component of natural
gas currently being used for home and industrial heating as well as for
generation of electrical power. Also, natural gas burns cleaner and produces
fewer pollutants than other fossil fuels. It has the largest heat of combustion
relative to the amount of CO
2
formed. It produces 45% less CO
2

than coal for
a comparable amount of energy, and also emits considerably less NOx and
SOx [De smet, 2000; Laurent et al. 2008].
During the last ten years, there has been a renewed interest in Gas-to-
Liquids (GTL) technology, in which natural gas is converted to liquids useful
as fuels and chemicals feedstock through the Fischer-Tropsch-Synthesis
(FTS). In the gas-to-liquid (GTL) technology, natural gas is converted into a
liquid product containing hydrocarbons and oxygenates. In general, the GTL

2
technology consists of the following three main processes: synthesis gas
manufacturing, Fischer-Tropsch synthesis and product upgrading as shown in
Figure (1.1). In this figure, the first unit (reactor) represents the synthetic gas
production process (H
2
Synthesis gas is a mixture of carbon monoxide (CO) and hydrogen
(H
and CO), while, the second reactor (slurry bubble
column reactor) represents the Fischer-Tropsch process and then, the final
process includes products separation [Godley et al. 2000; Tiefeng et al.2007].
2
The basic reaction is:
), which can be obtained from any carbon containing feedstock, such as
natural gas. On the other hand, the Fischer-Tropsch reaction represents the
heart of process, because it determines the product types and distributions in
GTL technology.
nCO+(2n+1) H
2
C
n
H
2n+2
+nH
2
O H
R
The highly exothermic Fischer-Tropsch reaction converts synthesis
gas into a large range of linear hydrocarbons including gasoline, diesel and
wax [Hindermann et al. 1993; Van der Laan and Beenackers, 1999;
Chowdhury et al.2006].
=-39.4 kcal/mol

Fig. (1.1) : Gas-to-liquid process steps and reactors.

3
The Fischer-Tropsch reaction can be carried out in different kinds of
reactor vessels such as [Jager et al., 1990; Sie, 1998]:
-Slurry bubble column reactors with internal cooling tubes.
-Multi-tubular fixed bed reactor with internal cooling.
-Circulating fluidized bed reactor with circulating solids, gas recycle and
cooling in the gas/solid recirculation loop.
-Fluidized bed reactors with internal cooling.
Currently, there is much interest in using slurry bubble column reactors for this
process because they have the following advantages in comparison with other
multiphase contactors:-
1. They are cheap to run.
2. They are inexpensive to build.
3. They need little maintenance due to simple construction and operation and
cause no problems with sealing due to the absence of moving parts.
4. They have excellent heat transfer properties and, hence, easy temperature
control.
A slurry reactor is a vessel containing the catalyst suspended in a liquid
hydrocarbon. The syngas is brought in at the bottom of the vessel and
bubbled up through the reactor. As the bubbles contact the catalyst, the
Fischer-Tropsch reaction takes place. On the other hand, the hydrodynamics
parameters in the reactor such as: gas holdup, bubble rise velocity, particles
size (catalyst size), pressure drop, and liquid circulation, are complicated and
interact in slurry bubble column and determine the overall transport processes
in such type of reactors. Therefore, the understanding of them is important to
achieve the high reaction rate needed for commercial GTL conversion.
Figure (1.2) shows a schematic representation of interrelations of liquid and
apparatus properties with flow regimes and bubble size in bubble columns.
Additionally, it shows how these factors influence holdup and liquid flow

4
patterns and therefore mass and heat transfer [Jager, 1997; Calemma et al.
2005; Alvarea and Al-Dahhan, 2006].

Fig. (1.2): Variables that affect SBCR performance [Alvarea and Al-
Dahhan, 2006].

However, the design of bubble columns is very difficult, principally because
the complex hydrodynamic behavior of such units, so that, numerous
investigators have studied the slurry bubble column experimentally and
prepared a wide range of hydrocarbons by using different types of catalysts
through GTL process [Joan et al. 1999; Krishna and van Baten, 2003; Ahmad
et al. 2008; Guillou et al. 2008]. On the other hand, few theoretical works
were developed in literature to predict the design parameters, mass transfer,
heat transfer, reaction kinetics and catalyst performance in slurry bubble
column under industrial operating conditions. Therefore, there is a real need

5
to develop a comprehensive theoretical simulation to describe the transport
processes in slurry bubble column.
1.2
The aims of the present study are: -
The Aims of this Work
1- To develop a comprehensive theoretical simulation by deriving mathematical
models, which are capable of predicting the main parameters of hydrodynamic,
reactor geometry, superficial gas velocity, catalyst concentration, operation
pressure, inlet H
2
2- To study the catalyst performance (the general types are Co and Fe catalysts) in
Fischer-Tropsch reaction under different operating conditions.
/CO ratio, mass, heat and reaction in slurry bubble column that
are conducted in GTL process.
3- To compare the theoretical results with experimental and theoretical results in
literature over a wide range of operating conditions in order to test the validity
of the present models.

Chapter Two Literature Survey

6
CHAPTER TWO
LITERATURE SURVEY
2.1
Gas to Liquid (GTL) process is an umbrella term for the process that
can create liquid hydrocarbon fuels from a variety of feed stocks. The
conversion of natural gas into liquid fuels is an attractive option to
commercialize abundant gas reserves. GTL, with virtually unlimited markets,
offers a new way to unlock large gas reserves, complementary to other
traditional technologies such as Liquefied-Natural-Gas and pipelines. GTL
has the potential to convert a significant percentage of the world estimated
and potential gas reserves which today holds little or no economic value
[Heng and Idrus, 2004; Levenspeil, 2005; Tiefeng et al., 2007].
Scope
In essence, GTL uses catalytic reactions to synthesize complex
hydrocarbons from carbon monoxide and hydrogen. There has been
significant improvement in reactor design and technology over the last
decade. However, many reactors have been used in GTL process such as:
fixed bed reactor, fluidized bed reactor, circulating fluidized bed reactor, and
slurry bubble column. In recent years, the slurry bubble column reactor is
regarded as the main reactor type that is used in GTL technology. Therefore,
the design and construction of such reactor depends on the transport
processes that occur in it. The main transport processes that determine the
performance of slurry bubble column reactor are: hydrodynamic, mass
transfer, heat transfer, and reaction kinetics [Sie, 1998; Saib et al. 2006].
Therefore, in this chapter, the literature review on GTL technology,
reactor types, catalyst types, operating conditions, hydrodynamic
characterizes, mass transfer, and heat transfer are presented.

7
2.2
The FT process had a lively history of about eight decades since its
discovery in Germany by Franz Fischer and Hans Tropsch in the 1920.
During world war-II, two processes for converting coal to liquid transport
fuels were tried in Germany. The first, direct liquefaction (Bergius process)
involves the direct catalytic hydrogenation of coal to liquids which are
further refined. In contrast, indirect liquefaction involves conversion of coal
by partial oxidation in the presence of steam to yield syngas, which after
purification reacts catalytically to form liquid hydrocarbon fuels. Both
Bergius and FT were discontinued after the war because of easy availability
of petroleum. However, FTS was started on a big scale at Sasol Company in
South Africa in the 1950 [Xing et al. 2006]. Sasol, a world-leader in the
commercial production of liquid fuels and chemicals from coal and crude oil,
started up its first FT plant (Sasol I) in Sasolburg, South Africa. The plants
capacity is 6 million tonnes /yr of FT products from coal [Dry, 1982].
History of Fischer-Tropsch Synthesis (FTS)

Sasol Company submitted three plants to produce hydrocarbons
successfully based on FTS (Sasol I, Sasol II and III) which came on line in
1980 and 1982, respectively. These plants are located in Secunda, South
Africa. Sasol II and III all have circulating fluid bed (CFB) reactors. From
1995 to 1999, these second generation CFB reactors were replaced with eight
fixed fluid bed (FFB) reactors [Van Nierop et al. 2000].

In the early 1990, two other FT plants came on line. Then, in 1992 the
Mossgas plant, which converts natural gas to FT products using high
temperature process and Iron catalyst, started up in South Africa [Dry, 2002].
This plant produces 1 million tonnes /yr of FT products including motor

8
gasoline, distillates, kerosene, alcohols and LPG. Additionally, Shell
commissioned a plant in 1993 in Bintuli, Malaysia, using the Shell Middle
Distillate Synthesis process, which is essentially enhanced FT synthesis. This
plant produces 500,000 tonnes /yr (12,000 BPD) of FT products from natural
gas using a Cobalt catalyst [Senden, et al. 1992; Haid, et al. 2000].

In early 2000, Sasol studied the feasibility of replacing coal with
natural gas. Therefore, they were built a network of natural gas pipelines in
2004. Sasol plans to use the natural gas as a supplementary feedstock at
Secunda and as a replacement feedstock for the coal in Sasolburg. A brief
history of FTS and the related events during the last century are given in
Table (2.1) [Dry, 2002; Jager, 2003].

Table (2.1): Brief history of commercial Fischer-Tropsch synthesis [Dry, 2002].

1902
Methanation reaction with Syngas over Ni catalyst.

1923
Franz Fischer & Hans Tropsch reported hydrocarbon synthesis at
higher pressure using Co, Fe Ru catalysts.
1936
4 FT Plants commissioned in Germany

1950
Hydrocol plant operated for sometime based on Fixed Fluidized Bed
rector with Fe-K catalyst, Cap. 5000 bpd at Brownsville, Texas.

1950-
1953
I n Germany, Koelbel set up 1.5 m dia. slurry phase reactor at
Rheinpreussen and operated it successfully
1955
German plants were shut down after brief operation using petroleum
residue. I nterest in FTS declined worldwide, when oil deposits were
discovered in abundance in the Middle East.
1970-
1980
Renewed interest in FTS due to increased oil prices and fear of oil
shortage
1990s
Further revival of FTS or GTL due to discoveries of huge stranded
natural gas reserves and requirement for clean fuels.
1992
First natural gas based plant (Mossgas) set up in S.Africa, based on
Sasols Synthol reactor.
1993
Shell Middle Distillate Synthesis (SMDS) plant (12,500 bpd) was set up
in Malaysia (natural gas based) using TFB reactor and Co catalyst

9
2.3
The FischerTropsch synthesis (FTS) is an important industry process
for the conversion of syngas (CO and H
Gas to Liquid (GTL) Technology
2

) derived from coal or natural gas
into hydrocarbons and oxygenates. As an important type of FTS reactors,
slurry bubble column reactor (SBCR) attracts more and more interest because
of its advantages relative to other types of reactors. These advantages mainly
include: (1) nearly isothermal operation, (2) small solids particle size that
results in good productivity, (3) good interface contacting, (4) low pressure
drop, and (5) low construction and operation costs [Godley et al. 2000; Ding
et al. 2004; Xing et al. 2006].
The strategy for GTL depends on the location of methane, demand for
products, construction costs, the economic and geopolitical stability etc.
Where natural gas is extracted along with crude oil, there may not be buyers
for the gas along with the crude in which case it becomes a liability and the
gas may be available at cheap cost. There is the other case where the gas
extracted is in abundance and the utilization is poor. In such cases
transportation through pipeline or conversion to LNG is expensive
alternatives. At present in many fields, the excess gas is re-injected into the
well and as the oil reserve gets depleted, an increasing amount of gas will be
recycled per barrel of oil produced. In a free market economy, the
profitability of these facilities will depend on the selling price of the product
and the cost of alternative technologies, both of which may fluctuate
significantly over a short period.
From an economic view point, Fischer-Tropsch derived fuels are easily
transported in standard vessels or pipelines relative to natural gas and LNG.


10
Therefore, the FT process of converting natural gas to marketable
liquid hydrocarbons comprises three main steps as shown in Figure (2.1):
a) Synthesis gas, a mixture of CO and H
2
b) Fischer Tropsch Synthesis (FTS) .
(syngas) production .
c) Product Upgrading and Separation

Fig. (2.1): The main three processes present in Fischer-Tropsch synthesis
[Tiefeng et al. 2007].

11
In FTS, the feed gas will be treated initially to remove the sulphur
compounds which otherwise poison the catalyst, in addition to causing
corrosion and environmental problems.
Many authors [Rostrup, 2000; Vosloo, 2001; Abbott and Crewdson,
2002] have recommended autothermal reforming or autothermal reforming in
combination with steam reforming as the best option for syngas generation.
This is primarily attributed to the resulting H
2
/CO ratio and the fact that there
is a more favorable economy of scale for air separation units than for tubular
reactors (steam methane reforming - SMR). If the feedstock is coal, the
syngas is produced via high temperature gasification in the presence of
oxygen and steam. Depending on the types and quantities of FT products
desired, either low temperature (200240C) or high temperature (300
350C) synthesis is used with either an Iron or Cobalt catalyst. Fischer-
Tropsch Synthesis temperatures are usually kept below 400C to minimize
CH
4

production. If maximizing the diesel product fraction, a slurry reactor
with a cobalt catalyst is the best choice. The FT reactors are operated at
pressures ranging from 10-40 bar (145580 psi).
2.3.1 Synthesis Gas Manufacturing
In GTL technology, FT conversion process is employed which requires
a specific molar ratio of hydrogen depending upon the product. One or more
of several processes, working in parallel, in a combined mode or with the
addition or extraction of hydrogen, can achieve the appropriate syngas
composition ratio. In an FT complex the syngas generation accounts for 60-
70% of the capital and running costs of the total plant. Reduction of the
synthesis gas costs could also be accomplished by a decrease in steam/carbon
and oxygen/carbon ratios in the feedstock [Basini, and Piovesan, 1998].

12
Xing et al. (2006) and Chowdhury et al. (2006) compared economical
evaluations of steam-CO
2
reforming, autothermal reforming, and combined
reforming processes. They concluded that combined reforming has the lowest
production and investment costs at a H
2
Synthesis gas can be obtained by steam reforming or (catalytic) partial
oxidation of fossil fuels: coal, natural gas, refinery residues, biomass or
industrial off-gases. The composition of syngas from the various feedstocks
and processes is given in Table (2.2)
/CO ratio of 2.

Table( 2.2): Synthesis gas composition of different feedstock [De smet, 2000].
Feedstock Process
Component (vol%)
H
2
CO CO
2
Other
Natural gas, steam SR 73.8 15.5 6-6 4-1
Natural gas, steam, CO CO
2

2
52.3 26.1 8-5 13-1 SR
Natural gas, O
2
, steam, CO ATR
2
60.2 30.2 7-5 2-0
Coal/heavy oil, steam Gasification 67.8 28.7 2-9 0-6
Coal, steam, oxygen Texaco gasifier 35.1 51.8 10-6 2-5
Coal, steam, oxygen
Shell/Koppers
gasifier
30.1 66.1 2-5 1-3
Coal, steam, oxygen Lurgi gasifier 39.1 18.9 29-7 12-3

In reforming, the feed stream is passed over a Ni-based catalyst
together with H
2
O and/or CO
2
CHR
4
R +HR
2
RO CO +3HR
2
R H=226 kJ /mole

13
In general, large furnaces are used, inflicting large capital investments.
The endothermicity of the steam reforming process is compensated by the
addition of oxygen in the autothermal reforming process. The synthesis gas
from industrial steam reformers has a high H
at high temperatures (1073-1173 K) and
medium pressures (10-30 bar). Steam reforming and oxy-steam reforming (or
so-called autothermal reforming) hold the leading positions among the
commercial processes of synthesis gas production in the synthesis of
methanol and ammonia. Steam reforming of methane is highly endothermic:
2
/CO ratio (H
2
/CO=3-7 and
CO/CO
2
In partial oxidation, the feed stream is mixed with oxygen and steam
and fed to a high temperature flame (1573-1773 K). The feed is partially
combusted followed by endothermic reforming steps and the water-gas shift
reaction. The synthesis gas from industrial partial oxidation has a low H
=0.3-1.5).
2
/CO
ratio (H
2
/CO=0.5-2 and CO/CO
2
In the catalytic partial oxidation a catalyst takes over the function of
the flame in the partial oxidation. The advantages of the catalytic partial
oxidation of methane over steam reforming of methane are the low
exothermicity of the process and the high reaction rates, leading to significant
smaller reactors [De smet, 2000]:
=5-15).
CH
4
+1/2 O
2
CO +2H
2

H=-22 kJ
/mole
2.3.2 Fischer-Tropsch Synthesis (FTS)
In the second step of the GTL process, syngas is converted into
paraffinic and olefinic hydrocarbons of varying chain length. The reaction
occurs in the slurry bubble column reactor (SBCR). GTL can also produce
methanol and DME. FTS typically uses Iron or Cobalt based catalysts. The
process takes place at moderate temperature (200-300
o

C) and moderate
pressure (10 40 bar). [de Swart et al. 1997; Song et al. 2003; Fernandes and
Fabiano, 2005; and Fernandes, 2006].


14

The basic reaction is:
nCO+(2n+1) H
2
C
n
H
2n+2
+nH
2
O H
R

=-39.4 kcal/mol
(Paraffin's)
Other reactions also take place in the process, resulting in the formation of
olefins and alcohols; besides, there are some side reactions.

n CO +2nH
2
C
n
H
2n
+nH
2
n CO +2nH
O
(Olefins)
2
C
n
H
2n+1
OH +(n-1)H
2

O
(Alcohols)
Much attention is focused on developing catalysts with appropriate
selectivity and physical properties. Catalyst selectivity, syngas composition
and process conditions (principally temperature) govern the product
distribution and the limit of the paraffinic chain length. The temperature,
pressure and catalyst determine whether light or heavy hydrocarbons are
produced. For example, high temperature process using Iron catalyst at about
340
o
C mainly produces gasoline and chemicals like alpha olefins. On the
other hand, the low temperature process using either Iron or Cobalt based
catalyst at about 230
o

C mainly produces waxes. Cobalt based catalyst is
preferred over Iron based due to its high activity and long life [Vosloo,
2001].
The exothermic nature of the Fischer-Tropsch reaction combined with
the high activity of the Cobalt catalyst makes the removal of heat from the
reactor of critical importance. The wax and hydrocarbon mixture produced

15
by the low temperature FT process consists of linear paraffins with a small
fraction of olefins and oxygenates. The hydrogenation of olefins and
oxygenates and the hydrocracking of wax to naphtha and diesel is done under
relatively mild conditions [Zhou et al. 2003; and wan et al. 2006].
The exact FT mechanism is complex and it can be described in a simplified
manner in the following steps:
1) Initiation or C
1
2) Hydrocarbon chain growth by successive insertion of the C
compound formation.
1
3) Chain termination by: (a) desorption of unsaturated surface species, and
(b) hydrogenation and desorption of saturated species.
.

The types of catalysts employed in syngas conversion are shown in
Table (2.3). FT process typically involves the recycle of unconverted gases to
the reactor, CO
2
removal from the recycle loop and dehydration of the
recycle gas. In some cases, the process separates H
2
for using in the product-
upgrading unit. The recycle gas may be used as fuel gas. In addition to
distillates, Fischer-Tropsch GTL plants can also produce a range of specialty
products, such as n-paraffins (C
10
-C
13

range), a feedstock used in the
detergent industry for the production of linear alkyl benzene sulphonate
(LAS), one of the worlds most widely used surfactants. Some plants
however, may not produce paraffin's suitable for LAS and suitability will
depend on GTL catalyst selection and process conditions.
Table (2.3): Potential FT catalysts.

Source of carbon Catalyst Property
Any source Ni Methanation

16
Carbon rich (coal) Fe WGS with CO
2
production
Hydrogen rich (natural gas) Co
Highly active and gives linear
hydrocarbons
Different carbon sources Ru Very active but expensive

2.3.3 Products Upgrading (Separation)
Conventional refinery processes can be used for upgrading of Fischer-
Tropsch liquid and wax products. A number of possible processes for FT
products are: wax hydrocracking, distillate hydrotreating, catalytic reforming,
naphta hydrotreating, alkylation and isomerization [Choi et al. 1996; Zhou et
al. 2003].
GTL-Fischer-Tropsch plants produce many of products that are
significantly different from that produced from a typical crude oil refinery as
shown in Figure (2.2). GTL plants are capable of producing many of
products with highly desirable properties, including LPG, gasoline, diesel
fuel, jet fuel, petrochemical naphtha and waxes. It is important to mention
here that the diesel fuel represents the main product of GTL products. On the
other hand, all GTL products are sulfur free with very low aromatic. These
products meet the environmental requirements for clean fuels.


17

Fig. (2.2): Comparison of the GTL barrel vs. conventional refined barrel
[Godley et al. 2000].
In GTL process, the final product stream usually consists of various
fuel types. The definitions and conventions for the composition and names of
the different fuel types are obtained from crude oil refinery processes and are
given in Table (2.4).

Table (2.4): Conventions of fuel names and composition [Kroschwitz,
and Howe, 1996].
Name Synonyms Components
Fuel gas C1 - C2
LPG C3 - C4
Gasoline C5 - C12
Naphtha C8-C12
Kerosene J et fuel C11-C13
Diesel Fuel oil C13-C17
Middle Distillates Light gas oil C10-C20
Soft Wax C19-C23
Medium Wax C24-C35

18
Hard Wax C35+

The produced diesel fraction by GTL process has a high cetane number
resulting in superior combustion properties and reduced emissions as shown
in Table (2.5). New and stringent regulations may promote replacement or
blending of conventional fuels with sulfur and aromatic free FT products
[Fox, 1993 and Gregor, 1990].
On the other hand, many products besides fuels can be manufactured
with Fischer-Tropsch in combination with upgrading processes, for example,
ethene, propene, olefins, alcohols, ketones, solvents, specialty waxes, and so
forth. These valuable by-products of the Fischer-Tropsch process have higher
added values, resulting in an economically more attractive process economy.
According to Table (2.5) the value of Fischer-Tropsch products used as
blending stocks for transportation fuels (diesel) is higher than that of crude
oil derived fuels due to their excellent properties. These superior properties of
GTL fuels are attracted to the clean feedstock which is the natural gas [Saib
et al. 2006; Tiefeng et al. 2007].

Table (2.5): The comparison between conventional and GTL diesel [Sie, 1998].

Diesel Property Conventional GTL
Cetane number 45 74
Sulfur, ppm 330 >10
Specific Gravity 0.84 0.78
Flash Point, C 71 81
Cloud Point, C -17 -12


19
2.4
The Fischer Tropsch synthesis section consists of: FT reactors, recycle
and compression of unconverted synthesis gas, removal of hydrogen and
carbon dioxide, reforming of methane produced and separation of the FT
products. The most important aspects for development of commercial
Fischer-Tropsch reactors are the high reaction heats and the large number of
products with varying vapor pressures (gas, liquid, and solid hydrocarbons).
The main reactor types which have been proposed and developed after 1950
are [Jager, et al. 1990; Jager, 1997; and Sie, 1998; Tiefeng et al. 2007]:
Fischer-Tropsch Reactors

1. Three-phase slurry bubble column reactors with internal cooling tubes
Sasol; Energy International, Exxon, see Figure (2.3a).
2. Multitubular fixed bed reactor with internal cooling (Sasol; SMDS: Shell,
see Figure (2.3b).
3. Circulating fluidized bed reactor with circulating solids, gas recycle and
cooling in the gas/solid recirculation loop (Sasol), Figure (2.3c).
4. Fluidized bed reactors with internal cooling (Sasol), Figure (2.3d).

Table (2.6) summarizes the general types of multiphase reactors that
are used in Fischer Tropsch synthesis. The same table shows the historical
development of such type of reactor besides the catalyst type and operation
mode. On the other hand, Figure (2.3) shows the main reactors types of FTS.


20

Fig. (2.3) Possible reactors for Fischer-Tropsch synthesis: a- Slurry
bubble column reactor; b- Multitubular trickle bed reactor;
c- Circulating fluidized bed reactor; d- Fluidized bed reactor
[J ager, 1990; Sie et al., 1998].
Many authors studied different types of FT reactors. De swart, (1996)
modeled a Cobalt-based FT process both in trickle bed reactors and in slurry
bubble column reactors. The major conclusion was that 10 multitubular
trickle bed reactors (6 m diameter, 20 m height) or 4 slurry reactors (7.5 m
diameter, 30 m height) can produce 5000 tonnes of middle distillates (C5) per
day. Mainly due to the high heat transfer rates occurring in the slurry system,
the capital costs of this system reportedly can be 60 % lower than that of the
multitubular system. Jager, (2003) stated that the costs of a single 10,000
bbl/day slurry reactor system is about 25 % of that of a tubular fixed bed
reactor.


21

Table (2.6): GTL reactors in commercial practice.
Reactor
Advantages/Disadvantages
Features
Tubular Fixed
Bed (TFB)

Relatively simple design, expensive
construction due to large No. of
tubes. Temp. gradient causes
sintering. Gives high pressure drop.
Catalyst replacement a major
undertaking. Fe catalysts, which are
inherently unstable, have to be
replaced periodically. Co catalysts
can be regenerated
TFB was used in Sasol I and in
Shell plant catalyst pellets are
packed in the tubes and the
cooling medium flows around
the outside of the tubes, similar
to a shell & tube exchanger.

22
Fluidized Bed
i) Circulating
Fluidized Bed
(CFB)

Better heat removal and
temperature control. Less pressure
drop problems. Physically complex
and suspended in a complex
structure. Circulation of large
tonnage of catalyst results in
considerable recycle gas
compression with added costs.
Operates normally at higher
temperature

Used in Sasol I & I I (Synthol
Reactor). Fused I ron catalyst is
circulated with syngas through
a complex reactor / hopper /
standpipe system and heat is
removed as steam through coils.
The reactor needs a complex
support system to cope with the
circulating catalyst loads and
temperature differences.
ii)Fixed
Fluidized Bed
(FFB)

I mproved stability and less catalyst
consumption. Less erosion than
CFB reactor Product must be
volatile at the reaction conditions
since non-volatile hc. may decrease
bed fluidization.
Used in Sasol I I & I I I (SAS
Reactor) Basically a vessel with
a gas distributor at the bottom
and heat exchange tubes
suspended in the F.B Catalyst
inventory and product
selectivity (low M.W) is same as
Synthol reactor.

Slurry Phase
Bubble
Column
Reactor
(SBCR)

Simple design and construction.
Ease of addition and removal of
catalyst. Good heat transfer and
temperature control. Good
selectivity, Low pressure drop. I deal
for high boiling products Potentially
high capacity (10,000-20,000 BPD).
I mproved catalyst economy and low
turn down ratio. Slurry - phase
reactor is about 45% cheaper in
construction TFB.
Most accepted future reactor
for GTL. Syngas is bubbled up
through a slurry, made of
paraffinic high boiling liquid
with the catalyst suspended in
50-80 m.

2.5
In general, Fischer Tropsch reactors for large-scale conversion of
natural gas to liquid hydrocarbons can be divided into three classes:
(a) fluidized bed reactor, (b) tubular fixed bed reactor (TFBR), and (c) slurry
bubble column reactor (SBCR). SBCR has been found to be the most suitable
Fischer-Tropsch reactor. Figure (2.4) shows the general arrangement of
slurry bubble column. In this reactor preheated synthesis gas is fed to the
Slurry Bubble Column Reactor

23
bottom of the reactor and bubbled up through the reactor. As the bubbles
contact the catalyst, the Fischer-Tropsch reaction takes place.

The hydrodynamics in the reactor are complicated but understanding
them is important to achieving the high reaction rate needed for commercial
GTL conversion. To achieve a high mass transfer rate, the goal is to have
good gas bubble distribution throughout the reactor with a large interfacial
surface area between bubbles and the liquid hydrocarbon media.

The Fischer-Tropsch reactions are exothermic, therefore, the heat
generated is removed through the reactor's cooling coils where steam is
generated for use in the process. Heat transfer coefficients up to 1000 W/m
2
De Swart et al. (1996) compared the multitubular fixed bed reactor
with the slurry reactor operating in either the homogeneous or heterogeneous
regime. With a maximum weight of 900 ton/reactor as a limiting criterion,
the number of reactors needed for a plant capacity of 5000 ton/day was found
to be 10 for the multitubular fixed bed reactor, 17 for the slurry reactor
operating in the homogeneous regime, and 4 for the slurry reactor operating
in the heterogeneous regime. Krishna and Sie, (2000) compared the several
reactor types for the Fischer-Tropsch synthesis process and concluded that
the slurry reactor is the best reactor type for large-scale plants. For the
K
can be obtained in this type of reactor [Tiefeng et al. 2007]. Heat transfer
coefficient increases with increasing gas velocity and with increasing solids.
Because of the churning nature of the slurry-gas bubble interaction, the slurry
phase is well mixed and tends to be isothermal. This gives better and more
flexible temperature control [Jager and Espinoza, 1995]. Online catalyst
removal and additions can also be done without difficulty in SBCR whereas
in TFBR catalyst has to be replaced from time to time.

24
specific case of conversion of syngas into a relatively heavy Fischer-Tropsch
synthesis product Deckwer (1993) mentioned that under specific conditions,
such as important heat removal, BCRs and SBCRs could be used for fast-
reaction processes. Thus, BCRs and SBCRs appear also to be suitable for
conducting highly exothermic fast reaction processes, which are widely used
in the chemical, biochemical, petrochemical applications.

Therefore, the advantages of SBCR type over both the fixed and fluidized-
bed reactors are summarized as follows [Dziallas et al. 2000; Fleisch et al.
2002; Wang et al. 2006; Alvarea and Al-Dahhan, 2006]:

1- The capability for processing gas of a low H
2
2- High conversion can be achieved in a single pass.
/CO ratio. CFBR and FBR
require hydrogen upgrading to avoid carbon deposition.
3- Formation of nonvolatile waxy hydrocarbons does not impair SBCR
performance, whereas the production of waxy hydrocarbons causes
catalyst agglomeration in a CFBR and pore filling in a FBR.
4- The catalyst in a SBCR does not require high crush strength, but, catalysts
in a FBR require high crush strength, and those in a FBR require high
resistance to attrition.
5- A spatially uniform temperature profile can be achieved in the SBCR
because the liquid carrier provides excellent heat transfer. This prevents
the hot spots which accelerate carbon deposition in fixed bed reactors.


25

Fig. (2.4): Fischer-Tropsch slurry bubble column reactor [Tiefeng et al. 2007].

2.6
The most common Fischer-Tropsch catalysts are group VIII metals
(Co, Ru, and Fe). Iron catalysts are commonly used, because of their low
costs in comparison to other active metals. Most early FT catalysts were
prepared with precipitation techniques. Novel catalyst preparation methods
are sintering and fusing metal oxides with desired promoters. Alkali-
promoted Iron catalysts have been applied industrially for the Fischer-
Fischer-Tropsch Catalysts

26
Tropsch synthesis during many years [Rao et al. 1995; Zhou et al. 2003; and
Brumby et al. 2005].
These catalysts have a high water gas shift activity; this high water-gas
shift activity causes these catalysts to be flexible towards the H
2
/CO feed
ratio of the synthesis gas. This allows the utilization of a large variety of
feedstocks, while every syngas manufacturing technology can be applied.
Because coal results in a syngas with a low H
2
The application of Fe-based catalysts in the production of heavy wax is
limited. This is mainly due to its tendency to form elemental carbon, causing
deactivation of the catalyst. Moreover, water, which is produced in large
quantities as side product, has an inhibiting effect on the activity, resulting in
low conversions per pass. The latter effect results in large recycle streams
after water removal.
/CO ratio, this feedstock can
only be used in combination with a Fe-based catalyst. However, the water-
gas-shift activity of the catalyst also results in a low carbon efficiency of the
gas-to-liquid process. [Kolbel and Ralek, 1980; Jager et al.1995].
On the other hand Cobalt catalysts give the highest yields and longest
life-time and produce predominantly linear alkanes. The water-gas shift
activity of Co-based catalysts is low. The Cobalt is generally poorly
dispersed on metal oxide supports and Ru, Re, or Pt promoters are applied to
prevent catalyst deactivation by carbon formation or oxidation. Compared to
Fe-based catalysts, olefins tend to reenter the chain growth process by
readsorption on Co-based catalysts, increasing the selectivity towards heavy
hydrocarbons. Disadvantages are the high costs of Cobalt and low water gas
shift activity. Therefore, Cobalt catalysts are viable for natural-gas based
Fischer-Tropsch processes for the production of middle distillates and high-
molecular weight products. Cobalt catalysts are not inhibited by water,
resulting in a higher productivity at a high synthesis gas conversion

27
[Tavasoli, 2005; Bartholomew et al. 2006]. Table (2.8) shows the comparison
between the two types of catalysts that are used in GTL plant.

Table (2.8): General Fischer-Tropsch catalyst characteristics.

I ron (Fe) Cobalt (Co)
Short life (limited to eight weeks)
Higher conversion rate and a longer
life (over five years)
Low cost Expensive (exotic promoters )
Generally preferred for coal-based
syngas
Generally preferred for natural gas-
based syngas
Precipitated / fused Support (Al
2
O
3
, SiO
2
, TiO
2
)
Syngas ratio H
2
Syngas ratio H /CO =1.5
2
/CO =2
By product H
2
By product H /CO / steam
2
O / steam
I nhibited by water Not inhibited by water
High water gas shift activity Low water gas shift activity
Selectivity to olefins Produce paraffin's in the diesel range
Higher molecular weight products
(higher alpha)
Lower molecular weight products
(lower alpha)

On the other hand Ruthenium is a very active but expensive catalyst
for the Fischer-Tropsch synthesis relative to Co and Fe. At relatively low
pressures (P < 100 bar) ruthenium produces much methane, while, at low
temperatures and high pressures, it is selective towards high molecular
waxes. The catalyst is active in its metallic form and no promoters are
required to stabilize its activity. However, the high price of ruthenium
excludes its application on industrial scale and the use of Ru-based catalysts

28
for the Fischer-Tropsch synthesis is limited to academic studies [Ding et al.
2004].
Cobalt catalysts are usually supported on metal oxides due to the
higher Cobalt price and better catalyst stability. These catalysts consist of
1220 wt% Cobalt, a second metal promoter (Ru or Re), an oxide promoter
(such as lanthana, zirconia, or alkali oxide), and a support (alumina, silica, or
titania). These three support materials were selected on the basis for most of
the patents assigned to many companies: Gulf/Chevron (alumina), Exxon
(titania), Shell (silica), and Statoil (alumina). [Pedrick, 1993; Tavasoli, 2005;
Sadaghiani et al. 2007]. The activity varied in the following order Al
2
O
3
>
SiO
2
>TiO
2

as shown in Figure (2.5).
Higher porosity modified titania supports were obtained and used to
produce Co Fischer-Tropsch catalysts. While the production of high surface
area supports may have been successful, these catalysts are probably only
good for fixed-bed reactor applications. The binders are combined with
titania in an extrusion process suitable for making large catalyst pellets not
suitable for slurry bubble column application. Grinding these pellets in order
to produce a catalyst with a suitable particle size distribution for slurry
bubble column application would result in a catalyst with low attrition
resistance.[ Saib et al. 2006]
Jothimurugesan et al. (2000) showed that, the type binder or binder-
and-precipitated, and the content of SiO
2
incorporated into Iron catalysts
have significant effects on catalyst attrition property. They reported that the
catalyst with 1214 wt. % binder SiO
2


29
In general Cobalt catalysts may be regenerated by calcinations at high
temperatures (burning off of the carbon residues) followed by reduction.
[Soled et al.1995].
exhibited good attrition resistances.
Pham et al. (2000) reported that the addition of silica as the binder improved
the attrition resistance of the Iron catalyst.

Fig. (2.5) Support effect on FTS over Cobaltbased catalysts in FBR and
SBCR [Yang et al. 2004].

Compared with SiO
2
, the addition of Al
2
O
3
facilitates the
adsorption of H
2
, but significantly suppresses the CO adsorption. It is well
known that strong surface basicity can promote CO adsorption and
suppress H
2
adsorption. [Yang et al. 2004; Wan et al. 2006]. Dry, (2002)
reported that more K was required when acidic compounds, e.g., SiO
2
or
Al
2
O
3
were present. In other words, the acidic SiO
2
or Al
2
O
3
can
combine with the basic K promoter, forming the strong K-SiO
2
or K-
Al
2
O
3
2.7
interaction. This interaction could decrease the effective potassium
content and further weaken the surface basicity.
The performance of multiphase reactors (i.e SBCR) is determined by
their hydrodynamic characteristics. It is well known that the transport
processes and reaction kinetic are function to the hydrodynamic parameters
such as: superficial gas velocity, gas holdup, flow pattern, pressure drop,
height / diameter ratio, sparger design, solid holdup and solid distribution in
Hydrodynamic of Slurry Bubble Columns

30
the reactor. Therefore the present section will focus on the most important
hydrodynamic parameter that affects the performance of SBCR directly.

2.7.1 Flow Regime Analysis
When a column filled with a liquid is sparged with gas the bed of
liquid begins to expand as soon as gas is introduced. As the gas velocity is
increased the bed height increases almost linearly with the superficial gas
velocity U
g
, provided the value of U
g
stays below a certain value U
trans
When the U
. This
regime of operation of a bubble column is called the homogeneous bubbly
flow regime. The bubble size distribution is narrow and a roughly uniform
bubble size, generally in the range 1-7 mm, is found. These small bubbles all
have approximately the same diameter and rise velocity and are modeled
with a plug flow equation. Figure (2.6) shows the flow regime in bubble
column. Liquid products and catalyst are withdrawn from the reactor at the
top. Concentrated fresh catalyst enters the reactor at the bottom, so the
reactor operates in a co-current mode with respect to slurry and gas. Due to
the high degree of back mixing in the slurry phase countercurrent operation
does not offer much advantage. Co-current operation however avoids catalyst
settling tendencies, which could result in serious heat transfer problems (hot
spots). Heat removal is by means of cooling tubes installed in the reactor
[Krishna and Van Baten, 2003; Vandu et al. 2004; Wang et al. 2005].
g
reaches the value U
trans
, coalescence of the bubbles takes
place to produce the first fast-rising large bubble. The appearance of the
first large bubble changes the hydrodynamic picture dramatically. The
velocity that exceeds U
trans
is referred to as the heterogeneous or churn-
turbulent flow regime. In the heterogeneous regime, small bubbles combine
in clusters to form large bubbles in the size range 20- 70 mm [Ellenberger et
al. 1994; De swart, 1996; Shaikh et al. 2005; Sardeing et al. 2006].

31

Fig. (2.6) : Homogeneous and churn-turbulent regimes in a gas-liquid
bubble column [Krishna and Van Baten, 2003].

The large bubbles travel up through the column at high velocities (in the
range 1-2 m/s), in a more or less plug flow manner. These large bubbles have
the effect of churning up the liquid phase. The large bubbles are mainly
responsible for the throughput of gas through the reactor. Small bubbles,
which co-exist with large bubbles in the churn-turbulent regime, are
entrained in the liquid phase and as a good approximation have the same
backmixing characteristics of the liquid phase. The two regimes are portrayed
in Figure (2.6) which shows also in a qualitative way the variation in the gas
holdup as a function of the superficial gas velocity U
g

. When the gas
distribution is very good, the regime transition region is often characterized
by a maximum in the gas holdup. The transition between homogeneous and
churn-turbulent regimes is often difficult to characterize [Hoefsloot et al.
1993; Wang et al. 2006]

32
2.7.2 Gas Hold-Up (
g
Gas hold-up is dimensionless key parameter for phenomena purposes
of bubble column systems. All studies examine gas hold up because it plays
an important role in design and analysis of bubble columns. The variation in
gas hold-up, i.e. gas hold up profile is an important factor which gives rise to
pressure variation and thus liquid recirculation. Since liquid recirculation
plays an important role in mixing and heat and mass transfer predictions of
radial gas hold up, profiles would lead to better understanding of this
phenomenon and thus more reliable bubble column scale-up [Krishna and
Van Baten, 2003].
)

In slurry bubble column reactor Deckwer et al. (1980) is calculate gas
holdup from the following empirical equation.
1 . 1
053 . 0
g g
U = . (2.1)

Equation (2.1) presents a good compromise at low gas velocities (u
g

4 cm/ sec) and obviously also applies to larger diameter columns and higher
gas velocities

Abdul-Rahman, (1989) studied the gas hold-up in three phase systems
and correlated the results with the general empirical equations:

s m U For C U
g v
L
g g
/ 07 . 0 32 . 1
06 . 0 028 . 0
< =

(2.2)
s m U For C U
g v
L
g g
/ 07 . 0 445 . 0
6 . 0 028 . 0 6 . 0
> =

(2.3)

33
Koide et al. (1984) used the electro resistively probe to measure the
gas hold-up locally in large cylindrical vessel at diameter of (550cm) and of
(900cm) height. The value of gas hold-up is measured between (0.145-0.065)
using the following equation:
dt
E
E
T
t
T
g
) 0 (
) (
0
1
= (2.4)
where,
T: the integration time equals (1.5-3) minutes.
) t ( E
: output voltage at time
s
E
: longitudinal dispersion coefficient for solid

Auroba, (1993) studied the effect of solid particles on hydrodynamics of SBC
with different liquid-phase (alcohols and electrolytes). The dimensional
analysis was used to correlate the gas hold-up with gas velocity and liquid
properties. The correlations which were used to measure the gas hold-up are:
Without adding solid particles:

22 . 0
3
4
92 . 0
.
) 1 (
4
|
|
|
.
|
\
|
|
|
|
.
|
\
|
L L
L
L
L g
g
U
A
g
g

(2.5)

With adding solid particles:
08 . 0 885 . 0 73 . 0 4
. .
25 . 1 1
.
.
.
) 1 (
22 . 0
3
4
92 . 0
|
|
|
.
|
\
|
|
|
|
.
|
\
|
|
|
|
.
|
\
|
|
|
|
.
|
\
|
|
|
|
.
|
\
|
+
=
L
L g c
L
L s
s
s
L L
L
L
L g
U D
C
g
U
A
g
g
(2.6)

34

Koide and Shibata, (1992) found that the gas hold-up in air-water-glass
spheres system; and that the larger solid particles showed a somewhat smaller
gas hold-up. Based on visual observations, they suggested that this is caused
by the larger rising velocity of coalesced bubbles in the presence of solid
particles.

Naseer, (1994) studied the effect of solid particles and column
dimensions on the gas hold-up and liquid phase mass transfer coefficient in
solid suspended bubble column with draught tube. The author found that the
gas hold-up is not affected by column diameter and the effect of (C
s
) on (
g

)
becomes less pronounced. The gas hold-up and the volumetric liquid phase
mass transfer coefficient are correlated by the two correlations:
2978 . 0 9891 . 1 429 . 0 10
10 05915 . 2
a o r g
G B F =

(2.7)
2
10 * 4 7811 . 0 10 * 73 . 1 769 . 1 10 * 9
2
6 8
6 . 4

= =

|
|
|
.
|
\
|
g r a o c a
F G B S
D
D
Kl
L
c
(2.8)
Li and Prakash, (2000) reported that the static height in three phase
SBCRs can be expressed as:
H g P
s s
L L
g g
+ + = ) ( (2.9)
By proper substitutions, starting with the equation (2.9), one can factor out
the
g
|
|
.
|
\
|
+
=
H
P
g
s s
g
) (
1
1 1

as:
(2.10)


35
Equation (2.10) can be directly applied for estimation of gas hold up in a
SBCRs.

van Baten et al (2003) studied the effect of column diameter and slurry
concentration on the gas hold up slurry bubble column reactors the major
conclusion of this work is that with increasing slurry concentrations. The
total gas holdup decreases, and gas holdup in the dense phase is practically
independent of the column diameter.
The magnitude of gas hold up radial gradients depends on superficial
gas velocity, column diameter, physical properties of the system and
operating conditions

2.7.3 Operation Pressure
Operation pressure has a significant influence on the Fischer-Tropsch
Synthesis and product distribution. The goal products are gasoline, kerosene,
and diesel. Gasoline forms in the highest quantity at low pressures and high
H
2
/CO mass ratios or at moderate pressures and low H
2
/CO mass ratios.
Kerosene is also formed in the highest quantities at low pressures and high
H
2
mass fraction or at moderate pressures and high H
2
mass fractions.
Finally diesel is synthesized best at low and moderate pressures, with little
influence from mass ratio, or at relatively high pressures and low H
2
2.7.4 Solid Suspension
/CO
ratios. [Fernandes and Fabiano, 2005; Calemma et al., 2005].
The solid concentration is defined as the volume fraction, (
s
), of
solids in the gas-free slurry. To design a column of this type as a slurry
reactor, the behavior of the suspended solid particles, that is, the values of the
critical gas velocity required for complete suspension of solid particles and

36
the concentration distribution of the solid particles, should be known [Letzel
et al. 1999].

2.8 UTransport Processes in SBCR
2.8.1 Mass Transfer
In SBCR, the gas-phase is conventionally sparged through the slurry at
the bottom of the reactor through a specially designed distributor, leading to
different flow regimes, and complex hydrodynamic as well as mass transfer
behavior. Due to the small size of catalyst particles in slurry reactors (particle
diameter typically of the order of 50 m), intra particle diffusion is not a
limiting factor. With catalysts of relatively low activity present in low
concentration in bubble columns operated in the homogeneous regime, gas-
liquid mass transfer is unlikely to be a limiting factor either in view of the
large surface area of the small bubbles or their long residence time in the
liquid. However, for reactors of increased productivity, because of the use of
more active catalysts in high concentrations and operation in the
heterogeneous regime, gas-liquid mass transfer becomes a factor that needs
serious consideration. Conventional calculation of mass transfer rates based
on the application of the surface renewal theory with the holdup and size of
the large bubbles (which represent the major part of the gas throughput) as
input yields relatively low rates which would considerably detract from the
attractiveness of bubble columns as Fischer-Tropsch reactors.
Letzel et al. (1999) measured the volumetric mass transfer coefficient
kR
L
Ra for the air-water system at various system pressures. Their experimental
data showed that the whole data set could be approximated by the simple
relation:

37
5 . 0
a K
L
(2.11)

De Swart et al. (1996) also determined that the exchange of gas
between various bubble classes occurs at a very high rate, at least 4 s
1
The influence of bubble-bubble exchanges is illustrated by simulations
carried out for conditions relevant for the Fischer-Tropsch synthesis.
Hydrogen absorption from synthesis gas into paraffin oil at a pressure of 40
bar and a temperature of 513 K is considered. Hydrogen and carbon
monoxide are present in the syngas feed at a ratio of 2. The superficial gas
velocity through the total large bubble population, of 0.079 m/s, is assumed
to be constant over the reactor height of 30 m. Figure (2.7) shows the
dimensionless hydrogen concentration C
, which
is higher than the characteristic renewal rate for mass transfer.
g.H2
/C
g0.H2

profile along the column
height obtained for each of three bubble size classes: 0.01, 0.04 and 0.1 m in
diameter. The three profiles coincide with one another because of very
frequent exchange rates between the bubble classes and the conversion at the
reactor outlet which is 68%. The conversion behaviour of the three-bubble
class system, with 0.01, 0.04 and 0.1 m diameter bubbles is found equivalent
to that of a single bubble class system of diameter 0.021 m.

38

Fig 2.7: Effect of bubble-bubble interaction on axial concentration profiles
of hydrogen concentration in the bubbles as determined by computer
modeling [De Swart et al.1996].

In another way, due to frequent bubble-bubble interchanges the
effective bubble diameters for the 0.04 and 0.1 m diameter classes are
reduced to about 0.02. This implies an enhancement for the 0.1 m bubble
class of a factor equal to 5. In order to further demonstrate the significance of
the bubble-bubble interchange, simulations were also carried out assuming
no exchanges between the three bubble classes. The results of this model are
shown as dashed line in Figure (2.7). The overall conversion achieved by the
non-exchanging bubble ensemble is only 43%, significantly lower than that
obtained taking interactions into account.
For a bubble column reactor operating with concentrated slurry in the
heterogeneous flow regime at elevated pressures, the relation (2.1) can be
applied after applying two corrections. Firstly, the total gas holdup is
predominantly made up of large bubbles and so
b
. Secondly, the mass

39
transfer coefficient needs to be corrected for the liquid phase diffusivity
under the actual conditions prevailing in the Fischer-Tropsch reactor:

ref L
L
b
L
D
D a K
.
5 . 0
.(2.12)

where D
L
is the diffusion coefficient in the liquid phase, while D
L. ref
is equal
to 2 109 m
2
/s (valid for the measurement systems in Vermeer and
Krishna,(1981)). The diffusivities D
L
of the H
2
and CO species at a reaction
temperature of 240C are 45.5 10
9
and 17.2 10
9
m
2

/s respectively.
For most gas liquid reactions that occur in present of suspended solid
catalyst. It is usually assumed that the catalyst particle diameter is large in
comparison with the thickness of the liquid film found at the phase interface
and that the catalytic reaction does not accelerate the absorption process, then
the well-known series arrangement of transport resistance can be applied
before the gas reactant can react at the catalyst surface, transport resistances
must be overcome, as shown in Figure (2.8) the following restrictions may
arise:

1- Mass transfer across the gas-liquid interface, i.e. transport between
bulk gas phase and liquid phase, may be impeded, in which case the
absorption rate
2- Passage of the dissolved gas reactant from the bulk of the liquid phase
to the external catalyst surface may be hindered.
3- Simultaneous pore diffusion and a first order reaction in a may arise
with in the catalyst.

40

Fig 2.8: Schematic representation of possible transport resistance in
catalytic reactions in suspension phase [Deckwer,.1991].

2.8.2 Heat Transfer
Bubble column and slurry bubble column reactors are widely
employed in petrochemical, chemical, and biochemical processes due to their
easy installation, easy operation, and high heat and mass transfer rates caused
by strong gasliquid interactions. These reactors are operated under high
pressure in many industrial applications, such as heavy oil upgrading,
FischerTropsch synthesis, and methanol synthesis. A number of studies
have been performed on the heat transfer coefficient in bubble columns
[Saxena et al.1990; Li and Prakash 2002; Kantarci et al. 2005].


41
Table (2.9) summarizes recent reported studies in both bubble and
slurry bubble columns. Generally there are two ways of obtaining the heat
transfer coefficient. One of them is calculating the heat transfer coefficient
based on measurement of the energy input from the heated source to the bulk
media and the temperature difference between them [Hikita et al. 1981;
Saxena, 1989; Cho et al. 2002]. In this case, the following equation is used
[Deckwer et al. 1980]:
T A
iU
h
= .. (2.13)
where, h is the heat transfer coefficient (kw/(m
2
K)), i is electric current (A),
U is voltage (V), A is the heat transfer area (m
2
In applying this methodology, error in the calculation of heat flux based on
the energy input is inevitable, because the heat loss in heating up all the
surrounding materials, including the connecting fittings and/or column wall,
was also counted into the heat transferred from the heat source to the bulk
flow.
) and T the temperature
difference between the heat source and the bulk media (K).
In recent years, heat flux measurement technology has progressed, and
led to a second method. In this method the heat flux from the heat source to
the bulk media is directly measured, and taken together with the
measurement of the temperature difference between them, the heat transfer
coefficient can be acquired in a more accurate way [Yang et al. 2000; Li and
Prakash, 2002; Kantarci et al. 2005]. For this method, the following equation
is used [Li and Prakash, 2002]:
=

=
=
n
i
T
qi
n T
qi
h
1
ave
,
1
h ,
.. (2.14)


42
where:
h
i
= the instantaneous local heat transfer coefficient (kw/m
2
q
K),
i
= the heat flux across the sensor (kw/m
2
T
),
i
= the instantaneous temperature difference between the heat source and
the bulk (K), which is the time averaged heat transfer coefficient (kw/
m
2
In the reported studies [Yang et al. 2000; Li and Prakash, 2002;
Khalid, 2004], many parameters can affect the heat transfer in bubble/slurry
bubble columns. It has been reported that the heat transfer coefficient
increases with superficial gas velocity, heat capacity, and thermal
conductivity of the liquid. However, it decreases with an increase in the
viscosity of the liquid in gasliquid or gasliquidsolid systems [Deckwer et
al. 1980; Saxena et al. 1990; Li and Prakash, 1997; Yang et al. 2000].
Pressure has a significant effect on the hydrodynamics and bubble dynamics
(especially the bubble size) in bubble/slurry bubble columns. There are only a
few studies about heat transfer coefficient in high-pressure reactors [Deckwer
et al. 1980; Luo et al. 1997; Yang et al. 2000], an area that needs further
evaluation. Deckwer et al. (1980) investigated the heat transfer coefficient
from an immersed heat source to the surrounding media in a system
prevailing in the FischerTropsch slurry process (P = 0.11.6MPa, T = 143
270 C), and they found increasing heat transfer coefficient with increasing
superficial gas velocity and catalyst concentration.
K) and n is the total number of the samples.
Yang et al. (2000) investigated the effect of pressure on the local heat
transfer coefficient in the center of a slurry bubble column. They found that
the heat transfer coefficient decreases with an increase in pressure. The
effective heat transfer and the good temperature equalisation in a slurry
bubble column, particularly when operated in the heterogeneous regime, are
important advantages of this type of reactor.

43
Table (2.9): Parameters in the literatures on heat transfer coefficients in bubble columns and slurry bubble columns

Researcher
System

Solids
diamet
er
(m)
Column
diameter
/height
(m)
Ug
(m/s)
Press
ure
(MPa)
Sparger Correlation
Fair et al.
(1962)
Airwater
No
solid
0.46/3.2,
1.07/3.04
0.006
0.045

0.1
Sparger
ring
22 . 0

g w
U N h =
where N=8850 J/m
3
K
Hart (1976)
Airwater,
airethylene
No
solid
0.1/1.07
0.003
0.2
0.1
Single
nozzle
25 . 0
3
6 . 0
125 . 0

|
|
.
|
\
|
=
|
|
.
|
\
|
g
U
K
C
U C
h
L
L g
L
L P
g P L
w

Deckwer et
al. (1980)
Nitrogen
xylene,
kogasin, decalin,
nitrogen
paraffin
powdered Al2O3
5 0.1/0.6
0.003
0.04
0.4
1.1
Sintered
plate
( ) | |
25 . 0
2
Pr Re 1 . 0

=
m m
Fr St

Hikita et al.
(1981)
Airwater,
air1butanol,
airsucrose
Methanol
No
solid
0.29/1.5
0.050
0.34
0.1
Single
nozzle
308 . 0 851 . 0 3 / 2
411 . 0
|
|
.
|
\
|
|
|
.
|
\
|
=
|
|
.
|
\
|

L
L
L g
L
L P
g P L
w
g
U
K
C
U C
h

Lewis et al.
(1982)

Airwater,
N2cumene,
N2glycol
No
solid
0.1/1.62,
0.19/2.4
0.02
0.165
0.1
Perforated
plate
-

44
Verma
(1989)
Airwater
No
solid
0.11/1.7 0.10.4 0.1
Perforated
plate
851 . 0
3
5 . 0
) 1 ( 121 . 0
|
|
.
|
\
|
|
|
.
|
\
|
=

g K
C
E
U C
h
L
L L
L
L P
g
g P L
w

Saxena
(1989)
Airwater,
airwater
magnetite
35.7
137.5
0.11/2.25
0.015
0.333
0.1
Porous
plate
) ( 12 . 0
3 / 1 6 / 1
2
max . Pm m m
m
g m
m
m
w
C K
g
h
|
|
.
|
\
|
|
|
.
|
\
|
=
Schlter et
al. (1995)
Airwater, air
propylene
No
solid
0.29/4.27
0.01
0.65
0.1 Sieve tray
Li and
Prakash
(1997, 2002)
Airwater
glass beads
35 0.28/2.4
0.05
0.35
0.1
Six-arm
distributor

Yang et al.
(2000)
Nitrogen
Paratherm NF
heat transfer
fluidglass beads
53 0.10/1.37
0.01
0.20
0.1
4.2
Perforated
plate
( )
22 . 0
87 . 1
1
Pr Re 037 . 0

(
(
|
|
.
|
\
|
=
g
g
m m
E
E
Fr St

Cho et al.
(2002)
Airviscous
liquid
No
solid
0.152/2.5
0.02
0.12
0.1
0.6
Perforated
plate

Kantarci et
al. (2005)
Airwateryeast,
airwatercell
10,
0.20.7
0.17/0.6
0.03
0.20
0.1
Six-arm
distributor
( )
E D
C B
R
r
H
X
Fr A St |
.
|
\
|
|
.
|
\
|
= Pr Re


44
2.9
Although the product distribution demonstrates the polymerization
character of the Fischer- Tropsch synthesis, a great deal of controversy still
exists on the chemical identity of the monomeric building block and, in
relation to this, of the growing hydrocarbon chain. This result from the vast
product spectrum of alkanes, alkenes, alcohols, and acids, observed during
the Fischer-Tropsch synthesis. From literature, the three major reaction
mechanisms for the Fischer-Tropsch synthesis are [Hindermann et al. 1993]:
Fischer Tropsch Mechanisms
1. The carbene mechanism;
2. The hydroxy-carbene mechanism;
3. The CO-insertion mechanism.
Figure (2.9) shows the main three mechanisms for the FT reaction

2.9.1 Carbene Mechanism
In the carbene mechanism, oxygen free C
1,ads
intermediates are formed
from the hydrogenation of surface carbon following the dissociation of
adsorbed CO. Chain growth proceeds via the insertion of a CH
x,ads
species
into the metal-carbon bond of a C
x
H
y,ads
There are a vast number of studies that support the carbene mechanism
and it is often referred to as the most probable Fischer-Tropsch mechanism.
These studies include the analysis of surface species, C-tracer techniques, the
addition of probe molecules, and olefin cofeeding studies [Dry, 2002; Yi-
Ning et al. 2003].
species. As shown in Figure (2.9)
the mechanism was first proposed by Fischer and Tropsch in 1926 and in
their proposal the synthesis proceeds via hydrogenation of surface carbides to
methylene groups. These methylene groups polymerize to surface alkyl
species that terminate in the reaction products.

45

Fig (2.9): Schematic of basic Fischer Tropsch reaction mechanisms, i.e.
the carbine mechanism, the hydroxycarbene mechanism, and
the CO-insertion mechanism [Yi-Ning et al. 2003].

2.9.2 CO-I nsertion Mechanism
In the CO-insertion mechanism, chain growth proceeds via the
insertion of a carbonyl intermediate (CO
ads

) into the metal-alkyl bond. For
the C-C coupling reaction to take place, the resulting species is first
hydrogenated to an alkyl chain. This mechanism explains the formation of
alcohols, aldehydes, and hydrocarbons. It is shown in Figure (2.9) where the
carbonyl species is the key intermediate.

46
Pichler and Schulz first proposed the CO-insertion mechanism in 1970,
it is based on the work on organometallic complexes. Assuming that the
active surface during heterogeneous catalysis should be considered to consist
of individual active sites possessing a specific coordination, organometallic
complexes represent chain growth sites during the Fischer- Tropsch
synthesis. Indeed, CO-insertion into a metal-alkyl complex is frequently
observed with Fe complexes and Ru-complexes. However, methylene
insertion according to the carbene mechanism is also reported for
organometallic systems [Hindermann et al. 1993; Anfray et al. 2007].
There is still no exclusive experimental evidence for the CO-insertion
as the key mechanism for the hydrocarbon formation during the Fischer-
Tropsch synthesis.

2.9.3 Parallel Mechanism
All three mechanisms mentioned above share one important common
feature: the presence of a single key intermediate. None of the mechanisms is
capable of predicting the whole product spectrum observed for the four
Fischer-Tropsch metals of interest, i.e. Iron, Cobalt, Ruthenium, and Nickel.
Moreover, the Fischer-Tropsch reaction over these catalysts produces
comparable product spectra, while a carbidic surface is active for Fe-based
catalysts and a metallic surface for Co- and Ru-based catalysts. In addition,
the water-gas shift reaction on Fe-oxides is important on Fe-based catalysts,
whereas this reaction is absent on Co- and Ru-based catalysts.
This has led researchers to assume that the Fischer-Tropsch
mechanism likely involves more than only one key intermediate [Dry, 2002;
Anfray et al. 2007]. In this respect, they proposed that a CO-insertion
mechanism is responsible for the formation of oxygenates, while

47
hydrocarbons are formed via the O-free carbene mechanism. Acids are
formed via the insertion of CO
2

. It is emphasized that a large variety of O-,
H-, and C-containing species are present on the catalyst surface that all may
be involved in the Fischer-Tropsch mechanism.
2.10
For engineering purposes, many researchers have carried out
theoretical work in direction of modeling and simulation on gas-liquid and
gas-liquid-solid reactors.
Modeling and Simulations

Dragomir and Bukur, (1983) showed the estimation of kinetic
parameter (e.g. the effective rate constant and the activation energy). They
concluded that the degree of axial mixing in the liquid phase has such
profound effect on the reactor performance at high values of reactant
conversion. This model is based on the assumption that the liquid phase is
completely mixed by rising bubbles. Mass balance equations for hydrogen in
gas and liquid phase are:
Gas phase:

) ( ) (
* H H g b
C C KLa C u
dx
d
=
................................ (2.15)

Liquid phase:

H L H L
L
H H L C
C E K V dx C C a K A =
0
*
) (
.......................... (2.16)


48
David et al. (1985) derived a mathematical model to describe the
performance of SBCR used for Fischer-Tropsch synthesis. The model
accounts for axial dispersion in both the gas and liquid phases. The authors
concluded that the finite resistance to gas liquid mass transfer decreases the
conversion of syngas that can be a achieved for affixed set of operating
conditions.

Gerard et al. (1999) developed a mathematical design model for
Fischer -Tropsch SBCR. The model takes into account the water gas shift and
Fischer-Tropsch reactions as well as individual hydrocarbon product
formation rates. Under the operating conditions investigated the Fischer-
Tropsch SBCR is mainly reaction controlled. The model predicts the
composition of the gaseous and liquid streams operating in the churn-
turbulent regime as a function of the operating parameters. The gas-phase
mass balance for component i in the large bubbles, rising in plug flow is

0 ) ( ) (
) (
.
arg arg
= +
L iH
GL
e l
ig
i L
e l
ig df b
C
m
C
a K
dL
C u u d
......................... (2.17)

The gas-phase mass balance for component i in the small bubbles
(completely mixed) is

) ( ) ( ) (
. , L iH
GL
small
ig
small
i L
small
ig g i
df
C
m
C
a K C C
L
u
=
........................ (2.18)


49
The mass balance for component i in the completely mixed liquid phase can
be written as
0
) ( ) ( ) ( ) (
1
.
1
. .
arg
0
arg
= +
+
=
L iH
n
j
s
j P P L
L iH
GL
small
ig
small
i L L iH
GL
e l
ig
L
e l
i L
C
L
u
R E E
C
m
C
a K dL C
m
C
a K
L
........................... (2.19)
The same author developed energy balance for the slurry phase reads,
assuming that catalyst and the liquid temperature are equal
0 ) ) (
) (( ) ( ) (
1
=
+
=
out p P
in
n
j
p P
s
W H j R P P L
T C
T C
L
u
T T a h R H E E

.......................... (2.20)

Krishna and De Swart (2002) develops a model to simulate the
dynamic and steady-state behaviour of FischerTropsch bubble column
slurry reactor operating in the churn-turbulent regime. A distinction is made
between large and small bubble classes and the axial dispersion model is
used to simulate their mixing behaviour. The results of the dynamic
simulations indicate that no thermal runaways are to be expected and that
steady-state is achieved within about 7 min from start-up. Analysis of the
steady-state behaviour shows that the hydrogen conversion in the reactor is
mainly dictated by the large bubbles, which account for a major fraction of
the gas throughput.

Krishna and Van Batten (2003) developed a strategy for a bubble
column slurry reactor; the strategy involves development of a proper

50
description for the large bubble swarm velocity in highly concentrated
paraffin-oil slurries in columns of varying diameters. The volume-averaged
mass and momentum conservation equations in the Eulerian framework are
given by

0 ) .(
) (
= +
k k K
k K
u
t

...................................... (2.21)
g M P u u u u
t
u
k KL K
T
k k K K k k k K
k k K

+ + = + +
)) ) ( ( .(
) (

.............................. (2.22)

Laurent et al. (2008) developed a mathematical model and showed that
the conversion and liquid hydrocarbon yield increased with increasing reactor
height. On the other hand, the conversion slightly decreased with increasing
reactor diameter.
The major objective of the present work is to develop comprehensive
theoretical simulation to describe the transport processes in slurry bubble
column reactor by deriving mathematical models, which are capable of
predicting the main parameters of hydrodynamic, mass, heat and reaction in
slurry bubble column that was conducted in GTL process, and studied the
catalysts performance (the general types are Co and Fe catalysts) in Fischer-
Tropsch reaction under different operating conditions.

Chapter Three Mathematical Model

51
CHAPTER THREE
MATHEMATICAL MODEL
3.1
In most transfer phenomenon problems, mathematical modeling is
regarded as one of the most important steps in the understanding and solving
these problems. The objective of modeling is to construct from theoretical
and physical knowledge of the process, a mathematical formulation that can
be used to predict the behavior of the process [Drahos et al. 1992; Brakel,
2000, Yu Wang et al. 2008]
I ntroduction

The slurry bubble column reactor is regarded as the heart of the
industrial GTL to produce hydrocarbons. Therefore, in this work a simulation
model is presented for a (industrial scale) slurry bubble column reactor
operating in the heterogeneous or churn-turbulent flow regime. The model
predicts the mass transfer rate, heat transfer rate and reaction Kinetics in the
Fischer-Tropsch Reactor.

The present model is based on a first order rate expression for
hydrogen consumption and considers all relevant hydrodynamic phenomena.
The parameters involved in the model equations were estimated from
literature correlations [Satterfield and Huff, 1980; Deckwer, 1991; and De
Swart and Krishna, 2002 ]
The basic set of operational conditions was selected in present model
for comparison requirement with practice. The objective of this chapter is to
present a model which can be used to estimate the behavior and performance
of Industrial scale Fischer-Tropsch slurry bubble column reactor.

52
The simulator was systematically used to predict the effects of reactor
geometry (inside diameter and height) as well as superficial gas velocity and
catalyst concentration on the performance of the large scale slurry bubble
column reactors provided with cooling pipes and operating under Fischer-
Tropsch condition with two types of catalyst used, Cobalt and Iron based
catalyst.

3.2
The design model involves numerous quantities which may influence
the performance of the Fischer-Tropsch slurry process. This requires
restriction on a certain set of basic parameter values used in most
computations is given in Table (3.1) in brackets. These dimensions are
representing a real industrial Fischer Tropsch plant and it was selected in
present model for comparison requirement with practice.
Reactor Model and Assumptions

In the Fischer-Tropsch process, the reactor operates at a pressure of 12
bar. In all the simulations the average reactor temperature equals 268
0
C and
the area available for heat transfer is 0.1 cm
2
(cm
3
reactor)
1
, depending on
the operating conditions. A constant coolant temperature T
W
of 258
0
C is
used in the simulations. In the reactor design, the contraction factor is
assumed to be equal to 0.5 [Deckwer et al.1982]. All computations were
carried out with a CO to H
2
In this study, the slurry bubble column reactor of Fischer-Tropsch
synthesis is simulated using an axial dispersion model, the developed model
incorporates the following assumptions:
inlet ratio of I=1.5 for this value of I the usage
ratio U is equal to I, which always desirable.


53
1- The reactor is operating in a steady-state with exothermic reaction.
2- There is axial dispersion in the gas and liquid phase.
3-The FischerTropsch reaction is first order in hydrogen and
hydrogen is considered to be the limiting component in the
reaction.

Table (3.1): Quantities Required in Computation [Deckwer, 1991].
Variable Value Units
Reactor diameter Dr 1.5 m
Reactor length L 8 m
Particle diameter dp 50 m
Inlet Gas Velocity ugo 0.01-0.12 m / sec

Inlet hydrogen mole fraction Yo 0.4 -
CO / H
2
1.5 inlet ratio I -
Pressure P 1.2 Mpa
Wall (cooling ) temperature Tw 531
0
K
Specific heat exchange area a 10
H
1/ m
CO / H
2
1.5 usage ratio U -
Contraction factor -0.5 -
Concentration of catalyst suspended in slurry phase
wt%
20-25 -
Preexponential factor, K
fo
(s% Fe in slurry)
-1
1.12 *10
(referred to as synthesis gas conversion )
-
5

Activation energy. E 70
A
KJ/mol
Heat of reaction HR 165
KJ/(mole
syngas)


54
3.3
3.3.1 Mass Balance for Hydrogen in Gas Phase
Formation of Model Equation
Rate of mass transfer in across surface at x by axial diffusion and motion is:
dy dz C u
dx
dC
dy dz D E
x
N
H g
H
g g H
+ = ............................ (3.1)

Rate of mass transfer out across surface at x + x by axial diffusion and
motion is:
x dy dz ) d C u
dx
dC
dy dz D (E
x
dy dz C u
dx
dC
dy dz D E
x x
N
H g
H
g g
H g
H
g g H
+
+ =
+

................................ (3.2)
The rate of mass generated by chemical reaction in the gas phase =0
The rate of mass consumption by chemical reaction in the gas phase
) - C
*
A (C K
H.L
H
L
.......................................... (3.3)
Applying the mass balance:

(Mass in Mass out) +Mass generated by chemical reaction Mass
consumption by chemical reaction =0

0 0 = +
+ + +
) - C A (C K dy dz) dx C u
dx
dC
dy dz D (E
x

dy dz C u
dx
dC
dy dz D E dy dz C u
dx
dC
dy dz D E
H.L H* L H g
H
g g

H g
H
g g H g
H
g g
................................... (3.4)

55
Rearranging Eq. (3.4) to get:
0 ) ( =
(
(
(
) - C A (C K dx dy dz C u
x dx
H
dC
)
g
D dy dz dx
g
( E
x
H.L H* L H g

...................................... (3.5)
Dividing by volume (dy dz dx) gives

0 ( ) =
(
(
) - C (C a K C u
x dx
H
dC
)
g
D
g
(E
x
H.L H* H L H g
....... (3.6)
where
V
A
a
H
= ................................... (3.7)
substitute
RT
p
y y C C
g H
= = ................................... (3.8)
0 =
) - C (C a K y ) C ( u
x
)
dx
dy
C D ( E
x
H.L H* H L g g g g g
........ (3.9)

3.3.2 Mass Balance for Hydrogen in Liquid Phase
Rate of mass transfer in across surface at x by axial dispersion

dx
dC
dy dz D E
x
N
H.L
L L H
= ........................ (3.10)
Rate of mass transfer out across surface at x+x by axial
dispersion
)dx
dx
dC
dy dz D E (
x
dx
dC
dy dz D E dx N
x
N
x x
N
H.L
L L
H.L
L L A A H

+
=
+ =
+

......................... (3.11)

56
The rate of mass generated by chemical reaction in the liquid phase
) - C A (C K
H.L H* L
................ (3.12)
The rate of mass consumption by chemical reaction in the liquid phase
) - C (C A K
H.P H.L p p
.......... .. (3.13)
Applying the mass balance:

(Mass in Mass out) +Mass generated by chemical reaction Mass
consumption by chemical reaction =0

0
.
=
+ +
) - C (C A )- K - C A (C K

)dx
dx
dC
dy dz D (E
x dx
dC
dy dz D E
dx
dC
dy dz D E
P H H.L P P H.L H* L
H.L
L L
H.L
L L
H.L
L L
....................... (3.14)
Rearranging Eq. (3.14) gives:
0 = +
) - C (C A )- K - C A (C K dx
dx
dC
dy dz D E
x
H.P H.L P P H.L H* L
H.L
L L

.......................... (3.15)
Dividing by volume (dy dz dx) yields

0 = +
) - C (C a ) - K - C (C a K
dx
dC
D E
x

H.P H.L P P H.L H* H L
H.L
L L

............................... (3.16)
0
2
2
= + ) - C (C a ) - K - C (C a K
dx
C d
) D (E
H.L
L L

.(3.17)

57
3.3.3 Energy Balance for Hydrogen
Rate of heat conduction transfer in across surface at x by axial
conductive is

dx
dT
dy dz K E
x
Q
ax L
= ...................... (3.18)
Rate of heat transfer out across surface at x+x by axial
conductive is
dx
dx
dT
dy dz K E
x dx
dT
dy dz K E Qdx
x
Q
x x
Q
ax L ax L |
|
.
|
\
|
+ =
+
......................... (3.19)
The rate of heat generated by chemical reaction is
dx dy dz Q V Q
o o
= ........................... (3.20)
The rate of heat removed by convection is calculated as follows:
) h A (T - T
w
................................ (3.21)
Applying the heat balance gives:
(Heat in Heat out) +Heat generated by chemical reaction Heat
removes by convection =0
0
) (
) h A (T - T dx dy dz Q
dx
dx
dT
dy dz K E
x dx
dT
dy dz K E
dx
dT
dy dz K E
w
ax
L
ax
L
ax
L
o
= +
+ +
......................... (3.22)
Rearranging Eq. (3.22) gives:
) h A (T - T dx dy dz Q dx
dx
dT
dy dz K E
w ax L

o
x
0 = +
|
|
.
|
\
|

..(3.23)

58
Dividing by volume (dydzdx) results in
0 ) ( = +
) (T - T h a Q
dx
dT
K E
x
w H ax L
o
........... (3.24)

Substitute
2
H R
) R H ( Q
o
=
........................ (3.25)
) (T - T h a )R H (
dx
T d
K E
w H H R ax L
0
2
2
2
= + .................... (3.26)

3.4
The rate limiting step is first order in H
Development of Model Equation
2
C K R
H H H
=
2
and zero order in CO as
proposed by [Dry, 2002] and successfully applied by [Krishna and De swart
2002; Novica et al. 2003] therefore, the kinetic law is given by
................................ (3.27)
And the rate of synthesis gas consumption is given by
2 2
H H CO
U) R (I R + =
+
..................................... (3.28)
where U is the Co to H
2
2

H
CO
N
N
U =
usage ratio
.................................... (3.29)
The gas phase balance is
0 ) - C (C a) y ) - (K C ( u
dx
d
) -
dx
dy
C E ( D
dx
d
H.L H* H L g g g g g
=
............................ (3.9)

59
And for the batch liquid phase we have
0
2
2
) - C (C a ) - K - C (C a) (K
dx
C d
D E
H.L
L L
= +

......................... (3.17)
The heat balance of the suspension phase is
0 H
2
2
2
) R (- ) (T - T - h a
dx
T d
K E
H R W H ax L
= + ................... (3.26)

At the catalyst phase liquid solid mass transfer is followed by reaction,
hence at steady state the balance is given by

2
H.P P L H.P H.L P P H
C C K E ) - C (C a K R = = ........................ (3.30)
The H
2
H.P P L H.P P P H.L P P
C C K E C a -K C a K =
concentration on the catalyst surface can be expressed as a function
of the liquid phase concentration from Eq. (3.30), it follows that
......................... (3.31)
) C K E a (K C C a K
P L P P H.P H.L P P
+ = ............................ (3.32)
Rearranging Eq. (3.32) yields
]
a K
C K E
[
C
C
P P
P L
H.L
H.P
+
=
1
.................................... (3.33)
H.L P H.P
C C = ..................................... (3.34)
where
P

.. (3.35)
]
a K
E K C
/ [
P P
L P
P
+ = 1 1

60
Therefore the reaction rate can be expressed by
(3.36)
2
H.L P p L H
C C K E R =
The variable gas velocity is given by[Krishna and De swart 2002]
. (3.37)
) X ( u u
H CO go g
2
1
+
+ =

where the synthesis gas conversion is related to the hydrogen conversion by
(3.38)
H H CO
X
I
U
X
+
+
=
+
1
1
2
The hydrogen conversion is defined by
(3.39)
) Y U (
y u
y u
-
y u
y -u y u
X
g
o go
g
o go
g o go
H
= = = 1

1

Substitute Eq. (3.39) into Eq. (3.38) to give
) Y U (
I
U
X
g H CO

+
+
=
+
1
1
1
2
.... (3.40)
) ) Y U )
I
U
( )
I
U
( u u
g go g
+
+
+
+
+ =
1
1
1
1
( 1 . (3.41)
) Y U * ( U
g g
* 1 + = . (3.42)
Where

I
U
*
+
+
=
1
1
... (3.43)
Rearrange Eq. (3.42) to give
(3.44)
g

Y *
*
U
+
+
=
1
1
Henry equation is given by
.(3.45) C
He
o
P y
) H * (x
=
= 0

61
The liquid phase concentration is due to the saturation value at the reactor
inlet
is the effectiveness factor

/He P y
C

C
C
X
o
H.L
) H * (x
H.L
= =
= 0
(3.46)
The mean superficial gas velocity is:
. (3.47)
go g g
U /u u =
.. (3.48) T R / P C
g
= From gas law
And introducing a dimensionless axial coordinate
x / L = ... (3.49)

o
y/y Y =
... (3.50)
The gas phase balance can be written as
0 1
2
2
2
)
C
C
- ( C a) -(K
L R T
P y u U
d
Y d
-
d
Y d
R T L
P y E D
H*
H.L
H* H L
o go
g
o g g
=

........ (3.51)
0 1
2
2
2
)
P y /He
C
- (
He
P y
a) - (K
L R T
P y u U
d
Y d
-
d
Y d
R T L
P y E D

H.L
H L
o go
g
o g g
=

... (3.52)
Dividing Eq. (3.52) by ( P yR
O
R ugo / L R T ) gives

0
2
2
)
/ He P y
C
Y (
He u
R T L
a) ) - (K U Y (
d
d
-
d
Y d
L u
E D
o
H.L
go
H L
g
go
g g
=
... (3.53)


62
0 ) X - Y (
u He
L T R
a) (K - ) Y U (
d
d
-
d
Y d
L u
E D

go
H L
g
go
g g
2
=

... (3.54)
From Eq. (3.44), it follows that
* U Y * U
g g
+ = + 1 ... (3.55)
Dividing Eq. (3.55) by * and rearranging gives
) U (
* *
U
*
Y U
g
g
g
+ = + = 1
1
1 1
1
... (3.56)
Derive Eq. (3.56) with respect to

1

d
U d
*
) Y U (
d
d g
g

=
...(3.57)
By using chain rule relation to give
d
Y d
.
Y d
U d

d
U d
g g
= ...(3.58)
Derive Eq. (3.44) and substitute into Eq. (3.43)
d
Y d

) Y * (
*)* ( ) * Y * (
d
U d

g
2
1
1 0 1
+
+ +
= ... (3.59)

d
Y d

) Y * (
*)* (
d
U d
g
2
1
1
+
+
=
... (3.60)

d
Y d
) Y * (
*) (
d
Y U d
g
2
1
1
+
+
=
... (3.61)

63
And the gas phase balance Eq. (3.54) can be written as
0

1
1 1
2
2
) X - Y (
He u
R T L
a) - (K
d
Y d
) Y * (
*) (
-
d
Y d
B

go
H L
OG
=
+
+

(3.62)
With dimensionless group
g g
go
E D
L u
B
OG
=
... (3.63)
By introducing Eq. (3.46) and (3.49) into Eq. (3.17) and referring to u
go

H.P H.L P P
H*
H.L
H* H L
H* L L
) - C (C a ) -K
C
C
- ( C a) (K
d
X d
L
C D E
0 1
2
2
2
= +
the
liquid phase balance is given by:
...(3.64)
0 C C E K - )
He y / P
C
- (1
He
y P
a) (K
d
X d
He L
y P D E
H.L P P L
H.L
H L
o L L
2
2

2
= +
...(3.65)

divided by u
go
0
1
2
2
X
He u
P y C L K E

) -
P y / He
C
- (
He u
P y L
a) (K
d
X d
L He u
P y D E
go
o P P L
H.L
go

H L
go
o L L
=
+
/ L
... (3.66)
divided by ( P y
O
0 1
2
2
X
u
C L K E
) -
/ He P y
C
- (
u
Y L
a) (K
d
X d
L u
D E
go
P P L
o
H.L
go
H L
go
L L
= +
/ He )
...(3.67)


64
Substituting Eq. (3.46) into Eq. (3.67) gives:
0
1

2
2
X
u
L
E C K ) X - Y (
u
L
a) (K
d
X d
B

go
L P P
go
H L
OL
= +

... (3.68)
with dimensionless group

L L
go
E D
L u
B
OL
= ... (3.69)

From the heat balance i.e Eq. (3.26), it follows introducing Eq. (3.30), (3.34)
and by dividing by Cp
go
u gives:

H.L P P L
go
R

w
go
H
go
ax L
C C ) K E
u Cp
-
(
) ( T - T
Cp u
h a
-
dx
T d
Cp u
K E
0
H

2
2

=
+
... (3.70)

Substituting Eq. (3.49) into Eq. (3.70) and multiplying by L gives:

0
H
2
2
X
go
u
L
E K C
He
o
P y
)
Cp
-
(
) (T - T
Cp
go
u
L h a
-
d
T d
L Cp
go
u
E

P L P
R
w
H ax
K
L
=
+
... (3.71)
By referring to the temperature of the wall or cooling coil (T
w
w
T / T =
),
the dimensionless temperature distribution is:
...(3.72)

65
And introducing the dimensionless numbers yields
ax L
go
K E
L Cp u
Pe =
...(3.73)
Cp u
L h a
St
go
H
H
=
...(3.74)

T He
y P
)
Cp
H -
( Be
w
o R
= ...(3.75)
And the Arrhenius law is
exp /) ( K K
f
= ...(3.76)
And the Arrhenius number is
/
w A
R T E = ...(3.77)
Eq. (3.71) can be written as:
0 exp 1 (
1
2
2
X C /) ( K E
u
L
Be ) - - St
d
d
Pe
p p f L
go
H
= +

...(3.78)
In this equation the dependency of
Cp
on temperature and catalyst
concentration has been neglected however the heat balance as well as the
liquid phase balance, i.e., equation (3.68) considers yet the local dependency
of the catalyst concentration. This concentration can be calculated from the
dispersion sedimentation model for batch suspension, this model yields [kato
et al. 1972]
0
2
2
= +
dx
dC
U
dx
C d
E
P
CS
P
C
...(3.79)
with the boundary condition at x=0 and x=L

P
dx
dC
0 =
...(3.80)

66
The E
C
presents the dispersion coefficient of catalyst particles and U
CS
The solution of Eq. (3.79) and (3.80) and considering the mean catalyst
concentration
is
their settling velocity in the particale swarm .
P
C gives
) B (
) B (
B
C
C

OC
OC
OC
P
P (Z)
exp
exp 1

=
........(3.81)
where
C
CS
OC
E
L U
B =
...(3.82)
When calculating effectiveness factor (
p
) one has to consider that
(a
P
p
) depends on the catalyst concentration profile then, from Eq. (3.35) and
(3.76) that effectiveness factor ( ) can be calculated as follows:
1
) / - exp
1
)

+ = )
a K
( E C K
(
P P
L
P
f
p(
(3.83)
And by defining

P P
L
P
f
Po
a K
E C K
= ... (3.84)

One obtains
1
)) exp 1
(
-
/ (- (
PO ) P
+ = ...(3.85)
Consideration of this equation and the dimensionless number
gives:
go
H L L
u
L
a) (K St =
...(3.86)
go
w
H L g
u He
L T R
a) (K St

=
...(3.87)

67

go

L f
u
L E K
Da = ...(3.88)
From the final form of the balance equation gas phase H
2

balance is obtained
0 (
1
1 1
2
2
) X - Y - St
d
Y d
) Y * (
*) (
-
d
Y d
B

g
OG
=
+
+

... (3.89)

Liquid phase H
2
0 exp
1
)
2
2
= + X /) ( C Da ) X - Y ( St
d
X d
B

P (Z) P( L
OL

balance is

... (3.90)
And Heat balance equation is
0 exp 1 -
1
) ( 2
2
= + X C /) ( Be Da ) ( - St
d
d
Pe
P p H
. (3.91)

Boundary condition
0 0
1
1
1
1 0 = =
+
+
= =
d
d
;
d
X d
;
d
Y d
B
Y *
Y *) (
:
OG

...(3.92)
0 0 0 1 = = = =
d
d
;
d
X d
;
d
Y d
:

...(3.93)


68
3.5
The finite difference method is used to solve the differential equations
that were derived in present work. An approximate solution of equations
(3.89), (3.90) and (3.91) will be obtained at a finite number of grid points
having coordinates: (
Numerical Formulation Using Finite Difference
Method
=i ) where ( i ) is integer see Fig (4-1),. The grid
spacing in x-directions is denoted by ( ).It is important to mention here,
the values of Y, X, at each grid point are considered as an average value
over small volume of fluid surrounding the point.

Fig (4-1) Grid points of the numerical solution

3.5.1 Solution of Mass Balance Equation
Equation (3.89) which represents mass balance in gas phase can be
solved numerically by explicit finite difference method which
will be described for each term as follows:-

0 (
1
1 1
2
2
) X - Y - St
d
Y d
) Y * (
*) (
-
d
Y d
B

g
OG
=
+
+

... (3.89)
(i, j )
(i+1,j) (i-1,j)


69
-Diffusion Flux Differencing: second order central differencing
method is used for diffusion of flux differencing term as follows:

2
1
1
2
2
2 1 1

Y Y Y
B

d
Y d
B
) (i (i)
) (i
OG OG

+
+
= ... (3.94)

-Motion Flux Differencing: first order central differencing
method is used for motion flux differencing term as follows:
2
1
1
1
1 1 1
2 2
*
Y Y
) Y * (
*) (
d
Y d
) Y * (
*) ( ) (i ) (i
(i)

+
+
+
=
+
+
... (3.95)

Substituting Eq. (3.94) and (3.95) into Eq. (3.89) we obtain:
0
2
1
1
2
1
1 1
2
2
1
1

= +
+
+
+
+
+
(i)
i)
i
(i)
) (i ) (i
(i)
) (i (i)
) (i
X St Y - St
*
Y Y
) Y * (
*) (
-
Y Y Y
B

( g
) (
g
OG

. (3.96)
Rearranging Eq. (3.96) gives

0 2
1
1 1

2
1 1
2
2
1 1
2
= +
+
+
+
= +
(
(
(
(
|
|
.
|
\
|
(
(
+ +
(i)
(i)
) (i ) (i
(i)
) (i ) (i
OG
(i)
(i)
OG
X St

*
Y Y
*
) Y * (
*) (
Y Y
B

Y St
B

g
g
. (3.97)

(i)
OG
(i)
(i)
) (i ) (i
(i)
) (i ) (i
OG
i)
St
B

X St
*
Y Y
*
) Y * (
*) (
Y Y
B

Y
g
g
(
+
+
+
+
+
|
|
.
|
\
|
=
+ +
2
1 1
2
2
1 1
2
2
1
1 1

(3.98)

70
Eq. (3.98) represents the numerical solution of the
differential equation for H
2
mass balance in the gas phase. And it
is used to calculate the concentration of H
2
Eq. (3.90) which represent, mass balance in liquid phase can
be solved numerically by explicit finite difference method which
will be described for each term as following:-
along the reactor
using Fortran program. The computer program and its algorithm
are shown in appendix A and B respectively.
0 exp
1
)
2
2
= + X /) ( C Da ) X - Y ( St
d
X d
B

P (Z) P( L
OL

... (3.90)
-Diffusion Flux Differencing: second order central differencing
method is used for diffusion flux differencing term as follows:-

2
1 1
2
2
2 1 1
X X X
B

d
X d
B
) i (i) ) (i
OL OL
(

+ +
= (3.99)
Substituting equations (3.99) into equation (3.90) we obtain

0 X ) / ( exp C Da
- X St Y St
X X 2 X
B
1
) (
(i)
(i)
2
1) (i (i) 1) (i
) P(
) ( P
L
(i)
L
=
+
+ +
i
OL

. (3.100)
Rearranging equation (3.100) to give
(i)
2
1) (i 1) (i
) (
(i) 2
Y St
B
X X

X ) / ( exp C Da St
B
L
) P(
) ( P
L
2

+
+
=
+ +
+
(
(
OL
i
OL

(3.101)

71

) / ( exp C Da St
B
Y St
B
X X
X
(i)
) (
2
(i)
2
1) (i 1) (i

) (
P ) ( P
L
2
L
+ +
+
+ +
=
OL
OL
i
...... (3.102)

Equation (3.102) represents the numerical solution of the
differential equation for H
2
mass balance in the liquid phase. And
it is used to calculate the concentration of H
2

along the reactor
using Fortran program. The computer program and its algorithm
are shown in appendix A and B respectively.
3.5.2 Solution of Energy Balance
Equation (3.91) in which represents energy balance can be
solved numerically by explicit finite difference method which
will describe each term as follows:-

P p H
X C ( /) ( Be Da ) ( - St
d
d
Pe
0 ) exp 1 -
1
2
2
= +

... (3.91)

-Conduction Heat Flux Differencing: second order central
differencing method is used for calculating conduction flux
differencing term as follows:

2
1) (i
(i)
1) (i
2
2
2

Pe
1
d
d
Pe
1

+
+
= .(3.103)

72
Substituting Eq. (3.103) into Eq. (3.91) we obtain

0 exp
2
1
) (

2
1 1
=
+ +
+
+
(i)
(i)
(i)
) (i (i) ) (i
X C ) / (
Be Da St - St

Pe
P P
H H

.. (3.104)
Rearranging Eq.(3.104) to give

(
exp
1
2 1 2
1 1
2
(
(
(
(
(
(
(
+ +
+
= +
+
(i)
(i)
) (i ) (i
(i)
X C ) / (
Be Da St

Pe
St
Pe
P
)
p
H
H

... (3.105)

H
P ) p( H
(i)

St
2
Pe
1
X C ) / ( exp Da Be St

Pe
1

2
(i)
(i) 2
1) (i 1) (i
(
(
(
(
(
+
+ +
+
=
+

. (3.106)

Eq. (3.106) represents the numerical solution of the
differential equation heat balance. And it is used to calculate the
temperature distribution along the reactor using Fortran program.
The computer program and its algorithm are shown in appendix A
and B respectively


73
3.5.3 Boundary Condition Solution
Equation (3.92) which represents boundary condition at =0
can be solved numerically by explicit finite difference method
which will be described as follows:-

2 1
1 1
0 0 X X
X X
d
X d
= =
= . (3.107)

2 1
2 1
0 0

d
d
= =
= . (3.108)

2
1
OG
) (
) (
OG
Y Y
B
1
Y * 1
Y *) (1
1
d
Y d
B
1
Y * 1
Y *) (1
1

i
i
+
+
=
+
+
=
. (3.109)

Equations (3.109) in which represents boundary condition at
=1 can be solved numerically by explicit finite difference
method which will be described as follows:-

m m
m m
X X
X X
d
X d
1
1
0 0
= =
=
. (3.110)

1 0 0
1
= =
=

m m Y Y
Y Y
d
Y d m m
. (3.111)

1 m m
m 1 m
0

0
d
d

= =
=

.. (3.112)


74
3.6
In order to solve equations (3.89),(3.90), and (3.91) their coefficients
must be estimated as follows:
Parameter Estimation

-Rate Constant for H
2
U
K
fo
f
+
=
1
K
Consumption.
. (3.113)

The heat of reaction is obtained by linear interpolation from the following
equation:
5 1 5 0 40 165 . )/ . *(U H
R
+ = . (3.114)

-Volume Fraction of Catalyst in Slurry:

) - ( W -
W
V
L P P P
P L
P

=
... (3.115)

-Temperature Dependent Quantities.

Density [Deckwer et al.1980]
3 3
373 10 555 0 758 0 ) g/cm (T * . - .
-
L
= . (3.116)
Viscosity [Deckwer et al.1980a]
sec . /cm g T)) / (3266 6.905 - ( exp 0.052
L
+ = ... (3.117)

Diffusivity [Satterfield and Huff, 1980]
sec T 2285/ - exp 10 35 7
2 3
/ ) cm ( * . D
-
L.H
= . (3.118)

Henrys constant [Deckwer, 1991]
)/mol cm /T) ( Kpa ( . ( * . He
3 7
583 2326 1 exp 10 291 2 + = . (3.119)


75
-Properties of Suspension.
The physical properties of the suspensions from the individual date of
solid and the paraffin are estimated. The mean densities are calculated from

3
g/cm 1
L
) V ( V
P P P
+ = . (3.120)

where, V represents the volume fraction and P, L refer to solid and liquid
paraffin.
The Viscosities are obtained from De Swart and Krishna, (2002) relation.
.sec g/cm 5 4 1 ) V . (
P
L
+ = . (3.121)

The heat capacity of the suspension is then given by [De Swart and Krishna,
2002]
L
P P
P
)Cp W ( Cp W Cp + = 1 . (3.122)

where W represents the weight fraction.
For estimating heat conductivities of suspensions [De Swart and Krishna,
2002] proposed the equation.
) ( V
) ( V

P L P P
L
P L P P L
L
+ +
+
=
2
2 2
. (3.123)

- Mass Transfer Gas / Liquid.
The gas was sparged by a porous plate sparger having a mean pore
diameter of 75m at temperature above 250
0
1 . 1
053 . 0
g g
U E =
C the gas holdup is calculated
from the following empirical equation [Deckwer et al, 1980]
. (3.124)


76
Interfacial area is [Deckwer et al. 1980]
1

1.1
cm U 4.5 a
g

= . (3.125)

Mass transfer coefficient is [Satterfield and Huff, 1980]
/sec cm ) T (-4570/ exp
0.1165 K
1/3
L |
|
.
|
\
|
=
. (3.126)
- Mass Transfer Liquid / Catalyst.
Interfacial area
P P
P
P
d
)
g
E ( W
a

=
1
6
. (3.127)
Mass transfer coefficient [Deckwer,1991]
(
(
(
|
|
|
.
|
\
|
|
|
.
|
\
|
+ =
d E
D
0.545 2
d
D
K
3
3 4
1/3
L
L P
L L
L
P
L
P
. (3.128)
with
sec 6 cm/ u g if u E
g g
= . (3.129)
/sec cm 6
g
u if
3
/sec
2
cm 5886 constant E = =

- Heat Transfer Coefficient
Heat transfer from walls and inserted coils was analyzed theoretically
by [Deckwer et al., 1980]
.sec.K J/cm 1 0
2
0.25
2
3

(
(
(
(
|
|
.
|
\
|
|
|
|
|
.
|
\
|
=
Cp
g
u
) u Cp ( . h
g
g
. (3.130)
-Dispersion Coefficients.
Gas phase is [Satterfield and Huff, 1980]
sec 10 5
2 5 1 3 4
/ cm Dr ) /E u ( * D
.
g g g

= . (3.131)

77
Liquid phase is [Deckwer, 1991]
34 0
2
83 2
.
OL
g Dr
u
. B
g
|
|
|
.
|
\
|
= . (3.132)
sec 676 3
2 34 1 32 0
/ cm Dr u . D
.

.
g L
= . (3.133)
Effective heat conductivity of suspension is
K sec. cm. / J C D K
p
L
ax
=
. (3.134)

- Solid Phase Dispersion and Sedimentation [Kato et al. 1972].
Dispersion coefficient
85 0
1
13
.
C
OC
Fr
Fr
E
Dr u
B
g
+
= = . (3.135)
with

. (3.136)

- Contraction Factor
The variability of the molar gas flow rate in the reactor can be taken
into account by application of a gas phase contraction factor ALPHA,
defined as in [Levenspiel, 1972; De Swart and Krishna, 2002]:

0) (X V
0) (X V 1) (X V
2
H CO g
2
H CO g
2
H CO g
=
= =
=
+
+ +
. (3.137)

From experimental results [Deckwer, and Schumpe, 1993] it can be
deduced that varies between -0.5 and -0.6 in the following computation a
constant value of =-0.5 will be used throughout.
g Dr / u Fr
g
=
Chapter Four Result and Discussion
78
CHAPTER FOUR
RESULTS AND DISCUSSION

4.1
The present chapter shows the results of the mathematical model that is
derived in chapter three. The model is based on the principles of transport
processes and reaction kinetic in multiphase flow. In this chapter the
influences of the superficial gas velocity, operating pressure and temperature,
solid concentration, column dimensions, heat transfer coefficient and gas
liquid distribution for Cobalt and Iron based catalyst are discussed.
I ntroduction

In order to get a clear picture of design and simulation of slurry bubble
column reactor (SBCR) in GTL process the results of the present model are
compared with the results of Fischer Tropsch process that was investigated
in literature [Krishna and de Swart,2002; Novica et al.,2003; Laurent et al.,
2008]. The reactor dimensions selected were 150 cm for diameter, dispersion
height L=800 cm and operating with a superficial gas velocity U
g

=12 cm /s.
These dimensions represent a real industrial Fischer Tropsch plant and it
was selected in the present model for comparison requirement with practice.

79
4.2

Hydrogen Profile in Liquid and Gas Phase
Figures (4.1) and (4.2) show the hydrogen concentration profiles over
the reactor height in the gas and the liquid phase for both Cobalt and Iron
based catalyst, in this figure Y represents hydrogen concentration in the gas
phase and X represents hydrogen concentration in the liquid phase, and it can
be seen that for Cobalt-based catalyst the hydrogen bubble concentration in
the gas phase decreases from 0.91 at the inlet of the reactor to 0.62 at the
outlet of the reactor and for the Iron-based catalyst the hydrogen bubble
concentration decreases from 0.79 at the inlet of the reactor to an equilibrium
value with the liquid phase of about 0.45 at the outlet of the reactor.

Such behaviour can be explained on the basis that, the rate of mass
transfer for all components is very high, therefore the inlet gas will
instantaneously equilibrate with the liquid, and the dimensionless
concentration for H
2
in liquid phase is significantly lower than those in the
gas phase due to the finite mass transfer resistance. These results are in
agreement with those reported by Dragomir (1983), Krishna and De swart
(2002), Laurent et al. (2008).
80
0 0.25 0.5 0.75 1
Reactor height
0.5
0.6
0.7
0.8
0.9
1
H
y
d
r
o
g
e
n
p
r
o
f
i
l
e
X
Y
Gas phase
Liquid phase

Fig. (4.1): Hydrogen profile over the reactor height with Cobalt catalyst.
0 0.25 0.5 0.75 1
Reactor height
0.4
0.5
0.6
0.7
0.8
0.9
1
H
y
d
r
o
g
e
n
p
r
o
f
i
l
e
X
Y
Gas phase
Liquid phase

Fig. (4.2): Hydrogen profile over the reactor height with I ron catalyst.
81
4.3 Catalyst Distribution Along the SBCR
In three phase reactor the catalyst distribution is an important task
because high dispersion catalyst means higher mass transfer and higher
synthesis gas conversion. Figure (4.3) shows the Cobalt catalyst distribution
along the reactor height. According to this figure the catalyst profile is very
flat, obviously distribution is high enough to suppress settling of catalyst
particles, It is clear that, the catalyst profile is highest at the bottom of the
reactor, this is due to the fact that the settling velocity of the particles in a
swarm is higher than the resistance of the liquid phase. Such explanations are
in agreement with explanation of Wallis. (1969), Van Baten et al. (2003), van
Baten and Krishna (2004).

The same behavior is noted for Iron based catalyst as shown in Figure
(4.4) which gives high distribution of catalyst. It is important to mention
here, that, the partical diameter of catalysts that is used in Fischer Tropsch
reaction is in range of 25 to 200 m. The more favorable particle diameter is
about 50 m for such type of reaction [Michael et al. 2005; Fabiano et al.
2007; Laurent et al. 2008].

The present study is concerned with the hydrodynamic effect of
Fischer-Tropsch reactor performance, pore diffusion limitations were not
considered in the model computations. Under all conditions simulated i.e., at
various temperatures, gas velocities, and column diameters, the particle sizes
have no significant influence on the conversion, in model computational if 50
m particles are applied, the catalyst is uniformly distributed over the reactor
volume even for the lowest gas velocities.

82
Figures (4.3) and (4.4) show the catalyst profile along the reactor
height for Cobalt and Iron catalyst respectively and indicate that the catalyst
sedimentation and liquid solid mass transfer resistances can be neglected in
the FT slurry process. Therefore, in the model equations (3.90) and (3.91) the
effectiveness factor
) (
P
can be set to one , and instead of C
CAT
0 exp
1
)
2
2
= + X /) ( C Da ) X - Y ( St
d
X d
B

P (Z) P( L
OL
(z) the
average catalyst concentration can be used .
.... (3.90)
X C ( /) ( Be Da ) ( - St
d
d
Pe
P p H
0 ) exp 1 -
1
2
2
= +
.. (3.91)
0 0.25 0.5 0.75 1
Reactor height
20
21
22
23
24
25
26
27
28
29
30
c
a
t
a
l
y
s
t
c
o
n
c
e
n
t
r
a
t
i
o
n
w
t
%

Fig. (4.3): Cobalt catalyst profile over the reactor height.
83
0 0.2 0.4 0.6 0.8 1
Reactor height
20
21
22
23
24
25
26
27
28
29
30
c
a
t
a
l
y
s
t
c
o
n
c
e
n
t
r
a
t
i
o
n
w
t
%

Fig. (4.4): I ron catalyst profile over the reactor height.

4.4 Temperature Distribution Along the SBCR
Temperature is a basic process variable that has a profound effect on
the overall yield of a Fischer-Tropsch reactor. Temperature is normally used
to control the distribution of products in the reaction, where one product may
predominate at lower temperatures (kinetically controlled) and another
predominates at a higher temperature (thermodynamically controlled). All
reactions that take place in the Fischer-Tropsch process are extremely
exothermic, so temperature control is extremely necessary to ensure the
reaction goes to significant products [Mills et al.,1996; Fernandes and
Fabiano, 2005].Therefore in the design and construction of SBCR the
monitoring of reaction temperature is important.

84
Figure (4.6) shows the temperature profile of Cobalt and Iron catalyst
respectively. The temperature profile is based on the result of model
according to energy balance equation (3.91).

X C ( /) ( Be Da ) ( - St
d
d
Pe
P p H
0 ) exp 1 -
1
2
2
= +
. (3.91)

The computations were done either for isothermic condition i.e the
specific heat exchanger area was set to such a high value that the slurry
temperature agreed with the wall temperature or for non-isothermic
conditions i.e, T
w
(wall temperature) was set to 258
o
C and a
H
0.1 cm
-1
. Then
the slurry temperature could rise to higher value than T
w
Figure (4.6) shows that for Cobalt-based catalyst the temperature of
reaction is approximate to be 260
because of heat
generated by reaction, and within the reactor a small temperature profile was
built up.
o
C, on the other hand for Iron based catalyst
the temperature rises to 267
o
Due to this little temperature difference in a tall reactor it is permitted
from a more practical viewpoint to assume an approximately constant
temperature along reactor. Nevertheless a heat balance i.e. Eq.(3.91), is
required to calculate the operating temperature under non isothermic
condition .
C from results of this figure it can be concluded
that, for the two types of catalysts the flat temperature profile exists due to
high dispersion in liquid phase and confirms to the well know fact that due to
the good mixing properties slurry bubble column reactor (SBCR) offers
relatively easy heat removal with less cooling area than some other types of
Fischer-Tropsch reactors (e.g. trickle bed ) .
85

Fig. (4.5): Temperature profile over the reactor height (Cobalt and I ron
catalysts).

4.5
According to many investigations [Krishna and van Baten, 2003;
Ahmad et al. 2008; Guillou et al. 2008] when gas is injected into the SBCR
from the bottom, the slurry bed expands, and holdup of each phase will be
formed. Then each phase presents different velocity and recirculation
patterns. Therefore Figure (4.6) shows the gradient of the superficial gas
velocity over the reactor height for two types of catalyst (Cobalt and Iron).
From this figure it is clear that the highest value of superficial gas velocity is
present at the reactor inlet, and it decreases gradually until it arrives to
Superficial Gas Velocity Profile Along the SBCR
86
constant rate at the reactor outlet. The explanation of such conclusion is
regard the gas volume contraction (), and it is cited in Eq.(3.137).
The same behavior is noted for both types of catalysts because the
same weight and particle size.
It is important to mention here that in the derivation of mathematical
model the gas contraction factor () is calculated under the following
simulation condition,Ug
0
= 112 cm/s , T = 258267
o
C, P = 1.2 MPa, H
2

/CO
= 1.5. The different product distributions under different conditions result in
the different values of ., the value of is given in the model equations like
some authors Ahon et al. (2005), Maretto and Krishna (1999).
0.2 0.4 0.6 0.8
Reactor height
0.5
0.6
0.7
0.8
0.9
1
S
u
p
e
r
f
i
c
a
l
g
a
s
v
e
l
o
c
i
t
y
Cobalt catalyst
Iron catalyst

Fig. (4.6): Superficial gas velocity profile with reactor height.

87
4.6 Heat Transfer Coefficient
Thermal control in slurry bubble columns is of importance since in
Fischer Tropsch processes, chemical reactions are usually accompanied by
heat removal (exothermic) operation. Many hydrodynamic studies investigate
the heat transfer process between the heating object and the system flow to
understand the effects of hydrodynamic parameters on the heat transfer for
improving the design and operation of bubble column reactors. [Li and
Prakash, 1997; Quiroz et al.2003; Chengtian et al.2007]

Literature studies reported on heat transfer measurements in three
phase systems can be divided into: (1) estimation of bed-to-wall heat transfer
coefficients, and (2) estimation of immersed object-to-bed heat transfer
coefficients. However, measurements of instantaneous heat transfer
coefficients provide more insight into bubble dynamics and mechanism of
heat transfer. The use of average heat transfer coefficient causes the loss of
information related to the effect of instantaneous bubble dynamics on heat
transfer. It is important for us the in instantaneous heat transfer in bubble
columns under wide range of conditions to have a comprehensive
understanding of the heat transfer mechanism and reliable modeling to
improve design and operation.
Many literature correlations exist for estimation of heat transfer
coefficient that can be applied to two-phase bubble columns and three-phase
slurry bubble columns, several of these correlations are presented in chapter
two. The basic parameters affecting the heat transfer are mainly the
superficial gas velocity, particle size and concentration, liquid viscosity, and
column dimensions. Therefore, the present model focuses on studying the
effect of superficial gas velocity, catalyst concentration on heat transfer
coefficient.
88
4.6.1 Effect of Superficial Gas Velocity
The superficial gas velocity is a dominant factor that affects the heat
transfer coefficient, generally the heat transfer coefficient increases with an
increase in the superficial gas velocity.
The model result of superficial gas velocity vs. heat transfer coefficient
is shown in Figure (4.7). From this figure it is clear that there is a direct
relationship between gas velocity and heat transfer coefficient. The heat
transfer coefficient increases due to superficial gas velocity increase and this
leads to high degree in liquid mixing and then to higher rate of heat transfer.
Moreover it is important to mention here that, the degree of mixing is also
related to the liquid circulation rate. On the other hand, the heat transfer
coefficient has a direct connection to the bubble size: it increases with an
increase in bubbles size, because large bubbles can create strong vortices and
intense mixing in the wake region. This result is in agreement with those of
Kumar et al. (1992) , Chen et al. (1994) , Luo et al. (1999) , Rados, ( 2002 ),
Ong, ( 2003), Xue, (2004).

4.6.2 Effect of Catalyst Concentration
The influence of the catalyst concentration on heat transfer coefficient
is a very important factor to understand the heat transfer behavior. The
influence of the catalyst concentration on heat transfer coefficients is shown
in Figure (4.8). From this figure it is clear that, as the solid contents increase
the heat transfer coefficient increases. It is possible that similar to gas solid
fluidized beds, the increase in heat transfer coefficient is caused by
independent motion of the particles leading to increased exchange frequency
of fluid elements at the heat surface area. Such explanation is in agreement
with work of Li and Prakash, (1997),Cho et al. (2002), Xue, (2004).
89
0 1 2 3 4
Superfical gas velocity m / sec
8400
8600
8800
9000
9200
9400
9600
9800
10000
H
e
a
t
t
r
a
n
s
f
e
r
c
o
e
f
f
i
c
i
e
n
t
W
/
m
k
2

Fig. (4.7): Superficial gas velocity profile with heat transfer coefficients.

The reason given for the heat transfer coefficients increase is the
alteration of thermo-physical properties of the slurry with the introduction of
solids and also enhanced exchange rate of fluid elements on the heated
surface of the exchanger that is inserted inside the reactor is due to motion of
solid particles. Moreover, the alteration of the bubble properties with solid
addition is also needed to be taken into account. Therefore, it can be
concluded that, the increasing the solids concentrations, increases the bubble
coalescence leading to the formation of larger size bubbles with higher rise
velocities, and thus higher heat transfer rates are likely to be obtained. This
result is in full agreement with those of Kolbe et al. (1960), Deckwer et al.
(1980).
90
On the other hand, Li and Prakash (1997) reported an opposite trend to
that of Deckwer. They reported that as solid concentration increases the heat
transfer coefficient decreases. This can be explained by the fact that the
slurry viscosity grows with the increment of main solid concentration and the
convective heat transfer coefficient reduction while the viscosity of the bed
increases .When the slurry viscosity increases, the space between particles
will be reduced, and that affects the fluid dynamics behavior in several ways:
1- The mobility or velocity of particles decreases.
2- The boundary sub layer thickness of laminar flow around the heater grows.
3- The turbulent decreases.
4- The viscous friction loss between phases grows.

10 20 30 40 50
Catalyst concentration wt %
8600
8800
9000
9200
9400
9600
9800
10000
H
e
a
t
t
r
a
n
s
f
e
r
c
o
e
f
f
i
c
i
e
n
t
W
/
m
k
2

Fig. (4.8): The effect of catalyst concentration on heat transfer
coefficients.
91
4.7
The conversion of natural gas to liquid fuel (GTL) via the Fischer
Tropsch synthesis (FTS) process continues to be an attractive option for
monetising stranded natural gas. Supported Cobalt catalysts are the system of
choice for the Fischer-Tropsch synthesis as compared to Iron due to the high
conversion, low water gas shift activity and paraffinic nature of the resulting
synthetic crude.
Syntheses Gas Conversion

4.7.1 Effect of Superficial Gas Velocity and Catalyst
Concentration
The important process variable present in the Fischer-Tropsch process
is the catalyst. The main purpose of a catalyst is to break apart the syngas
molecules and dramatically increase their reactivity. In the kinetic catalyst is
shown splitting the molecules into the very reactive radical atoms, which
stabilize by combining into hydrocarbon radicals, which can combine with
other catalyzed radicals and form stable chains.
Figures (4.9) and (4.10) show the model results of the effect of
superficial gas velocity on synthesis gas conversion at different weights of
catalyst. Figure (4.9) is for Cobalt based catalyst, while Figure (4.10) for Iron
based catalyst. It is noted that, the synthesis gas conversion decreases with
increase in superficial gas velocity and it increases with catalyst
concentration. Therefore for Cobalt and Iron catalysts the reactor
performance could be improved by increasing catalyst concentration these
result are agree with that given by Inga et al. (1996). Then, the reactor would
approach a mass transfer controlled regime, especially at high catalyst
concentration which would markedly increase the bubble size. When mass
transfer is very rapid the conversion of H
2
in the reactor depends only on the
92
total mass of catalyst in the reactor and is not influenced by the spatial
distribution of catalyst. The synthesis gas conversion decreases with
increasing superficial gas velocity suggesting small increases of mass transfer
rate compared to the decrease in the residence time of the gaseous reactant
(CO and H
2

) which becomes too short for conversion.

2 4 6 8 10 12
Superficial gas velocity cm / sec
0.6
0.65
0.7
0.75
0.8
0.85
0.9
S
y
n
t
h
e
s
e
s
g
a
s
c
o
n
v
e
r
s
i
o
n
20 %wt Co
12 %wt Co
8 %wt Co

Fig.(4.9): The effect of superficial gas velocity on the synthesis gas
conversion at different weights of Cobalt based catalyst.

From the comparison of the results for both types of catalysts, it is
clear that , the Cobalt catalyst shows higher conversion value of about (0.9)
than Iron catalyst (0.78) at different weights of catalyst (8-12-20 wt%), and
it can be seen that for Cobalt based catalyst the synthesis gas conversion
93
decreases from (0.9) at superficial gas velocity 2 cm/s to about (0.6) at
superficial gas velocity 12 cm/s and for the Iron based catalyst the synthesis
gas conversion decreases from (0.78) at superficial gas velocity 2 cm/s to
about (0.45) at superficial gas velocity 12 cm/s.
It is important to mention here the weaker dependence of the
conversion of synthesis gas on superficial gas velocity for the case of finite
mass transfer resistance is due to the increase in mass transfer coefficient
KLa with u
go

. As KLa increases the liquid phase approaches equilibrium with
the gas phase and as a result the reaction rate increases. This conclusion is in
accord with explanation of Deckwer, (1991).
2 4 6 8 10 12
superficial gas velocity cm / sec
0.45
0.5
0.55
0.6
0.65
0.7
0.75
0.8
s
y
n
t
h
e
s
e
s
g
a
s
c
o
n
v
e
r
s
i
o
n
20 % wt Fe
12 % wt Fe
8 % wt Fe

Fig.(4.10): The effect of superficial gas velocity on the synthesis gas
conversion at different weights of I ron based catalyst.
94
4.7.2 Effect of Reactor Height
The effect of reactor height on the performances of slurry bubble
column reactor operating at initial superficial gas velocity of 9.5 cm /sec is
shown in Figures (4.11) and (4.12). As can be seen in Figure (4.11) for
Cobalt based catalyst the synthesis gas conversion increases from 0.15 at the
inlet of the reactor to 0.9 at the outlet of the reactor. While Figure (4.12) for
Iron based catalyst shows the synthesis gas conversion increases from 0.1 at
the inlet of the reactor to 0.71 at the outlet of the reactor.
For both types of catalyst the synthesis gas conversion increases over
the reactor height, the higher value of synthesis gas conversion is expected at
the reactor outlet, these results on this behavior agrees with the results that
given by de swart (1996).
0 0.2 0.4 0.6 0.8 1
Reactor height
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
S
y
n
t
h
e
s
i
s
g
a
s
c
o
n
v
e
r
s
i
o
n

Fig. (4.11): Syntheses gas conversion profile with reactor height (Cobalt
based catalyst).
95
0 0.2 0.4 0.6 0.8 1
Reactor height
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
S
y
n
t
h
e
s
i
s
g
a
s
c
o
n
v
e
r
s
i
o
n

Fig. (4.12): Syntheses gas conversion profile with reactor height (I ron
based catalyst).

4.7.3 Effect of Operating Pressure
In SBCR the operation pressure is regarded one of the most important
parameters. Variation in pressure in Fischer-Tropsch process is important
because of their direct effect on product distribution. It is known that, the two
major products of the Fischer-Tropsch reaction are olefin and paraffin.
Paraffin tends to be synthesized more readily at low pressures (0.5- 1.0 MPa
H
2
) and at low mass ratios of H
2
/CO (0.6-1.0). Olefin is produced in higher
concentrations at high pressures (2.0-4.0 MPa H
2
) and high mass ratios of
H
2

/CO (1.5-2.5) [Yu Wang et al.2008].
96
Figures (4.13) and (4.14) show influence of operating pressure in
SBCR on synthesis gas conversion in the case of isothermal and non
isothermal condition. These figures show that, the synthesis gas conversion is
not influenced by changing of the operating pressure under isothermal
condition. On the other hand, if the reactor operates under non-isothermal
condition, the pressure increases due to temperature increase and in this
cause the synthesis gas conversion increases. The linear increase in the
conversion with synthesis pressure is a result of first order rate expression.
Such results are in agreement with work of Hall et al. (1952) and Calemma et
al. (2005).
From the comparison of the results for both types of catalysts, it is
clear that, the Cobalt catalyst shows higher conversion value of about (0.9)
than Iron catalyst (0.8) at non-isothermal reaction condition.
1 2 3 4
Pressure MPa
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
S
y
n
t
h
e
s
i
s
g
a
s
c
o
n
v
e
r
s
i
o
n

Fig. (4.13): I nfluence of pressure on the synthesis gas conversion (Cobalt
catalyst).
97
1 2 3 4
Pressure MPa
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
S
y
n
t
h
e
s
i
s
g
a
s
c
o
n
v
e
r
s
i
o
n

Fig. (4.14): I nfluence of pressure on the synthesis gas conversion (I ron
catalyst).

4.7.4 Effect of Reactor Diameter
In the slurry bubble column reactor (SBCR) the column diameter is a
very important factor especially with the studies that deal with the
hydrodynamic, dispersion coefficients, heat and mass transfer coefficients,
and synthesis gas conversion.

Therefore, in this section the simulation program was tested with
different column diameter ranging from 2 to 5 m. This treatment aims to
understand the effect of column diameter on the synthesis gas conversion.
Figure (4.15) and (4.16) show the synthesis gas conversion profile with
98
reactor diameter for Iron and Cobalt catalyst respectively, in the case of
isothermal and non isothermal reaction condition.
And it can be seen from these figures under isothermal and non
isothermal reaction conditions the synthesis gas conversion for Cobalt based
catalyst decreases from (0.94) to about (0.5) and for the Iron based catalyst
the synthesis gas conversion decreases from (0.8) to about (0.32).
It is important to mention here that, the main reason for synthesis gas
conversion decreases with increasing reactor diameter, it is that dispersion
increase that present in wider column, and decreased plug flow of the liquid
phase character leads to lower conversion of syntheses gas. However this
consideration is important when scaling up slurry reactors.

2 2.5 3 3.5 4 4.5 5
Reactor diameter M
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
S
y
n
t
h
e
s
i
s
g
a
s
c
o
n
v
e
r
s
i
o
n
Non isothermal
Isothermal

Fig. (4.15): Synthesis gas conversion profile with reactor diameter (cobalt
catalyst).
99

2 2.5 3 3.5 4 4.5 5
Reactor diameter M
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
S
y
n
t
h
e
s
i
s
g
a
s
c
o
n
v
e
r
s
i
o
n
Non isothermal
Isothermal

Fig.(4.16): Synthesis gas conversion profile with reactor diameter (I ron
catalyst).

4.7.5 Effect of I nlet Ratio
The (H
2
/CO) ratio of the synthesis gas is an important designing
variable for maximizing the production of high quality diesel. From the
Figure (4.17) for Cobalt based catalyst, the synthesis gas conversion
increases with increase in inlet ratio (H
2

/CO), and it was found that the best
inlet ratio is about (2), which gives the highest value of conversion of about
(0.9).
100
0 0.5 1 1.5 2
Inlet ratio H / CO
0.4
0.5
0.6
0.7
0.8
0.9
1
S
y
n
t
h
e
s
i
s
g
a
s
c
o
n
v
e
r
s
i
o
n
2

Fig. (4.17): Dependence of synthesis gas conversion on inlet H
2

/CO ratio
for (cobalt based catalyst).
On the other hand, Figure (4.18) shows the effect of (H
2
/CO) ratio on
synthesis gas conversion for Iron catalyst. From Figure (4.18) it is clear that
the synthesis gas conversion also increases with increase in the inlet ratio
(H
2
/CO), and the best value is about (1.6), which gives the highest value of
conversion of about (0.86). Depending on the water gas shift reaction (WGS)
activity, the water gas shifts reaction is important to change the (H
2
CO + H
/CO) ratio
for Iron (high WGS-activity) and Cobalt catalysts (no WGS activity).
2
O CO
2
+ H
2
(WGS) - H
WGS
= 41.3
kJ/mol
101
For Iron catalyst, the (H
2
/CO) ratio in the reaction media is very high
even when the feed ratio is low (<1.5), because of the production of more H
2
An important consequence of the occurrence of water gas shift is that
the consumption ratio is maintained close to the H
by the WGS reaction.
2

/CO ratio in the feed.
This contributes to efficient utilization of the feed. This result is in agreement
with those David et al. (1985).

0 0.5 1 1.5 2
Inlet ratio H / CO
0.4
0.5
0.6
0.7
0.8
0.9
1
S
y
n
t
h
e
s
i
s
g
a
s
c
o
n
v
e
r
s
i
o
n
2

Fig. (4.18): Dependence of synthesis gas conversion on inlet H
2

/CO ratio
for (I ron based catalyst)

102
4.8
In order to test the validity of the present model, this Section is focused
on the comparison of the results of the present model with that of a different
models and experimental work.
The Validity of the Present Model
The comparison with other work must be made under the same
physical properties and operating conditions (i.e., temperature range, column
Geometry, and superficial gas velocity) therefore, the comparison process is
based on applying the real operation conditions and dimensions of different
authors in present model. The present model is based on three differential
equations derived in present work:

Mass balance in gas phase
0 (
1
1 1
2
2
) X - Y - St
d
Y d
) Y * (
*) (
-
d
Y d
B

g
OG
=
+
+

... (3.89)

Mass balance in liquid phase
0 exp
1
)
2
2
= + X /) ( C Da ) X - Y ( St
d
X d
B

P (Z) P( L
OL

... (3.90)
Heat balance
0 exp 1 -
1
) ( 2
2
X C /) ( Be Da ) ( - St
d
d
Pe
P p H
= +

(3.91)

Therefore, the present section focuses on comparison between the
hydrogen profile (Y, X) in gas and liquid phase respectively, heat transfer
coefficient and Synthesis gas conversion with the data of authors.
103
4.8.1 Synthesis Gas Conversion
The comparison of synthesis gas conversion that is calculated from
present model with that calculated from the model of David et al. (1985) is
shown in Figure (4.19). The comparison was carried out by substitution of
the values of reactor dimensions and hydrodynamic parameters of this model
David et al. (1985) in present model. It is concluded that the present model is
in accord with model data of the David et al. (1985) with deviation of 8%.

2 4 6 8 10 12
Superfical gas velocity cm / sec
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
S
y
n
t
h
e
s
i
s
g
a
s
c
o
n
v
e
r
s
i
o
n
David et al model
Present model

Fig. (4.19): The comparison between the present model Synthesis gas
conversions with model of David et al. (1985).

104
4.8.2 Heat Transfer Coefficient
Figure (4.20) shows the comparison of heat transfer coefficients of
present model with that of the Fan et al (1999).The comparison was carried
out by substitution of the values of reactor dimensions and hydrodynamic
parameters of this investigator Fan et al (1999) in the present model. It was
concluded that the present model is in accord with experimental data of the
Fan et al (1999) with deviation of 9%.

0 1 2 3 4
Superfical gas velocity m / sec
8000
8200
8400
8600
8800
9000
9200
9400
9600
9800
10000
H
e
a
t
t
r
a
n
s
f
e
r
c
o
e
f
f
i
c
i
e
n
t
W
/
m
k
Present model
Fan et al. experimental
2

Fig. (4.20): The comparison between the heat transfer coefficient of
present models with experimental data of Fan et al. (1999).

105
4.8.3 Hydrogen Profile in the Gas Phase
Figure (4.21) shows the comparison of hydrogen profile in the gas
phase that is calculated from equation (3.89) with the model of Krishna and
De swart (2002). As can be seen from this figure the present model is in
accord with data of the Krishna and De swart (2002) with deviation of 6%.

0 0.25 0.5 0.75 1
Reactor height
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
H
y
d
r
o
g
e
n
p
r
o
f
i
l
e
i
n
g
a
s
p
h
a
s
e
Krishna et al model
Present model

Fig. (4.21): The comparison between the hydrogen gas profiles of the
present model with the model of Krishna (2002).

106
4.8.4 Hydrogen Profile in the Liquid Phase
Figure (4.22) shows the comparison of hydrogen profile in the liquid
phase that is calculated from equation (3.90) with the model of Krishna and
de swart.(2002). As can be seen from this figure the present model is in
accord with model data of the Krishna and de swart.(2002).with deviation of
7%.

0 0.25 0.5 0.75 1
Reactor height
0.2
0.3
0.4
0.5
0.6
0.7
H
y
d
r
o
g
e
n
p
r
o
f
i
l
e
i
n
l
i
q
u
i
d
p
h
a
s
e
Krishna et al. model
Present model

Fig. (4.22): The comparison between the hydrogen liquid of the profile
present model with the model of Krishna (2002).

Chapter Five Conclusions & Recommendations

107
CHAPTER FIVE
CONCLUSIONS & RECOMMENDATIONS
5.1
The overall aim of this thesis is to get an understanding of the effect of the
design parameters, hydrodynamics parameters, and reaction kinetics on transport
processes in slurry bubble column reactor that is conducted in GTL process to
produce clean fuels of hydrocarbons.
Conclusions
The following major conclusions can be drawn from the present study: -

1- The results obtained in this work clearly point to the direct link between the
hydrodynamics, mass transfer, heat transfer, and reaction kinetics in slurry
bubble column reactor.
2- From the comparison of the results for both types of catalysts (Co and Fe), it is
clearly noted that, the Cobalt catalyst shows higher conversion value of about
(0.9) than that of the Iron catalyst (0.78). Therefore, Cobalt catalyst is the best
choice for the Fischer-Tropsch Synthesis due to the high conversion, and low
water gas shift activity compared with Iron catalyst.
3- The results point to that, both types of catalysts show a flat temperature profile a
long reactor height. This can be explained on the basis of a high dispersion in
liquid phase and confirms the well known fact that due to the good mixing
properties, slurry bubble column reactor offers relatively easy heat removal with
less cooling area than some other types of Fischer-Tropsch reactors.
4- The present model has studied the relation between superficial gas velocity and
heat transfer coefficient. The results indicate that the heat transfer coefficient
increases with superficial gas velocity increase, also the heat transfer coefficient
increases with increasing of the solid concentration.

108
5- Synthesis gas conversion decreases with increasing superficial gas velocity
because decrease in the residence time of the gaseous reactant (CO and H
2
6- The effect of reactor geometry on the performances of slurry bubble column
reactor is a very important factor. And it is noted that, the synthesis gas
conversion increases with increase in reactor height and decreases with increase
in reactor diameter.
)
which becomes too short for conversion. On the other hand the synthesis gas
conversion increases with catalyst concentration. Therefore for Cobalt and Iron
catalysts the reactor performance could be improved by increasing the catalyst
concentration.
7- The H
2
8- The results of the present model are compared with that of different models and
experimental work. The present model is in accord with model and experimental
data of authors with an error of about (5-10) %.
/CO ratio of the synthesis gas is an important design variable. For Cobalt
catalyst the favorable ratio is about 2, while for Iron catalyst it is in the range of
1.5 to 1.7.


109
5.2
Recommendations for future work are: -
Recommendations:

1- Study experimentally the conversion reaction in gas to liquid process
(GTL) by building a pilot plant and investigating different new types of
catalysts.
2- Develop the kinetic model to include the second and third order chemical
reactions for Cobalt and Iron catalysts.
3- An extension of the theoretical work can be done by using Computational
Fluid Dynamic (CFD), which is a new technique used recently for solution
and modeling of the transport phenomenon in bubble columns.
References

110
REFEREMCES

Abbott, J., and Crewdson, B., "Gas Heated Reforming Improves Fischer-
Tropsch Process.", Oil & Gas Journal, Vol. 16, P: 64-66, (2002).
Abdel-Rahman, Z., A., "Mixing in Three-Phase Gas Sparged System". Ph.D.
Thesis, University of Baghdad, Chem. Eng. Dep.,(1989).
Ahmad Tavasoli, Reza M. Malek Abbaslou, Ajay K. Dalai "Deactivation
Behavior of Ruthenium Promoted Co/g-Al
2
O
3
Ahon, V.R., Costa Jr. E.F.,.Monteagudo, J.E.P., Fontes, C.E., Biscaia Jr.
E.C., and Lage, P.L.C., "A Comprehensive Mathematical Model for Fischer
Tropsch Synthesis in Well-Mixed Slurry Reactors", Chem. Eng. Sci., Vol 60,
P: 677694 (2005).
Catalysts in FischerTropsch
Synthesis", Applied Catalysis, Vol. 346, P: 5864 (2008).
Alvarea, J.; and Al-Dahhanb, M. H., "Liquid Phase Mixing in Trayed
Bubble Column Reactors", Chem. Eng. Sci., Vol. 61, P: 1819 (2006).
Anderson, R.B., "The Fischer-Tropsch Synthesis", Academic Press Inc.,
Orlando, Florida, (1984).
Anfray, J., Bremaud, M., Fongarland, P., Khodakov, A., Jallais, S. Schweich,
D., "Kinetic Study and Modeling of FischerTropsch Reaction Over a
Co/Al
2
O
3
Auroba-Nafaa-Abdulla, "Gas Hold-Up and Volumetric Liquid-Phase Mass
Transfer Coefficient in Solid Suspended Bubble Columns". M.Sc. Thesis,
University of Technology, Chem. Eng. Dep.(1993).
Catalyst in a Slurry Reactor", Chemical Engineering Science Vol.
62, P: 5353 5356 (2007).
Bartholomew, C.H., and Farrauto, R.J., "Fundamentals of Industrial Catalytic
Processes", JohnWiley & Sons, New Jersey, 2nd ed. (2006).
References

111
Basini, L., and Piovesan, L., "Reduction on Synthesis Gas Costs by Decrease
of Steam/Carbon and Oxygen/Carbon Ratios in the feedstock", Ind. Eng.
Chem. Res.1998, vol.37, P258266.
Brakel, J. V., "Modeling in Chemical Engineering", Int.J. Philosophy of
Chemistry, Vol. 6, No. 2, P: 101 (2000). (Internet Site,
Korlsruhe.de/edol/Hyle6/Vonbrak.htm).
Brumby, A., Verhelst, M., and Cheret, D., "Recycling GTL Catalysts a New
Challenge", Catal. Today, Vol.106, P: 166169 (2005).
Calemma, V., Correra, S., Perego, C., Pollesel, P., and Pellegrini, L.,
"Hydroconversion of Fischer-Tropsch Waxes: Assessment of the Operating
Conditions Effect by Factorial Design Experiments", Catalysis Today. Vol.
106 Issue 1-4, P:282-287 September (2005).
Chaumat, H., Billet-Duquenne, A. M., Augier, F.; Mathieu, C., and Delmas,
H., "Mass Transfer in Bubble Column for Industrial Conditions - Effects of
Organic Medium, Gas and Liquid Flow Rates and Column Design", Chem.
Eng. Sci., Vol 60, P: 5930 (2005).
Chengtian Wu, Muthanna H. Al-Dahhana,, Anand Prakash "Heat Transfer
Coefficients in a High-Pressure Bubble Column" Chemical Engineering
Science, Vol. 62, P:140 147 (2007).
Chen, R.C., Reese, J., Fan, L.S., "Flow Structure in a Three-Dimensional
Bubble Column and Three-Phase Fluidized Bed". A.I.Ch.E. Journal, Vol. 40,
P:10931104 (1994).
Choi, G.N., Kramer, S.J., Tam, S.T., and Fox, J.M., "Design / Economics of
a Natural Gas Based Fischer-Tropsch Plant", in Spring National Meeting,
American Institute of Chemical Engineers, Houston, (1996).
Chowdhury, V.R., Mondal, K.C., and Choudhary, T.V., "Partial Oxidation of
Methane to Syngas with or without Simultaneous Steam or CO
2
Reforming
References

112
over a High-Temperature Stable - NiCoMgCeOx Supported on Zirconia
Hafnia Catalyst", Appl. Catal., A Gen. 306, P: 4550 (2006).
Cho, Y.J., Woo, K.J., Kang, Y., Kim, S.D., "Dynamic Characteristics of Heat
Transfer Coefficient in Pressurized Bubble Columns With Viscous Liquid
Medium" Chemical Engineering and Process, Vol. 41, P: 699706 (2002).
David stern, Alexis T. Bell, and Heinz Heinemann. "A Theoretical Model
For The Performance Of Bubble Column Reactors Used For Fischer-Tropsch
Synthesis" Chemical Engineering Science, Vol.40, No.9, P:1665-1677
(1985).
Deckwer, W.D., and Schumpe, A., "Improved Tools for Bubble Column
Reactor Design and Sscale-up", Chem. Eng. Sci. Vol. 48. No 5 , P: 889911
(1993).
Deckwer, W.D., "Bobble Column Reactors", John Wiley and sons, New
York (1991).
Deckwer W.D., Louisi, Y., Zaidi, A., and Ralek, M., "Hydrodynamic
Properties of the FisherTropsch Slurry Process". Ind Eng Chem Process Des
Dev, Vol. 19, P:699708 (1980).
De Smet, C.R.H., "Partial Oxidation of Methane to Synthesis Gas Reaction
Kinetics and Reactor Modelling", Ph.D.dissertation, Eindhoven, (2000).
De Swart, J.W.A., Krishna, R., and Sie, S.T., "Selection, Design, and Scale-
up of the FischerTropsch Reactor", Studies in Surface Science and Catalysis
107, P: 213218 (1997).
De Swart, J.W.A., "Scal-up of Fischer-Tropsch Slurry Reactor", Ph.D thesis,
University of Amsterdam, Amsterdam, Netherlands (1996).
De Swart, J.W.A., van Vliet, R.E. and Krishna, R., " Size, Structure and
Dynamics of Large Bubbles in a 2-D Slurry Bubble Column", Chem. Eng.
Sci., Vol.51, P: 4619-4629 (1996).
References

113
Ding, W. Ma, Y., Carreto, V.H., Guez, V., and Bukur, D.B., "Study on
Catalytic Performance and Attrition Strength of Ruhrchemie Catalyst for the
FischerTropsch Synthesis in a Stirred Tank Slurry Rreactor", Appl. Catal. A
Gen.268, P: 99106(2004).
Dragomir, B. Bukur,"Some Comments on Models For Fischer-Tropsch
Reaction in Slurry Bubble Column Reactors", Chem. Eng. Sci., Vol.38, No.3,
P:441-446 (1983).
Drahos,J., Zahradnik, J., Fialova ,M., and Braka, F., "Identification and
Modeling of Liquid Flow Structures in Bubble Column Reactors" Chem.
Eng. Sci., Vol. 47, No. 13/14, P: 3313 (1992).
Dry, M. E., "Catalytic Aspects of Industrial Fischer-Tropsch Sunthesis."
Journal of Molecular Catalysis Vol.71 P: 133-144 (1982).
Dry, M. E., "The Fischer-Tropsch Process 1950-2000." Catalysis Today ,
Vol. 71, No.3-4 P:227-241 (2002).
Dziallas, H., Michele, V., and Hempel, D. C., "Measurement of Local Phase
Holdups in a Two- and Three-Phase Bubble Column", Chem. Eng. Technol.,
Vol. 23, P: 877 (2000).
Ellenberger, J., and Krishna, R., "A Unified Approach to the Scale up of Gas-
Solid Fluidized and Gas-Liquid Bubble Column Reactors", Chem. Eng. Sci.,
Vol. 49, P: 5391-5411 (1994).
Fabiano A.N., Fernandes, F.A.N., Ulisses, M., "Modeling and Optimization
of FischerTropsch Products Hydro Cracking" Fuel Processing Technology,
Vol. 88, P: 207214 (2007).
Fair, J.R., Lambright, A.J., Anderson, J.W., "Heat Transfer and Gas Holdup
in a Sparged Contactor". Industrial and Engineering Chemistry, Process
Design and Development, Vol.1, P: 3336 (1962).
References

114
Fan, L.S., Yang, G.Q., Lee, D.J., Tsuchiya, K. and Luo, X., "Some Aspects
of High-Pressure Phenomena of Bubbles in Liquids and Liquid-Solid
Suspensions", Chem.Eng. Sci., Vol. 54, P:4681-4709 (1999).
Fernandes, F.A.N., and Fabiano A.N., "Polymerization Kinetics of Fischer-
Tropsch Reaction on Iron Based Catalysts and Product Grade Optimization",
Chemical Engineering and Technology, Vol. 28, No. 8, P: 930-938 August
(2005).
Fernandes, F.A.N., "Modeling and Product Grade Optimization of Fischer
Tropsch Synthesis in a Slurry Reactor", Ind. Eng. Chem. Res., Vol. 45, P:
10471057 (2006).
Fleisch, T. H., Sills, R. A., Briscoe, M. D., "Emergency of the Gas-to-Liquids
Industry: a Review of Global GTL Developments", J. Nat.Gas Chem. Vol.
11, P: 1 (2002).
Fox, III, J.M., "The Different Catalytic Routes for Methane Valorization: an
Assessment of Processes for Liquid Fuels", Catal. Rev. Sci. Eng., Vol. 35, P:
169212 (1993).
Gerard P., van Der Laan, Antonie A.C.M., Beenackers, and Rajamani
Krishna, "Multicomponent Reaction Engineering Model for Fe-Catalyzed
Fischer-Tropsch Synthesis in Commercial Scale Slurry Bubble Column
Reactors" Chemical Engineering Science, Vol. 54, P: 5013-5019 (1999).
Gregor, J.H., "Fischer-Tropsch Products as Liquid Fuels or Chemicals. An
economical evaluation", Catal. Lett., Vol. 7, P: 317332 (1990).
Godley N, and Thijssen, J H J. "GTL Technology Update, ADL Web- site:
www.adltechnology.com/industrydocs/oillinks.htm, (2000).
Guillou, L., Paul, S., Le Courtois, V., "Investigation of H2 Staging Effects on
CO Conversion and Product Distribution for FischerTropsch Synthesis in a
References

115
Structured Micro Channel Reactor", Chemical Engineering Journal, Vol. 136,
P: 6676 (2008).
Haid, M. O., Schubert, P. F., and Bayens, C. A., "Synthetic Fuel and
Lubricants Production Using Gas-to-Liquids Technology", DGMK
Tagungsbericht, Vol.3, P: 205-212 (2000).
Hall, C.C., Gall, D., Smith, S.L.J., Inet .pet., Vol. 38 , P: 845 (1952) cited in
Deckwer (1991).
Hart, W.F., "Heat Transfer in Bubble-Agitated Systems", A general
correlation. Industrial and Engineering Chemistry Research, Vol. 15, P:109
114 (1976).
Heng, H.C., and Idrus, S., "The Future of Gas-to-Liquids as a Gas
Monetisation Option", J. Nat. Gas Chem.,Vol. 13, P: 6370 (2004).
Hikita, H., Asal, S., Kikukawa, H., Zaike, T., Ohue, M., "Heat Transfer
Coefficient in Bubble Columns", Industrial and Engineering Chemistry,
Process Design and Development, Vol. 20, P: 540545 (1981).
Hindermann, J.P., Hutchings, G.J., and Kiennemann, A., "Mechanistic
Aspects of the Formation of Hydrocarbons and Alcohols from CO
Hydrogenation", Catalysis Reviews: Science & Engineering, Vol. 35, P: 1-
127 (1993).
Hoefsloot, H.C.J., and Krishna, R., "Influence of Gas Density of Flow
Regime Transitions in Homogenous Flow in Bubble Columns", Ind. Eng.
Chem. Research, Vol.32, P: 747-750 (1993).
Inga, J. R., and Morsi, B. I., "A Novel Approach for the Assessment of the
Rate-Limiting Step in Fischer-Tropsch Slurry Process", Energy Fuel, Vol.10,
P: 566 (1996).
Jager, B., "Developments in Fischer-Tropsch technology", Stud. Surf. Sci.
Catal. Vol. 107, 219224 (1997).
References

116
Jager, B., "Development of Fischer-Tropsch Reactors", In AIChE Spring
meeting, New Orleans, Louisiana April 1, (2003).
Jager, B., Dry, M.E., Shingles, T., and Steynberg, A.P., "Experience With a
New Type of Reactor for Fischer-Tropsch Synthesis", Catal. Lett., Vol. 7, P:
293302 (1990).
Jager, B.; Espinoza, R., "Advances in Low-Temperature Fischer-Tropsch
Synthesis", Catal. Today, Vol.23, P:1728 (1995).
Joan M. Biales, Ying Di Wan, Peter K. Kilpatrick, and George W. Roberts,
"Separation of Fischer-Tropsch Wax from Catalyst Using Near-Critical Fluid
Extraction" Analysis of Process Feasibility Energy & Fuels, Vol. 13, P: 667-
677 (1999).
Jothimurugesan, K., Goodwin Jr. J.G., Gangwal, S.K., and Spivey, J.J.,
"Development of Fe FischerTropsch Catalysts for Slurry Bubble Column
Reactors", Catal. Today, Vol. 58, P: 335344 (2000).
Khailed A.Sukkar " Heat Convection and Performance in Bubble Columns"
Ph.D. Thesis, University of Technology, Chem. Eng. Dep.,(2004).
Kantarci, N., Ulgen, K.O., Borak, F., "A Study on Hydrodynamics and Heat
Transfer in a Bubble Column Reactor With Yeast and Bacterial Cell
Suspensions", The Canadian Journal of Chemical Engineering Vol.83, P:
764773 (2005).
Kato, Y., Nishiwaki, A., Fukuda, T., Tanaka, S.J.,Chem. Eng. Jpn., Vol. 5,
P:112, (1972) cited in Deckwer (1991).
Koide, K., and Shibata, J., of chem. Eng. of Japan, Vol. 25, No.1, (1992)
cited in Deckwer (1991).
Koid, K., Taka-Zawa, A., and Komaram, "Gas Hold- up and Volumetric
Lquid-Phase Mass Transfer Coefficient in Solid Suspended Bubble
Columns", J., of Chem. Eng. of Japan, No.5, Vol.17, P:459 (1984).
References

117
Kolbel, H, and Ralek, M., "The Fischer-Tropsch Synthesis in the Liquid
Phase", Catal. Rev. Sci. Eng., Vol. 21, P: 225274 (1980).
Kolbel, H., Borchers, E., and Martins, J., "Warmeubergang in Blasensaulen.
III. Messungen an Gas Durchstromten Suspensionen", Chem.Eng.Tech.,
Vol.32, P: 8-84 (1960).
Kroschwitz, I., and Howe-Grant, M., "Kirk-Othmer encyclopedia of chemical
technology", Wiley & Sons, New York, fourth edn. (1996).
Krishna, R., and de Swart, J.W.A., "Simulation of the Transient and Steady
State Behaviour of a Bubble Column Slurry Reactor for FischerTropsch
Synthesis", Chemical Engineering and Processing, Vol. 41, P: 3547 (2002).
Krishna R., and Sie, S.T., "Selection, Design and Scale-up Aspects of
FischerTropsch Reactors", Fuel Processing Tech., Vol. 64, P: 73105
(2000).
Krishna, R., and van Baten J.M., "A Strategy for Scaling up the Fischer
Tropsch Bubble Column Slurry Reactor", Topics in Catalysis, Vol. 26, P: 1
4 December (2003).
Krishna, R., Ellenberger, J., and Hennephof, D.E., "Analogous Description of
Gas-Solid Fluidized Beds and Bubble Columns". Chem. Eng. J., Vol. 53, P:
89-101 (1993).
Laurent Sehabiague, Romain Lemoine , Arsam Behkish, Yannick J.Heintz,
Mariela Sanoja, Rachid oukaci, Badie I.Morsi ,. "Modeling and Optimization
of a Large-Scale Slurry Bubble Column Reactor for Producing 10.000
bbl/day of Fisher-Tropsch Hydrocarbons". Journal of the Chinese Institute of
Chemical Engineers, Vol. 39, P: 169-179 (2008).
Levenspeil, O., "What will Come After Petroleum?", Ind. Eng. Chem. Res.
Vol. 44, No.14, P: 50735078 (2005).
References

118
Letzel, H.M., Schouten, J.C., van den Bleek, C.M., and Krishna, R., "Gas
Holdup and Mass Transfer in Bubble Column Reactors Operated at Elevated
Pressure". Chem. Eng.Sci., Vol. 54, P: 2237-2246((1999).
Lewis, D.A., Field, R.W., Xavier, A.M., Edwards, D., "Heat Transfer in
Bubble Columns", Transactions of the Institution of Chemical Engineers,
Vol. 60, P:4047 (1982).
Li, H., Prakash, A., "Analysis of Flow Patterns in Bubble and Slurry Bubble
Columns Based on Local Heat Transfer Measurements", Chemical
Engineering Journal, Vol. 86, P: 269276 (2002).
Li, H., and Prakash, A., "Heat Transfer and Hydrodynamics in a Three-
Phase Slurry Bubble Column", Industrial and Engineering Chemistry
Research, Vol. 36, P: 46884694 (1997).
Li, H., Prakash, A., "Influence of Slurry Concentrations on Bubble
Population and Their Rise Velocities in Three-Phase Slurry Bubble Column".
Sited in: Powder Technol., 113 P:158-167 (2000).
Luo, X., Lee, D.J., Lau, R., Yang, G.Q., Fan, L.S., "Maximum Stable Bubble
Size and Gas Hold Up in High-Pressure Slurry Bubble Column", A.I.Ch.E.
Journal, Vol. 45, P: 665680 (1999).
Maretto, C., and Krishna, R., "Modelling of A bubble Column Slurry Reactor
for FischerTropsch Synthesis", Catal. Today, Vol.52 ,P: 279289 (1999).
Michael, C.J., Bradford, Mure, Te., Allen Pollack, "Monolith Loop Catalytic
Membrane Reactor for FischerTropsch Synthesis", Applied Catalysis A:
General 283, P: 3946 (2005).
Mills P.L., Turner, J.R. , Ramachandran, P.A., Dudukovic, M.P., "The
FischerTropsch Synthesis in Slurry Bubble Column Reactors: Analysis of
Reactor Performance Using the Axial Dispersion Model", in: A. Schumpe,
References

119
K.D.P., Nigam (Eds.), "Three Phase Sparged Reactors", Gordon and Breach,
New York, Chapter 5. (1996).
Naseer Aboud Al-Hapoby, "Gas Hold-Up and Volumetric Liquid-Phase
Mass Transfer Coefficient in Solid Suspended Bubble Columns with Draught
Tube". M.Sc. Thesis, Univesity of Technology, Chem. Eng. Dep., (1994).
Novica Rados, Muthanna H. Al-Dahhan, Milorad P. Dudukovic, "Modeling
of the Fischer-Tropsch Synthesis in Slurry Bubble Column Reactors",
Catalyst Today, Vol. 79-83, P: 211-218 (2003)
Ong, B.C., "Experimental Investigation of Bubble Column Hydrodynamics:
Effect of Elevated Pressure and Superficial Gas Velocity", Ph.D. Thesis,
Washington University in Saint Louis, (2003).
Pedrick, L.E., Mauldin, C.H., and Behrmann, W.C., U.S. Patent, 5268,344
(1993).
Pham, H.N., and Datye, A.K., "The Synthesis of Attrition Resistant Slurry
Phase Iron FischerTropsch Catalyst", Catal. Today, Vol. 58, P: 233240
(2000).
Pichler, H., Schulz, H., Eistner, M., "Gesetzmassigkeiten Bei Der Synthese
Von Kolenwasserstoffen" Aus Kolenoxid und Wasserstoff, Breenstoff-
Chemie, 3, 78-87, (1967)
Quiroz, I., Herrera, I., and Gonzales-Mendizabal, "Experimental Study on
Convective Coefficients in a Slurry Bubble Column", Int. Comm. Heat Mass
Transfer, Vol. 30, No. 6, P: 775-786 (2003).
Rachid Oukaci, Alan H. Singleton, and James G. Goodwin Jr., "Comparison
of Patented Co FT Catalysts Using Fixed-bed and Slurry Bubble Column
Reactors" Applied Catalysis A: General 186, P: 129144 (1999).
Rados, N., "Slurry Bubble Column Hydrodynamics: Experimentation and
Modeling", Ph.D. Thesis, Washington University in Saint Louis, (2002).
References

120
Rao K R P M., Huggins F. E., Mahajan V., Huffman G.P., Rao V U S., Bhatt
B L., Bukur D B., Davis B H., OBrien R J., "Mossbauer Spectroscopy Study
of Iron-Based Catalysts Used in Fischer-Tropsch Synthesis", Top Catal., Vol.
2, No. 1-2, P: 71-78 (1995).
Rostrup-Nielsen, J. R., "New Aspects of Syngas Production and Use."
Catalysis Today, Vol. 63, P: 159-167 (2000).
Sadaghiani, A., Nakhaeipour, A., Tavasol, K., Ghalbi M. Ahangari, "Cobalt
Loading Effects on the Structure and Activity for FischerTropsch and
Watergas Shift Reactions of Co/Al
2
O
3
Saib, A.M., Borgna, A., van de Loosdrecht, J., van Berge, P.J., and
Niemantsverdriet, J.W., Appl. Catal. A: Gen. 312, P:1219 (2006).
Catalysts", Iran. J., Chem. Chem.
Eng., Vol. 26 (2007).
Saib, A.M., Borgna, A., van de Loosdrecht, J., van Berge, P.J.,
Niemantsverdriet, J.W., " XANES Study of the Susceptibility of Nano-Sized
Cobalt Crystallites to Oxidation During Realistic Fischer-Tropsch Synthesis",
Appl Catal. A: Gen. 312 (2006).
Sardeing, R., Painmanakul, P., and Hebrard, G., "Effect of Surfactants on
Liquid-Side Mass Transfer Coefficients in Gas-Liquid Systems: A First Step
to Modeling", Chem. Eng. Sci., Vol. 61, P: 6249 (2006).
Satterfield, C.N.; and Huff, G.A., Chem. Eng. Sci., Vol.35 P:195 (1980) cited
in Deckwer (1991).
Saxena, S.C., "Heat Transfer From a Cylindrical Probe Immersed in a Bubble
Column". Chemical Engineering Journal, Vol. 41, P:2539 (1989).
Saxena, S.C., Rao, N.S., Saxena, A.C., "Heat Transfer From a Cylindrical
Probe Immersed in a Three-Phase Slurry Bubble Column", Chemical
Engineering Journal, Vol. 44, P:141156 (1990).
References

121
Schluter, S., Steiff, A., Weinspach, P.-M., "Heat Transfer in Two- and Three-
Phase Bubble Column Reactors With Internals". Chemical Engineering and
Processing, Vol. 34, P:157172 (1995).
Senden, M. M. G., Sie, S. T., Post, M. F. M., and Ansorge, J., "Engineering
Aspects of the Conversion of Natural Gas into Middle Distillates." NATO
ASI Series, Series E: Applied Sciences 225, "Chemical Reactor Technology
for Environmentally Safe Reactors and Products", Vol. 47, P: 227 (1992).
Shaikh, A., and Al-Dahhan, M., "Characterization of the Hydrodynamic
Flow Regime in Bubble Columns via Computed Tomography", Flow Meas.
Instrum. Vol. 16, P: 91(2005).
Sie, S.T., "Process Development and Scale up: IV Case History of the
Development of a Fischer-Tropsch Synthesis Process", Rev. Chem. Eng.,
Vol. 14, P: 109157 (1998).
Soled, S.L., Iglesia, E., Fiato, R.A., Ansell, G.B., U.S. Patent, 5,397,806
(1995).
Tavasoli, A., "Catalyst Composition and its Distribution Effects on the
Enhancement of Activity, Selectivity and Suppression of Deactivation Rate
of FTS Cobalt Catalysts", Ph.D. Thesis, University of Tehran (2005).
Tiefeng Wang, Jinfu Wang, and Yong Jin, "Slurry Reactors for Gas-to-
Liquid Processes", A Review Ind. Eng. Chem. Res., Vol. 46,P: 5824-5847
(2007).
Van Baten J.M, Ellenberger, J., Krishna, R., Scale-up Strategy for Bubble
Column Slurry Reactors Using CFD Simulations", Catalysis Today, Vol. 79
80, P: 259265 (2003).
Van der Laan, G.P., and Beenackers, A.A.C.M., "Kinetics and Selectivity of
the Fischer-Tropsch Synthesis" A Literature Review, Catal. Rev., Sci. Eng.,
Vol. 41, P: 255 (1999).
References

122
Vandu, C. O., Koop, K., and Krishna, R., "Large Bubble Sizes and Rise
Velocities in a Bubble Column Slurry Reactor". Chem. Eng. Technol., Vol.
27, P: 1195 (2004).
Van Nierop, P., Erasmus, H.H., and van Zyl, J.J., "Sasol's Achievements if
the 20th Century as a Building Block for the 21st." Presented at the 2000
Gasification Technologies Council, San Francisco, CA P: 8-11, October
(2000).
Verma, A.K., "Heat Transfer Mechanism in Bubble Column". Chemical
Engineering Journal, Vol. 42, P: 205208 (1989).
Vermeer, D.J., and Krishna, R., "Hydrodynamics and Mass Transfer in
Bubble Columns Operating in the Churn-Turbulent Regime", Ind. Eng.
Chem. Process Design and Dev., Vol. 20, P : 475-482 (1981).
Vosloo, A. C., "Fischer-Tropsch: a Futuristic View", Fuel Processing
Technology, vol. 71, No. 1-3, P: 149-155 (2001).
Wallis.W.G.,"One Dimensional two Phase Flow", McGraw-Hill, New york
(1969) .
Wan, H .J., Wu, B. S., Zhang, C. H., Teng, B. T., Tao, Z. C., Yang, Y., Zhu,
Y. L., Xiang, H. W., and Li, Y. W., "Effect of Al
2
O
3
/SiO
2
Wang, T. F., Wang, J. F., and Jin, Y.A, "Theoretical Prediction of Flow
Regime Transition in Bubble Columns by the Population Balance Model",
Chem. Eng. Sci., Vol. 60, P: 6199 (2005).
Ratio on Iron-
Based Catalysts for Fischer-Tropsch Synthesis", Fuel, Vol. 85, No. 10-11, P:
1371-1377 (2006).
Xing, T., Hu, J., Jia, Q., Hao, H., Yang, D., Guo, Y., Hu, X., "Methane
Partial Oxidation to Syngas in YBa
2
Cu
3
O
7
x Membrane Reactor", Appl.
Catal., A Gen. 306, P: 2933 (2006).
References

123
Xue, J., "Bubble Velocity, Size and Interfacial Area Measurements in Bubble
Columns". Ph.D. Thesis, Washington University in Saint Louis, (2004).
Yang, G.Q., Luo, X., Lau, R., Fan, L.-S., "Heat Transfer Characteristics in
Slurry Bubble Columns at Elevated Pressures and Temperatures". Industrial
and Engineering Chemistry Research, Vol. 39, P: 25682577 (2000).
Yang, Y., Xiang, H.W., Xu, Y.Y., Bai, L, and Li, Y. W., "Effect of
Potassium on Precipitated Iron-Manganese Catalyst for Fischer-Tropsch
Synthesis". Appl Catal A, 266(2) P: 181-194 (2004).
Yi-Ning Wang , Wen-Ping Ma, Yi-Jun Lu, Jun Yang, Yuan-Yuan Xu, Hong-
Wei Xiang,Yong-Wang Lia, Yu-Long Zhaoa, Bi-Jiang Zhanga, "Kinetics
Modelling of FischerTropsch Synthesis Over an Industrial FeCuK
Catalyst", Fuel, Vol. 82, P:195213 (2003).
Yu Wang, Wei Fan, Ying Liu, Zhiyong Zeng, Xu Hao, Ming Chang,
Chenghua Zhang, Yuanyuan Xu, Hongwei Xianga, Yongwang Li "Modeling
of the FischerTropsch Synthesis in Slurry Bubble Column Reactors"
Chemical Engineering and Processing, Vol. 47, P: 222228 (2008).
Zhang, C.H., Yang, Y., Teng, B.T., Li, T.Z., Zheng, H.Y.,Xiang, H.W., and
Li, Y.W., "Study of an Iron-Manganese FischerTropsch Synthesis Catalyst
Promoted With Copper", J. Catal., A Gen. 237 P:405415 (2006).
Zhang, J., Chen, J., Li, Y., and Sun, Y., "Recent Technological
Developments in Cobalt Catalysts for FTS", J. Nat. Gas Chem., Vol. 11, P:
99108 (2002).
Zhou, Z., Zhang, Y., Tierney, J.W., Wender, I., "Hybrid Zirconia Catalysts
for Conversion of FisherTropsch Waxy Products to Transportation Fuels",
fuel Process. Techno., Vol. 83, P: 6780 (2003).

Appendix A
A -1
APPENDIX A
COMPUTER SIMULATION FORTRAN
PROGRAM

PROGRAM ALI
IMPLICIT NONE
INTEGER,PARAMETER::M=21
REAL,DIMENSION(1:M)::Y,TH,X,Z,Ccat,XH,XH2
REAL,DIMENSION(1:M)::StG,UGd,EG,DG,BOG,a,E,StL,ETA_SO,Pe
REAL,DIMENSION(1:M)::aS,KS,ETA_S,Fr,Boc,h,StH,DL,Lmda_ax,BOL
REAL::UGO,L
REAL::U,I,ALFAS,ALFA,dR
REAL::R,T,Tw,He,Wcat,KL
REAL::rouL,meuL,DLH,Vcat,roud,meud,rou_cat
REAL::EL,Da,Kf,GAMA,EA,Ccatd,dcat,G
REAL::Kfod,MKAM
INTEGER::IT,J,MJ1
REAL::LZ,DZ,Rel
REAL::Be,aH,Cp,Lmda_cat,LmdaL,Lmdad,Cp_cat,CpL
REAL::dHR,P,yo
REAL::ANS
REAL::ERROER,ERMAX,XH2OLD

OPEN(1,FILE='Y-X.PLT')
OPEN(2,FILE='Ccat.PLT')
OPEN(3,FILE='XH2.PLT')
OPEN(4,FILE='TEMP.PLT')
OPEN(5,FILE='UGd.PLT')
OPEN(10,FILE='INT.PLT')
OPEN(20,FILE='CONV.PLT')

MJ1=M-1
LZ=
Rel=
DZ=LZ/REAL(MJ1)
DO J=1,M
Z(J)=DZ*(J-1)
Appendix A
A -2
TH(J)=
ENDDO

R=
!EQUATION1
U=
I=
L=
UGO=
dR=
ALFA=
P=
yo=

IT=0
DO
IT=IT+1

DO J=1,M
!EQUATION1

!---BOG-----------------------------
ALFAs=ALFA*(1+U)/(1+I)
UGd(J)=(1+ALFAs)/(1+ALFAs*Y(J))
EG(J)=0.053*UGd(J)**1.1
DG(J)=5E-4*(UGd(J)/EG(J))**3*dR**1.5
BOG(J)=UGO*L/DG(J)/EG(J)

PRINT*,"ALFAs,UGD,EG,DG,BOG"
PRINT*,ALFAs,UGD,EG,DG,BOG
!----------------------------------
T=
rou_cat=
Wcat=
rouL=0.758-0.555E-3*(T-373)
meuL=0.052*EXP(-6.905+3266./T)
DLH=7.35E-3*EXP(-2285/T)
He=2.291E7*EXP(-1.2326+(583/T))
Vcat=rouL*Wcat/(rou_cat-Wcat*(rou_cat-rouL))
roud=Vcat*rou_cat+(1-Vcat)*rouL
meud=meuL*(1+4.5*Vcat)
Appendix A
A -3
!---StG-----------------------------
Tw=
a(J)=4.5*UGd(J)**1.1
KL=0.1165*(roud/meud*EXP(-4570/T))**(1/3.0)
StG(J)=KL*a(J)*L/UGO*R*Tw/He*1000.0
!--------------------------------------
!EQUATION2
!---BOL-----------------------------
EA=
Ccatd=
G=
Kfod=
EL=
IF(UGd(J)<=6)THEN
E(J)=UGd(J)*G
ELSE
E(J)=5886
ENDIF
DL(J)=3.676*UGd(J)**0.32*dR**1.34
BOL(J)=2.83*(UGd(J)**2/G/dr)

!-Da--------------------------
Kf=Kfod/(1+U)
PRINT*,KF,EL,L,UGO
Da=Kf*EL*L/UGO
!---------------------------
StL(J)=KL*a(J)*L/UGO
GAMA=EA/R/TW*1000.0
dcat=
aS(J)=6*Wcat*(1-EG(J))*roud/dcat/rou_cat
KS(J)=DL(J)/dcat*(2+0.545*(meuL/rouL/DL(J))**(1/3.0)*(E(J)*dcat**4*
rouL**3/meuL**3))

!---ETA_S-----------------------------
ETA_SO(J)=Kf*Ccatd*EL/KS(J)/aS(J)
ETA_S(J)=(1+ETA_SO(J)*EXP(-GAMA/TH(J)))**(-1)

!---Ccat-----------------------------
Fr(J)=UGd(J)/SQRT(G*dR)
Boc(J)=13.*Fr(J)/(1+8*Fr(J)**0.85)
Ccat(J)=Ccatd*Boc(J)*EXP(-Boc(J)*Z(J))/(1-EXP(-Boc(J)))
Appendix A
A -4

!EQUATION3
!---StH-----------------------------
aH=
CpL=
Cp_cat=
LmdaL=
Lmda_cat=
Cp=Wcat*Cp_cat+(1-Wcat)*CpL
Lmdad=LmdaL*(2.*LmdaL+Lmda_cat-2.*Vcat*(LmdaL-Lmda_cat))/&
(2.*LmdaL+Lmda_cat+Vcat*(LmdaL-Lmda_cat))
h(J)=0.1*roud*Cp*UGd(J)*(UGd(J)**3*roud/G/meud*(meud*Cp/Lmdad)
**2)**(-0.25)
StH(J)=h(J)*aH*L/UGO/roud/Cp
Lmda_ax(J)=DL(J)*roud*Cp
Pe(J)=UGO*roud*Cp*L/EL/Lmda_ax(J)

!--Be---------------------------------
dHR=(165+40*(U-0.5)/1.5)
Be=dHR/roud/Cp*P*yo/He/Tw
XH(J)=1-UGd(J)*Y(J)
XH2(J)=(1+U)/(1+I)*XH(J)

ENDDO

DO J=2,MJ1
Y(J)=(1-Rel)*Y(J)+Rel*( 1/BOG(J)*(Y(J+1)+Y(J-1))/DZ**2-
(1+ALFAs)/(1+ALFAs*Y(J))**2*(Y(J+1)-Y(J-1))/2.0/DZ+&
StG(J)*TH(J)*X(J) )/(2/DZ**2/BOG(J)+StG(J)*TH(J))

MKAM=( 2.0/BOL(J)/DZ**2+StL(J)+Da*ETA_S(J)*Ccat(J)*EXP
(-GAMA/TH(J)) )
PRINT*,MKAM,STL,GAMA,BOL,Da,ETA_S ,Ccat

X(J)=(1-Rel)*X(J)+Rel*( 1/BOL(J)*(X(J+1)+X(J-1))/DZ**2+StL(J)*Y(J) )
/MKAM

TH(J)=(1-Rel)*TH(J)+Rel*(1/Pe(J)*(TH(J+1)+TH(J-1))/DZ**2+StH(J)+
Be*Da*ETA_S(J)*&
Ccat(J)*EXP(-GAMA/TH(J))*X(J))/(2./Pe(J)/DZ**2+StH(J))
Appendix A
A -5
ENDDO
Y(1)=Y(2)+BOG(1)*DZ*( 1-( (1+ALFAS)*Y(1)/(1+ALFAS*Y(1)) ) )
X(1)=X(2)
TH(1)=TH(2)

Y(M)=Y(MJ1)
X(M)=X(MJ1)
TH(M)=TH(MJ1)

ERMAX=1E-5
XH2OLD=ANS

CALL INTG(XH2,DZ,ANS)

ERROER=ABS(ANS-XH2OLD)
PRINT*,IT,ERROER
WRITE(20,*)IT,ERROER,ANS
IF(ERROER<ERMAX)EXIT

ENDDO !FOR MAIN ITRATION

DO J=1,M
WRITE(1,"(3F20.15)")Z(J),Y(J),X(J)
ENDDO

DO J=1,M
WRITE(4,"(2F20.15)")Z(J),TH(J)*TW-273
ENDDO

DO J=1,M
WRITE(2,"(2F20.15)")Z(J),Ccat(J)*100.0
ENDDO

DO J=1,M
WRITE(3,"(3F20.15)")Z(J),XH2(J),UGd(J)
ENDDO

DO J=1,M
WRITE(5,"(3F20.15)")Z(J),UGd(J),EG(J)
ENDDO
Appendix A
A -6

CALL INTG(XH2,DZ,ANS)
WRITE(10,"(A,F20.15)")"XH2",ANS

CALL INTG(X,DZ,ANS)
WRITE(10,"(A,F20.15)")"X",ANS

END PROGRAM ALI

!0000000000000000000000000000000000000000000000000000000000000
00
SUBROUTINE INTG(FIA,DZ,I)
IMPLICIT NONE
INTEGER,PARAMETER::NT=21
REAL,DIMENSION(1:NT)::FIA
REAL::SUMOLD,SUMEVEN
REAL::DZ,I,LZ
INTEGER::N
LZ=
SUMEVEN=0.0
SUMOLD=0.0
DO N=2,NT-1,2
SUMEVEN=SUMEVEN+4.*FIA(N)
ENDDO
DO N=3,NT-2,2
SUMOLD=SUMOLD+2.*FIA(N)
ENDDO

I=DZ/3.*(FIA(1)+SUMOLD+SUMEVEN+FIA(NT))/LZ
END SUBROUTINE INTG
!----------------------------------------------------------------

Appendix B
B -1
APPENDIX B
ALGORITHM OF FORTRAN PROGRAM

START
MJ
1
=M - 1

Read I nput Data
Ugo , L , dR , P , I , U etc

D
Z
=L
Z
/ Real (MJ
1
)
Do J =1, M
Z (J ) =D
Z
* ( J -1 )
TH ( J ) =1
I f
J >M
No
Yes
I
U
*
+
+
=
1
1

Y *
*
g
U
+
+
=
1
1
I T =0
I T =I T +1
Appendix B
B -2

1 . 1
053 . 0
g
U
g
E =

) (T * . - .
-
L
373 10 555 0 758 0
3
=
5 1 3 4
10 5
.
Dr )
g
/E
g
u ( *
g
D

=
g
E
g
D
L
go
u
BOG =
)) T / (3266 6.905 - ( exp 0.052
L
+ =
) ( * . D
-
L.H
T 2285/ - exp 10 35 7
3
=
/T) ( . ( * . He 583 2326 1 exp 10 291 2
7
+ =

) - ( W -
W
V
L P P P
P L
P

=
L
1 ) V ( V
P P P
+ =
) V . (
P
L
5 4 1+ =

1.1
g
U 4.5 a =
Appendix B
B -3

1/3
) T (-4570/ exp
0.1165 K
L |
|
.
|
\
|
=
go
u He
L T R
a) (K
g
St
W
H L

=
34 1 32 0
676 3
.

.
Dr
g
u . D
L
=
I f
6 g U

Yes
No
g
g
u E * =
5886 E =
34 0
2

83 2
.
OL
g Dr
g
u
. B
|
|
|
.
|
\
|
=
U
fo
K
f
+
=
1
K

go
u
L E
f
K
Da

L
=
Appendix B
B -4

W A
/ R T E =
go
u
L
a) (K St
H L L
=
P P
P
P
d
)
g
E ( W
a

=
1
6
(
(
(
|
|
|
.
|
\
|
|
|
.
|
\
|
+ =
d E
D
0.545 2
d
D
K
3
3 4 1/3
L
L P
L L
L
P
L
P

P P
L
P
PO
a K
E C
f
K
=
1
)) exp 1
(
-
/ (- (
PO ) P
+ =
g Dr / u Fr
g
=
85 0
1
13
.
OC
Fr
Fr
E
Dr
g
u
B
C
+
= =
) B (
) B (
B
C
C
OC
OC
OC
P
P (Z)

= exp
exp 1

Appendix B
B -5

L
P P
P
)Cp W ( Cp W Cp + = 1
) ( V
) ( V

P L P P
L
P L P P L
L
+ +
+
=
2
2 2

0.25
2
3
1 0
(
(
(
(
|
|
.
|
\
|
|
|
|
|
.
|
\
|
=
Cp
g
g
u
)
g
u Cp ( . h
Cp
go
u
L h a
St
H
H
=
C D
p
L
ax
=
OL B
K E
L Cp
go
u
Pe
ax L
= =
5 1 5 0 40 165 . )/ . *(U H
R
+ =

T He
o
y P
)
Cp
R
H -
( Be
W
=

) Y
g
U ( X
H
=1
Appendix B
B -6

) Y
g
U (
I
U
X
H CO

+
+
=
+
1
1
1
2
(J)
OG
(J)
(J)
) (J ) (J
(J)
) J ) (J
(J)
g
St
B

X
g
St
*
Y Y
*
) Y * (
*) (
Y Y
B

Y
OG
+
+
+
+
+
|
|
.
|
\
|
+ +
=
2
2
2
2
2
1
1 1 1 1 1 ( 1

I f
J >M
No
Yes
Do J =2 , MJ
1
Go To
Do
Loop

) / ( exp C Da St
B
Y St
B
X X
X
(J)
) P(
) ( P
L
2
(J)
L
1) (J 1) (J

) (
2
OL
2
OL
+ +
+
+ +
=

St
2
Pe
1
(i) X C ) / ( exp Da Be St
z

Pe
1

H
P ) p(
(i) H
1) (i 1) (i
(i)
2
2
(
(
(
(
(
+
+ +
+
=
+

I f
J >M
Yes
No
Appendix B
B -7

Calculate Boundary Condition
1-
2
1
OG
) (
) ( Y Y
B
1
Y * 1
Y *) (1
1
i
i
+
+
=
2-
1 1
X X =
3-
2 1
=
4- m m X X 1 =
5- 1 = m m Y Y
6- 1 m m =
ER Max =1E-5
X
CO+H2
old =Mean X
CO+H2

Calculate Mean X
CO+H2
by using
simsun role program
Error =ABS =( Mean X
CO+H2
- X
CO+H2
old )

Write I T, Error, X
CO+H2
Mean
I f
Error <
ER Mxa
Yes
No
Go To
I tration
Loop
Do J =1 , M

Write Y , X , TH , X
CO+H2
, Pe ,ST
H ,
h ,
Fr etc
Appendix B
B -8

I f
J >M
Yes
No
Go To Do
Loop
End

Appendix B
B -9

START
Read I nput Data
FI A ,SUMOLD,
SUMEVEN etc

Do J =2, NT-1 ,2
SUMEVEN =SUMEVEN +4 * FI A
I f
J <M
No
Yes
SUMEVEN =0
SUMOLD =0
Do J =3, NT-2 ,2
SUMOLD =SUMOLD +2 * FI A
I f
J <M
No
Yes
Z
Z
L NT FIA SUMEVEN SUMOLD FIA
D
I / ) ( ) 1 ( *
3
+ + + =
END

- 1 -
U

.
.
.

.

:

- :
0 (
1
1 1
2
2
) X - Y - St
d
Y d
) Y * (
*) (
-
d
Y d
B

g
OG
=
+
+

- :
0 exp
1
)
2
2
= + X /) ( C Da ) X - Y ( St
d
X d
B

P (Z) P( L
OL

- :
0 exp 1 -
1
) ( 2
2
X C /) ( Be Da ) ( - St
d
d
Pe
P p H
= +

) finite difference method (
.

- 2 -

.
) (
.
90 % 78 %
.
HR
2
R/CO
2 1.5 1.7 .

.
6 - 9 .%

Simulation of GTL Process in Slurry Bubble Column Reactor

Uploaded by

Document Information

Original Description:

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Simulation of GTL Process in Slurry Bubble Column Reactor

Uploaded by

Copyright:

Available Formats

A Thesis

Heat conductivity of catalyst ( W/ m K )

You might also like