POLITECNICO DI MILANO

School of Industrial and Information Engineering

Master of Science in Chemical Engineering

Development of a Model for Packed foam

Fischer-Tropsch Reactors and
Optimization through Artificial Neural Networks

Supervisor: Prof. Enrico Tronconi

Co-Supervisors: Dr. Ing. Laura Fratalocchi, Ph.D.

Prof. Gianpiero Groppi
Dr. Ing. Tommaso Selleri, PhD

Master Thesis of: Mohamad Abou Daher ID:10601121

Academic Year: 2018/2019

1|Page
2|Page
 Acknowledgment
The project leading to this Thesis has received funding from the European Research Council under
Grant Agreement no. 694910 (INTENT).

3|Page
Abstract

Packed metallic foam are proposed as a promising solution for the problem of heat removal in Fischer-
Tropsch processes. Such type of configuration allows for high catalyst loading, whilst maintaining low
pressure drops, and high degree of intermixing and thermal exchange.

This work aims to develop a 2-dimensional mathematical model in accounting for the mass, energy and
momentum balancesof a packed-foam Fischer-Tropsch tubular reactor. It takes also into account the
variation of selectivity and heat of reaction with temperature. After that Artificial Neural Networks (ANN)
are employed to predict the performance of the system in a more computationally effective way.
Moreover, ANN provide a less complex problem from the mathematical point of view; thus, facilitating
the optimization of operating conditions.

The first chapter is dedicated to provide adequate background about Gas to Liquid Process in general and
Fischer-Tropsch Synthesis (FTS) in specific. Followed by detailed discussion of the heat removal problem
and the proposed solutions. Then the second chapter would go in depth with the discussion of structured
reactors.

The third chapter would describe the 2-dimensional hybrid heterogeneous model. This model consists of
two phases: the foam and the pseudo-fluid phase, which consists of the catalyst and the gaseous fluid.

The fourth chapter would go through the preliminary results and the sensitivity analysis of the proposed
model, followed by the simulation of experimental results that were reported in a previous work at the
Laboratories of Catalysis and Catalytic Processes (LCCP) of Politecncio di Milano. The experimental results
demonstrated outstanding performance of the packed foam reactor in managing the thermal profiles
during FTS reaction and for CO conversion values up to around 67%.

After the demonstration of the performance of the proposed model, the fifth chapter would introduce
the notion of ANN, it’s applications and design. ANN is applied as mean for the prediction of CO conversion
and selectivity to 𝐶5+. The developed ANN model was then used in optimizing the operating conditions of
the packed foam reactor to maximize the productivity of 𝐶5+ prodcts.

KEYWORDS: modeling, packed foam reactor, Fischer-Tropsch synthesis, Artificial Neural Networks,
genetic algorithm

4|Page
Sommario
La schiuma metallica compatta viene proposta come soluzione promettente al problema della rimozione
del calore nei Fischer-Tropsch. Tale tipo di configurazione consente un elevato carico del catalizzatore,
mantenendo basse perdite di carico e un elevato grado di miscelazione e scambio termico.

Questo lavoro mira a sviluppare un modello matematico bidimensionale del reattore Fischer-Tropsch con
schiuma metallica basato sui relativi bilanci di massa, energia e quantità di moto. Tiene inoltre conto della
variazione della selettività e del calore di reazione con la temperatura. Successivamente vengono
utilizzate le reti neurali artificiali (ANN) per prevedere le prestazioni del sistema in modo più efficace dal
punto di vista computazionale. Inoltre, ANN fornisce un problema meno complesso dal punto di vista
matematico; quindi, facilitando l'ottimizzazione delle condizioni operative.

Il primo capitolo è dedicato a fornire un adeguato background sul processo da Gas a Liquido in generale e
Fischer-Tropsch in particolare. Segue una discussione dettagliata del problema di rimozione del calore e
delle soluzioni proposte. Quindi il secondo capitolo approfondirà la discussione sui reattori strutturati.

Il terzo capitolo descriverà il modello eterogeneo ibrido bidimensionale. Questo modello è costituito da
due fasi principali: la schiuma e la fase pseudo-fluida, che consiste nel catalizzatore e nel fluido gassoso.

Il quarto capitolo presenterà i risultati preliminari e l'analisi di sensibilità del modello proposto, seguita
dalla simulazione di risultati sperimentali che erano stati precedentemente riportati in un precedente
lavoro svolto presso i Laboratori di Catalisi e Processi Catalitici (LCCP) del Politecnico di Milano. I risultati
sperimentali hanno dimostrato prestazioni eccezionali del reattore a schiuma impaccata durante la
reazione FTS e valori di conversione di CO fino a circa il 67%.

Dopo la dimostrazione delle prestazioni del modello proposto, il quinto capitolo introduce la nozione di
ANN, applicazioni e progettazione. ANN viene applicato per la previsione della conversione di CO e della
selettività in C5+. Il modello ANN sviluppato è stato quindi utilizzato per ottimizzare le condizioni operative
del reattore a schiuma impaccata per massimizzare la produttività dei prodotti C5+.

PAROLE CHIAVE: modellazione, reattore a schiuma aperta, sintesi di Fischer-Tropsch, reti neurali artificiali

5|Page
Contents
Abstract ......................................................................................................................................................... 4
Sommario ...................................................................................................................................................... 5
Chapter 1: Introduction .............................................................................................................................. 10
1. Global Energy Demand ................................................................................................................... 10
2. GtL processes. ................................................................................................................................. 11
2.1. Production of Synthesis Gas ................................................................................................... 12
2.2. Different GtL Processes ........................................................................................................... 13
Chapter 2: Reactors and catalytic aspect of FTS ......................................................................................... 14
1. Introduction .................................................................................................................................... 14
2. Historical Evolution ......................................................................................................................... 14
3. Catalysts for FTS .............................................................................................................................. 15
3.1. Catalyst Candidates for FTS..................................................................................................... 15
3.2. Cobalt-based catalyst .............................................................................................................. 16
3.3. Composition and preparation of employed Co-based catalyst .............................................. 18
4. Reaction Mechanism....................................................................................................................... 18
5. Product Distribution........................................................................................................................ 23
5.1. ASF distribution ....................................................................................................................... 23
5.2. The deviation of methane and ethylene ................................................................................. 25
5.3. Double chain growth probability ............................................................................................ 25
5.4. Products Upgrade ................................................................................................................... 27
6. Reactors for Fischer-Tropsch synthesis .......................................................................................... 29
6.1. Multi-tubular Fixed Bed Reactor (MTFBR) .............................................................................. 30
6.2. Slurry Bubble Column Reactor (SBCR) .................................................................................... 31
6.3. Fluidized bed reactors ............................................................................................................. 32
7. Alternative to scale down FTS ......................................................................................................... 33
7.1. Velocys FTS technology ........................................................................................................... 33
7.2. CompactGTL FTS technology................................................................................................... 34
8. Foam Catalyst and Packed foam Reactor ....................................................................................... 35
8.1. Foam Catalyst .......................................................................................................................... 35
8.2. Packed foam reactor ............................................................................................................... 36
Chapter 3: Packed Foam Model .................................................................................................................. 38
1. Introduction .................................................................................................................................... 38

6|Page
 2. Open-cell foam properties .............................................................................................................. 38
3. Lab-scale Reactor ............................................................................................................................ 39
4. Packed Foam Model........................................................................................................................ 40
5. Boundary Conditions....................................................................................................................... 43
6. Gas and catalytic pellets physical parameters ................................................................................ 44
6.1. Linear Gas Velocity .................................................................................................................. 44
6.2. Specific Heat Capacities .......................................................................................................... 44
6.3. Mixture Density....................................................................................................................... 44
6.4. Mixture Dynamic Viscosity ...................................................................................................... 45
6.5. Gas Thermal Conductivity ....................................................................................................... 45
6.6. Axial and radial effective mass diffusion coefficients ............................................................. 45
7. Heat transfer parameters ............................................................................................................... 46
7.1. Specchia et al. wall heat transfer coefficient .......................................................................... 46
7.2. Specchia et al. radial effective thermal conductivity .............................................................. 47
7.3. Specchia et al. axial effective thermal conductivity................................................................ 48
8. Thermodynamic Properties ............................................................................................................ 48
8.1. Selectivity and chain growth probability ................................................................................ 48
8.2. Enthalpy of reaction ................................................................................................................ 48
9. Kinetic Properties ............................................................................................................................ 50
10. Foam Parameters ........................................................................................................................ 51
10.1. Wall Solid Heat Transfer Coefficient ................................................................................... 51
10.2. Radial and Axial Solid Conductivities .................................................................................. 51
10.3. Specific Surface Area ........................................................................................................... 51
10.4. Overall heat transfer coefficient ......................................................................................... 52
11. Overall heat transfer model in packed foam .............................................................................. 52
12. Numerical Solution method ........................................................................................................ 53
13. Numerical Solver ......................................................................................................................... 55
14. Mesh Sensitivity .......................................................................................................................... 56
Chapter 4: Preliminary Results.................................................................................................................... 58
1. Base case: Results ........................................................................................................................... 60
2. Importance of External Mass transfer Limitations ......................................................................... 60
3. Foam Parameters ............................................................................................................................ 63
3.1. Cell diameter ........................................................................................................................... 63

7|Page
 3.2. Foam void fraction .................................................................................................................. 65
3.3. Foam Material Thermal conductivity ...................................................................................... 66
3.4. Overall Foam heat transfer coefficient ................................................................................... 68
4. Catalyst Particle Parameters ....................................................................................................... 69
4.1. Pellet Diameter ....................................................................................................................... 69
4.2. Packed bed Void fraction ........................................................................................................ 71
4.3. Activity of catalyst ................................................................................................................... 72
4.4. Effective Thermal Conductivity of pseudo-fluid ..................................................................... 74
5. Pseudo-fluid wall heat transfer coefficient..................................................................................... 75
6. Solid wall heat transfer coefficient ................................................................................................. 77
Chapter 5: Simulation of Experimental Results .......................................................................................... 78
1. Preliminary simulation of experimental results.............................................................................. 78
2. Fitting wall Temperature profile ..................................................................................................... 81
2.1. Fixed wall temperature through over the foam length .......................................................... 81
2.2. Adjusted wall temperature for each region of the foam ........................................................ 85
3. Conclusion ....................................................................................................................................... 90
Chapter 6: ANN Model ................................................................................................................................ 91
1. Introduction .................................................................................................................................... 91
2. Concept of Artificial Neural Networks ............................................................................................ 91
2.1. Feedforward ............................................................................................................................ 92
2.2. ELU Activation function........................................................................................................... 94
2.3. Training FNN by Conjugate-Gradient Backpropagation Method ............................................ 96
2.4. The issue of Overfitting ........................................................................................................... 97
3. Design of Neural Networks ........................................................................................................... 100
3.1. Optimization Neural Network Parameters ........................................................................... 100
3.2. Genetic Algorithm ................................................................................................................. 100
3.3. Optimization Function and Optimization Strategy ............................................................... 102
3.4. Dataset Generation and Data Pre-processing....................................................................... 103
4. Evaluation of ANN performance ................................................................................................... 103
5. Optimization of Operating Conditions .......................................................................................... 106
Chapter 7: Conclusion ............................................................................................................................... 106
References ................................................................................................................................................ 108
Appendix A: Physical and Transport Properties........................................................................................ 116

8|Page
Appendix B: Artificial Neural Networks part ............................................................................................. 118

9|Page
Chapter 1: Introduction
1. Global Energy Demand
The energy demand is expected to keep on increasing, driven by both economic and population growth,
especially in developing economics in India and China. The forecasted energy scenario demonstrates a
50% increase in energy demand between 2018 and 2050, based on the assumption of an annual economic
growth of 3% and an annual population growth of 0.7%. This expected increase is projected as increase in
global consumption of marketed energy from all sources except for coal, which almost remains the same
with a slight variation. Even though the renewable and nuclear energy sources energy share is 30% of
world energy consumption (figure 1.1), fossil fuels would still account for around half the global energy
consumption in 2050. The increasing trend in natural gas and petroleum fuels is maintained throughout
the time span between 2018 and 2050, which reflects the continuing global energy dependence on fossil
fuels [1].

Figure 1.1 Trends in energy consumption by energy source[1]

However, this dependence on fossil fuels stimulates environmental concerns due to increased 𝐶𝑂2
emissions that cause devastating impact on the environment. On the other hand, the amount of 𝐶𝑂2
varies with the fossil fuel type and the amount of 𝐶𝑂2 produced per amount of energy produced is the
lowest for natural gas (NG). Moreover, natural gas combustion produces mainly 𝐶𝑂2 and water vapor. On
the contrary, coal and oil combustion produce higher levels of harmful emissions, such as nitrogen oxide
(𝑁𝑂𝑥 ) and particulates matter (Table 1.1) [2].

Table 1.1 Fossil fuel emission levels (Pounds per billion Btu of energy input) [2]

Pollutant Natural Gas Oil Coal

Carbon Dioxide 117000 164000 208000
Carbon Monoxide 40 33 208
Nitrogen Oxides 92 448 457
Sulfur Dioxide 0.6 1.122 2591

10 | P a g e
 Particulates 7.0 84 2744
Formaldehyde 0.750 0.220 0.221
Mercury 0.000 0.007 0.016

At the end of 2018 the total proven natural gas reserves are 196.9 trillion cubic meters, while it was 13.8
at the end of 1998 [3]. This increase in proven gas reserves could be attributed to the technological
evolution in the last 20 years that aided in exploiting unconventional gas resources. This increase in gas
proven reserves was accompanied by a rising gas production that led in turn to drop in gas prices
compared to those of petroleum products [4]–[6]. However, a considerable proportion of the proven gas
reserves are stranded or isolated in remote locations. Moreover, these reserves are usually characterized
by low production flow and lifetime. The monetization of these resources is of crucial important for
companies and gas-resource rich nations, but commonly require large amounts of capital investment to
build processing and export infrastructure and long term contracts to underpin such investment [5].

Different technologies are available to deliver gas into the markets, but for stranded gas sources the
available ones are liquefaction and re-gasification of natural gas (LNG) and the Gas-to-Liquid (GtL) process.
Both technologies require pretreatment of natural gas to remove acid gas, water, other contaminants and
heavier hydrocarbons. In LNG process the pretreatment step is followed by liquefaction of the treated NG
and transportation to the regasification terminal, mainly through ships. On the other hand, GtL technology
enables the production of wide range of products with added value compared to raw natural gas. GtL pass
involves three core units, where syngas is produced from treated NG, then syngas undergoes chemical
reaction to produce the desired product that in turn is subjected to an upgrading process. Even though
GtL development stage and commercial viability are far behind LNG, the full capital chain investment is
comparable between GtL and LNG. However, small-scale GTL technology requires relatively smaller capital
investment. Therefore, the GtL process is more flexible and can easily be regulated according to the
market demand and international circumstances, which makes it more suitable for small stranded NG
resources [7]. In addition, another substantially important source of natural gas is the associated natural
gas that is flared or vented to facilitate oil production. Gas to liquid conversion can play a promising role
in the reduction of flaring [5].

2. GtL processes.

Gas-to-Liquid (GtL) technologies are of interest due to their potential in monetizing abundantly available
gas sources and the market demand for cleaner fuels, as GtL products are free from Nitrogen, Sulphur,
aromatics and metals, which makes them more environmentally friendly. In fact, fuels from GtL are of
premium grade and can be used in pure form or as a fuel additive. As an example, GtL diesel can be used
in existing vehicles and delivery systems without modification. There are three main classes of GtL
processes: Gas-to-Methanol (GtM), Gas to Dimethyl ether (GtDME) and Fischer-Tropsch synthesis (FTS)
process (Figure 1.2). Before discussing these different processes it is essential to give some insights about
the production of synthesis gas, since it is considered an intermediate step in all GtL processes [5].

11 | P a g e
 Figure 1.2 Scheme of Gas to Liquid processes

2.1. Production of Synthesis Gas

Synthesis gas is a crucial intermediate resource for production of hydrogen, ammonia, methanol, and
synthetic hydrocarbon fuels. It can be produced from various feedstock sources including natural gas,
biomass, coal and almost all hydrocarbon feedstock through the reaction with oxygen or steam, where
the products are mainly CO and 𝐻2 [5].

In industrial practice syngas is produced through partial oxidation, steam reforming or autothermal
reforming. Partial oxidation of methane (or other hydrocarbon) (Eq. 1.1) can be divided into two main
categories: non-catalytic and catalytic processes (figure 1.3). The non-catalytic partial oxidation (PO) of
methane is suitable for large scale applications and produce 𝐻2 /𝐶𝑂 ratio around 2, which is optimal for
GtL plants. The catalytic partial oxidation (CPO) is based on short contact time conversion of the
hydrocarbon feedstock over a catalyst (e.g. rhodium) and is suitable for small scale applications. [8],[9].
1
𝐶𝐻4 + 𝑂2 ==> 𝐶𝑂 + 2𝐻2 (𝐸𝑞. 1.1)
2
Steam methane reforming (SMR) (Eq. 1.2 & Figure 1.3) is a strongly endothermic process that is carried
out in tubular reactors that are heated externally. The reaction is carried out over nickel-based catalyst
and the support must be resistant to harsh process conditions. The generated syngas is of 𝐻2 /𝐶𝑂 ratio
between 3-4, which is suitable for hydrogen production [9],[10].
𝑜
𝐶𝐻4 + 𝐻2 𝑂 <==> 𝐶𝑂 + 3𝐻2 ∆𝐻298 = 206 𝑘𝐽/𝑚𝑜𝑙 (𝐸𝑞. 1.2)
Autothermal reforming (ATR) (Figure 1.3) is hybrid process that combines both partial oxidation and steam
reforming, as the heat needed for steam reforming is generated from the oxidation process. ATR is
suitable for large scale production of syngas or large scale methanol synthesis [9],[11].

12 | P a g e
 Figure 1.3 Reactors and processes layout for syngas production from natural gas and shale gas [9]

2.2. Different GtL Processes

Methanol could serve as both raw material for the organic chemical industry and as an automotive fuel
or fuel additive[5]. Indeed, methanol as other low-carbon alcohol fuels guarantee higher octane number
and combustion efficiency, which is ensured by the presence of the oxygen inside the alcohol molecule.
Moreover, the combustion of methanol mainly produces 𝐶𝑂2 and 𝐻2 𝑂 and is more environmentally
friendly compared to conventional automotive fuels. However, blends of methanol with gasoline are
proposed due to the low calorific value of methanol combustion on its own[12].

For the case of dimethyl ether, it is also characterized by the versatility of its uses, as it can be used as:
replacement for propane in liquid petroleum gas (LPG), replacement for diesel fuel, fuel for electric
generators, intermediate for olefins production and as hydrogen carrier in fuel cells [13],[14].

Fischer-Tropsch synthesis (FTS) is an effective method to convert synthesis gas derived from coal, natural
gas, and biomass to liquid fuel chemicals. The reaction mechanism is based on sequential –𝐶𝐻2– additions
following a polymerization-like scheme, that can be described with the Anderson–Schultz–Flory (ASF)
product distribution, which is characterized by the chain growth probability parameter (α) [15]. This
parameter α and consequently the selectivity significantly depend on the temperature due to the fact that
the activation energy of the termination step is higher than that of the growing step[16]–[18]. FTS
processes dominate both large-scale and small-scale projects targeting middle distillate liquid
transportation fuel markets[5]. The next chapter is dedicated for the detailed discussion of FTS process.

13 | P a g e
Chapter 2: Reactors and catalytic aspect of FTS
1. Introduction
This chapter introduces the Fischer-Tropsch synthesis (FTS) as a catalytic process, analyzing the state of
the art and demonstrating its historical evolution. The key points tackled in this chapter would be the
process catalyst, the reaction mechanism, product distribution and the FTS process intensification.

2. Historical Evolution
It has been more than 100 years since Sabatier and Sendersen [19] reported that methane could be
formed by CO hydrogenation over nickel catalysts (1902). In 1913 and 1914, patents were awarded to
Badische Anilin and Soda Fabrik (BASF) for the production of hydrocarbons and mainly oxygenate
derivatives (Synthol) from syngas, by using alkali promoted osmium and cobalt catalysts at high pressure
[20]. In 1923, Franz Fischer and Hans Tropsch developed a synthesis process over an alkalized iron catalyst,
which unfortunately deactivated rapidly[18]. Two years later, the same scientists synthesized high
molecular weight hydrocarbons over cobalt-nickel catalyst at atmospheric pressure[16]. Even though
this marks the historical birth of Fischer-Tropsch, the modern process of CO hydrogenation at high
pressure is reported a decade later: in 1936 with cobalt-based catalyst [17], in 1937 with iron [21]
and in 1938 with ruthenium [22]. By 1938, nine Fischer-Tropsch plants were running at 10 bar in
Germany. In 1955, two commercial plants have been also built in the USA by Carthage-Hydrocol and
Fuelco. Sasol I (1955) started its production using the combination of fixed and fluid bed reactors in
South Africa, then in 1980 Sasol added its unit in the Sasol II project followed by Sasol III two years
later in 1982. In 1991, the PetroSA (Mossgas) plant came on stream in South Africa[23].
Till now South Africa is still a key player in FTS process, as 35% of liquid fuels produced in the country are
produced through FTS. Another FTS plant, Oryx plant, was built by Sasaol in 2007 in collaboration with
Qatar Petroleum. Another key player in FTS industry is Shell that started developing GTL in the 1970s. It
operates FTS plants in in Malaysia (Bintulu GtL since 1993) and in Qatar (Pearl GtL since 2011)[23].

In September 2016, Velocys plc (VLS.L) company completed the construction of the ENVIA Energy’s
GtL plant in Oklahoma City. The project, which is based on the compact/modular GtL technology, is a
result of collaboration between Waste Management, NRG Energy, Ventech and Velocys (ENVIA
Energy) [24].

14 | P a g e
 Figure 2.1 Sasol II and III flow scheme[25]

3. Catalysts for FTS

3.1. Catalyst Candidates for FTS
The metals considered for FTS applications, due to their level of activity, are nickel, cobalt, iron and
ruthenium. Several factors play a role in selecting the suitable metallic catalyst, which are the catalyst
price, the desired final product and the source of syngas. Ruthenium is not used commercially
because, despite the fact it is the most active metal in the FTS, it has low availability and high cost.
On the other hand, due to its high activity in hydrogenation reaction nickel leads to high methane
selectivity, which is undesirable, under viable reaction conditions[26]. Moreover, when exposed to
FTS operating conditions nickel forms volatile nickel carbonyls. Thus, resulting in catalyst loss and
deactivation[26]. Catalyst candidates for FTS industrial applications could be then limited to cobalt and
iron.

Cobalt is preferred for Low Temperature Fischer-Tropsch Synthesis (LTFTS) between 200 and 240℃, which
favors the formation of higher molecular weight products (e.g. waxes) that are upgraded to diesel and jet
fuel range. On the other hand, to produce gasoline and high value α-alkenes, High Temperature Fischer-
Tropsch Synthesis (HTFTS) over iron-based catalyst, between 300 and 350℃, is deemed the best option.
Iron-based catalyst are characterized by high rates of Water Gas Shift (WGS) reaction, which makes it

15 | P a g e
 𝐻
possible to operate with low 2⁄𝐶𝑂 .syngas. This is the typical situation for syngas obtained from coal or
biomass feedstock, where the ratio is considerably lower than the FTS reaction consumption ratio
𝐻
( 2⁄𝐶𝑂=2.15)[27],[28].

On the contrary, Cobalt-based catalyst is characterized by low WGS activity and thus it is used when the
𝐻
synthesis gas is produced from natural gas, which results in 2⁄𝐶𝑂 ratios close the stoichiometric value
of 2.15 [29].

The LTFTS is characterized by several advantages over HTFTS. In this regard, LTFT produces hydrocarbon
products that are less energy intensive to upgrade and premium quality fuels with high cetane
number (up to 75) related to ignition delay time in diesel engines. Moreover, the production of
greenhouse emissions in LTFTS is lower ( 𝑙𝑜𝑤𝑒𝑟 𝐶2 − 𝐶4 ). While in HTFTS the target gasoline range
fuels results in hydrocarbons with poor octane rating and, due to the lower chain growth probability
factor, significantly more methane and other light gases are produced[27], [28],[30].

3.2. Cobalt-based catalyst

The currently used cobalt-based catalysts are made of promoted cobalt dispersed on an oxide
support, and thus similar to the ones prepared by Fischer and Tropsch. The FTS occurs on the surface
cobalt metal centers (𝐶𝑜0 ). Cobalt is an expensive material and thus it is important to obtain a suitable
dispersion on the catalytic support. From the particle size, catalyst morphology, extent of reduction,
and particle stability depends on the number of Co0 surface sites [31]. The catalyst activation step is
achieved through at least 60% extent of reduction, even though cobalt undergoes further reduction
under FTS reaction conditions [31]. Frequently catalysts are promoted with secondary noble metals,
which improves the reducibility of cobalt oxide particles, which are formed after the calcination step
involved in the catalyst preparation procedure [31]. Thus, resulting in an increase in the number of
available active sites for FTS reaction and higher CO conversion values per gram of catalyst. The more
facile cobalt reduction in the case of promoted catalyst is due to the faster hydrogenation and
subsequent spillover of hydrogen to cobalt oxide and reduction of cobalt species. Another important
effect of Hydrogen spillover is increasing the cobalt dispersion. [32]. Furthermore, other structural
promoters like Zr and La play key role in stabilizing the support oxide and gluing the cobalt particles
on the support. The figure below demonstrates the different modes of action of structural promoters
[33].

16 | P a g e
Figure 2.2 The different modes of action of structural promoters in Co-based FT catalysis: (a) structural promoters can lead to a
decreased compound formation with the support oxide; (b) H2 spillover effect, leading indirectly to a higher dispersion of the
supported Co particles; (c) oxide promoters can be used to modify the support leading to increased dispersions; and (d) structural
promoters can act as an oxidic interface between the supported Co particle and the support oxide[33].

Other type of promoter effects are electronic and synergistic promotion effects. Electronic promotion
occurs only when there is a direct chemical interaction between the promoter and the cobalt active
surface. Electronic promotion can be best understood in terms of ligand effects. The surrounding
(electronic) environment of an active Co site can be altered by the presence of a promoter element. This
leads to an electronic donation or withdrawal leading to an increased intrinsic turnover frequency or
change in product selectivity. Ligand effect can also decrease the deactivation process by changing the
adsorption/desorption properties of the reagents/reaction products [33].

The synergistic effect occurs when the promoter affects indirectly the behavior of the catalytically active
element. This could occur via the alteration of the local feed composition, due to its catalytic property and
influencing the overall product distribution. The promoter could catalyze WGS reaction thus shifting the
𝐻2⁄
𝐶𝑂 ratio. The promoter could play a role in increasing the catalyst tolerance to 𝐻2 𝑆, as elements such
as Zn and B form stable surface compounds with sulfur. Promoters can also play a role in lowering the
temperature for coke burning during regeneration. The final product distribution could be vastly altered

17 | P a g e
via catalyzing hydrogenation/dehydrogenation reactions as the final products of FTS are a mixture of
higher alkanes and alkenes[33].

The catalyst oxide support has two key roles: the production of stable cobalt metal particles after
reduction and the cobalt particles dispersion. Mechanical strength and thermal stability to the catalyst
are also provided by the support. Robustness is also an important characteristic of the support.
Accordingly, resistance to attrition is required under FTS conditions, especially in a slurry bubble-
column environment. The most used supports for FTS catalysts are silica, alumina and titania. These
supports are characterized by their high surface area. When alumina is used interaction between the
support and cobalt may occur. Consequently mixed compounds inactive in FTS can be formed, such
as cobalt-aluminate [34].

3.3. Composition and preparation of employed Co-based catalyst

The catalyst that was used in the experimental work was prepared by a single impregnation of 𝛾 − 𝐴𝑙2 𝑂3
with an aqueous solution of 𝐶𝑜(𝑁𝑂3 )2 . 6𝐻2 𝑂 (Sigma Aldrich, 98 wt.%) in order to reach a Co loading of
5.7 wt%. The sample was then dried for 1h at 120℃ and calcined at 900℃ for 4h. This treatment leads
to the formation of cobalt aluminates. The formed material is referred to as 𝐴𝑙2 𝑂3 in subsequent
discussion and the used cobalt is sacrificial and serves as a stabilizer for the support. Then, Pt is
impregnated onto the stabilized support using an aqueous solution of 3.4 wt% of 𝑃𝑡(𝑁𝐻3 )2 (𝑁𝑂2 )2 in
𝑁𝐻4 𝑂𝐻 (Sigma Aldrich, 99 wt%). The Pt solution impregnation was followed by four times impregnation
of 𝐶𝑜(𝑁𝑂3 )2 . 6𝐻2 𝑂 solution in order to reach a loading of 18 wt% of active cobalt. After each
impregnation step the sample was dried for 1h at 120℃ and calcined at 500℃ for 4h [35] [36]. It is worth
noting that the employed impregnation method was the incipient wetness impregnation (IWI) method. In
this method the impregnation occurs as a result of capillary action in the porous support when it is
contacted with the solution of the metal to be impregnated. The condition for IWI to occur is that all the
support pores are filled with liquid without any excess moisture [32].

4. Reaction Mechanism
Fischer-Tropsch consists of set of reactions that forms a wide spectrum of products starting from CO and
𝐻2 . Even though these products are mainly linear paraffinic hydrocarbons, α-olefins, internal olefins and
oxygenated products (alcohols) are also formed.

The proper knowledge of the reaction mechanism serves as a mean of formulating a reliable kinetic model
that predicts the product formulation under process conditions, along with playing fundamental
importance in developing more active or selective catalysts.

The reaction scheme can be represented as a simplified polymerization scheme and can be described by
the following main reactions[37]:

𝑛𝐶𝑂 + (2𝑛 + 1)𝐻2 ==> 𝐶𝑛 𝐻2𝑛+2 + 𝑛𝐻2 𝑂 (𝐸𝑞. 2.1)

𝑛𝐶𝑂 + 2𝑛𝐻2 ==> 𝐶𝑛 𝐻2𝑛 + 𝑛𝐻2 𝑂 (𝐸𝑞. 2.2)
𝑛𝐶𝑂 + (2𝑛 + 1)𝐻2 ==> 𝐶𝑛 𝐻2𝑛+2 𝑂 + (𝑛 − 1)𝐻2 𝑂 (𝐸𝑞. 2.3)
which describe respectively the formation of paraffin, olefins and linear alcohols.

18 | P a g e
Other undesired reactions occur such as the water gas shift, the Boudouard reaction and the methanation
reaction[38].

𝐶𝑂 + 𝐻2 𝑂 ==> 𝐶𝑂2 + 𝐻2 (𝑊𝐺𝑆 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛) (𝐸𝑞. 2.4)

2𝐶𝑂 ==> 𝐶𝑂2 + 𝐶 (𝐵𝑜𝑢𝑑𝑜𝑢𝑎𝑟𝑑 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛) (𝐸𝑞. 2.5)
𝐶𝑂 + 3𝐻2 ==> 𝐶𝐻4 + 𝐻2 𝑂 (𝑚𝑒𝑡ℎ𝑎𝑛𝑎𝑡𝑖𝑜𝑛 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛) (𝐸𝑞. 2.6)
The FTS proceeds through the formation of the growth monomeric unit and then proceeds according to
the kinetic steps listed below [37]–[41]:

I. Reagent adsorption

𝐻2 + 2 ∗==> 2𝐻 ∗
𝐶𝑂 +∗==> 𝐶𝑂 ∗

II. In situ formation of the monomer

𝐶𝑂 ∗ +𝑎𝐻2 ∗==> 𝐶1 ∗ +𝑜𝑥𝑦𝑔𝑒𝑛𝑎𝑡𝑒𝑑 𝑠𝑝𝑒𝑐𝑖𝑒𝑠

III. Chain initiation

𝐶1 ∗==> 𝑅1 ∗
IV. Chain growth

𝐶1 ∗ +𝑅𝑛 ∗==> 𝑅𝑛+1 ∗ + ∗

V. Chain termination

𝑅𝑛 ∗==> 𝑝𝑟𝑜𝑑𝑢𝑐𝑡 𝐴𝑛 ∗
VI. Product desorption

𝑝𝑟𝑜𝑑𝑢𝑐𝑡 𝐴𝑛 ∗==> 𝑝𝑟𝑜𝑑𝑢𝑐𝑡 𝐴𝑛 +∗

VII. Product readsorption and secondary process
𝑝𝑟𝑜𝑑𝑢𝑐𝑡 𝐴𝑛 +∗==. > 𝑝𝑟𝑜𝑑𝑢𝑐𝑡 𝐴𝑛 ∗
𝑝𝑟𝑜𝑑𝑢𝑐𝑡 𝐴𝑛 ∗==> 𝑝𝑟𝑜𝑑𝑢𝑐𝑡 𝐵𝑛 ∗
The first step of the reaction involves the dissociative adsorption of hydrogen and molecular adsorption
of carbon monoxide (I). The adsorbed monomer unit, labeled as 𝐶1 ∗, is formed as a result of the reaction
between adsorbed atomic hydrogen and adsorbed carbon monoxide (II). The adsorbed monomer forms
the smallest radical unit (𝑅1 ∗) and by that the polymerization reaction (III) is initiated. The radical units
(𝑅𝑛 ) undergo successive addition of monomer unit to form longer radical chains (IV). The formed radical
is also prone to termination (V) to produce adsorbed hydrocarbon products (𝐴𝑛 ∗). After termination the
products can desorb (VI) or resorb and undergo secondary reactions (VII). The paraffinic products are
olefinic products with n carbon atoms are indicated as 𝐴𝑛 and 𝐵𝑛 respectively and their corresponding
adsorbed species are respectively 𝐴𝑛 ∗ and 𝐵𝑛 *.

19 | P a g e
Regarding the second stage proposed theories vary, but all agree on the formation of a single carbon
monomer unit 𝐶1 ∗ as a result of the reaction between adsorbed atomic hydrogen and adsorbed CO
(molecular or dissociated) [42]–[45]. The proposed monomer unit varies with theory and consequently
the structure of growing carbon chain varies accordingly. To explain the formation of alcohols Eiidus et
al.[46] proposed the oxymethylene theory, in which the monomeric unit is adsorbed hydroxycarbon,
HCOH*, (also called enol). It is formed by partial hydrogenation of carbon monoxide molecule adsorbed
on the surface according to the following reactions:

𝐶𝑂 +∗==> 𝐶𝑂 ∗
𝐶𝑂 ∗ +2𝐻 ∗==> 𝐻𝐶𝑂𝐻 ∗
Chain growth occurs through condensation reaction with water elimination, according to the following
reaction:

𝐻𝐶𝑂𝐻 ∗ +𝑅𝑛 𝐶𝑂𝐻 ∗ +2𝐻 ∗==> 𝑅𝑛+1 𝐶𝑂𝐻 ∗ +𝐻2 𝑂 +∗

The termination route would determine the final products that are formed. The equations below
demonstrate the possible final products[27]:

𝑅𝑛 𝐶𝑂𝐻 ∗ +2𝐻 ∗==> 𝑅𝑛 𝐶𝐻2 𝑂𝐻 + 3 ∗

𝑅𝑛 𝐶𝑂𝐻 ∗ +2𝐻 ∗==> 𝑅𝑛−1 𝐶𝐻 = 𝐶𝐻2 + 3 ∗ +𝐻2 𝑂
𝑅𝑛 𝐶𝑂𝐻 ∗ +4𝐻 ∗==> 𝑅𝑛 𝐶𝐻3 + 5 ∗ +𝐻2 𝑂

The carbide theory was proposed by Fischer and Tropsch in 1926 olefins, and still largely recognized by
scientists, is the most adequate to explain the formation of linear paraffins and olefins [15], [42]–[44],
[47]. It assumes that CO undergo dissociative adsorption before the carbon atom is partially hydrogenated
to a 𝐶𝐻𝑥 species. This formed carbide specie combines with one monomer at a time leading to
hydrocarbon chain growth. The growing intermediate can be terminated in various ways thus explaining
the formation of alkanes, alkenes and oxygenates. Several variations of the basic carbide mechanism have
been considered, arising from, for instance, whether the CO dissociation is unassisted or occurs via
interaction with hydrogen, and the number of hydrogen atoms in the monomer (CH* or 𝐶𝐻2 ∗ )[27]. The
carbide reaction mechanism in general can be represented by the set of reactions below[27]:

The carbide monomer is formed according to these reactions:

𝐶𝑂 +∗==> 𝐶𝑂 ∗
𝐶𝑂 ∗ + ∗==> 𝐶 ∗ +𝑂 ∗
𝑂 ∗ +𝐻2 ==> 𝐻2 𝑂 +∗
𝐶 ∗ +𝑧𝐻 ∗==> 𝐶𝐻𝑧 ∗ + ∗
Z=1,2

The propagation set of reactions consists of:

𝑅𝑛 ∗ +𝐶𝐻𝑧 ∗==> 𝑅𝑛 𝐶𝐻𝑧 ∗ + ∗

20 | P a g e
𝑅𝑛 𝐶𝐻𝑧 ∗ +(2 − 𝑧)𝐻 ∗==> 𝑅𝑛+1 ∗ + ∗
The termination step that was initially proposed only explains the formation of alkanes and alkenes as
demonstrated in scheme below:

Figure 2.3 Schematic drawing of the most likely paths in termination step in carbide mechanism for formation of alkanes and
alkenes. Here M represents the reaction site (*)[48]

However, to account for formation of oxygenates Dry [46], [49], [50] proposed the following additional
set of terminating equations to explain the formation of aldehydes, alcohols and carboxylic acids:

𝑅𝑛 𝐶𝐻 ∗ +𝐶𝑂 +∗==> 𝑅𝑛 𝐶𝐻𝐶 ∗ 𝑂 ∗

𝑅𝑛 𝐶𝐻𝐶 ∗ 𝑂 ∗ +𝐻2 ==> 𝑅𝑛 𝐶𝐻2 𝐶𝐻𝑂 + 2 ∗ (aldehyde formation)

𝑅𝑛 𝐶𝐻𝐶 ∗ 𝑂 ∗ +2𝐻2 ==> 𝑅𝑛 𝐶𝐻2 𝐶𝐻2 𝑂𝐻 + 2 ∗ (alcohol formation)

𝑅𝑛 𝐶𝐻𝐶 ∗ 𝑂 ∗ +𝐻2 𝑂 ==> 𝑅𝑛 𝐶𝐻2 𝐶𝑂𝑂𝐻 + 2 ∗ (carboxylic acid formation)

The CO insertion theory provides an alternative route for explaining the growth of alkyl species. This
mechanism was proposed by Pichler and Schultz in the 1970 [51] and it assumes a similar initiation step
to the carbide mechanism, but it differs in the proposed chain growth path as it is mainly by direct CO
insertion into the growing intermediate followed by oxygen atom removal via hydrogenation. This
mechanism can also predict the formation of both hydrocarbons and oxygenates. The chain growth and
termination reactions are demonstrated below[27], [51]:

Chain growth:

𝑅𝑛 − 𝐶𝐻 ∗ +𝐶𝑂 ∗==> 𝑅𝑛 − 𝐶𝐻 − 𝐶𝑂 ∗ + ∗
𝑅𝑛 − 𝐶𝐻 − 𝐶𝑂 ∗ +2𝐻2 ==> 𝑅𝑛+1 𝐶𝐻 ∗ +𝐻2 𝑂
Termination:

𝑅𝑛 − 𝐶𝐻 ∗ +2𝐻 ∗==> 𝑅𝑛 𝐶𝐻3 +∗

21 | P a g e
𝑅𝑛 − 𝐶𝐻 − 𝐶𝑂 ∗ +𝑚𝐻 ∗==> 𝑜𝑥𝑦𝑔𝑒𝑛𝑎𝑡𝑒𝑠
Neither one of the discussed mechanisms above was able to resemble the all the products in FTS reaction,
what makes it clear that a more detailed mechanism with more than one key intermediate. Moazami et
al.[52] developed based on set of previously developed mechanistic approaches (8 sets of elementary
reactions for FTS and 7 sets for WGS were evaluated) a model that was able to predict the experimental
values within ±10% of error.

Figure 2.4 Proposed reaction mechanism for FTS and WGS reactions. (𝜓 is the FTS reaction site and σ is the WGS reaction site)[52]

The reported results by the authors were very close to experimental ones and this proposed scheme
(Figure 2.4) relates more to this work as it was developed specifically for FTS over cobalt based catalyst.
The aforementioned model is able to predict conversion and selectivities including 𝐶𝑂2 with a mean
absolute percentage variation (MAPD) of 5.93%, which is much better than the previously postulated
models by Yang et al.[53] Wang et al.[54] and Teng et al.[55] as they resulted ,at their best performance,
with the following MAPD values of 18.6%, 33.99%, and 35.52% respectively [52].

In this work selectivities were not evaluated based on a detailed mechanism and, instead, a lumped
reaction scheme was used for simplicity and due to lack of adequate experimental data. Nevertheless ,
the necessity of more accurate and detailed FTS scheme is still very important.

22 | P a g e
 5. Product Distribution
5.1. ASF distribution
The Fischer-Tropsch reaction is a combination of CO hydrogenation and polymerization reactions; thus, it
is anticipated to be characterized by wide range of product distribution. The selectivity is dependent on
the temperature, pressure, catalyst and other factors. During FTS reaction, chain grows via successive
addition of monomer unit as described in the reaction mechanism section. The probability of chain
growing rather than terminating is defined as the growth probability (α). The chain growth is assumed
unidirectional and probability of growing a hydrocarbon of chain length (n) is 𝑥𝑛 = 𝛼 𝑛−1 (1 − 𝛼), where
𝑥𝑛 is the mole fraction of hydrocarbon of chain length (n)[28].

A complete derivation for the case of weight fractions (𝑊𝑛 ) was done by done by Schulz and Flory and
𝑊𝑛
Steyberg [47] and it is expressed as = 𝛼 𝑛−1 (1 − 𝛼)2 . Therefore, leading to the following equation of
𝑛
the ASF plot:
𝑊𝑛 (1 − 𝛼)2
𝑙𝑛( ) = 𝑛𝑙𝑛(𝛼) + 𝑙𝑛( )
𝑛 𝛼
This equation fits a straight line that generates the typical ASF plot and carbon atom selectivity diagram
reported below.

Figure 2.5 Typical ASF plot for α=0.85

23 | P a g e
Figure 2.6 Hydrocarbon product spectrum that is produced during Fischer–Tropsch synthesis for varying chain growth probability
a. High-temperature Fischer–Tropsch technology (HTFT) corresponds approximately to 0.70<a<0.75, and low-temperature
Fischer–Tropsch (LTFT) to about 0.85<a<0.95.[27]

Although ASF distribution predicts fairly well FTS product distribution, there are significant deviations in
FTS product distribution obtained from cobalt, iron and ruthenium catalyst from what is predicted by the
ASF distribution, as shown below [56],[57]:

• Molar fraction of methane is higher than that predicted by ASF

• Anomality in the produced molar fraction of 𝐶2 as it’s lower than predicted by ASF plot.
• For hydrocarbons with high chain length the curvature of the plot deviates from the ASF plot and
decrease in olefin/paraffin, which lead to two distinct values of chain growth probability.

Figure 2.7 Experimental FTS product distribution along with ASF distribution[57]

24 | P a g e
A possible explanation for these deviations has been given by Dijk [58] showing that the ASF model
treats FTS as ideal polymerization. The monomer itself have to be formed in situ on the catalyst
surface also the rates of surface reactions are chain length dependent and the primary products can
undergo secondary reactions. Actually, in addition to linear alkanes and 1-alkenes, a variety of other
products are also formed, including branched aliphatic compounds, alcohols, aldehydes, ketones,
acids, and (at sufficiently high operating temperatures) even aromatics. This shows the complexity of
the reaction and explains why many issues regarding the reaction mechanism remains unresolved.
Therefore, Dijk sheds light on several important points concerning the simplification introduced by
the ASF model as it treats FTS as ideal polymerization.

5.2. The deviation of methane and ethylene

The methane underestimation by ASF was explained by several postulated mechanisms. The most
accepted explanation is the existence of different catalytic sites or different reaction pathways[45][59].
Other theories were proposed and include hydrogenolysis by successive demethylation [60], high surface
mobility of methane precursor[61], lower activation energy for methane formation compared to other
products[62], [63] and the existence of different pathways leading to methanation reaction[64], [65].

The overestimation of 𝐶2 fraction was attributed by Wojciechowski et al. [42] to high surface mobility and
reactivity of the precursor of this species. In addition, ethylene is reintroduced into the chain growth
process and ethylene is more prone to hydrogenolysis.

5.3. Double chain growth probability

The deviation in curvature of FTS products shows double chain growth probability in correspondence of
the hydrocarbon with carbon number equals to 8. The cause of this deviation is a disputed topic in the
specialized literature [66]–[68]. This deviation could be attributed to the presence of different active sites,
different chain growth mechanisms and also accounting for olefins readsorption and consecutive
incorporation into the chain growth. The latter proposed reason explains the exponential decrease in the
olefin to paraffin ratio with increase in number of carbon atoms. Paraffins on the contrary does not
undergo readsorption, while experimental evidence indicates that olefins can be readsorbed on the
catalytic site and reinserted into chain growth mechanism or hydrogenated to the corresponding
paraffin[58].

Kuipers et al. [69] explained this trend considering olefins as the main primary product of FTS and
that their main secondary are: (i) hydrogenation, (ii) reinsertion, (iii) hydrogenolysis and (iv)
isomerization. This reinsertion mechanism is attributed mainly to three physical phenomena:
diffusivity, solubility and physisorption[58].

25 | P a g e
Figure 2.8 Schematization of the concentration profile of olefins according to the distance from the catalytic surface[60].

As shown in the figure above the concentration of olefins dissolved for x = d can be related, using balance
considerations, to the corresponding bulk concentration of the vapor phase. In the wax phase
(hydrocarbon film covering the catalyst for 0<x<d) a concentration gradient is formed based on the
thickness of the film, the diffusivity of the olefin specie in it and the speed of formation of this olefin
product. For the diffusivity (𝐷𝑛 ) of the olefin product in wax Kuipers et al.[60] suggested an exponential
dependence on the number of carbon atoms in the chain (n), such that:
2
𝐷𝑛 = 𝐷0 𝑒 −0.6𝑛 [𝑚 ⁄𝑠]
, where 𝐷𝑜 is the reference diffusion coefficient. This equation indicates decrease in olefin mobility with
increase in chain length. This phenomenon leads to an increase in contact time of these species and
increase in the probability of their readsorption , which in turn leads to an increase in the chain growth
probability with increase in carbon number[60].

Figure 2.9 Scheme of Diffusion enhanced readsorption model[57]

26 | P a g e
 Similar correlation with exponential coefficients between -0.3 and -0.6 was proposed by Iglesia et al.[70].
However, this diffusion dependence can’t explain the exponential drop in olefin/paraffin ratio in
experimental results. Davis et al. [71] demonstrated that the diffusion enhanced readsorption of olefins
is only significant at carbon numbers>17. Rather they suggested that the chain length dependent solubility
in the liquid phase is the key factor for the olefin secondary reactions dependency.

In the solubility enhanced readsorption model, it is based on the argument that solubility increases
exponentially with carbon number and its dependence is much higher than that of diffusivity. In this model
the catalyst pores filled with liquid/wax are considered an Eley–Rideal system in which interaction
between the dissolved olefins and surface species on the catalyst is either activation or diffusion
controlled. The interaction is considered as activation controlled as the experimental evidence shows that
diffusion limitation isn’t sufficient to explain the olefin readsorption carbon number dependency. The
olefin readsorption rate is assumed to be proportional to the concentration of the activated complex,
which in turn depends on the solubility in liquid phase, the rate equation is then demonstrated as:
𝛾𝑜 𝑘𝑐 𝛾𝑠
𝑘=
𝛾𝑜𝑠
, where 𝑘𝑐 is gas phase or ideal solution rate constant, 𝛾𝑜 , 𝛾𝑜 and 𝛾𝑜𝑠 are respectively the activity
coefficients of the dissolved olefin, surface species and their activated complex[57]. On the other hand,
the solubility enhanced readsorption model is dependent on many parameters and complicated
expression. Moreover, the assumption had been challenged from a thermodynamic point of view. As at
equilibrium the activation in both liquid and gaseous phase are equal, hence the rate of readsorption of
olefin should be independent of concentration/solubility in liquid[57].

At the catalytic surface (x=-𝛿 )physisorption of olefins take place in a manner that can be described by
Henry’s law with linear dependence on the carbon number, 𝐻𝑛 ∝ 𝑒 1.2𝑛 . The carbon number dependency
for larger olefins has been employed in predicting the chain growth probability increase with increase in
chain length[72],[60].

5.4. Products Upgrade

The FTS products upgrade is considered as the last step in the GTL process, and it is driven by the
market need and requirements. The key aim of products upgrade is to convert the wide spectrum of
FTS products into set of desirable products. Due to the mechanistic complexity of the FTS process it is
hard to optimize the process conditions to obtain the desired set of products with required
concentrations. The product upgrade consists mainly of the fractionation stage followed by one or
more appropriate treatment method. The main treatment techniques are hydrotreating,
hydrocracking, isomerization and catalytic reforming. The FTS product upgrade process is
demonstrated in the scheme below[73].

27 | P a g e
Figure2.10 Upgrading of raw products from the FTS process[73]

Even though the refining of FTS-crude and crude oil is of comparable complexity, FTS-crude refining is
preferred over that of crude oil due to the absence of Nitrogen and Sulphur compounds and low
aromaticity. Therefore, the overall FTS-crude refinery process is considered more environmentally
friendly. The low Nitrogen and Sulphur content are due to the pretreatment process before the syngas
enters the FTS process. The FTS-crude refinery process also exploits the possibility to benefit from the
valuable by products that are produced in the FTS process, such as alcohols and 𝛼-olefins [73], [30].
Table 2.1 Comparison of the components for FT-crude and crude oil[30]

Property 𝐻𝑇𝐹𝑇𝑆 𝑎 𝐿𝑇𝐹𝑇𝑆 𝑏 Crude oil

Paraffins >10% Major product Major product
Naphtelenes <1% <1% Major Product
Olefins Major product >10% None
Aromatics 5-10% <1%
Oxygenates 5-15% 5-15% <1%
Sulphur Species None None 0.1-5%
Nitrogen Specie None None <1%
Water Major product Major product 0-2%
a Sasol
Advanced Synthol (Secunda); Synthol CFB (Mossel Bay).
b Shell
Middle Distillate Synthesis (Bintulu); Sasol Slurry Phase Distillate process (Ras Laffan and
Sasolburg); ARGE (Sasolburg)

The table above clearly indicates that HTFTS products are mainly olefins with a smaller amount of
paraffins. Thus, the octane number in HTFTS-crude is higher than that from LTFTS-crude and from
conventional crude oil. The octane number indicates the gasoline resistance to knocking, this resistance
is enhanced by the high branched alkanes. On the contrary the cetane number, which gives the diesel fuel
better quality of combustion during compression ignition, is higher in LTFTS products due to the high linear
paraffin and low aromatic content. Thus LTFTS-crude is recommended and it is characterized by a much
higher cetane number compared to the EU required one [30],[74].

28 | P a g e
Table 2.2 Exemplary cetane and octane number for FTS-crude and crude oil [30][74]

Property HTFTS LTFTS Crude Oil Euro 6

Cetane number 55 72 56 51 (Minimum)
RON 68 43 25-60 95(Minimum)
a Research Octane Number

6. Reactors for Fischer-Tropsch synthesis

The high exothermicity of FTS necessitates the presence of efficient heat transfer from the particle to the
surrounding. Indeed, if the particle temperature increases this will lead to increase in selectivity to light
hydrocarbons, especially methane, and loss of activity due to sintering and fouling[75]. The two industrial
reactors mainly used in LTFTS are Slurry Bubble Column Reactor (SBCR) and Multi-tubular Fixed Bed
Reactor (MTFBR). On the other hand, 2-phase fluidized bed reactors are employed at an industrial level
for the case of HTFTS. [27]. The main characteristics of the LTFTS reactor technologies are summarized in
the table below, as the focus of this work is on LTFTS.
Table 2.3 Fischer-Tropsch reactor comparison [76]

Reactor SBCR MTFBR

Catalyst Powder(10-100𝜇m) Ball or extruded (2-3mm)
Co Co or Fe
Slurry Fixed bed
Operating Conditions
Temperature [℃] 200-250 200-250
Pressure(barg) 15-25 15-25
Phases Gas-liquid-solid Gas-liquid-solid
Heat extraction Bundle Shell and tube
Isotherm Very Good Medium
Pressure drop Low High
Catalyst Attrition Low to High Very Low
Catalyst/product separation Settling, filtering Natural
Scale up Difficult Easy
Capacity per train (bpd) 15000 2000

29 | P a g e
Figure 2.11 FTS current commercial plants and plants under construction[27]

The figure above indicates the versatility of FTS operation conditions that in turn dictates the reactor type.
Also, this indicates a growth in FTS plants production capacity to reach over 400000 barrel per day by
2013, which signifies an increased global interest in FTS process.

6.1. Multi-tubular Fixed Bed Reactor (MTFBR)

In LTFTS the spectrum of heavy product extends well into the domain of waxes, which are liquid under
reaction operating conditions. This production of liquid products leads to the formation of a three-phase
gas-liquid-solid system. Originally only multi-tubular fixed-bed reactors were adopted for this synthesis.
The MTFBR is built up of thousands of long (9 ÷ 20 [m]) and narrow (1 ÷ 2 [inch]) tubes. The catalyst
pellets are loaded inside the reactor tubes. The syn gas reactive feed is fed from above and the liquid
products trickle downstream. The generated reaction heat is mainly removed through the tube walls
that are in contact with the coolant. These reactors are characterized by high catalyst loading, simple
operation and as wax trickles down the reactor no need for wax-catalyst separation unit. This type of
reactors is operated under fluid-dynamic conditions close to those of plug-flow reactors. The heat
transfer is dominantly through convection in the fluid and the conductive contribution of solid phase
is negligible [77] [27][78]. This mechanism of heat transfer leads to strong axial and radial temperature
gradients with the presence of hot-spot, even runaway can occur in worst case [77]. Industrially to resolve
this issue they resort to limiting CO conversion per pass and recycling fraction of the liquid products at
high flow rates. However, such practices increases pressure drops and complicates the process of reactor
being scaled down [79].

The reactor is operated at high gas velocities to increase the heat transfer coefficient and decrease the
thickness of the stagnant layer, which limits heat transfer, at the tube wall and catalyst surface. To avoid
high values of pressure drop, the catalyst particles are limited to millimeter range, which in turn

30 | P a g e
introduces intra-particle diffusion limitations. This affects not only the reaction effectiveness factor, but
also the selectivity of the reaction due to the increase in 𝐻2 /CO ratio as the reactants diffuse towards the
pellet center[27]. To overcome this mass transfer issue eggshell catalyst configuration is a possible
solution, despite the reduced active density in the reactor and the increased difficulty of catalyst makeup
[4], [36], [80].

Figure 2.11 Illustration of MTFBR for LTFTS [76]

6.2. Slurry Bubble Column Reactor (SBCR)

On the other hand, SBCR operate with very small catalyst particles, thus overcoming the internal mass
transfer limitations. They are preferred over MTFBR for large scale operations as they are characterized
by lower construction cost, lower pressure drops and more isothermal temperature profiles. The basic
concept of the SBCR is based on the bubbling of syn gas, from the bottom of the reactor, into the product
wax medium, where the catalyst particles are suspended. The gaseous phase consisting of unreacted
syngas and volatile products are recovered from the top of the reactor, while the slurry mixture is sent to
the filtration unit to recover the catalyst that is sent back to the reactor. The well mixed liquid phase result
in almost isothermal operation that gives the possibility to reach higher CO conversions per pass.
Moreover, this type of reactors allows for continuous make-up/withdrawal of the catalyst[4].

31 | P a g e
However, the catalyst particles must be optimized to resist mechanical stress and attrition [4]. Also, this
type of reactors require efficient filtration system for liquid/catalyst separation as their densities are close
𝑔
(0.68 and 0.7 [ ⁄ 3 ] respectively)[81]. Another drawback of this type of reactors is its operational
𝑐𝑚
complexity due to the complex hydrodynamics of the reactive system. These complexities in turn makes
it inefficient to scale down the slurry reactor[79].

Figure 2.12 Scheme of SBCR for LTFTs [76]

6.3. Fluidized bed reactors

The high operating temperatures in the case of HTFTS (320-350℃ ) lead to gas-solid system without any
bulk liquid phase. Initially this type of processes was operated in circulating fluidized bed reactors, but
recently fixed bed reactors were also employed. The only catalyst valid for these operating conditions is
an alkali-promoted iron as cobalt catalyst would catalyze almost methanation reaction only. The turbulent
nature of the fluidized bed result in an almost isothermal operation conditions, but these operating
conditions impose mechanical demand on the catalyst particle strength. Thus, only fused bulk iron
catalysts are employed commercially in these reactors. A critical condition in the operation of fluidized
bed reactors is to avoid wax production, as wax buildup over the catalyst surface would cause catalyst
deactivation. Even though catalyst deactivation is inevitably high at high temperatures, the deactivated

32 | P a g e
catalyst is easily removed and fresh catalyst is added on-line, which results in the possibility of long
continuous runs[27],[82].

Figure 2.13 HTFTS fluiidized bed reactors (A) CFB reactor (B) FFB reactor[83]

7. Alternative to scale down FTS

As discussed above heat removal plays a key role in limiting the possibility of scaling down industrially
utilized FTS reactors. In conventional GTL applications, the Fischer-Tropsch (FT) process is carried out
in huge fixed bed or slurry reactors. They require a capital investment of $ 3 billion, thus constituting
a solution economically valid for plants with a production of at least of 30000 barrels per day (Bpd).
Only about 6% of the gas fields in the world are large enough to support a GTL plant of this size.
Another important intensive for scaling down FTS is to produce fuels from biomass derived syngas,
since their design capacities is expected to be much lower than minimum economic capacity of
industrial reactors[84], [85]. In addition, several technical limitations on the scale down of industrial
reactors were demonstrated in sections 6.1-6.3of this chapter. Several research groups have proposed
structured reactors as a possible mean of enhancing heat removal suitable for small scale GTL applications
[4], [59], [73], [76], [78], [79], [85]–[87].

The main features enlisted by Guttel et al.[88] for developing an intensified reactor technology are: (i)
plug-flow behavior that can control residence time distribution, (ii) fixed-bed catalyst with no separation
demand for products/catalysts, (iii) short diffusion distances i.e. catalyst with high effectiveness factor,
and (iv) low pressure drops which can reduces operational costs.

7.1. Velocys FTS technology

Velocys Inc. based in Columbus, Ohio, USA, recently (2013) launched on the market a new technology for
the exploitation of remote and stranded natural gas. The technology is considered economically feasible
for production volumes ranging from 1500 to 15000 barrels of oil per day. The Velocy’s technology is
based on the coupling of microchannel reactors with a highly active catalyst. In the reactor (Figure 2.14)
the catalyst is placed in between wave-like fin metallic structures that enhance heat transfer from the

33 | P a g e
catalyst bed. Syngas enters from the top and flows downward through the catalyst bed, with FTS products
exiting at the bottom. The reaction heat is removed by the pressurized-water coolant within cross-flow
microchannels. The fin spacing and coolant channels are on the order of a millimeter. The highly efficient
heat transfer associated with microchannels delivers a compact, high-performance reactor[89].

Figure 2.14 Schematic of a commercial Velocys microchannel unit[89]

7.2. CompactGTL FTS technology

The technology developed by CompactGTL, a British company headquartered in Abingdon (Oxfordshire,
UK), is to exploit associated natural gas reserves through the production of synthetic crude (syncrude). In
case of associated gas, the syncrude can be blended with the field main crude stream without the need
for separate transportation or storage systems. This contrasts with other GtL technologies such as
methanol and DME production, where the GtL liquid product can’t be mixed with crude oil. Moreover,
this technology doesn’t require a separate hydrocracker stage for products upgrading as the syncrude is
mixed with raw crude oil. This technology is modular, allowing it to be matched with declining oil field
production [90].

The process is based on two set of modular reactor blocks (Figure 2.15) with precise control of heat and
mass flow. The first reactor uses methane from steam reforming (SMR) to convert natural gas into syngas.
The syngas is fed into the second reactor where it is converted by the Fischer-Tropsch process into
synthetic crude, water and a tail gas composed of hydrogen, carbon monoxide and light hydrocarbon

34 | P a g e
gases. The produced water can be treated to remove impurities and recycled to the steam reforming
process [90].

Figure 2.15 Scheme of CompactGTL SMR -FTS cycle[90]

8. Foam Catalyst and Packed foam Reactor

8.1. Foam Catalyst
Open-cell metal foams, also called metal sponges are thermally continuous structures that have
several interesting characteristics which candidate them for industrial heterogenous catalysis
applications. For example, metallic foams have high porosity, low density, high mechanical strength
and large specific surface area. This type of structures are made of conductive metallic part, which are
called struts and enclose empty pores [91]. Washcoated open-cell foams, “open-sell foam catalyst”,
were proposed earlier and they showed better performance in terms of heat removal compared to
pellet catalyst in terms of heat transfer enhancement and hotspot control during FTS reaction The
heat transfer is strongly enhanced because the primary heat transfer mechanism is through static
conduction within the thermally connected foam structure instead of radial [92]. On the contrary
adopting washcoated foams suffer from several drawbacks mainly from difficulties in the coating
process and the limited catalyst loading, because high loadings block the foam macropores [92]. Other
important limitations are related to the loading and unloading of the washcoated catalyst as these
steps are crucial at an industrial level, since they require the development of a completely different
methods from those used in packed bed reactors[91].

35 | P a g e
 Figure 2.16 Al highly conductive open-cell metal foam

8.2. Packed foam reactor

LCCP group of Politecnico di Milano have lately proposed the new concept of “packed structured”
reactors (figure 2.17). This novel type of reactors is based on unreactive structure (monolith, foam or
crossflow structures) in which catalyst pellets are loaded. Packed foam reactors are a type of packed
structure reactors that combines the high conductivity associated with metallic foam and the high
catalyst loading associated with packed beds. The combination of these two features candidates
packed foams to be employed in the intensification of non-adiabatic processes at an industrial level
[87], [91], [93]–[95].

The optimization of the foam design can highly affect the overall heat transfer coefficient, this change
is a direct implication of the changes that occur at the level of foam conductivity, fluid-foam heat
transfer, wall-foam and wall-fluid heat transfer coefficients. A detailed discussion of these design
parameters would be provided in chapter 3 (section 2 & 10) and the evaluation of the process
sensitivity would be provided in chapter 4 (section 4).

The performance of packed foam reactors loaded with highly active cobalt-based catalyst (described
in section 3.3 of this chapter) was evaluated at industrially relevant operating conditions (stated in
chapter 4) in comparison to the performance of a packed fixed-bed reactor. The packed fixed-bed
reactor experienced thermal runaway at operating temperatures as low as 190℃. On the contrary,

36 | P a g e
 the packed foam reactor showed outstanding heat removal performance with duty up to 1300 kW/𝑚3
at CO conversion values around 67% and expressed almost flat axial temperature profiles (figure 2.18)
[87].

Figure 2.17 Bare and Packed foam [91]

Figure 2.18 Axial temperature profiles at different operating temperatures[87]

37 | P a g e
Chapter 3: Packed Foam Model
1. Introduction

The interesting performance demonstrated by packed foam reactors in terms of thermal management
incite the need for the development of a mathematical model that is capable of describing the mass,
energy and momentum balances across the packed foam reactor. Furthermore, a crucial feature that was
incorporated into the model is its ability to approximate the FTS selectivity towards different product
ranges.

The aim of this chapter is to develop a mathematical model to simulate Fischer-Tropsch process over
packed foam reactors, based on a set of partial differential equations (PDE) and their related algebraic
equations (AE). A detailed presentation of all the assumptions, equations, correlation and numerical
strategies adopted to simulate a lab-scale packed foam reactor will be provided in this chapter. The model
was based on the reactor configuration described in the paper of Fratalocchi et al.[87].

2. Open-cell foam properties

Foams properties vary in reason of their bulk material, production process and their geometrical
configuration, but in general they are characterized by a relevant combination of physical and
mechanical properties, such as high stiffness jointly to low specific weight, high gas permeability and
high thermal conductivity [96].

The properties of metallic open-cell foams vary according to their bulk material, geometrical
configuration and production process. In general, the metallic foam is characterized by its thermal
conductivity of foam material (𝑘𝑠𝑜𝑙𝑖𝑑 ), porosity (𝜀𝑓 ), cell diameter (𝑑𝑐𝑒𝑙𝑙 ) and specific surface area(𝑆𝑣 ).
The cell is defined as each one of the bubbles constituting the packed structure of the foam, and the void
interface between two adjacent cells is called pore. Moreover, the packing effectiveness of catalyst pellets
is an important aspect that is determined by the ratio of catalyst pellets diameter (𝑑𝑝 ) to the foam cell
diameter (𝑑𝑐𝑒𝑙𝑙 ) [97].

The proper characterization of the cell shape is crucial for the evaluation of foam properties, this can be
achieved through a tortuous process based on complex image analysis (magnetic resonance imaging, X-
ray microtomography) , or through a more practical method based on the following assumptions: cells
have 12-14 pentagonal or hexagonal faces, with ligaments ,also called struts, of circular or triangular cross-
section and material clustering at the stand vertices. Another important geometrical property is the strut
cross section, which is thick at the conjunction point among struts (𝑡𝑛 ), while it is thinner at the center
(𝑡𝑠 ) (figure 3.1) [98].

38 | P a g e
Figure 3.1 Identification of cell and pore diameters in foams & slim section and lumped intersection of foam

3. Lab-scale Reactor
The cylindrical packed foam reactor (figure 3.1) considered in this work consists of three regions, as shown
in the figure below. The first 1 cm of the foam is packed with inert 𝛼 − 𝐴𝑙2 𝑂3 pellets. The next 2cm are
packed with 7.2 g of Co/Pt/𝐴𝑙2 𝑂3 catalyst pellets that were diluted with 𝛼 − 𝐴𝑙2 𝑂3 by a ratio of
catalyst: 𝛼 − 𝐴𝑙2 𝑂3 =6:1. The last 1cm of the foam is filled with : 𝛼 − 𝐴𝑙2 𝑂3 pellets.

Figure 3.1 Packed foam scheme

39 | P a g e
Pellets are characterized by uniform dimension (𝑑𝑝 ) through over the foam and constant density (𝜌𝑐𝑎𝑡 ).
For the metallic foam it is characterized by thermal conductivity of foam material (𝑘𝑠𝑜𝑙𝑖𝑑 ), porosity (𝜀𝑓 )
and the cell diameter (𝑑𝑐𝑒𝑙𝑙 ).

4. Packed Foam Model

The model is developed in order to evaluate the thermal profiles and mass fractions along the cylindrical
reactor in both axial and radial directions. Even though the model is based on lumped kinetics the
evaluation of reaction selectivity and chain growth probability were incorporated into the model. The
model would solve five mass balances for CO, 𝐻2 , 𝑁2 , 𝐻2 𝑂 and 𝐶𝑛 𝐻𝑚 ; along with two energy balances to
solve for the fluid temperature (𝑇𝑔 ) and foam temperature (𝑇𝑓𝑜𝑎𝑚 ). Moreover, momentum balance was
introduced to solve for the pressure drop, this equation is crucial for process scale-up, where pressure
drops becomes more evident.

The main assumptions employed in this model are:

• Steady state conditions: transient dynamic effects are neglected.

• Hybrid heterogeneous model: this model combines characteristics from the pseudo-
homogeneous model as well as the heterogeneous one. The model accounts for a pseudo fluid
that combines the gaseous fluid and the catalyst pellets; in other word neglecting any mass or
heat transfer among them. On the other hand, there is a differentiation between the pseudo-fluid
and the foam, which represents the solid phase. This consideration of two different phases is a
characteristic of heterogeneous model.
• Reactions only take place in the pseudo-fluid phase and the foam is inert.
• Two-dimensional model: in order to account for the temperature gradients both axially and
radially due to the high exothermicity of the FTS reaction.
• Catalyst deactivation is neglected
• Internal mass and heat transfer limitations are neglected.
• The ideal gas law was the employed equation of state in the model.
• The liquid phase is neglected as more than 99% of the products are in gaseous state under the
reaction conditions [86], [99].
• The lumped kinetics are based on the scheme proposed by Yates and Satterfield [100].

The assumption of pseudo-fluid was based on the results reported by Fratalocchi et al [87], concerning
heat transfer between gaseous fluid and catalyst particles, that indicated absence of external mass
transport limitations based on Mears criterion [101].The importance of external mass transfer limitations
is proven to be negligible through simulating the performance of the model in their presence.
Furthermore, the absence of internal temperature gradients is secured by the small value of the internal
Prater number under the reaction conditions adopted in this study[87].

Based on the equation reported by Forment et al. [102] , the mass balance for each of the five individual
species would be:
𝐴𝑚𝑜𝑢𝑛𝑡 𝑜𝑓 𝑠𝑝𝑒𝑐𝑖𝑒𝑠 𝑖 𝐴𝑚𝑜𝑢𝑛𝑡 𝑜𝑓 𝑠𝑝𝑒𝑐𝑖𝑒𝑠 𝑖 𝐴𝑚𝑜𝑢𝑛𝑡 𝑜𝑓 𝑠𝑝𝑒𝑐𝑖𝑒𝑠 𝑖 𝐴𝑚𝑜𝑢𝑛𝑡 𝑜𝑓 𝑠𝑝𝑒𝑐𝑖𝑒𝑠 𝑖
(𝑒𝑛𝑡𝑒𝑟𝑖𝑛𝑔 𝑝𝑒𝑟 𝑢𝑛𝑖𝑡 𝑡𝑖𝑚𝑒
) − (𝑙𝑒𝑎𝑣𝑖𝑛𝑑 𝑝𝑒𝑟 𝑢𝑛𝑖𝑡 𝑡𝑖𝑚𝑒
) − (𝑐𝑜𝑛𝑣𝑒𝑟𝑡𝑒𝑑 𝑝𝑒𝑟 𝑢𝑛𝑖𝑡 𝑡𝑖𝑚𝑒
) = (𝑎𝑐𝑐𝑢𝑚𝑢𝑙𝑎𝑡𝑒𝑑 𝑝𝑒𝑟 𝑢𝑛𝑖𝑡 𝑡𝑖𝑚𝑒
)

40 | P a g e
 2 𝑒𝑓𝑓
𝜕𝑦𝑖 𝑒𝑓𝑓 𝜕 𝑦𝑖 1 𝜕𝑦𝑖 𝐷𝑎𝑥 𝜕 2 𝑦𝑖 𝜕𝐷𝑎𝑥 𝜕𝑦𝑖 𝜕𝐷𝑟 𝜕𝑦𝑖
−𝐺 + 𝜌𝑚𝑖𝑥 𝐷𝑟 ( 2 + ∗ ) + 𝜌𝑚𝑖𝑥 2 2
+ 𝜌𝑚𝑖𝑥 ( ) + 𝜌𝑚𝑖𝑥 ( )
𝜕𝑧 𝜕𝑟 𝑟 𝜕𝑟 𝐿 𝜕𝑧 𝜕𝑧 𝜕𝑧 𝜕𝑟 𝜕𝑟
+ 𝜔𝑎𝑐𝑡 𝑅𝑖 = 0 [𝑘𝑔/𝑚3 /𝑠] ( Eq. 3.1)

Since the equations in the model would be solved numerically, they would be written in terms of
𝑧
dimensionless spatial variables. Therefore, dimensionless axial and radial position are defined as 𝑧 ∗ = 𝐿
𝑟
and 𝑟 ∗ = 𝑅 respectively. This leads to a more numerically stable set of equations to be solved:
𝑖𝑛𝑡

𝑒𝑓𝑓
−𝐺 𝜕𝑦𝑖 𝐷𝑟 𝜕 2 𝑦𝑖 1 𝜕𝑦𝑖 𝐷𝑎𝑥 𝜕 2 𝑦𝑖 1 𝜕𝐷𝑎𝑥 𝜕𝑦𝑖
∗
+ 𝜌𝑚𝑖𝑥 2 ( ∗2
+ ∗ ∗ ) + 𝜌𝑚𝑖𝑥 2 ∗2
+ 𝜌𝑚𝑖𝑥 2 ( ∗ )
𝐿 𝜕𝑧 𝑅𝑖𝑛𝑡 𝜕𝑟 𝑟 𝜕𝑟 𝐿 𝜕𝑧 𝐿 𝜕𝑧 𝜕𝑧 ∗
𝑒𝑓𝑓
1 𝜕𝐷𝑟 𝜕𝑦𝑖
+ 𝜌𝑚𝑖𝑥 2 ( 𝜕𝑟 ∗ 𝜕𝑟 ∗ ) + 𝜔𝑎𝑐𝑡 𝑅𝑖 = 0
[𝑘𝑔/𝑚3 /𝑠] (Eq. 3.1′)
𝑅𝑖𝑛𝑡

and the reactive term is expressed as reaction is 𝑅𝑖 = 𝜌𝑏𝑒𝑑 𝑀𝑀𝑖 𝜈𝑖 𝑅𝑓𝑡𝑠 [𝑘𝑔/𝑚3 /𝑠] (𝐸𝑞. 3.2)

Where:

• G [𝑘𝑔 𝑠 −1 𝑚−2]: specific mass velocity

• 𝑦𝑖 [-]: mass fraction of component i
𝑒𝑓𝑓
• 𝐷𝑟 [𝑚2 /𝑠]: gas radial diffusivity
• 𝐷𝑎𝑥 [𝑚2 /𝑠]: gas axial diffusivity
• 𝜌𝑚𝑖𝑥 [𝑘𝑔/𝑚3 ]: mass density of fluid phase
• 𝜔𝑎𝑐𝑡 [−]: activity factor
• 𝜌𝑏𝑒𝑑 [𝑘𝑔/𝑚3 ]: mass density of the catalytic fraction of the packed bed
• 𝑅𝑓𝑡𝑠 [𝑚𝑜𝑙/𝑔𝑐𝑎𝑡 /𝑠]: the reaction rate of FTS (lumped reaction)
• 𝑀𝑀𝑖 [𝑔/𝑚𝑜𝑙]: molar weight of component i
• 𝜈𝑖 [-]: stoichiometric coefficient of component i
• 𝑧 ∗[-]: dimensionless axial coordinate
• 𝑟 ∗[-]: dimensionless radial coordinate
• 𝐿[m]: reactor length
• 𝑅𝑖𝑛𝑡 [m]: reactor internal radius

The activity factor 𝜔𝑎𝑐𝑡 was introduced to account for the three regions of the packed foam, so the
reaction reactive termed would be only activated in the reactive zone (𝜔𝑎𝑐𝑡 = 1) and turned off elsewhere
(𝜔𝑎𝑐𝑡 =0) (Figure 3.3).

41 | P a g e
 axial variation of pellets activity factor
1.2

1
pellets activity
0.8

0.6

0.4
Reaction zone Inert zone

0.2

0
0 0.5 1 1.5 2 2.5 3 3.5 4 4.5
reactor length [cm]

Figure 3.3 Axial variation of pellets activity factor across the packed foam reactor

Following the same approach as before, for the case of chemical reactor with negligible work, potential
and kinetic energy, the heat balance is as follows:

𝐴𝑚𝑜𝑢𝑛𝑡 𝑜𝑓 ℎ𝑒𝑎𝑡 𝐴𝑚𝑜𝑢𝑛𝑡 𝑜𝑓 ℎ𝑒𝑎𝑡 𝐻𝑒𝑎𝑡 𝑒𝑓𝑓𝑒𝑐𝑡 𝑜𝑓 𝑉𝑎𝑟𝑖𝑎𝑡𝑖𝑜𝑛 𝑜𝑓 ℎ𝑒𝑎𝑡

(𝑎𝑑𝑑𝑒𝑑 𝑝𝑒𝑟 𝑢𝑛𝑖𝑡 𝑡𝑖𝑚𝑒
) − (𝑟𝑒𝑚𝑜𝑣𝑒𝑑 𝑝𝑒𝑟 𝑢𝑛𝑖𝑡 𝑡𝑖𝑚𝑒
) − (𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛 𝑝𝑒𝑟 𝑢𝑛𝑖𝑡 𝑡𝑖𝑚𝑒
) = (𝑐𝑜𝑛𝑡𝑒𝑛𝑡 𝑝𝑒𝑟 𝑢𝑛𝑖𝑡 𝑡𝑖𝑚𝑒
)

Applying the assumptions stated above, the heat balance for the pseudo-fluid is the following:
𝑒𝑓𝑓 𝑒𝑓𝑓
−𝐺𝑐𝑝,𝑚𝑖𝑥 𝜕𝑇𝑔 𝑘𝑟 𝜕2 𝑇𝑔 1 𝜕𝑇𝑔 𝑘𝑎𝑥 𝜕2 𝑇𝑔 1 𝜕𝑘 𝜕𝑇𝑔 1 𝜕𝑘𝑟 𝜕𝑇𝑔
𝐿 𝜕𝑧 ∗
+ 2
𝑅𝑖𝑛𝑡
( 𝜕𝑟∗2 + 𝑟 ∗ 𝜕𝑟∗ ) + 𝐿2 𝜕𝑧 ∗2
+ 𝐿2 ( 𝜕𝑧𝑎𝑥
∗ 𝜕𝑧 ∗ ) + 𝑅 2 ( 𝜕𝑟 ∗ 𝜕𝑟 ∗
) + 𝑈𝑜𝑣 𝑆𝑣 (𝑇𝑔 −
𝑖𝑛𝑡
𝑇𝑓𝑜𝑎𝑚 ) + 𝜔𝑎𝑐𝑡 𝑞𝑣𝑜𝑙 = 0 [𝑊/𝑚3 ] (𝐸𝑞. 3.4)

and the reaction heat is computed as: 𝑞𝑣𝑜𝑙 = −𝜌𝑏𝑒𝑑 𝑅𝑓𝑡𝑠 𝛥𝐻𝑓𝑡𝑠 [𝑊/𝑚3 ] (𝐸𝑞. 3.5) .

Where:

• 𝑐𝑝,𝑚𝑖𝑥 [J/kg/K]
𝑒𝑓𝑓
• 𝑘𝑟 [W/m/K]: effective fluid radial conductivity
• 𝑘𝑎𝑥 [W/m/K]: effective axial conductivity
• 𝑈𝑜𝑣 [W/𝑚2 /𝐾]: overall heat transfer coefficient
• 𝑆𝑣 [𝑚−1]: specific foam surface area
• 𝛥𝐻𝑓𝑡𝑠 [J/mol]: enthalpy of FTS reaction

The energy balance for the metallic foam is as follows:

𝐽
𝑘𝑒𝑓𝑓 𝜕 2 𝑇𝑓𝑜𝑎𝑚 1 𝜕𝑇𝑓𝑜𝑎𝑚 𝑘𝑒𝑓𝑓 𝜕 2 𝑇𝑓𝑜𝑎𝑚 𝑚 3
2 ( 𝜕𝑟 ∗2 + 𝑟 ∗ 𝜕𝑟 ∗ )+ 2
𝐿 𝜕𝑧 ∗2
+ 𝑈𝑜𝑣 𝑆𝑣 (𝑇𝑔 − 𝑇𝑓𝑜𝑎𝑚 ) = 0 [
𝑠
] (𝐸𝑞 3.5)
𝑅𝑖𝑛𝑡

42 | P a g e
Where the effective conductivity of the foam (𝑘𝑒𝑓𝑓 [𝑊/𝑚/𝐾]) is uniform in both radial and axial
directions.

For the momentum balance the Ergun equation[103] was used to evaluate pressure drop where:
𝑑𝑃 𝑓𝑝 𝜌𝑚𝑖𝑥 𝑣𝑎𝑐𝑡 2 (1−𝜀) 150 𝑣𝑎𝑐𝑡 𝜌𝑚𝑖𝑥 𝑑𝑝
𝑑𝑧 ∗
=𝐿∗ 𝑑𝑝 𝜀 3
[𝑃𝑎], 𝑓𝑝 = 𝑅𝑒 + 1.75 𝑎𝑛𝑑 𝑅𝑒𝑝 = 𝜇𝑚𝑖𝑥 (1−𝜀)
(𝐸𝑞. 3.6)
𝑝

Where:

• P [bar] is the fluid pressure

• 𝜀 is the packed bed void fraction
• 𝑓𝑝 is the packed friction factor
• 𝑣𝑎𝑐𝑡 [m/s] is the superficial velocity
• 𝑅𝑒𝑝 is the modified Reynolds number

5. Boundary Conditions
The boundary conditions are necessary input to guarantee the uniqueness of the PDE solution.

a) At inlet (z=0) Cauchy boundary conditions are used:

- mass fractions of gas species: 𝑦𝑖 = 𝑦𝑖𝑖𝑛 (𝐸𝑞. 3.7)
- pseudo-fluid and foam temperature: 𝑇𝑓𝑜𝑎𝑚 = 𝑇𝑔 = 𝑇𝑖𝑛 (𝐸𝑞. 3.8)
- inlet pressure: 𝑃 = 𝑃𝑖𝑛 (𝐸𝑞. 3.9)
b) At axial outlet (z=L) the derivatives with respect to axial coordinates for temperatures and mass
fractions were imposed to be zero.
1 𝜕𝑦𝑖
= 0 (𝐸𝑞. 3.10)
𝐿 𝜕𝑧 ∗
1 𝜕𝑇𝑓𝑜𝑎𝑚
= 0 (𝐸𝑞. 3.11)
𝐿 𝜕𝑧 ∗
1 𝜕𝑇𝑔
= 0 (𝐸𝑞. 3.12)
𝐿 𝜕𝑧 ∗
c) At the radial center (r=0) due to symmetry the radial derivative of composition and temperature
are imposed to be zero.
1 𝜕𝑦𝑖
= 0 (𝐸𝑞. 3.13)
𝑅𝑖𝑛𝑡 𝜕𝑟 ∗
1 𝜕𝑇𝑓𝑜𝑎𝑚
= 0 (𝐸𝑞. 3.14)
𝑅𝑖𝑛𝑡 𝜕𝑟 ∗
1 𝜕𝑇𝑔
= 0 (𝐸𝑞. 3.15)
𝑅𝑖𝑛𝑡 𝜕𝑟 ∗
b) At the reactor wall (r=𝑅𝑖𝑛𝑡 ) the wall is impermeable for all the species, so the radial derivative is zero.
However, for the case of energy balance heat transfer still occurs between the wall and both the foam

43 | P a g e
and pseudo-fluid, so the heat diffusing radially in each phase is imposed to be equal to the heat flux
between the wall and the considered phase.
1 𝜕𝑦𝑖
= 0 (𝐸𝑞. 3.16)
𝑅𝑖𝑛𝑡 𝜕𝑟 ∗
𝑘𝑓𝑜𝑎𝑚 𝜕𝑇𝑓𝑜𝑎𝑚
− ℎ𝑤𝑎𝑙𝑙,𝑓𝑜𝑎𝑚 (𝑇𝑤𝑎𝑙𝑙 − 𝑇𝑓𝑜𝑎𝑚 ) = 0 (𝐸𝑞. 3.17)
𝑅𝑖𝑛𝑡 𝜕𝑟 ∗
𝑒𝑓𝑓
𝑘𝑟 𝜕𝑇𝑔
− ℎ𝑤𝑎𝑙𝑙,𝑔𝑎𝑠 (𝑇𝑤𝑎𝑙𝑙 − 𝑇𝑔 ) = 0 (𝐸𝑞. 3.18)
𝑅𝑖𝑛𝑡 𝜕𝑟 ∗

6. Gas and catalytic pellets physical parameters

This part of the chapter is dedicated to report all the correlations employed to evaluate the fluid
physical properties, mass diffusivity and thermal conductivity.

6.1. Linear Gas Velocity

𝑄
First, the value of inlet linear velocity at STP conditions is evaluated as 𝑣@𝑆𝑇𝑃 = 𝐴 @𝑆𝑇𝑃𝜀. Then the linear
𝑟𝑒𝑎𝑐𝑡
velocity is modified to account for change in total number of moles as well as the value of gas temperature
and pressure. While neglecting radial variation, the actual value of superficial velocity is expressed as:
𝑇𝑔 ∗ 𝑛𝑡𝑜𝑡 ∗ 𝑃𝑟𝑒𝑓,𝑎𝑚𝑏
𝑣𝑎𝑐𝑡 = 𝑣@𝑆𝑇𝑃 𝑖𝑛
[𝑚/𝑠] (𝐸𝑞. 3.19)
𝑇𝑟𝑒𝑓,𝑎𝑚𝑏 ∗ 𝑛𝑡𝑜𝑡 ∗𝑃

6.2. Specific Heat Capacities

The specific heat capacity of each species is evaluated by using the 3rd order polynomial form reported by
Poling et al [104].
2 3
𝑐𝑝,𝑖 = 𝐴𝑜 + 𝐴1 𝑇𝑎𝑐𝑡 + 𝐴2 𝑇𝑎𝑐𝑡 + 𝐴3 𝑇𝑎𝑐𝑡 (𝐸𝑞. 3.20)

This equation is in accordance with the results generated by fourth order polynomial Shomate [105]
equation till temperatures over 800°C.

The mixture massive specific heat is obtained through the following expression:
𝑦𝑖
𝑐𝑝,𝑚𝑖𝑥 = 𝛴𝑐𝑝,𝑖 [𝑘𝐽/𝑘𝑔/𝐾] (𝐸𝑞. 3.21)
𝑀𝑀𝑖

6.3. Mixture Density

The density of individual species is evaluated based on individual molecular masses:
105 𝑃𝑎 𝑔 10−3 𝑘𝑔
𝑘𝑔 𝑃[𝑏𝑎𝑟] ∗ [ ] ∗ 𝑀𝑀 [
𝑖 𝑚𝑜𝑙 ] ∗ [ 𝑔 ]
𝑏𝑎𝑟
𝜌𝑖 [ 3 ] = (𝐸𝑞. 3.22)
𝑚 𝑗
𝑅𝑔𝑎𝑠 [ 𝑚𝑜𝑙 ] ∗ 𝑇𝑔 [𝑘]
𝑘
While for the case of mixture density the average molar average molecular weight is used:
𝑃 ∗ 𝑀𝑀𝑚𝑖𝑥
𝜌𝑚𝑖𝑥 = (𝐸𝑞. 3.23)
𝑅𝑔𝑎𝑠 ∗ 𝑇𝑔
where

44 | P a g e
 𝑁𝐶
𝑔
𝑀𝑀𝑚𝑖𝑥 ∑ 𝑥𝑖 ∗ 𝑀𝑀𝑖 [ ] (3.24)
𝑚𝑜𝑙
1

6.4. Mixture Dynamic Viscosity

The individual dynamic viscosity is evaluated based on the correlation reported in Perry’s handbook [106]:

1/2 2/3 𝑇𝑔
𝜇𝑖 [𝑐𝑃] = 1.286𝑀𝑀𝑖 [𝑔/𝑚𝑜𝑙]𝑃𝑐,𝑖 [𝑎𝑡𝑎] 10−4 (𝐸𝑞. 3.25)
𝑇𝑐,𝑖 [𝐾]

The mixture dynamic viscosity is computed according to the Wilke method [107]:
𝜇 𝑀𝑀𝑚
[1 + ( 𝑚⁄𝜇𝑛 )1/2 ( ⁄𝑀𝑀 )1/4 ]2
𝑛
𝜑𝑚,𝑛 = , 𝜑𝑚,𝑚 = 1 (𝐸𝑞. 3.26)
𝑀𝑀𝑚
[8(1 + ⁄𝑀𝑀 )]1/2
𝑛
𝑦𝑚 𝜇𝑚
𝜇𝑚𝑖𝑥 = ∑ [𝑐𝑃] (𝐸𝑞. 3.27)
∑𝑛 𝜇𝑚 𝜑𝑚,𝑛
𝑚

6.5. Gas Thermal Conductivity

The thermal conductivity estimation is analogous to the computation of dynamic viscosity shown above.
The individual thermal conductivity is evaluated based on the following equation [106]:
𝑊 2.5
𝑘𝑖 [ ] = 3.6𝜇𝑖 (𝑐𝑝,𝑖 + ) (𝐸𝑞. 3.28)
𝑚𝐾 𝑀𝑀𝑖
The mixture thermal conductivity is approximated via Wassiljewa method that was further modified and
corrected by Mason and Saxena [104]. Thus, the correlation is as follows:
𝑘 𝑀𝑀𝑚
[1 + ( 𝑚⁄𝑘 )1/2 ( ⁄𝑀𝑀 )1/4 ]2
𝑛 𝑛
𝐴𝑚𝑛 = , 𝐴𝑚𝑚 = 1 (𝐸𝑞. 3.29)
𝑀𝑀𝑚
[8(1 + ⁄𝑀𝑀 )]1/2
𝑛

𝑊 𝑦𝑚 𝑘𝑚
𝑘𝑚𝑖𝑥 [ ]=∑ , (𝐸𝑞. 3.30)
𝑚𝐾 ∑𝑛 𝑘𝑚 𝐴𝑚,𝑛
𝑚

6.6. Axial and radial effective mass diffusion coefficients

Computation of mass diffusion coefficients is based on the assumption that Peclet number equal to 2 in
axial direction and is equal to 12 in radial one, this assumption is verified by experimental evidence
presented in literature[108]. Therefore, the axial and radial diffusion coefficients are computed via:
2
𝐺𝑑𝑝 𝑒𝑓𝑓 𝑚 𝐺𝑑𝑝
𝑃𝑒 = 2 = 𝑒𝑓𝑓
=>> 𝐷𝑎𝑥 [ ] = (𝐸𝑞. 3.31)
𝜌𝑚𝑖𝑥 𝐷𝑎𝑥 𝑠 𝜌𝑚𝑖𝑥 2
2
𝐺𝑑𝑝 𝑒𝑓𝑓 𝑚 𝐺𝑑𝑝
𝑃𝑒 = 12 = 𝑒𝑓𝑓
=>> 𝐷𝑟 [ ]= (𝐸𝑞. 3.32)
𝜌𝑚𝑖𝑥 𝐷𝑟 𝑠 𝜌𝑚𝑖𝑥 12

45 | P a g e
 7. Heat transfer parameters
The heat transfer coefficients for axial, radial and wall heat transfer in the pseudo-fluid are adopted from
the correlations reported by Specchia et al. [109]. correlations have demonstrated their validity simulating
reactions packed bed cases and have been also successfully used in packed foam case in recent works of
our group [110], [111].

7.1. Specchia et al. wall heat transfer coefficient

The wall heat transfer consists from two main contributions the static and the convective one.

𝑐𝑜𝑛𝑣 0)
𝑊
ℎ𝑤 = (ℎ𝑤 + ℎ𝑤 [ 2 ] (𝐸𝑞. 3.33)
𝑚 𝐾
For the static contribution the heat transfer occurs through two main paths as shown below. Via fluid
present in void between the catalyst pellets and the reactor wall and via the stagnant fluid in series with
the solid particles near the wall-particle contact points.

Figure 3.5 Heat Transfer model for stagnant contribution at the wall [102]

46 | P a g e
The expression for the static contribution is:
0
ℎ𝑤 𝑑𝑝 1−ԑ
= 2ԑ + (𝐸𝑞. 3.34)
𝑘𝑚𝑖𝑥 𝑑𝑝 1 𝑘
0.0024(𝐷 )1.58 + 3 ( 𝑚𝑖𝑥 )
𝑒𝑞 𝑘𝑠

Where 𝐷𝑒𝑞 [𝑚] is the characteristic length, and it is assumed to be equal to the reactor internal diameter
in this case.

The convective contribution is affected by effect of turbulence around the catalytic pellet. This
contribution is expressed as:
𝑐𝑜𝑛𝑣
ℎ𝑤 𝑑𝑝
= 0.0835𝑅𝑒𝑑𝑝 0.91 𝑖𝑓 20 < 𝑅𝑒𝑑𝑝 < 1200 (𝐸𝑞. 3.35)
𝑘𝑚𝑖𝑥
𝑐𝑜𝑛𝑣
ℎ𝑤 𝑑𝑝
= 1.23𝑅𝑒𝑑𝑝 0.53 𝑖𝑓 𝑅𝑒𝑑𝑝 > 1200 (𝐸𝑞. 3.36)
𝑘𝑚𝑖𝑥
𝑣𝑎𝑐𝑡 𝜌𝑚𝑖𝑥 𝑑𝑝
Where 𝑅𝑒𝑑𝑝 = 𝜇𝑚𝑖𝑥
(𝐸𝑞. 3.37)

7.2. Specchia et al. radial effective thermal conductivity

For the case of radial effective conductivity, experimental evidence indicated the dependence of thermal
conductivity on gas velocity. However, experiments done at zero velocities indicated the existence of
conductivity. Therefore, the effective radial thermal can be expressed as the sum of static and convective
contributions, where the static contribution, which is the contribution due to the conduction through the
fluid and catalyst phases, is considered to be independent from the system hydrodynamics, while the
convective contribution accounts for radial mixing and is affected by fluid velocity and physical properties.
𝑒𝑓𝑓
𝑘𝑟 = (𝑘𝑟0 + 𝑘𝑟𝑐𝑜𝑛𝑣 ) (𝐸𝑞. 3.38)
To estimate the static contribution the authors employed the Kunii and Smith (1960) model, which
correlates void fraction, fluid conductivity and catalyst conductivity to evaluate the static contribution as
[109]:

𝑘𝑟0 1−ԑ
=ԑ+ (𝐸𝑞. 3.39)
𝑘𝑚𝑖𝑥 2 𝑘
0.22𝜀 2 + 3 ( 𝑚𝑖𝑥 )
𝑘𝑠
Specchia et al.[109] proposed a correlation between Reynold’s, Prandtl and the reference Peclet numbers.
The product of Reynold’s number and Prandtl number is the hydraulic Peclet number.
𝑘𝑟𝑐𝑜𝑛𝑣 𝑅𝑒𝑑𝑝 𝑃𝑟
= (𝐸𝑞. 3.40)
𝑘𝑚𝑖𝑥 𝑃𝑒𝑟𝑒𝑓
𝜇𝑚𝑖𝑥 ∗𝑐𝑝,𝑚𝑖𝑥 𝑑𝑝
Where 𝑃𝑟 = 𝑘𝑚𝑖𝑥
and 𝑃𝑒𝑟𝑒𝑓 = 8.65[1 + 19.4(𝐷 )2 ] and 𝐷𝑒𝑞 is the characteristic length and it is
𝑒𝑞
equal to 𝐷𝑖𝑛𝑡 .

47 | P a g e
 7.3. Specchia et al. axial effective thermal conductivity
The axial effective thermal conductivity is assumed equal to the radial one [109].

8. Thermodynamic Properties
The dependence of the system under study on temperature is vivid, especially in the case of reaction
selectivity and chain growth probabilities. The change in the aforementioned variables not only would
cause change in product composition [47] , but also in the heat of formation of reactants and thus in the
heat of reaction itself [112]. These effects would be extensively discussed in the following paragraphs.

8.1. Selectivity and chain growth probability

The selectivity of reaction towards 𝐶𝐻4 and 𝐶𝑂2 was obtained as a function of operating temperature
through analyzing the experimental data reported by Fratalocchi et al.[87] a nonlinear regression was
applied to obtain the following correlations:
(0.007183284 − 0.4022108)
𝑆𝐶𝐻4 = 0.4022108 + 𝑤𝑖𝑡ℎ 𝑅 2 = 0.9833 (𝐸𝑞. 3.41)
𝑇𝑔
1+( )29.23618
492.3826
(0.00270205 − 0.2541303)
𝑆𝐶𝑂2 = 0.2541303 + 𝑤𝑖𝑡ℎ 𝑅 2 = 0.9998 (𝐸𝑞. 3.42)
𝑇𝑔 40.77366
1+( )
525.8762
The reaction selection was also reported for hydrocarbons between 2 and 4 (𝑆𝐶2 𝐶4 ), based on ASF model
distribution [47], where 𝑥𝑛 = (1 − 𝛼)𝛼 𝑛−1, the value of 𝑆𝐶2 𝐶4 =(1 − 𝛼)𝛼 1 + (1 − 𝛼)𝛼 2 + (1 − 𝛼)𝛼 3 . By
solving the cubic equation of 𝑆𝐶2 𝐶4 in terms of 𝛼 gives the value of the first chain growth probability (𝛼1 ),
where 𝛼1 is the solution of the quadratic equation. The second chain growth probability was already
reported at different temperatures. The regression of the obtained data leads to the following
expressions:
(21557.15 − 0.9370555)
𝛼1 = 0.9370555 + 𝑤𝑖𝑡ℎ 𝑅 2 = 0.9371 (𝐸𝑞. 3.43)
𝑇𝑔 34.38953
1+( )
312.5071
(0.8836347 − 0.8339526)
𝛼2 = 0.8339526 + 𝑤𝑖𝑡ℎ 𝑅 2 = 0.9524 (𝐸𝑞. 3.44)
𝑇𝑔
1 + (486.9879)71.21572

It is worth noting that these expressions are not only bounded by temperatures between 453K and 513K,
but also restricted to the operating pressure used and hour space velocity and catalyst type. As
experiments indicated dependence of chain growth probability on these conditions [113], [114].

8.2. Enthalpy of reaction

The enthalpy of the reaction is estimated based on modified version of the equation proposed by
Chaumette et al. [112] for cobalt-based catalysts, which are characterized by low olefin to paraffin ratio
and limited WGS reaction [115]. The modifications aim to incorporate the effects of water gas shift
(WGS) reaction and the deviation in slope in the ASF diagram. The adopted correlation estimates the
heat of formation of paraffins based on the correlation proposed by Reid et al.[116]:

48 | P a g e
 ∆𝐻𝑓,𝑘 = −4.89412 ∗ 𝑘 − 10.8527 (𝐸𝑞. 3.45)

Where ∆𝐻𝑓,𝑘 is the heat of formation for paraffin with chain length (k), but this approximation
underestimates the heat of formation of methane. To account the problem of underestimation of
produced methane by ASF plot, Chaumette et al.[112] proposed the following correlation to estimate the
summation of heat of formation of all paraffinic products:
(1 − 𝛼)𝜁
∆𝐻𝑝𝑟𝑜𝑑𝑢𝑐𝑡 = 𝑆𝐶𝐻4 ∗ ∆𝐻𝑓,𝐶𝐻4 + (15.75
𝛼
∞

+ ∑(−4.89412 ∗ 𝑘 − 10.8527)𝛼 𝑘−1 ) [𝑘𝑐𝑎𝑙/𝑚𝑜𝑙] (𝐸𝑞. 3.46)

𝑘=1

This proposal accounts for the selectivity and heat of formation of methane separately and corrects for
the estimated heat of formation for methane by adding 15.75 [𝑘𝑐𝑎𝑙/𝑚𝑜𝑙]. The 𝜁 term represents the
number of 𝐶2+moles per one mole of CO converted and it is calculated as:
(1 − 𝑆𝐶𝐻4 )(1 − 𝛼)
𝜁= (𝐸𝑞. 3.47)
(2 − 𝛼)
In the same paper Chaumette et al.[112] also proposed a correction to account for the condensation of
products with chain length of 6 and above (Eq. 3.48).
(1−𝛼)𝜁
∆𝐻𝑝𝑟𝑜𝑑𝑢𝑐𝑡 = 𝑆𝐶𝐻4 ∗ ∆𝐻𝑓,𝐶𝐻4 + (15.75 + ∑∞
𝑘=1((−4.89412 ∗ 𝑘 − 10.8527)𝛼
𝑘−1
+
𝛼
𝛿𝑘≥6 (+0.9675 ∗ 𝑘 − 1.152) ) [𝑘𝑐𝑎𝑙/𝑚𝑜𝑙] (𝐸𝑞. 3.48)
Therefore, the overall heat of reaction is approximated via the following equation:
(1−𝛼)𝜁
∆𝐻𝑓𝑡𝑠 = 𝑆𝐶𝐻4 ∗ ∆𝐻𝑓,𝐶𝐻4 + (15.75 + ∑∞
𝑘=1((−4.89412 ∗ 𝑘 − 10.8527)𝛼
𝑘−1
+
𝛼
𝛿𝑘≥6 (+0.9675 ∗ 𝑘 − 1.152) )) + ∆𝐻𝑓,𝐻2 𝑂 − ∆𝐻𝑓,𝐶𝑂 [𝑘𝑐𝑎𝑙/𝑚𝑜𝑙] (𝐸𝑞. 3.49)

To account for the effect of WGS reaction (Eq. 2.4) and the double chain growth on the overall reaction
enthalpy, the following equation is proposed by this work:

(1 − 𝛼𝑖 )𝜁𝑖
∆𝐻𝑓𝑡𝑠 = 𝑆𝐶𝐻4 ∗ ∆𝐻𝑓,𝐶𝐻4 + 𝑆𝐶𝑂2 ∗ (∆𝐻𝑓,𝐶𝑜2 − ∆𝐻𝑓,𝐻2 𝑂 ) + (15.75
𝛼𝑖
∞

+ ∑((−4.89412 ∗ 𝑘 − 10.8527)𝛼𝑖𝑘−1 + 𝛿𝑘≥6 (+0.9675 ∗ 𝑘 − 1.152)))

𝑘=1
+ ∆𝐻𝑓,𝐻2 𝑂 − ∆𝐻𝑓,𝐶𝑂 [𝑘𝑐𝑎𝑙/𝑚𝑜𝑙] (𝐸𝑞. 3.50)

And
(1 − 𝑆𝐶𝐻4 − 𝑆𝐶𝑂2 )(1 − 𝛼𝑖 )
𝜁𝑖 = (𝐸𝑞. 3.51)
(2 − 𝛼𝑖 )
The difference in approximated heat of reaction in case of considering WGS reaction or not, while
accounting for double chain growth probability in both cases, is reported in the figure below.

49 | P a g e
 Figure 3.6 Heat of reaction estimated by the proposed correlation

It is worth noting that the reported value of heat of reaction in the work of Fratalocchi et al.[87] at 503K
is -165 [kJ/mol], while that evaluated by the correlation proposed by the equation proposed by Chaumette
et al.[112] is -164.36 [kJ/mol] and by considering the WGS reaction it is -165.94 [kJ/mol]. Through the rest
of this work the correlation that accounts for WGS is adopted.

9. Kinetic Properties
For simplicity, in this work a lumped reaction mechanism (Eq. 3.52) and Yates Satterfield kinetics
expression (Eq. 3.53) [100] are adopted. This rate expression contains an inhibition term due to CO
adsorption and it was numerically more stable ,for conversion values higher than 40%, than the Zennaro
expression[117] that follows a power law (𝑅𝑓𝑡𝑠 = 𝑃𝐶𝑂 −0.24 𝑃𝐻2 0.74 ). This instability in the Zennaro
expression is due to the negative exponent of CO pressure so with increase in conversion the rate would
keep in increasing which is unrealistic.

The lumped reaction scheme is represented as the following:

1
𝐶𝑂 + 2.2948𝐻2 ==> 𝐶 𝐻 + 𝐻2 𝑂 (𝐸𝑞. 3.52)
3.211 3.211 8.192

50 | P a g e
And the kinetic expression is:
𝑘𝑃𝐶𝑂 𝑃𝐻2
𝑅𝑓𝑡𝑠 = (𝐸𝑞. 3.53)
(1 + 𝐾𝑎 𝑃𝐶𝑂 )2
−𝐸𝑎
𝑚𝑜𝑙
where 𝑘 = 727𝑒 𝑅𝑇 [𝑠𝑔 2 ], the activation energy Ea=76.26 [kJ/mol] and 𝐾𝑎 = 0.3 𝑎𝑡𝑚−1. The
𝑐𝑎𝑡 𝑎𝑡𝑚
above values are valid for temperature between 473 and 513K.

10. Foam Parameters

10.1. Wall Solid Heat Transfer Coefficient
To estimate the wall heat transfer coefficient for the correlation proposed by Bianchi et al. [117]. This
correlation is a function of gas conductivity, foam cell diameter and Reynolds number evaluated at the
foam cell diameter.
𝑘𝑚𝑖𝑥
ℎ𝑤𝑎𝑙𝑙,𝑓𝑜𝑎𝑚 = (𝐸𝑞. 3.54)
𝑑𝑐𝑒𝑙𝑙 (7.18 + 0.29𝑅𝑒𝑑𝑐 0.8 )
Where:
𝑣𝑎𝑐𝑡 𝜌𝑚𝑖𝑥 𝑑𝑐𝑒𝑙𝑙
𝑅𝑒𝑑𝑐 = (3.55)
𝜇𝑚𝑖𝑥

10.2. Radial and Axial Solid Conductivities

The conductivity of the foam is assumed uniform in both radial and axial directions. The foam conductivity
is estimated based on the expression proposed by Bracconi et al. [118].
1 − 𝜀𝑓
𝑘𝑒𝑓𝑓 = 𝑘𝑠𝑜𝑙𝑖𝑑 (3.56)
2 1
(3 (1 − 𝜀𝑓 ) + 3)−1

This correlation is the outcome of the investigation of foam geometrical parameters (void fraction,
porosity, cell diameter) effect on the foam effective thermal conductivity, by means of 3D numerical
simulations carried out on virtually reconstructed structures [118].

10.3. Specific Surface Area

The determination of specific surface are is essential in determining the heat transfer between the foam
and the pseudo-fluid. The empirical correlation employed in this work is based on the expression reported
by Ambrosetti et al. [119], which is developed on the basis of pure geometrical considerations. The main
assumptions used in the model are:

• Foam unit cell is considered equal to the tetrakaidekahedron (TKKD) model.

• In each node four different struts converge, and they form an angle of about 109.5°.
• If the strut has a triangular cross section it converges with a tetrahedral geometry, while circular
struts converge with a truncated sphere.
• Lateral surface of strut has a parabolic profile.

This model requires as inputs the foam hydraulic velocity (𝜀𝑓 ) and the cell diameter (𝑑𝑐𝑒𝑙𝑙 ) as inputs and
estimates the strut diameter (𝑑𝑠𝑡𝑟𝑢𝑡 ). For circular strut the following equation is used to evaluate the
𝑑𝑠𝑡𝑟𝑢𝑡 :

51 | P a g e
 −0.3985𝑑𝑠𝑡𝑟𝑢𝑡 3 + 2.8803𝑑𝑠𝑡𝑟𝑢𝑡 2 𝑑𝑐𝑒𝑙𝑙 + 0.00708𝑑𝑐𝑒𝑙𝑙 3
= (1 − 𝜀𝑓 ) (𝐸𝑞. 3.57)
0.419(𝑑𝑐𝑒𝑙𝑙 + 𝑑𝑠𝑡𝑟𝑢𝑡 )3
And the specific surface area for circular struts is estimated as the following:

−7.377𝑑𝑠𝑡𝑟𝑢𝑡 2 + 10.082𝑑𝑠𝑡𝑟𝑢𝑡 𝑑𝑐𝑒𝑙𝑙 + 0.3548𝑑𝑐𝑒𝑙𝑙 2

𝑆𝑣 = (𝐸𝑞. 3.58)
0.419(𝑑𝑐𝑒𝑙𝑙 + 0.577𝑑𝑠𝑡𝑟𝑢𝑡 )3

10.4. Overall heat transfer coefficient

The overall heat transfer coefficient is estimated based on the approximation of the foam as a set of
parallel packed bed reactors with diameter equal to the cell diameter. The heat transfer is estimated as
the heat transfer between the wall of the hypothetical reactor and the pseudo-fluid. Dixon[120]
correlation is used to evaluate the overall heat transfer coefficient.
1 𝐷𝑐ℎ 𝐵𝑖 + 3
𝑈𝑜𝑣 = + 𝑒𝑓𝑓
(𝐸𝑞. 3.59)
ℎ𝑤𝑎𝑙𝑙,𝑒𝑞 3𝑘𝑟,𝑒𝑞 𝐵𝑖 + 4

𝐷𝑐ℎ is the characteristic diameter and in this case it is equivalent to the cell diameter. The equivalent wall
𝑒𝑓𝑓
heat transfer is (ℎ𝑤𝑎𝑙𝑙,𝑒𝑞 ) and equivalent radial effective thermal conductivity (𝑘𝑟,𝑒𝑞 ) are computed based
on the Specchia correlations [109] (section 7 of this chapter) and characteristic diameter equivalent to
𝑑𝑐𝑒𝑙𝑙 .

The Biot number that relates the external heat transfer at catalyst pellets with internal conduction is
computed as:
𝑑𝑐𝑒𝑙𝑙 ℎ𝑤𝑎𝑙𝑙,𝑒𝑞
𝐵𝑖 = 𝑒𝑓𝑓
(𝐸𝑞. 3.60)
𝑘𝑟,𝑒𝑞
.

The equation for overall heat transfer coefficient was initially developed by Dixon et al.[120] for the case
of packed bed reactors, and was obtained from one-point collocation analysis performed on two-
dimensional pseudo homogeneous model. Extending the applications of the Dixon equation to
approximate 𝑈𝑜𝑣 has been employed effectively in a previous work in our group for simulating the steam
reforming of methane on packed foam reactors[110]. However, further studies and experimental work
are required to validate this approximation.

11. Overall heat transfer model in packed foam

Based on the notion of analogy between heat flow and current flow in an electric circuit, heat transfer is
modeled as a function of set of heat resistances in series and in parallel starting from the reactor wall
towards the reactor center in radial direction.

52 | P a g e
 Figure 3.7 Overall equivalent heat transfer circuit

As shown in the figure above the heat transfer process is complex, but a general term to represent the
overall heat transfer from the wall to the reactor radial center could be estimated.

For wall heat transfer terms which are in parallel they are estimated in one equivalent wall heat transfer
𝐷𝑖𝑛𝑡
term ℎ𝑒𝑞 = ℎ𝑤 + ℎ𝑤𝑎𝑙𝑙,𝑓𝑜𝑎𝑚 . The equivalent heat resistance in the pseudo fluid is 𝑅𝑓𝑙𝑢𝑖𝑑 = 𝑒𝑓𝑓 . For
6.13𝑘𝑟
the case of heat transfer in foam it faces two resistances in series one due to the heat conduction in the
foam and the other due to the heat transfer between the foam and the pseudo-fluid. The equivalent
𝑖𝑛𝑡 𝐷 4
heat resistance in the foam is therefore computed as is 𝑅𝑓𝑜𝑎𝑚 = 6.13𝑘 +𝐷 Both the thermal
𝑒𝑓𝑓 𝑖𝑛𝑡 𝑈𝑜𝑣 𝑆𝑣
resistances in pseudo-fluid and in foam are in parallel and would lead to an equivalent resistance
𝑅𝑓𝑙𝑢𝑖𝑑 𝑅𝑓𝑜𝑎𝑚
𝑅𝑒𝑞 = (𝐸𝑞. 3.61)
𝑅𝑓𝑙𝑢𝑖𝑑 + 𝑅𝑓𝑜𝑎𝑚

Therefore, the overall thermal resistance is:

1
𝑅𝑜𝑣𝑒𝑟𝑎𝑙𝑙 = ( + 𝑅𝑒𝑞 ) (𝐸𝑞. 3.62)
ℎ𝑒𝑞

since the equivalent wall thermal resistance and the equivalent resistance of the internal part of the
reactor are in series. Simply from the above the overall heat transfer coefficient is:
1
𝑈𝑜𝑣𝑒𝑟𝑎𝑙𝑙 = (𝐸𝑞. 3.63)
𝑅𝑜𝑣𝑒𝑟𝑎𝑙𝑙

12. Numerical Solution method

The set of partial differential equations PDE are hard to be solved analytically, rather it is transferred into
set of algebraic equations that are more easily solved. The set of algebraic equations are obtained via
finite difference method to obtain an approximation of the first order and second order derivative. Three
main finite difference methods are present to estimate the first order derivative.
𝑓𝑖+1 −𝑓𝑖
Forward difference: 𝑓𝑖 ′ = ℎ
error: O(h) (𝐸𝑞. 3.64)
𝑓𝑖+1 −𝑓𝑖−1
Central difference: 𝑓𝑖 ′ = 2ℎ
error: O(ℎ2 ) (Eq. 3.65)

53 | P a g e
 𝑓𝑖 −𝑓𝑖−1
Backward difference: 𝑓𝑖 ′ = ℎ
error: O(h) (Eq. 3.66)

Where h is the distance between grid points. The error is lowest for the case of central difference, so it
will be adopted for evaluating the derivatives for all inner points, Forward is used to evaluate the first
order derivative at the first point whether axially or radially and for the last outlet boundary condition
Backward difference is employed.

For the second order derivative it is approximated as:

𝑓𝑖+1 − 2𝑓𝑖 + 𝑓𝑖−1
𝑓𝑖 ′′ = error: O(ℎ2 ) (Eq. 3.67)
ℎ2

Figure 3.8 Symmetric discretization of the Reactor volume

Symmetric discretization was adopted. This type of numerical grids is constructed by group of points that
are equally distant. To generate this scheme the following equations are used:
𝐿
ℎ𝑧 = (𝐸𝑞. 3.68)
𝑁𝑃 − 1
𝑅𝑖𝑛𝑡
ℎ𝑟 = (𝐸𝑞. 3.69)
𝑁𝑅 − 1
Where ℎ𝑧 is the distance between the axial grid points, NP is the number of axial points in the grid, ℎ𝑟 is
the distance between radial grid points and NR is the number of radial points of the grid. Both NP and NR
must be fine-tuned in order to reach a mesh independent solution, where the error is attributed to the
machine rather than the truncation error.

54 | P a g e
 Figure 3.9 Variation of error vs inverse of step size

As shown in the figure above after certain number of grid points the grid is fine to the extent that it is not
improving the accuracy of the solution, rather it just requires further computational effort.

13. Numerical Solver

To solve the model set of nonlinear algebraic equations in MATLAB, fsolve, that tries to minimize the sum
of the squares of the components of the system, command was used. Depending on the problem that
must be solved, the program chooses the best algorithm among Trust-region, Trust region dogleg and
Levenberg-Marquardt. To minimize the computation time and effort the precomputed Jacobian matrix
was implemented in the algorithm. The Jacobian matrix was written in a routine that computes the
position of nonzero components as the matrix is sparse. The nonzero components of the Jacobian for a 2-
dimensional grid are tridiagonal matrix as depicted below.

55 | P a g e
 Figure 3.10 Jacobian Pattern

14. Mesh Sensitivity

As aforementioned in section 12, the grid size optimization is crucial. The method of achieving this goal,
starting from initial guess of NR and NP, consists of reaching mesh independence in two steps:

• Guarantee independence with respect to NR by increasing its value gradually.

• Guarantee independence with respect to NP by increasing its value gradually.

To guarantee mesh independence the axial temperature profiles and CO conversion are simulated for the
case of 𝑇𝑖𝑛 =221.7℃ and 𝑇𝑤𝑎𝑙𝑙 =239 ℃. These are the most extreme conditions that would be simulated in
this work and guarantying mesh independence at them, in theory, ensures mesh independence in the rest
of operating conditions.

The initial values for NR and NP are 7 and 21 respectively. To satisfy mesh independence two criteria must
be satisfied: equal values of conversion as well as overlapping axial temperature profiles. The results are
reported in tables and figures below.
Table 3.1 effect of NR on conversion (NP=21)

NR CO conversion
7 0.8747
15 0.8643
21 0.8608
29 0.8581

56 | P a g e
 280

270
Temperature [C]
260

21/7
250
21/15

240 21/21
21/29
230

220
0 1 2 3 4 5
Length (cm)

Figure 3.11 Effect of NR on Axial Temperature profiles (NP=21)

As shown in Table 3.1 the conversion value decrease from 0.874722 to 0.860767 with an increase of NR
from 7 to 21 and reached a plateau after that. The temperature profiles overlap after NR value of 21
(figure 3.11). Therefore, NR value of 21 is adopted as the optimum number of discretization in radial
direction.

For the optimum NP value it was increased gradually from 21 to 81. The results below show an increase
in CO conversion until it reaches a plateau at NP of 61 (Table 3.2). However, in the case of axial
Temperature profiles overlap after an NP of 41. Therefore, the optimum mesh grid size is NR=21 and
NP=61 (figure 3.12).
Table 3.2 Effect of change in NP on conversion (NR=21)

NP CO conversion
21 0.8608
41 0.8636
61 0.8657
81 0.8664

57 | P a g e
 270

265

260

Temperature [C] 255

250
21/21
245
41/21
240
61/21
235 81/21

230

225

220
0 1 2 3 4 5
Length [cm]

Figure 3.12 Effect of NP on axial temperature profiles (NR=21)

Chapter 4: Preliminary Results

The preliminary simulations were based on the reaction apparatus described in chapter 3 (section 3) and
used in the experimental work done by Fratalocchi et al.[87]. The packed foam properties along with
operating conditions are summed in the table below.
Table 4.1 Foam and operating parameters

Parameter Value Dimension

Ε 0.38 -
𝜀𝑓 0.906 -
L 4 cm
𝐷𝑖𝑛𝑡 2.78 cm
𝑘𝑠𝑜𝑙𝑖𝑑 200 W/m/k
𝜌𝑏𝑒𝑑 630 𝑘𝑔/𝑚3
𝑑𝑝 300 𝜇𝑚
𝑑𝑐𝑒𝑙𝑙 2 mm
GHSV 6400 𝑐𝑚3 (𝑆𝑇𝑃)/ℎ/𝑔𝑐𝑎𝑡
P 25 bar
𝑥𝐻2 0.5158 -
𝑥𝐶𝑂 0.2492 -
𝑥𝑁2 0.235 -

58 | P a g e
Moreover, another set of data was provided concerning the temperature at the foam inlet (𝑇𝑖𝑛 ), the
temperature at half axial and half radial distance (𝑇𝑟𝑎𝑑 ), temperature at half axial distance and external
wall of the reactor (𝑇𝑒𝑥𝑡 ) and the average operating temperature in the reaction zone (𝑇𝑜𝑝𝑒𝑟 ) respectively
for each run as summarized in table below.
Table 4.2 Inlet radial and wall external Temperatures

𝑇𝑖𝑛 [ ͦ𝐶 ] 𝑇𝑟𝑎𝑑 [ ͦ𝐶 ] 𝑇𝑒𝑥𝑡 [ ͦ𝐶 ] 𝑇𝑜𝑝𝑒𝑟 [ ͦ𝐶 ]

197.3 199.8 195.9 200
201.4 205 199.2 205
204.9 210.1 201.4 210
207 214.5 203.6 215
208.2 219.4 205.5 220
212.2 224.3 206.4 225
215.9 229.2 210 230
221.7 239 215 240

To obtain these temperature data points three thermocouples were used in the experimental apparatus
(figure 4.1), where the two thermocouples at half radius and at the external reactor wall are fixed, while
the thermocouple at radial center slides through over the packed foam to aquireaxial temperature
profiles.

Figure 4.1 Scheme of the packed foam reactor and the position of the packed foam and the different thermocouples.

For the case studies discussed in the passages below the foam and operating conditions used are those
mentioned above and only the changed parameters will be reported. The simulations for the sensitivity

59 | P a g e
analysis are done for each inlet temperature listed above while imposing an isothermal wall temperature
equal to the corresponding 𝑇𝑒𝑥𝑡 .

The packed foam reactor as described in previous chapter is divided into three regions, two inert regions:
the 1st centimeter of the foam and the last centimeter and between them lies the reactive region. Thus,
while evaluating the rate of the reaction it is multiplied by an activity profile vector that is 1 for all axial
points between 1 and 3cm and 0 elsewhere.

For all cases simulated the pressure drop across the packed foam dP is 0 bar (Eq. 3.6), since the reactor
length and 𝑅𝑒𝑝 are very low. However, the contribution of pressure drop must be evaluated for the case
of reactors operating with higher length and/or higher flow rates. The mean value of physical properties
in each case study are reported for 𝑇𝑖𝑛 =221.7 ℃ (Appendix A).

Another important aspect concerning sources of error in this chapter and the next one is the fact that all
the simulations were done based on a lumped kinetics scheme and the evaluation of mixture physical
properties based on the initial inlet composition.

1. Base case: Results

As mentioned before the reference case in the following case studies would be based on simulating each
inlet temperature listed in the introduction of this chapter while imposing an isothermal wall temperature
equal to the corresponding 𝑇𝑒𝑥𝑡 . The reported results are the CO conversion value at each 𝑇𝑖𝑛 and the
axial temperature profile at the last 𝑇𝑖𝑛 =221.7 ℃. The conversion plot and temperature profile for base
case are reported below.

Figure 4.2 The conversion values and temperature profile for base case

2. Importance of External Mass transfer Limitations

To evaluate the importance of external mass transport limitations two cases were considered:

• Only CO mass balance at the pellet surface is performed and

• Surface mass balance for both CO and 𝐻2 .

60 | P a g e
The mass balance equation at the pellet surface is:
𝑘𝑔
𝐾𝑚,𝑖 ∗ 𝜌𝑚𝑖𝑥 ∗ 𝑎𝑣 ∗ (𝑦𝑖 − 𝑦𝑠,𝑖 ) + 𝑅𝑖 = 0 [ 𝑚3 ] (𝐸𝑞. 4.1)
𝑠

6(1−𝜀) 𝑚2
Where 𝑎𝑣 = 𝑑𝑝
[𝑚3 ] is the pellet specific surface area and 𝐾𝑚,𝑖 is the mass transfer coefficient [m/s]
for species i, which was evaluated by the correlations demonstrated by Mamonov et al.[121].
𝜌𝑚𝑖𝑥 𝑣𝑎𝑐𝑡
𝐾𝑚,𝑖 = 1.9 (𝐸𝑞. 4.2)
𝑅𝑒𝑑𝑝 0.5 𝑆𝑐𝑖 0.67
𝜇𝑚𝑖𝑥
𝑆𝑐𝑖 = (𝐸𝑞. 4.3)
𝜌𝑚𝑖𝑥 𝐷𝑖
1−𝑥𝑖 𝑚2
And 𝐷𝑖 = 𝑥𝑗 [ ] is the diffusion coefficient of species i in the fluid. The binary diffusion coefficient
∑𝑗≠𝑖 𝑠
𝐷𝑖,𝑗
𝑚2
𝐷𝑖,𝑗 [𝑠
] is evaluated using the Fuller–Schettler–Giddings equation[122]:

1 1
𝑇𝑎𝑐𝑡 1.75 √𝑀𝑀 + 𝑀𝑀
𝑖 𝑗
𝐷𝑖,𝑗 = 10−7 (𝐸𝑞. 4.4)
𝑐𝑚3 1⁄3 1
𝑃[𝑎𝑡𝑚](𝑉𝑐,𝑖 [ ] + 𝑉𝑐,𝑗 ⁄3 )
𝑚𝑜𝑙

𝑐𝑚3
Where 𝑉𝑐,𝑖 [ ]is the diffusion volume of species i. The rate of reaction was estimated based on the
𝑚𝑜𝑙
𝑦𝑠,𝑖
partial pressures at the surface 𝑃𝑠,𝑖 = 𝑃𝑖 𝑦𝑖
such that 𝑃𝑖 is the partial pressure in the bulk fluid.

The results reported below (Figure 4.3 & 4.4) shows a complete overlap between all the cases in terms of
conversion and axial temperature profile of the fluid. Therefore, it is safe to assume pseudo-fluid and
ignore the contribution of external mass transfer limitation.

61 | P a g e
 Figure 4.3 Sensitivity of conversion to external mass transfer limitations

Figure 4.4 Sensitivity of axial temperature profile to mass transfer limitations

62 | P a g e
 3. Foam Parameters
3.1. Cell diameter
To investigate the model sensitivity to change in cell the diameter, 𝑑𝑐𝑒𝑙𝑙 value was varied within ±50% of
the base case value. The increase in the cell diameter has negative effect on the foam-wall heat transfer
coefficient (Eq. 3.54), the overall heat transfer coefficient between foam and fluid (Eq. 3.59) and foam
specific surface area (Eq. 3.58). The mean values of ℎ𝑤𝑎𝑙𝑙,𝑓𝑜𝑎𝑚 , 𝑈𝑜𝑣 and 𝑆𝑣 at different 𝑑𝑐𝑒𝑙𝑙 values are
reported in the table below for the final inlet temperature.
Table 3.1 Effect of dcell on foam parameters for Tin=221.7C

𝑑𝑐𝑒𝑙𝑙 [mm] 𝑊 𝑊 𝑚2
ℎ𝑤𝑎𝑙𝑙,𝑓𝑜𝑎𝑚 [𝑚2 𝐾] 𝑈𝑜𝑣 [𝑚2 𝐾] 𝑆𝑣 [𝑚3]
1 976.03 673.30 2238.42
2 491.73 382.87 1119.21
3 330.95 266.28 746.14

As reported in Table 3.1 the foam parameters related to heat transfer decrease drastically with the
increase in cell diameter. Even though these values are reported for the last inlet temperature, they
provide an intuition about the behavior of the foam heat transfer parameters at lower inlet temperatures.
Nevertheless, specific surface area is not affected by the operating conditions, so the drop in specific
surface area is the same for all temperatures. This drop in foam capability of transferring heat from the
pseudo fluid via the 𝑈𝑜𝑣 𝑆𝑣 term (Eq. 3.5) and from foam to the internal wall at the boundary by ℎ𝑤𝑎𝑙𝑙,𝑓𝑜𝑎𝑚
term, explains the increase in conversion, up to 15.8%, as well as the increase in hot spot temperature
(from 223.6 to237.9℃) with the increase in 𝑑𝑐𝑒𝑙𝑙 as shown in the figures below (Figure 4.5 &4.6).

63 | P a g e
 Figure 4.5 Sensitivity of conversion to change in dcell

Figure 4.6 Sentivity of Temperature profile at Tin=221.7C to change in dcell

64 | P a g e
 3.2. Foam void fraction
The foam void fraction affects not only the foam specific surface area (Eq. 3.58), but also the effective
thermal conductivity of the foam (Eq. 3.56). The impact of adopting void fractions of 0.85 and 0.95 was
evaluated against the system behavior base case. The effect of this alteration is reported in the table
below for both 𝑆𝑣 and 𝑘𝑒𝑓𝑓 values. These are purely geometric properties and are not affected by system
fluid dynamics.
Table 4.2 Effect of foam void fration on foam specific surface are and heat conductivity

𝜀𝑓 𝑚2 𝑊
𝑆𝑣 [𝑚3] 𝑘𝑒𝑓𝑓 [ ]
𝑚𝐾
0.85 1307.23 13
0.906 1119.21 7.44
0.95 852.24 3.67

As shown above (Table 4.2)the effective foam conductivity and specific surface area decrease with
increase in foam void fraction. Thus, the heat transfer by convection from the pseudo-fluid to the foam
and heat transfer by conduction within the foam are both reduced consequently (Eq. 3.5). This explains
the increase in conversion values, up to 13%, and in the hotspot temperature (from 225.6 to 239.6℃)
depicted in the figures below (Figure 4.7&4.8).

Figure 4.7 sensitivity of conversion to change in foam void fraction

65 | P a g e
 Figure 4.8 Sensitivity of axial temperature profile at Tin=221.7 to change in foam void fraction

However, the difference in performance in terms of conversion values and hot spot temperature doesn’t
differ between the case of 0.85 void fraction and base case as they do between base case and 0.95 void
fraction. This could show that the foam void fraction is near optimal value while preserving the possibility
of good packing capacity in the reactor.

3.3. Foam Material Thermal conductivity

The thermal conductivity of the foam material (𝑘𝑠𝑜𝑙𝑖𝑑 ) affects solely the effective foam conductivity (𝑘𝑒𝑓𝑓 )
𝑊
(Eq. 3.56). The effect of foam material conductivity is evaluated at 100 and 400 [𝑚𝐾] along with the base
case conductivity. The respective effective conductivities are reported below.
Table 4.3 Variation of effectctive foam conductivity with material conductivity

𝑘𝑠𝑜𝑙𝑖𝑑 [𝑚𝐾]
𝑊 𝑊
𝑘𝑒𝑓𝑓 [ ]
𝑚𝐾
100 3.72
200 7.44
400 14.89

The hotspot is diminished, decreases from 237 to 225.6℃, with the increase in material conductivity and
the conversion values are decreased up to 10% too. This performance variation depicted in the figures
below (Figure 4.9& 4.10) is attributed in the increased heat transfer capability of the foam structure not

66 | P a g e
only radially, but also in the axial direction as the change in the axial temperature profile during transition
from/to the nonreactive zones is less steep for the case with higher conductivity.

Figure 4.9 Sensitivity of conversion values to change in 𝑘𝑠𝑜𝑙𝑖𝑑

Figure 4.10 Sensitivity of axial temperature profile at Tin=221.7C to change in 𝑘𝑠𝑜𝑙𝑖𝑑

67 | P a g e
The performance of the adopted foam is similar to that with a material conductivity of 400 W/m/K, which
in case is the conductivity of copper [123]. However, based on the work performed by Chanenchuck et al.
[124] a physical mixture of copper and cobalt based catalyst enhanced the water gas shift reaction which
is not desired in our case. Therefore, pure aluminum foam adopted in this work is proved to be a well
performing choice.

3.4. Overall Foam heat transfer coefficient

This passage aims at evaluating the impact of uncertainty in predicting the overall foam heat coefficient
(𝑈𝑜𝑣 ) that was evaluated using Dixon formula [120]and the equivalent wall heat transfer coefficient was
evaluated based on Specchia et al. equations[109] (refer to chapter 3 section 10.4).
1 𝐷𝑐ℎ 𝐵𝑖 + 3 𝑊
𝑈𝑜𝑣 = + 𝑒𝑓𝑓
[ ] (𝐸𝑞. 3.59)
ℎ𝑤𝑎𝑙𝑙,𝑒𝑞 3𝑘𝑟,𝑒𝑞 𝐵𝑖 + 4 𝑚𝐾

The 𝑈𝑜𝑣 value was varied in margin of 20% of its value. It is expected that for an increase in the overall
heat transfer coefficient the conversion would decrease as well as the hot spot value. However, the impact
of the change was not drastic as shown in the figures below (Figure 4.11&4.12), the conversion values
almost overlap and the maximum difference between the two extreme cases is less than 2℃. Thus, it is
confident to adopt the approach used in approximating 𝑈𝑜𝑣 .

Figure 4.11 Sensitivity of conversion to change in overall foam heat transfer coefficient

68 | P a g e
 Figure 4.12 Sensitivity of axial temperature profile at Tin=221.7C for change in foam overall heat transfer coefficient

4. Catalyst Particle Parameters

This part of chapter is dedicated to the evaluation of the sensitivity of the model to changes in the catalyst
particle parameters such as the pellet diameter, the packed bed void fraction, the catalytic activity and
the effective thermal conductivity of the pseudo-fluid.

4.1. Pellet Diameter

The pellet diameter affects several physical transport properties. The major physical properties that are
affected are pressure drop [103] (Eq. 3.6) and the heat transfer of coefficients evaluated using Specchia
correlations[109] (Eq. 3.34-3.37,3.40,3.59) (Appendix A). The void fraction was imposed to be constant
even though it would vary with pellet diameter [120], but for simplicity in this work it was assumed
constant as the 𝐷𝑖𝑛𝑡 is two orders of magnitude larger than 𝑑𝑝 .

The results reported below show almost an overlap between the conversion values of the base case
results along with those corresponding to 𝑑𝑝 values of 200 and 400 𝜇𝑚 and the difference in the hotspot
temperature for the case of the highest and lowest 𝑑𝑝 value is less than 1℃(Figure 4.13,4.14). The only
significant role pellet diameter could play at current order of magnitude and low flow rates would be
related to the selectivity of the FTS process. The optimum pellet size that guarantees maximum selectivity
to 𝐶5+ is that with a diffusional length of 50-60 𝜇𝑚 [125], which applies to our base case pellet diameter.
This optimality in pellet diameter dimension relates to the mass diffusion limitation of CO and 𝐻2 diffusing
into the pellet and olefins diffusing out [80].

69 | P a g e
 Figure 4.13 Sensitivity of conversion to change in dp

Figure 4.13 Sensitivity of temperature profile at Tin=221.7C to change in dp

70 | P a g e
 4.2. Packed bed Void fraction
The pellet void fraction is varied within 0.3 and 0.46. The packed bed void fraction affects the heat transfer
coefficients evaluated using Specchia correlations (Eq. 3.34,3.39) [109], the overall heat transfer
coefficient 𝑈𝑜𝑣 (Eq. 3.59) and the pressure drop evaluated by Ergun equation (Eq. 3.5) [103].
Table 4.4 Sensitivity of physical parameters at Tin=221.7C to change in packed bed void fraction

𝜀 𝑒𝑓𝑓 𝑊 𝑊
ℎ𝑤 [𝑚2 𝐾] 𝑈𝑜𝑣 [W/𝑚2 /𝐾] ∆𝑃[𝑏𝑎𝑟]
𝑘𝑟 = 𝑘𝑎𝑥 [ ]
𝑚𝐾
0.3 0.338 378.22 420.25 0.0
0.38 0.305334 439.79 382.87 0.0
0.46 0.274 501.45 346.62 0.0

The pressure drop is neglegible as the foam length is so small. The effective pseudo-fluid heat transfer
coeffecients, both axially and radially, and the overall heat transfer coefficent are decreased with increase
in packed bed void fraction, while the wall heat transfer coefficient is increased.The simulation results
shows a slight increase in conversion and hotspot, less than 1℃, with increase in packed bed void fraction
(Figure 4.14 &4.15). Therefore the effect of decrease in the heat transfer between the foam and pseudo-
fluid prevails that of enhanced foam wall heat transfer. Nevertheless, the changes due to adopted packed
bed void fraction did not affect the performance significantly at this stage but could become more
significant in case of a larger reactor apparatus.

Figure 4.14 Sensitivity of conversion to change in packed bed void fraction

71 | P a g e
 Figure 4.15 Sensitivity of axial temperature profile to change in packed bed void fraction

4.3. Activity of catalyst

In this passage the effect of increase in activity of the catalyst is studied. To simulate this set of case studies
the pre-exponential kinetic factor in the numerator of the rate expression was multiplied by the activity
factor while maintaining the rest of the expression term unmodified. This procedure that assumes the
same dependence of the rate on the CO and 𝐻2 partial pressures and same activation energy resembles
an increase in the density of the catalyst which is a well-established method to increase the activity. The
activity factor was limited to 1.4 as this condition leads to a conversion of 70%, which is the maximum
conversion value permissible to avoid accelerated deactivation of cobalt-based catalyst due to high water
content produced.

The figures below (Figure 4.16&4.17) show a slightly lower difference in conversion value and hotspot
temperature between case of activity factor of 1.2 and 1.4 compared to the difference between the base
case and 1.2 activity factor case. The process increases in productivity, as result of increased conversion,
up to 19% , is accompanied by increasing in the hotspot temperature, from 228.7 to 234.7℃. For that to
exploit the possibility of increasing the catalyst activity and operating at higher syngas space velocities,
necessitate to operate at lower inlet gaseous temperatures and/or wall temperatures.

72 | P a g e
 Figure 4.16 Sensitivity of conversion to activity factor

Figure 4.17 Sensitivity of axial Temperature profile at Tin=221.7 to change in activity factor

73 | P a g e
 4.4. Effective Thermal Conductivity of pseudo-fluid
In the work of Zhu et al. [114] the effective thermal conductivity in radial direction ,which was found to
be the main route of heat transfer in the packed bed case, showed an increase in the order of 2 to 3 folds
after FTS reaction depending on the cobalt-based catalyst support used. However, in this work the
increase in effective thermal conductivity of the pseudo-fluid phase was assumed independent of the
produced amount of liquid, as this amount was assumed negligible. To assess the effect of this assumption
the effective thermal conductivities in both radial and axial direction were multiplied by a factor of 2 then
a factor of 3 and the sensitivity of the model to these changes was evaluated.

As expected, increasing the effective thermal conductivity of the pseudo-fluid would decrease the
conversion and hot spot with higher contribution of cooling via enhanced heat transfer within the pseudo-
fluid phase itself. Analyzing the results reported below the maximum difference in terms of conversion
between the base case and case of 3 folds effective conductivity is around 3% and the maximum
difference in hotspot is less than 3℃ (Figure 4.18&4.19). Even though these differences are not that
significant, it is worth exploring the effect of liquid production on the actual value of effective thermal
conductivity for the case of employed catalyst in Fratalocchi’s work[87].

Figure 4.18 Sensitivity of conversion to change in keff

74 | P a g e
 Figure 4.19 Sensitivity of axial Temperature profile at Tin=221.7C to change in keff

5. Pseudo-fluid wall heat transfer coefficient

The sensitivity to the value of pseudo-fluid wall heat transfer is assessed in this passage as the value that
was evaluated using Specchia’s correlation (Eq. 3.33) [109] is varied within ±20% of its actual value. The
predicted performance would be a decrease of conversion value and hotspot temperature as a result of
the enhanced fluid wall heat transfer. However, the results, shown below, showed almost overlapping
results for both cases while demonstrating the expected trend (Figures 4.20&4.21). Thus, the model is
characterized by low sensitivity to change in fluid wall heat transfer. This could suggest that the heat
transfer at the wall occurs mainly through the solid wall heat transfer pass.

75 | P a g e
 Figure 4.20 Senstivity of conversion to change in hw

Figure 4.21 Sensitivity of axial temperature profile to change in hw

76 | P a g e
 6. Solid wall heat transfer coefficient
The foam (solid) wall heat transfer coefficient was evaluated earlier using the equation proposed by
Bianchi et al.[93]. However, a key source of experimental error is the procedure of inserting the foam in
the reactor tube as this process is done manually and can lead to overestimation of actual contact points.
To assess the importance of this coefficient it was varied within ±20% of its actual value and the results
are reported below (Figure 4.22&4.23).

The results demonstrate the expected trend of decrease in conversion and hotspot in a more apparent
way compared to the previous case study, but still the maximum difference between the two extreme
cases is 3% in terms of conversion and less than 2℃ in terms of hotspot temperature. After interpreting
the above results two points could be made clear:

• The main route of heat transport between the inner part of the reactor and the wall is via foam
wall heat transfer.
• The resistance to heat transfer at the wall could be avoided by adding metallic skin to the foam
structure.
• The main heat transfer limitation is due to wall heat transfer as the model was more sensitive to
change in ℎ𝑤𝑎𝑙𝑙,𝑓𝑜𝑎𝑚 than to that to 𝑈𝑜𝑣 .
• The performance of the packed foam reactor in heat removal in presence of incomplete contact
of contact points between the internal wall and the foam is close to ideal case for a case of 25%
overestimation of actual solid wall heat transfer coefficient.

Figure 4.22 Sensitivity of conversion to change in hw,solid

77 | P a g e
 Figure 4.23 Sensitivity of axial Temperature profile to change in hw,solid

Chapter 5: Simulation of Experimental Results

This chapter aims to evaluate the model capability of simulating the CO conversion, Temperature profiles,
both axially and radially, and the selectivity of the reaction to 𝐶𝐻4 , 𝐶𝑂2 and 𝐶2 _𝐶4. The experimental
apparatus was described in the chapter of Preliminary Results. The provided experimental data reported
by Fratalocchi et al.[87] didn’t specify the wall temperature profile, except for indicating the eternal wall
temperature at the axial center of the foam.

1. Preliminary simulation of experimental results

This passage aims to evaluate the model capability to simulate experimental data by imposing a constant
value of the wall temperature corresponding to each inlet temperature value. As a first attempt the
corresponding value of 𝑇𝑒𝑥𝑡 for each 𝑇𝑖𝑛 was imposed as the wall temperature and the simulation results
are shown below.

78 | P a g e
 Figure 5.1 Simulated vs experimental conversion values for Twall=Text

Figure 5.2 Simulated vs Experimental Temperature profiles for Twall=Text

It is evident from the results above (Figures 5.1&5.2) that both the CO conversion and thermal profiles
are underestimated when 𝑇𝑤𝑎𝑙𝑙 = 𝑇𝑒𝑥𝑡 , except for the first two operating temperature where simulated
and experimental results are close. Thus, the other given set of temperatures 𝑇𝑟𝑎𝑑 serve as the second
possibility to be evaluated as possible set of wall temperatures. However, adopting this choice, as
depicted in the results below, led to overestimation of CO conversions as well as the axial temperature
profiles (Figure 5.3&5.4).

79 | P a g e
 Figure 5.3 Simulated vs experimental conversion values for Twall=Trad

Figure 5.4 Simulated vs experimental Temperature profiles for Twall=Trad

80 | P a g e
 2. Fitting wall Temperature profile
2.1. Fixed wall temperature through over the foam length
As an intuitive decision the results above indicates that for each experimental case there exists a wall
temperature 𝑇𝑤𝑎𝑙𝑙,𝑓𝑖𝑡 that guarantees the simulation results to be close to experimental ones. This
temperature would lie between 𝑇𝑒𝑥𝑡 𝑎𝑛𝑑 𝑇𝑟𝑎𝑑 and it was determined by trial and error to guarantee the
best fit of experimental conversion profile at each operating temperature 𝑇𝑜𝑝𝑒𝑟 . The fitted wall
temperatures (𝑇𝑤𝑎𝑙𝑙,𝑓𝑖𝑡 ) are reported below for each run along with 𝑇𝑒𝑥𝑡 and 𝑇𝑟𝑎𝑑 for sake of
comparison. Moreover, an important assumption that was made when reporting the radial temperature
profiles at the axial center is that the internal wall temperature is equal to the external one, since the
wall thickness is 2.8 mm and heat dissipation in the reactor was neglected.
Table 5.1 Wall fitted temperatures for each Toper along with respective Text and Trad

𝑇𝑜𝑝𝑒𝑟 [ ͦ𝐶 ] 𝑇𝑤𝑎𝑙𝑙,𝑓𝑖𝑡 [ ͦ𝐶 ] 𝑇𝑟𝑎𝑑 [ ͦ𝐶 ] 𝑇𝑒𝑥𝑡 [ ͦ𝐶 ] 𝑇𝑤𝑎𝑙𝑙,𝑓𝑖𝑡

− 𝑇𝑒𝑥𝑡 [ ͦ𝐶 ]
200 195.9 199.8 195.9 0
205 199.5 205 199.2 0.3
210 204.2 210.1 201.4 2.8
215 208 214.5 203.6 4.4
220 213.7 219.4 205.5 8.2
225 216.5 224.3 206.4 10.1
230 218.5 229.2 210 8.5
240 225 239 215 10

The simulation results demonstrated below indicated the ability of the model to predict the conversion
(Figure 5.5) with an average absolute error of 4.54% and the hotspot temperature (Figure 5.6) with an
average absolute error of 0.23%. On the other hand, the simulation results didn’t resemble accurately the
axial temperature profiles (Figure 5.6) and radial temperature profiles at the axial center (Figure 5.7).
Moreover, the predicted position of the hotspot is at the beginning of the reactor, while it is shifted to
the right in experimental results, at the beginning of the second inert region, which is counter intuitive.
This peculiarity in the temperature profile indicate the presence of heat transfer phenomena that are out
of control and are not reaction related as they occur in part of the packed foam. This can be attributed to
heat dissipation in the reactor metallic tube or the presence of different thermal zones in the furnace or
both.

Moreover, the simulated radial temperature profiles experienced lower drop at the vicinity of the wall
compared to the experimental radial profile (Figure 5.8), which in turn could give a hint that the reactive
part of the foam must be exposed to wall temperatures lower than 𝑇𝑤𝑎𝑙𝑙,𝑓𝑖𝑡 to insure the required cooling
at the wall vicinity. However, imposing a uniform wall temperature profile with lower value than 𝑇𝑤𝑎𝑙𝑙,𝑓𝑖𝑡
led to underestimation of the temperature profiles as well as conversion (Figures 5.1&5.2). This led to the
assumption of three different heating zones, where the inert zones would be subjected to wall
temperatures higher than those imposed in the reactive zone.

81 | P a g e
 Figure 5.5 Experimental vs simulated conversion values for Twall,fit

Figure 5.6 Simulated vs Experimental Hotspot Temperature for Twall,fit

82 | P a g e
 Figure 5.7 Experimental vs Simulated axial temperature profiles for Twall,fit

Figure 5.8 Experimental vs Simulated radial temperature profiles at axial center for Twall,fit

The simulated selectivity values had good correspondence to the experimental results. The average
absolute errors and the corresponding plots are reported below.
Table 5.2 Average absolute for predicted selectivity values

Selectivity of reaction to [%] Average absolute error [%]

83 | P a g e
 𝐶𝐻4 8.66
𝐶𝑂2 4.22
𝐶2 − 𝐶4 2.19

Simulated vs experimental Sch4

35

30

25

20
Sch4 [%]

15

10

0
195 200 205 210 215 220 225 230 235 240 245
Toper [C]

Sch4exp Sch4 sim

Figure 5.9 Simulated vs Experimental SCH4

84 | P a g e
 Simulated vs experimental Sco2
8

5
Sco2 [%]

0
195 200 205 210 215 220 225 230 235 240 245
Toper [C]

Sco2exp Sco2sim

Figure 5.10 Simulated vs experimental SCO2

Chart Title
17
16.5
16
15.5
Sc2c4 [%]

15
14.5
Sc2c4
14
13.5 Sc2-c4 sim
13
12.5
12
195 200 205 210 215 220 225 230 235 240 245
Toper [C]

Figure 5.11 Simulated vs Experimental SC2C4

2.2. Adjusted wall temperature for each region of the foam

As pointed in section 2.1, one of the possible reasons for the difference in the position of the hotspot
between the simulated and experimental results and the difference in experimental and simulated radial
temperature profiles could be the presence of different heating zones in the furnace itself.

85 | P a g e
 For this part three flat wall temperature profiles were imposed for each region of the foam in order to
mimic the performance of the furnace. The first wall temperature profile is imposed between 0-1cm of
the foam the second is between 1.5-2.5 cm and the third is between 3-4cm. Linear interpolation is used
to estimate the wall temperature at the transition points between each region and the other. The fitted
wall Temperature profiles are demonstrated below.

Figure 5.12 Fitted wall Temperature profiles (3Regions)

These adopted wall temperature profiles were able to fit the axial and radial temperature profiles
reasonably well. The average error in simulated conversion values is 5.08 % and in simulated hotspot
temperatures is 0.22 %. The following results are demonstrated below.

86 | P a g e
 Figure 5.13 Simulated vs Experimental conversion values

Figure 5.14 Simulated vs Experimental axial Temperature Profiles

87 | P a g e
 Figure 5.15 Simulated vs Experimental radial Temperature profiles

Figure 5.16 Simulated vs Experimental Hotspot Temperature

In this case, predicted selectivity values were all within 10% of average absolute error as reported in the
following table and the figures below.

88 | P a g e
Table 5.3 Average absolute for predicted selectivity values

Selectivity of reaction to [%] Average absolute error [%]

𝐶𝐻4 8.51
𝐶𝑂2 5.11
𝐶2 − 𝐶4 2.56

Simulated vs experimental Sch4

35

30

25
Sch4 [%]

20

15

10

0
195 200 205 210 215 220 225 230 235 240 245
Toper [C]

Sch4exp Sch4 sim

Figure 5.17 Simulted vs Experimental SCH4

Simulated vs experimental Sco2

8
7
6
5
Sco2 [%]

4
3
2
1
0
195 200 205 210 215 220 225 230 235 240 245
Toper [C]

Sco2exp Sco2sim

Figure 5.18 Simulated vs Experimental SCO2

89 | P a g e
 Chart Title
17
16.5
16
15.5
SC2C4 [%]

15
14.5
Sc2c4
14
13.5 Sc2-c4 sim
13
12.5
12
195 200 205 210 215 220 225 230 235 240 245
Toper [C]

Figure 5.19 Simulated vs Experimental SC2C4

3. Conclusion
The preliminary simulations of the experimental results indicated the presence of inaccuracies in
describing the actual wall temperature profile and the possibility of heat dissipation. The model was
capable to predict accurately model is able to predict the CO conversion value, hotspot temperature and
reaction selectivity, if reasonable wall temperature profile is presented. The major advantage of adopting
three regions wall temperature profiles is the ability to predict more accurately the temperature profiles,
both axially and radially, and more importantly the position of the hotspot.

Figure 5.20 Scheme of proposed reactor structure and the set of thermocouples used

90 | P a g e
Nevertheless, this demonstration of model performance in simulating experimental data suggested the
need to adopt a different setup. The reactor setup must give a proper indication of the temperature profile
both axially and radially and also should indicate the importance of heat dissipation in the reactor tube.
The scheme for the proposed reactor (Figure 5.20) contains three sliding thermocouples, where the first
is at the radial center, the second is at half radius and the third is at the foam wall interface. Another fixed
static thermocouple is located at the external wall of the tube at the axial enter, and it can give an
indication on the importance of heat dissipation.

Chapter 6: ANN Model

1. Introduction
The mathematical model, presented in chapter 3, was able to predict CO conversion, selectivity of FTS to
different product ranges and hotspot temperatures to a considerably high level of accuracy. However, the
model suffers from a relatively high computation cost associated with solving PDE numerically. To
overcome this problem and provide a robust function approximation for the three aforementioned output
variables, we have used artificial neural networks (ANN). The ANN model can serve as a basis for the
development of the objective function used in the optimization of FTS lab-scale reactor operating
conditions to maximize 𝐶5+production.

2. Concept of Artificial Neural Networks

The processing of information in the human nervous system occurs at a cellular level through neurons
(figure 6.1) that communicate with each other via electric signals traveling through a thick net of
connections[126]. From a simplified perspective the neuron consists of three main components: the
dendrites, the nucleus or soma, and the axon. Dendrites serve as a bundle of input signal receptors from
different sources and conveying them directly to the nucleus of the neuron. The nucleus accumulates
input signals and generates an output pulse under the condition that the accumulated signals overcome
a certain threshold. In other words, neuron acts as a switch that introduces non-linearity to input-output
mapping. The output signal is transported through the axon and the connection to the dendrites is
established at the synaptic terminal. This connection, also called synapsis, could be either chemical or
physical, where the latter is established through direct contact between the axon and the dendrite. In the
case of chemical synapsis, it consists of a synaptic cleft, physically separating the presynaptic side from
the postsynaptic side. Then, for the action potential to reach the postsynaptic side, the electric signal at
the presynaptic side is converted to chemical signal. The chemical signal takes place through the release
chemical substances called neurotransmitters, which cross the cleft and bind to receptors at the
postsynaptic side to be reconverted to into an electrical potential [127], [128].

91 | P a g e
 Figure 6.1. Anatomy of Biological Neural Networks [129]

Artificial Neural Networks (ANN) are computational models inspired by the mode of action of biological
brain; ANN can recognize complex relationships between different parameters and are therefore used to
solve and model different classes of problems. ANN are capable to learn from observational data, i.e., by
example, thus providing an alternative to the algorithmic programming paradigm [127]. ANN-based
models are in theory able to approximate any continuous function – a fact supported by several studies
in variety of fields [128], [130], [131]. This ability have been exploited in different applications including
clustering, classification, pattern recognition, control, regression, signal processing, etc.[130]. On the
other hand, ANN suffer from certain drawbacks due to the high computation cost required in the training
phase in most cases, the large number of design variables (number of layers and of neurons in each layer,
activation function, …) and the risk of data overfitting [130].

In the chemical process industry artificial neural networks have been employed for modeling of complex
processes, fault detection and perform diagnosis and process control [132]. However, there is lack of
studies on the use of ANN and other machine learning techniques in the field of catalysis. Li et al. (2017)
argued that this lack of ANN-based studies in catalysis field is mainly attributed to the high degree of
mechanistic complexity of catalytic reactions and to the large amount of time and resources required by
catalytic experiments, which in turn leads to lack in sufficiently large datasets [133].

2.1. Feedforward
Feedforward Neural Networks (FNN), also called perceptrons, are one of the most implemented
topologies in ANN-models, are characterized by their structural representation that can be perceived in a
network form which makes it a universal function approximator, which is able to approximate any
continuous function[130]. In FNN the neurons are arranged in (L) layers (Figure 6.2), which are fall under
one of these three categories: input layer, hidden layers and output layers. The input layer consists of

92 | P a g e
𝑀𝐼 +1 neurons, where 𝑀𝐼 is the number input variables and the additional neuron accounts for the bias
neuron. The output layer consists from 𝑀𝑂 neurons, such that each neuron in the output layer represents
an output variable. In other words, the structure of FNN can be interpreted as a mapping between the 𝑀𝐼
inputs and 𝑀𝑂 outputs, where an activation pattern that is supplied to the input layer induces 𝑀𝑂 output
activations at the output layer. The hidden layers consist of 𝑛𝑙 +1 neurons each, where n is the number of
non-bias neurons in each hidden layer, 𝑙 is the index of the hidden layer[128].

Figure 6.2 Schematic representation of the FNN with 3 input variables, 1 output and L layers

From a mathematical point of view the activation or output of a neuron in layer 𝑙 +1 (Figure 6.3.) is simply
evaluated through the following equation:
𝑛
(𝑙) (𝑙) (𝑙)
𝑎𝑘𝑙+1 = 𝑓 (𝜃𝑘0 𝑏 (𝑙) + ∑ 𝜃𝑘𝑚 𝑎𝑚 ) = 𝑓(𝑢𝑘𝑙 ) (𝐸𝑞. 6.1)
𝑚=1
(𝑙)
where 𝑎𝑘𝑙+1 is the output of neuron k in layer 𝑙 +1, 𝜃𝑘𝑚 is the weight of connection between neuron m in
layer 𝑙 to neuron k in layer 𝑙 + 1, 𝑏 (𝑙) is the bias neuron in layer 𝑙, and 𝑓 is the activation function with
input 𝑢𝑘𝑙 [128]. The activation function reacts in a particularly sensitive way when the summed weighted
activations (𝑢𝑘𝑙 ), which is in turn the input to the activation function, hits the threshold value (𝜏𝜃 ) i.e. 𝑢𝑘𝑙 ≥
𝜏𝜃 . Mathematically the threshold value represents the point at which the absolute value of the activation
function |𝑓′| derivative acquires its maximum value. However, 𝜏𝜃 is included in the activation function,
which makes its run time access difficult, for that the concept of the bias neuron. The bias is a neuron
added to all the layers preceding the output one and it is characterized by an activation value of 1. The
(𝑙) (𝑙)
main role of the bias to change the required ∑𝑛𝑚=1 𝜃𝑘𝑚 𝑎𝑚 value to hit the threshold value [134].

93 | P a g e
 Figure 6.3 Scheme of neuron activation

The feedforward neural networks could be classified into two main categories depending on the number
of hidden layers or in other words the number of trainable weights. The single-layer perceptron(SLP)
consist of the input layer and the output one, without the employment of any hidden layer. The SLP layer
is the output layer itself as the input layer does not require any computational effort. The SLP networks
are considered simple, but their applications are essentially limited to linear prediction functions[128].

On the other hand, multi-layer perceptrons (MLP) structure of FNN is considered a universal function
approximator. A MLP with one hidden layer and continuously differentiable activation function is capable
of approximating any continuous function, while MLP with more than one hidden layer and continuously
differentiable activation function is capable of approximating any function [130].

2.2. ELU Activation function

The choice of the suitable activation function is a critical step in the design of neural networks. In literature
the mostly used activation function is the Rectified Linear Unit (ReLU) (figure 6.4), where it is an identity
function for positive inputs and zero elsewhere [135]. One of the major drawbacks of using ReLU is the
absence of negative activation values, which leads to a non-zero mean activation that acts as a bias for
the next layer. This bias shift is defined as the difference in mean activation from one layer to the other,
to give a comprehensible example considering input data normalized between [-1,1] i.e. mean of zero and
using a ReLU activation function the mean activation would be always larger than zero. As the bias shift
increases the difference between the ordinary gradient (𝑔) and the natural gradient (𝑔𝑛𝑎𝑡 = 𝐹̃ −1 𝑔)
increases, where 𝐹̌ is the Fisher information vector. The natural gradient represents the steepest direction
of perceptrons parameter space, but the ordinary gradient does not. The importance of determining the
steepest direction is for the training of the network as the methods are based on calculating the gradient
of the cost function with respect to the connection weights. For a detailed demonstration of this concept
please refer to the work of Amari (1998) [136]. The natural gradient would account for the bais shift by
adjusting the weights update. Clevert et al.[137] demonstrated that the larger is the imposed adjustment
by the natural gradient the larger is the required training time. Therefore, the lower is the bias shift the
faster is the learning process as the ordinary gradient tend toward the natural gradient, since 𝐹̃ −1
becomes simply an identity matrix at zero mean activation value (no correction imposed).

94 | P a g e
In this work the exponential linear unit (ELU) (figure 6.4) activation function is adopted, as it possesses
superior performance in terms of speed of learning and generalization accuracy. The generalization
property is the network ability to provide reasonable responses for unknown problems of the same class
of the training set. ELU is characterized by the presence of negative values, which pushes the mean of the
activations towards zero and thus increasing the learning speed.The ELU function overcomes the
vanishing gradient problem through the adoption of a linear identity for positive inputs, as it attains a
derivative value of 1 and does not suffer from the behavior of contractive derivatives ( 𝑓′(𝑥) < 1) as in
the case of tanh and sigmoid functions [137]. The equation of the ELU function and its derivative are the
following:
𝛼 (𝑒 𝑥 − 1), 𝑥≤0
𝑓(𝑥) = { 𝐸𝐿𝑈 (𝐸𝑞. 6.2)
𝑥, 𝑥>0
𝛼𝐸𝐿𝑈 𝑒 𝑥 , 𝑥≤0
𝑓′(𝑥) = { (𝐸𝑞. 6.3)
1, 𝑥>0
where 𝛼 controls the value to which ELU saturates for negative inputs. The smooth saturation of the ELU
function means a small derivative, which decreases the variation and the propagated information to the
next layer. This characteristic of ELU decreases its complexity and make it to noise-robust. Another
important property that is shared by both ELU and ReLU is the non-informative deactivation state, where
they code the presence of input concepts while they neither quantify their absence nor they distinguish
the cause of their absence. Thus only active units are considered to carry relevant information that would
be transmitted to other units[137]. However, one possible drawback of using ELU function, as well as for
using ReLU, is the activation blow up for positive inputs. This drawback is a tradeoff of ELU ability to
overcome the vanishing gradient problem.

3.5

2.5

1.5
f(x)

0.5

0
-6 -5.5 -5 -4.5 -4 -3.5 -3 -2.5 -2 -1.5 -1 -0.5 0 0.1 0.5 1 1.5 2 2.5 3
-0.5

-1

-1.5
x
ReLU ELU

Figure 6.4 Rectified linear unit (ReLU) and exponential linear unit (ELU) with 𝛼𝐸𝐿𝑈 = 1

95 | P a g e
 2.3. Training FNN by Conjugate-Gradient Backpropagation Method
A principle characteristic of neural networks is its ability to learn from the environment through storing
the acquired knowledge in the internal network parameters i.e. through modifying the connection
weights. The weights are modified based on certain performance measurement criterions that evaluates
the performance of the neural network over a training set of data. The training algorithm, or the learning
procedure, typically iterative, aims to improve the generalization accuracy of the network. The learning
algorithm can be classified based on the type of the learning set, where three learning paradigms could
be distinguished, which are supervised, unsupervised and reinforced learning. For the case of supervised
learning problems also referred to as labeled, such as function approximation, the network is provided
with training input (𝑥 𝑞 ) and their corresponding responses (𝑦 𝑞 ). Thus, any training algorithm aims at
𝑞
minimizing the difference between training output (ℎ𝜃 ) and the desired output (𝑦 𝑞 ). For the case of
unsupervised learning, such as clustering, the neural networks are provided only with the training pattern
that is considered to be unlabeled as no associated output is provided. In this case the Neural Network is
expected to figure out independently the rules to group items. For the reinforced learning case after the
completion of series of input patterns, the pattern is supplied with a real or Boolean number, reward or
feedback, that indicates to which extent the network is wrong. Thus, the learning paradigm in reinforced
learning is to find a balance between exploration (unknown territory) and exploitation (current
knowledge) [134],[138].

Indeed, the choice of learning paradigm is task dependent. As for the aspect of this work supervised
learning paradigm is the best choice. A cost function is (𝐽𝜃 ) is assigned to measure the performance of the
FNN in approximating the desired output (𝑦 𝑞 ) based on the input training set (𝑥 𝑞 ) and the currently
assigned weights. One possible form of cost functions is the squared error cost function, which is often
used in regression or function approximation problems, and it can be represented through the following
equation[138]:
𝑀𝑂 𝑁
1 𝑞
𝐽𝜃 = ∑ ∑(ℎ𝜃,𝑖 − 𝑦𝑞𝑖 )2 (𝐸𝑞. 6.4)
2𝑁
𝑖=1 𝑞=1

where N is the number of training samples. Therefore, the supervised training of FNN networks can be
formulated as a nonlinear unconstrained optimization problem. The target of the training algorithm would
be to find the optimal set of weights that minimize the cost function.

The Conjugate-Gradient Backpropagation Method (CG) is the optimization method adopted in training
our neural networks. The basic steps of the algorithm can be summarized up as the following[128],
[138],[139]:

(1) Forward pass: The set of input activation is fed through the FNN with initial guess of randomly
initialized set of weights 𝜃(1).
(2) The difference between the desired output and the training output is computed, and the error
vector at output layer (L) and output node (i) is obtained as:
𝑁
𝑞 𝑞
𝛿𝑖𝐿 (𝑡) =𝑓 ′ 𝐿
(𝑢𝑖 ) ∑(ℎ𝜃,𝑖 − 𝑦𝑖 ) (𝐸𝑞. 6.5)
𝑞=1

96 | P a g e
 where t is the index of iteration usually called epoch. The iterations would continue until either
one of the stopping criteria is met: reach the maximum number of iterations (𝑡𝑚𝑎𝑥 ) or the cost
function 𝐽𝜃 <𝜀𝐶𝐺 , where 𝜀𝐶𝐺 is the preassigned value of the sopping criteria and a value of 10−5
was assigned to it.
(3) Backward pass: The error signal is propagated backward through the network by evaluating error
vectors.
𝑛𝑙
(𝑙) 𝑙
𝛿𝑗𝑙−1 (𝑡) =𝑓 ′
(𝑢𝑗𝑙 )(∑ 𝜃𝑖𝑗 𝛿𝑖 (𝑡)) (𝐸𝑞. 6.6)
𝑖=1
𝜕𝐽𝜃
It is worth mentioning that 𝛿𝑖𝑙 (𝑡) = and from chain rule
𝜕𝑢𝑖𝑙
𝜕𝐽𝜃,𝑞 𝜕𝐽𝜃,𝑞 𝜕𝑢𝑖𝑙
= (𝐸𝑞. 6.7)
𝜕𝜃𝑖𝑗
(𝑙) 𝜕𝑢𝑖𝑙 𝜕𝜃 (𝑙)
𝑖𝑗
𝜕𝑢𝑖𝑙 𝜕𝐽𝜃 ,𝑞
,and as (𝑙) = 𝑎𝑖𝑙−1 therefore it is obtained that (𝑙) = 𝛿𝑖𝑙 (𝑡)𝑎𝑖𝑙−1 . For combining the partial
𝜕𝜃𝑖𝑗 𝜕𝜃𝑖𝑗
𝑙 𝜕𝐽𝜃 1 𝜕𝐽𝜃 ,𝑞
derivatives for each input-output pair 𝑔𝑖,𝑗 (𝑡) = (𝑙) (𝑡) = 𝑁 (𝑙) (𝑡).
𝜕𝜃𝑖𝑗 𝜕𝜃𝑖𝑗
(4) Updating the weights based on the results of the forward and backward passes. The basic notion
𝑙
of conjugate gradient method in computing the search direction 𝑑𝑖,𝑗 (𝑡) as a linear combination
of negative gradient at current iteration with the previous search direction.
𝑙 𝑙 𝑙 𝑙 𝑙 𝑙
𝑑𝑖,𝑗 (𝑡 + 1) = −𝑔𝑖,𝑗 (𝑡 + 1) + 𝛽𝑖,𝑗 (𝑡)𝑑𝑖,𝑗 (𝑡), 𝑑𝑖,𝑗 (1) = −𝑔𝑖,𝑗 (1) (𝐸𝑞. 6.8)
𝑙
The scalar parameter 𝛽𝑖,𝑗 (𝑡), which gives rise to conjugate gradient methods, is computed here
based on Polak-Ribiere equation[140] as:
𝑙 𝑙
𝑙
𝛽𝑖,𝑗 (𝑡 + 1)𝑇 𝛽𝑖,𝑗 (𝑡 + 1)
𝛽𝑖,𝑗 (𝑡) = 𝑙 (𝑡)𝑇 𝑙 (𝑡) (Eq. 6.9)
𝛽𝑖,𝑗 𝛽𝑖,𝑗
For the case of strongly convex cost functions, as in the case of currently used one, the learning
rate is computed based on the following equation:
𝑑𝐽𝜃 (𝜃(𝑡) + 𝛼𝐶𝐺 𝑑(𝑡))
= 𝑔(𝑡 + 1)𝑇 𝑑(𝑡) (𝐸𝑞. 6.10)
𝑑𝛼𝐶𝐺
Therefore, each weight of connection is updated as the following:
(𝑙) (𝑙)𝑙
𝜃𝑖𝑗 (𝑡 + 1) = 𝜃𝑖𝑗 (𝑡) + 𝛼𝐶𝐺 𝑑𝑖,𝑗 (𝑡) (𝐸𝑞. 6.11)

2.4. The issue of Overfitting

Two main problems arise during training of FNN as they are prone to either underfitting or overfitting
(Figure 6.4). In the case of underfitting the model is neither able to fit the training data nor able to predict
new data. The case of underfitting is usually not discussed in literature as it is easily detected as a result
of the model poor performance. On the contrary, overfitting is the case where the model is able to fit the
training data very well, as it learns the detail and noise in the training data to the extent that affects the
model ability to fit new data. Thus, to maintain the generalization property of the model or attain
optimum fitting, the model must lie in the sweet spot between underfitting and overfitting (figure 6.4).
For that many strategies have been proposed in the literature to decrease the test error, even if the
training error is increased[128], [130], [141],[142].

97 | P a g e
Figure 6.4 Visual representation of overfitting, optimum fitting and unerfitting [143]

There are several methods to limit the extent of overfitting, which can be summarized as:

• Limiting the number of epochs during the FNN training to the number that ensures a minimum
value of cross-validation error, which evaluates the error of the model in estimating new data.
This concept is based on the fact that the training error would keep on decreasing with increase
in epochs, while the cross validation would undergo a minima and increase after that as the model
starts suffering from overfitting (figure 6.5) [138],[144].
Error

Epoch
hs
Figure 6.5 Train and validation curve showing an overfit model [144]

• Dropout is a technique that addresses the overfitting problem through turning off temporarily
and randomly some neurons, which would force the network to learn an independent feature,
which in turn prevents hidden units from relying on other units (co-adaptation). The various
obtained network architectures are trained over different mini-batches, then during model

98 | P a g e
 testing all the neurons are unmasked (active again) and the output is averaged by weight
scaling[141].

Figure 6.6 Dropout Neural Net Model. Left: A standard neural net. Right: An example of a thinned net produced by applying
dropout to the network on the left. Crossed units have been dropped [141]

• The network architecture itself is a critical aspect that must be optimized during the design of
FNN, as for large number of neurons and layers is prone to overfitting, while too few neurons and
layers lead to underfitting[145].
• Regularization is a mean of reducing overfitting through constraining the model “freedom”, based
on a prior assumption on the model. A well-known and easily implemented regularization strategy
is based on 𝐿2 Parameter Regularization, the basic goal of this strategy is to drive the weights near
the origin by adding a regularization term (𝛺𝜃 ), which is the sum of all non-bias weights squared
to the cost function[138],[127], [142] as shown in the expression below:

𝑀𝑂 𝑁 𝐿−1 𝑛𝑙+1 𝑛𝑙
1 𝑞
𝜆𝑟𝑒𝑔 (𝑙)
𝐽𝜃 = ∑ ∑(ℎ𝜃,𝑖 − 𝑦𝑞𝑖 )2 + ∑ ∑ ∑ (𝜃𝑘𝑚 )2 (𝐸𝑞. 6.4′)
2𝑁 2𝑁
𝑖=1 𝑞=1 𝑙=1 𝑘=1 𝑚=1

such that 𝜆𝑟𝑒𝑔 ∈ [0, ∞) is the hyperparameter, predefined before training process, that weights
the relative contribution of (𝛺𝜃 ), the model performance is sensitive to the regularization
parameter value as high values of 𝜆𝑟𝑒𝑔 lead to underfitting, while low values lead to overfitting.
The implementation of regularization necessities the application of some modifications on the
cost function partial derivative equation used in backpropagation (Eq. 6.7), while the main training
strategy and the rest of the equations remain unchanged [138].

99 | P a g e
 𝜕𝐽𝜃 , 𝑞 (𝑙)
(𝑙)
= 𝛿𝑖𝑙 (𝑡)𝑎𝑖𝑙−1 + 𝜆𝑟𝑒𝑔 𝜃𝑖𝑗 𝑓𝑜𝑟 𝑗 ≠ 0
𝜕𝜃𝑖𝑗
(𝐸𝑞. 6.7′)
𝜕𝐽𝜃 , 𝑞
(𝑙)
= 𝛿𝑖𝑙 (𝑡)𝑎𝑖𝑙−1 𝑓𝑜𝑟 𝑗 = 0 (𝑏𝑖𝑎𝑠)
{ 𝜕𝜃𝑖𝑗

As for the scope of this work only the latter two methods were adopted to avoid overfitting.

3. Design of Neural Networks

3.1. Optimization Neural Network Parameters
As aforementioned two main set of design variables, 𝜆𝑟𝑒𝑔 and FNN architecture must be optimized to
ensure the generalization property of the model. Nevertheless, the saturation value (-𝛼𝐸𝐿𝑈 ) of the ELU
function, which is the main source of the model nonlinearity, has an important impact on the model
performance and must be optimized, as it dictates the maximum value of negative activations and
gradient values at these activations. Therefore, the problem boils down to an optimization problem of an
objective function (𝑓𝑜𝑏𝑗 ) that is dependent on all the parameters mentioned above. The proposed strategy
of solving the optimization problem is to use genetic algorithm (GA), where random individuals (solutions)
are created and evolved until the optimal solution is reached or other stopping conditions are met.

3.2. Genetic Algorithm

The genetic algorithm (Figure 6.7) is an optimization technique that is inspired by Darwinian theory of
evolution. The basic idea of the algorithm is to start with an initial population of individuals (possible
solutions), where each individual is characterized by set of variables, called genes, which join in a
chromosome-like structure. The raw fitness of each individual, ability to compete with other individuals,
is evaluated based on the objective function value of this solution. After that genetic algorithm operators
are applied to the current population to generate a new population of better solutions. The GA operators
consist of selection, crossover and mutation [146], [147].

The selection phase consists of assigning a score to each individual based on its raw fitness value and
generate what is called a mating pool. Thus, individuals with higher fitness have a higher probability to be
selected into the mating pool. The individuals in the mating pool are called parents, where each two
individuals would mate to produce two offspring that are formed by exchanging the parent genes among
themselves up to a crossover point that is chosen arbitrary (Figure 6.8). The crossover is based on the idea
of crossing only the individuals with high fitness in the hope that only good genes are preserved. However,
this approach preserves the properties from the parents without adding any new properties and the same
drawbacks the parents suffered from would persist in the new generation. To avoid this situation some
modifications are applied to the offspring genome in a process called mutation. For each offspring some
genes are selected randomly, and their value is modified. Furthermore, introducing the mutation aids in
avoiding premature convergence to local optima. Finally, due to the fact that population size is fixed,
individuals with least fitness would die and leave their space for new offspring [146]–[148].

100 | P a g e
 Figure 6.7 Schematic representation of the GA

Figure 6.8 Crossover operation in GA, where A1 and A2 are parents from the mating pool and A3 and A4 are the produced offspring
from their crossover and gi encodes genes from A1 and gi’ encode genes from A2

The newly formed population would undergo the same procedure of fitness evaluation and the
application of GA operators. This iterative procedure continues until one of the stopping criterions is met,
where in this work it was specified as reaching the fitness limit or exceeding generations limit.

101 | P a g e
 3.3. Optimization Function and Optimization Strategy
Despite the fact that several objective functions and approaches have been proposed in the literature for
optimizing neural networks parameters, they all shared common parameters, including training error and
cross validation error [131]. The training of each FNN individual was limited to 200 epochs, in order to
reduce the training time. The genetic algorithm tackles the following problem:

[𝜆𝑟𝑒𝑔 , 𝑛2 , 𝑛3 , 𝑛4 , 𝑛5 , 𝛼𝐸𝐿𝑈 ] = 𝑎𝑟𝑔𝑚𝑖𝑛[𝑓𝑜𝑏𝑗 (𝜆𝑟𝑒𝑔 , 𝑛2 , 𝑛3 , 𝑛4 , 𝑛5 , 𝛼𝐸𝐿𝑈 ) = 𝐸𝑎𝑣𝑔 ] (𝐸𝑞. 6.12)

𝐸𝑎𝑣𝑔 = 𝛾𝑇𝑟𝑎𝑖𝑛 𝑆𝑆𝐸𝑇𝑟𝑎𝑖𝑛 + 𝛾𝐶𝑟𝑜𝑠𝑠 𝑆𝑆𝐸𝐶𝑟𝑜𝑠𝑠 (𝐸𝑞. 6.13)

𝑁
𝑞
𝑆𝑆𝐸 = ∑(ℎ𝜃 − 𝑦 𝑞 )2 (𝐸𝑞. 6.14)
𝑞=1

Train and Cross subscripts denote the training and cross-validation data set respectively. 𝛾𝑇𝑟𝑎𝑖𝑛 and 𝛾𝐶𝑟𝑜𝑠𝑠
denote the weighing factors є[0,1], such that 𝛾𝑇𝑟𝑎𝑖𝑛 < 𝛾𝐶𝑟𝑜𝑠𝑠 in order to favor individuals that perform
better with new data. For this study the values of 0.4 and 0.6 were assigned to 𝛾𝑇𝑟𝑎𝑖𝑛 and 𝛾𝐶𝑟𝑜𝑠𝑠
respectively.

As for the optimization variables, the following constraints on the variable limits were imposed:

• The regularization parameter 𝜆𝑟𝑒𝑔 є[0,10], which also exploits the effectiveness of architecture
optimization in the absence of regression (𝜆𝑟𝑒𝑔 = 0).
• The number of hidden layers is limited to four since three to four hidden layers are usually enough
for function approximation [128].
• The number of neurons in each layer is limited the range [0,15], where 0 neurons indicates an
unnecessary layer.
• The 𝛼𝐸𝐿𝑈 is limited to the domain of [0,2], where the 𝛼𝐸𝐿𝑈 = 0 is identical to adopting a ReLU
function and thus evaluating the effectiveness of activation by ELU.

The upper limits of 𝛼𝐸𝐿𝑈 , number of neurons and 𝜆𝑟𝑒𝑔 were set based on experience. To validate those
boundaries the GA was employed for 5 generations and the regions that were exploited and led to the
highest fitness by GA fell all in between the upper and lower boundaries so no adjustments were
performed.

The optimization of the neural network parameters in this study would be performed according to the
following algorithm (for GA parameters refer to Appendix B):

(1) Initialize random population of FNN

(2) Train each FNN using backpropagation
(3) Evaluate the fitness of each network based on 𝑓𝑜𝑏𝑗
(4) Apply GA operators to the new generation of networks
(5) Repeat steps 2-4 until the stopping condition is satisfied
(6) Extract the trained neural network with the best performance.

To produce a more robust model and avoid the need to compromise between accuracies of each output
during the GA run, for that three separate neural networks were designed, and each contains only one

102 | P a g e
output neuron. This is based on the fact that the optimal set of neural network parameters and connection
weights would vary from case to another (Table 6.1).

3.4. Dataset Generation and Data Pre-processing

In this study the data set of 729 simulations were generated, where the reaction conditions described in
Chapter 3 and 4 were maintained except for the inlet temperatures 𝑇𝑖𝑛 , wall temperatures 𝑇𝑤𝑎𝑙𝑙 and
conductivity of the foam material 𝑘𝑠𝑜𝑙𝑖𝑑 . The input data values, features, are within the following limits
𝑊
𝑇𝑖𝑛 є[190,230]℃, 𝑇𝑤𝑎𝑙𝑙 = 𝑇𝑖𝑛 + 𝑑𝑇𝑤𝑎𝑙𝑙 such that 𝑑𝑇𝑤𝑎𝑙𝑙 є[−10,10]℃ and 𝑘𝑠𝑜𝑙𝑖𝑑 є[75,400][𝑚𝐾]. Three
output values were recorded after each simulation., these values are the CO conversion value(𝑋𝐶𝑂 ), the
reaction selectivity to 𝐶5+ products (𝑆𝐶5+) and the hotspot temperature (𝑇ℎ𝑜𝑡𝑠𝑝𝑜𝑡 ) [C]. The selectivity to
𝐶5+ was calculated through the following expression:

𝑆𝐶5+ = 1 − 𝑆𝐶𝐻4 − 𝑆𝐶𝑂2 − 𝑆𝐶2 −𝐶4 (𝐸𝑞. 6.12)

Due to the high discrepancy in the domain values of ANN features and to ease backpropagation,
normalization was applied to all the inputs in the dataset in order to fall within [-1,1] range[136]. The
dataset was split into two sets, where 80% of the data was used in training the network and the rest 20%
was used for cross-validation.

4. Evaluation of ANN performance

FNN having at least three hidden layers and non-zero values of 𝜆𝑟𝑒𝑔 and 𝛼𝐸𝐿𝑈 have been conceived by
the GA to optimally estimate the output variables (Table 6.1). Before discussing the model performance,
it is worth noting that the non-zero values of 𝜆𝑟𝑒𝑔 and 𝛼𝐸𝐿𝑈 , show the effectiveness of applying
regularization and adopting ELU activation function instead of ReLU one. The robustness performance of
the ANN model is observed for all the network models as reflected in the mean-squared-error (MSE),
coefficient of determination (𝑅 2) and the standard deviation of the error (σ) exhibited by the networks
on the whole set of data (Table 6.1). The model robustness is also reflected by the regression plots data
points fall very close to the 45° line, despite the slight deviation that occurs in the plot of 𝑇ℎ𝑜𝑡𝑠𝑝𝑜𝑡 at
temperature values above 270℃ and can be explained by the lack of sufficient number of data points at
high hotspot temperatures.

Table 6.1 FNN parameters from GA and their corresponding MSE,, 𝑅2 and σ exhibited by the network on the whole set of data

Output Network 𝜆𝑟𝑒𝑔 𝛼𝐸𝐿𝑈 MSE 𝑅2 σ

Architecture
CO conversion 13x6x4 3.8827 1.1039 0.000363 0.993635 0.019074
𝑆𝐶5+ 9x3x9x5 0.1724 0.9789 0.000159 0.993727 0.012497
𝑇ℎ𝑜𝑡𝑠𝑝𝑜𝑡 [℃] 8x12x10x14 0.3887 0.9398 10.160801 0.982658 3.185472

103 | P a g e
 Figure 6.9 CO conversion value:ANN predicted values vs actual dataset values

Figure 6.10 𝑆𝐶5+ values: ANN predicted vs actual dataset values

104 | P a g e
 Figure 6.11 𝑇ℎ𝑜𝑡𝑠𝑝𝑜𝑡 values: ANN predicted vs actual dataset values

To demonstrate the computation effectiveness of using ANN for estimating the output variables,
compared to solving a set of PDE and AE equations numerically, set of simulations were conducted for
cases that were not included in the data set that was generated earlier. The output values and the
required time for computation (𝑡𝑐𝑜𝑚𝑝 ) are reported in the table below. The output values From ANN are
very close to those obtained numerically. On the other hand, numerically solved model required a
computation time at least 4 orders of magnitude larger than that required by ANN. This superiority in
performance of ANN can be attributed to the fact that the neuron activation, in all layers proceeding the
input one in FNN, is represented by an analytical expression that is function of activations in the
previous layer (Eq. 6.1). Thus, the output itself can be represented by an analytical expression that is
function of the input variables, while the numerical method involves iterative procedures (Chapter 3,
sections 12&13). To clarify what is meant by an analytical expression of the output in terms of input
variables a simplified example of a MLP with one hidden layer can be expressed as the following:
𝑛2 𝑀𝐼
(2) (2) (1) (1) (1)
ℎ𝜃,𝑘 = 𝑓 (𝜃𝑘0 𝑏 (2) + ∑ 𝜃𝑘𝑚 𝑓(𝜃𝑚0 𝑏 (1) + ∑ 𝜃𝑚𝑒 𝑎𝑒 )) (𝐸𝑞. 6.13)
𝑚=1 𝑒=1

Table 6.2 Performance Comparison of PDE model and ANN model

Model 𝑇𝑖𝑛 𝑇𝑤𝑎𝑙𝑙 [℃] 𝑘𝑠𝑜𝑙𝑖𝑑 [W/m/K] 𝑋𝐶𝑂 𝑆𝐶5+ 𝑇ℎ𝑜𝑡𝑠𝑝𝑜𝑡 [℃] 𝑡𝑐𝑜𝑚𝑝 [𝑠]
[℃]
Numerical 213 220 205 0.564176 0.538431 232.301748 87.98

105 | P a g e
 ANN 213 220 205 0.587313 0.519359 230.824075 0.002875
Numerical 193 196 127 0.191624 0.761617 200.947832 73.75
ANN 193 196 127 0.189359 0.766547 200.057224 0.054127
Numerical 225 219 189 0.601606 0.516000 235.879699 88.55
ANN 225 219 189 0.638294 0.498970 236.739497 0.002171

To give a better judgement on the performance of each approach, it is worth mentioning that to generate
the dataset used in this study the numerical code was kept running overnight and the design of each of
the three networks required around 45-50 min. Thus, the design of ANN becomes more practical when
the computation time for dataset generation and ANN design is lower than that required by numerical
method to perform the same final task. One of the cases, where designing ANN is worth it, is optimizing
the operating conditions of FTS over packed foam reactor as would be demonstrated in the next chapter.

5. Optimization of Operating Conditions

This passage aims to demonstrate the concept of employing ANN models for maximizing the production
of 𝐶5+products per mole of CO converted (𝑃𝐶5+ ). The optimization problem however in this case is
subjected to constraint on the hotspot temperature to avoid catalyst deactivation, and can be represented
by the set of equations below:

[𝑇𝑖𝑛 , 𝑇𝑤𝑎𝑙𝑙 , 𝑘𝑠𝑜𝑙𝑖𝑑 ] = 𝑎𝑟𝑔𝑚𝑎𝑥 [𝑃𝐶5+ (𝑇𝑖𝑛 , 𝑇𝑤𝑎𝑙𝑙 , 𝑘𝑠𝑜𝑙𝑖𝑑 ) = 𝑆𝐶5+ ∗ 𝑋𝐶𝑂 ] (𝐸𝑞. 6.14)

𝑠𝑢𝑏𝑗𝑒𝑐𝑡𝑒𝑑 𝑡𝑜 𝑇ℎ𝑜𝑡𝑠𝑝𝑜𝑡 ≤ 250℃ (𝐸𝑞. 6.15)

The optimization strategy adopted to solve this problem is also based on using GA, and can be summarized
in the following set of steps (Appendix B):

(1) Initialize random population of individuals encoding different operating conditions

(2) Evaluate the fitness of each network based on 𝑃𝐶5+
(3) Check if constraint is satisfied, else assign a value of 0 to 𝑃𝐶5+
(4) Apply GA operators to the new generation of networks
(5) Repeat steps 2-4 until the stopping condition is satisfied
(6) Extract the trained neural network with the best performance.

The maximum productivity 𝑃𝐶5+ , that satisfies the constraint on hotspot temperature, was obtained under
the following reaction conditions: 𝑇𝑖𝑛 = 228.3℃, 𝑇𝑤𝑎𝑙𝑙 = 222.52℃ 𝑎𝑛𝑑 𝑘𝑠𝑜𝑙𝑖𝑑 = 248.8[𝑊/𝑚/𝐾]. These
optimal conditions correspond to 𝑃𝐶5+ = 0.33 and 𝑇ℎ𝑜𝑡𝑠𝑝𝑜𝑡 = 237.51.

This approach is not restricted to these three inputs, but can be extended to other design parameters
especially those of the open cell foam itself.

Chapter 7: Conclusion

Conductive structured reactors are promising technologies for the intensification of FTS, as they are
characterized by enhanced thermal exchange. Packed foam is a configuration of structured reactors that
is based on the concept of loading catalyst pellets inside a conductive metallic foam. The performance of

106 | P a g e
this type of reactors stimulates the need to develop a model that can describe accurately the FTS in packed
foam reactors.

A detailed 2-D hybrid heterogeneous mathematical model was developed to simulate mass, energy and
momentum balances for FTS over a packed foam reactor. The module was discussed in details and several
case studies were conducted to investigate the impact of foam and catalytic pellets related parameters.

According to the high number of simulations performed the model proves to be flexible and can handle
systems with different foam geometries. The increase in the foam cell diameter led to a drop in heat
transfer efficiency; a similar behavior was observed for increase in the foam void fraction. On the contrary
the increase in the foam conductivity enhanced heat transfer and led to less pronounced hotspot
temperatures. Furthermore, the foam structure proved to be the major heat transfer path in the system
is through conduction inside the foam structure and the major resistance for heat transfer is located at
the wall vicinity. For that the adoption of metallic foam with skin was recommended.

The developed mathematical model could simulate fairly well experimental temperature profiles,
conversion and selectivity values. Nevertheless, further developments and more detailed expressions
must be developed to approximate more accurately the heat transfer mechanisms. Along with the need
for a more detailed kinetic scheme for better description of the reacting system. Additionally, an
alternative reactor scheme was proposed in order to describe the thermal profiles and heat transfer
mechanisms more precisely.

Furthermore, a conceptual demonstration was performed in this study to shed light on the use of artificial
neural networks for approximating model outputs. Neural networks showed robust performance in
approximating CO conversion, reaction selectivity to 𝐶5+ and hotspot temperature for a wide range of
operating conditions and with much higher computation efficiency compared to numerical solutions. The
developed ANN model was also used to optimize the operating conditions through the use of genetic
algorithm optimization technique and imposing constraint on the hotspot temperature.

This work demonstrated insights for future works and process development on the effectiveness of the
developed 2-D hybrid heterogeneous model and ANN model. As George E. P. Box said: ”all models are
wrong, but some are useful”[149], we hope this work satisfies the latter criterion too.

107 | P a g e
References
[1] J. Staub, “International Energy Outlook 2019 with projections to 2050,” 2019.
[2] “Energy Information Administration, Office of Oil and Gas, Issue and Trends, April 1999.”
[3] “BP Statistical Review of World Energy,” 2019.
[4] C. Perego, R. Bortolo, and R. Zennaro, “Gas to liquids technologies for natural gas reserves
valorization: The Eni experience,” Catal. Today, vol. 142, no. 1–2, pp. 9–16, 2009.
[5] D. A. Wood, C. Nwaoha, and B. F. Towler, “Gas-to-liquids (GTL): A review of an industry offering
several routes for monetizing natural gas,” J. Nat. Gas Sci. Eng., vol. 9, pp. 196–208, 2012.
[6] F. Asche, A. Oglend, and P. Osmundsen, “Gas versus oil prices the impact of shale gas,” Energy
Policy, vol. 47, no. April 2010, pp. 117–124, 2012.
[7] L. Dong, S. Wei, S. Tan, and H. Zhang, “GTL or LNG: Which is the best way to monetize ‘stranded’
natural gas?,” Pet. Sci., vol. 5, no. 4, pp. 388–394, 2008.
[8] S. S. Bharadwaj and L. D. Schmidt, “Catalytic partial oxidation of natural gas to syngas,” Fuel
Process. Technol., vol. 42, no. 2–3, pp. 109–127, 1995.
[9] J. W. Niemantsverdriet, J. van de Loosdrecht, Synthesis gas to hydrogen, methanol and synthetic
fuels. Berlin, 2013.
[10] H. Heinemann, “Methane-steam reforming,” Catal. Rev. Sci. Eng., no. 21, pp. 1–51, 1987.
[11] Q. Zhu, X. Zhao, and Y. Deng, “Advances in the partial oxidation of methane to synthesis gas,” J.
Nat. Gas Chem., vol. 13, no. 4, pp. 191–203, 2004.
[12] J. W. G. Turner et al., “Alcohol fuels for spark-ignition engines: Performance, efficiency and
emission effects at mid to high blend rates for binary mixtures and pure components,” Proc. Inst.
Mech. Eng. Part D J. Automob. Eng., vol. 232, no. 1, pp. 36–56, 2018.
[13] A. Anselmo, “Pathway to Market for a Superior Fuel,” 2018.
[14] Q. Li, G. Wu, C. M. Johnston, and P. Zelenay, “Direct Dimethyl Ether Fuel Cell with Much
Improved Performance,” Electrocatalysis, vol. 5, no. 3, pp. 310–317, 2014.
[15] C. C. R. Zenanaro, S. Rossoni., C.G. Visconti, E. Tronconi , L. Lietti , G. Groppi , P. Forzatti, “An
experimental investigation of Fischer–Tropsch synthesis,” Appl. Catal. A Gen. 370, pp. 93–101,
2009.
[16] H. Tropsch, F. Fischer, “No Title,” German Patent 484337.
[17] H. Pichler, F. Fischer, German Patent 731295
[18] T. F. Fischer, H, Brennstoff-Chemie, no. 4, pp. 276–285, 1923.
[19] J. D. Senderens, P. Sabatier, “Nouvelles synthèses du méthane,” Comptes Rendus Hebd. des
Séances l’Académie des Sci., vol. 134, pp. 514–516, 1902.
[20] SODA-FABRIK BADISCHE ANILIN- UND, “Hydrocarbons From Carbon Monoxide and Hydrogen.,”
British Patent 20,488, 1915.

108 | P a g e
[21] H. Pichler, F. Fischer, Gesammelte Abhandlungen zur Kenntnis der Kohle, no. 13, p. 407, 1937.
[22] H. Buffleb, H. Pichler, Brennstoff-Chemie, no. 19, p. 226, 1938.
[23] B. B. Berman, A. P. Steynberg, M. E. Dry, B. H. Davis, “Fischer-Tropsch technology,” Stud. Surf. Sci.
Catal., vol. 152, 2004.
[24] “Velocys announces construction complete at ENVIA’s GTL plant.” [Online]. Available:
https://www.greencarcongress.com/2016/09/20160921-velocys.html.
[25] “Fischer-Tropsch synthesis,” 2013. [Online]. Available: https://www.tc2.ch.tum.de/.
[26] S. T. Sie, J. W. A. De Swart, R. Krishna, “Reactors and catalytic aspects of the FTS,” Stud. Surf. Sci.
Catal., no. 107, pp. 213–28, 1997.
[27] J. Van de Loosdrecht et al., Fischer-Tropsch Synthesis: Catalysts and Chemistry, vol. 7, no. August.
2013.
[28] H. A. Choudhury, S. Chakma, and V. S. Moholkar, Biomass Gasification Integrated Fischer-Tropsch
Synthesis: Perspectives, Opportunities and Challenges. 2015.
[29] J. W. M. Dry, in: G. Ertl, H. Knozinger, F. Schuth, Handbook of Heterogeneous catalysis. Wiley-
VCH, Weinheim, 2008.
[30] A. De Klerk, “Environmentally friendly refining : Fischer – Tropsch versus crude oil,” Green Chem.,
no. 9, pp. 560–565, 2007.
[31] J. L. V. J. van de Loosdrecht, F.G. Botes, I.M. Ciobica, A. Ferreira, P. Gibson, D.J. Moodley, A.M.
Saib, Reference Module in Chemistry, Molecular Sciences and Chemical Engineering
Comprehensive Inorganic Chemistry II (Second Edition), From Elements to Applications, 2013,
Pages 525–557, Volume 7: Surface Inorganic Chemistry and Heterogeneous Catalysis. .
[32] P. Fongarland, A.Y. Khodakov, W. Chu, Chem. Rev., no. 107, p. 1692, 2007.
[33] S. Sun, N. Tsubaki, and K. Fujimoto, “Promotion Effects in Cobalt-based Fischer-Tropsch Catalysis
– A Review-,” no. 1, pp. 176–177, 2000.
[34] S. Barradas, P. J. van Berge, J. van De Loosdrecht, WO 2003012008 A2.
[35] L. Fratalocchi, C. G. Visconti, L. Lietti, N. Fischer, and M. Claeys, “A promising preparation method
for highly active cobalt based Fischer-Tropsch catalysts supported on stabilized Al2O3,” Appl.
Catal. A Gen., vol. 556, no. January, pp. 92–103, 2018.
[36] L. Fratalocchi, C. G. Visconti, L. Lietti, E. Tronconi, U. Cornaro, and S. Rossini, “A novel preparation
method for ‘small’ eggshell Co/γ-Al2O3 catalysts: A promising catalytic system for compact
Fischer-Tropsch reactors,” Catal. Today, vol. 246, pp. 125–132, 2015.
[37] D. Pinna, “Modelli cinetici per la sintesi di Fischer-Tropsch,” 2002.
[38] L. Jacobus, P. J. van Berge, J. van De Loosdrecht US 5718844
[39] J. van De Loosdrecht, S. Barradas, E. A. Caricato, B. H. Sigwebela, J. P. van Berge, WO 2003012008
A2
[40] J. G. Goodwin, J. R. Oukaci, A. H. Singleton, Appl. Catal. A Gen., no. 186, pp. 129–144, 1999.

109 | P a g e
[41] S. Rugmini, S. C. Leviness, F. Daly, L. A. Richard, US9359271 B2
[42] W. W. B. Sarup, “Studies of the Fischer-Tropsch Synthesis on a Cobalt Catalyst. I. Evaluation of
Product Distribution Parameters from Experimental Data,” Catal.Rev. – Sci. Eng, no. 30, p. 629,
1988.
[43] H. Schulz, “Major and Minor Reactions in Fischer-Tropsch Synthesis on Cobalt Catalysts,” Top.
Catal., vol. 26, pp. 73–85, 2003.
[44] H. S. E. Van Steen, “Polymerisation Kinetics of the Fischer-Tropsch CO Catalysts, Hydrogenation
using Iron and Cobalt Based,” Appl. Catal. A Gen., vol. 186, pp. 309–320, 1999.
[45] H. Schulz, “Kinetic modelling of Fischer-Tropsch product distribution,” Appl. Catal. A Gen., vol.
186, pp. 91–107, 1999.
[46] M. E. Dry, “Practical and Theoretical Aspects of the Catalytic Fischer-Tropsch Process,” Appl.
Catal. A Gen., vol. 138, p. 319, 1996.
[47] H. Schulz, “Short history and present trends of Fischer–Tropsch synthesis,” Appl. Catal. A., no.
186, pp. 3–12, 1999.
[48] H. Mahmoudi, M. Mahmoudi, O. Doustdar, and H. Jahangiri, “A review of Fischer Tropsch
synthesis process , mechanism , surface chemistry and catalyst formulation,” pp. 11–31, 2017.
[49] P. Winslow, “Application of transient response techniques for quantitative Ruthenium,
determination of adsorbed carbon monoxide and carbon present on the surface of Synthesis,
catalyst during Fischer-Tropsch,” J. Catal., vol. 86, pp. 158–172, 1984.
[50] X. Zhou, “CO hydrogenation on Ru/Al2O3; selectivity under transient conditions,” J. Catal. vol.
105 (1987), pagg. 499-510.
[51] H. S. H. Pichler, “Neuere Erkenntnisse auf dem Gebiet der Synthese von Kohlenwasserstoffen aus
CO und H2,” Chemie Ing. Tech., vol. 42, pp. 1162–1174, 1970.
[52] N. Moazami, M. L. Wyszynski, K. Rahbar, A. Tsolakis, and H. Mahmoudi, “A comprehensive study
of kinetics mechanism of Fischer-Tropsch synthesis over cobalt-based catalyst,” Chem. Eng. Sci.,
vol. 171, pp. 32–60, 2017.
[53] J. Yang et al., “Detailed Kinetics of Fischer - Tropsch Synthesis on an Industrial Fe - Mn Catalyst,”
pp. 5066–5090, 2003.
[54] Y. Wang et al., “Kinetics modelling of Fischer – Tropsch synthesis over an industrial Fe – Cu – K
catalyst q,” vol. 82, pp. 195–213, 2003.
[55] B. Teng, J. Chang, C. Zhang, D. Cao, and J. Yang, “A comprehensive kinetics model of Fischer –
Tropsch synthesis over an industrial Fe – Mn catalyst,” vol. 301, pp. 39–50, 2006.
[56] A. de Klerk, Fischer–Tropsch Facilities at a Glance, in ‘Fischer–Tropsch Refining. Wiley-VCH Verlag
GmbH & Co. KGaA, First Edition, 2011.
[57] O. O. James, B. Chowdhury, M. Adediran, and S. Maity, “RSC Advances Reflections on the
chemistry of the Fischer – Tropsch synthesis,” pp. 7347–7366, 2012.
[58] H. A. J. Dijk, van, The Fischer-Tropsch synthesis : a mechanistic study using transient isotopic
tracing The Fischer-Tropsch synthesis : A mechanistic study using transient isotopic tracing

110 | P a g e
 Proefschrift Henricus Adrianus Johannes van Dijk. 2001.
[59] D. B. Bukur, “Catalysis Science & Technology Opportunities for intensification of Fischer –
Tropsch over cobalt catalysts in microreactors,” pp. 1400–1411, 2015.
[60] H. Oosterbeek, E. W. Kuipers, C. Scheper, J. H. Wilson, I. H. Vinkenburg, J. Catal., no. 158, p. 288,
1996.
[61] M. E. Dry, ” J. Mol. Catal., no. 17, p. 133, 1982.
[62] G. J. B. Todic, T. Bhatelia, G. F. Froment, W. Ma and D. B. B. B. H. Davis, “No Title,” Ind. Eng.
Chem. Res., no. 52, p. 669, 2013.
[63] A. Holmen, S. Storsæter, D. Chen, Surf. Sci., no. 600, p. 2051, 2006.
[64] A. I. Tripol'skii, I. I. Chernobaev, M. N. Yakubovich and V. L. S. N. V. Pavlenko, Theor. Exp. Chem.,
vol. 33, p. 38, 1997.
[65] A. H. J. Yang, Y. Qi, J. Zhu, Y.-A. Zhu, D. Chen, J. Catal., vol. 37, 2013.
[66] G. L. M. M. V. E. J. Creyghton, C. M. A. M. Mesters, M. J. Reynhout, “No Title.”
[67] P. H. E. J. T. Kummer, H. H. Podgurski, W. B. Spencer, “No Title,” J. Am. Chem. Soc., vol. 73, pp.
564–569, 1951.
[68] J. G. G. R. Oukaci, A. H. Singleton, “No Title,” Jr, Appl. Catal. A Gen., vol. 186, pp. 129–144, 1999.
[69] P. Gerard, “Kinetics and Selectivity of the Fischer-Tropsch Synthesis: A Literature Review,” Catal.
Rev. – Sci. Engineeing, vol. 41, pp. 255–318, 1999.
[70] E. Iglesia, “Transport enhanced α-olefin readsorption pathways in Ru-catalyzed hydrocarbon
synthesis,” J. Catal., vol. 129, pp. 238–256, 1991.
[71] G. C. M. Masuku, W. D. Shafer, W. Ma, M. K. Gnanamani and B. H. D. Jacobs, D. Hildebrandt, D.
Glasser, J. Catal., no. 287, pp. 93–101, 2012.
[72] H. P. C. E. Kuipers ,J. J. C. Geerlings, J. H. Wilson, G. J. Kramer and H. M. H. A. Hoek,,” Appl. Catal.,
A, no. 186, pp. 27–40, 1999.
[73] J. G. Speight, Hydrocarbons from Synthesis Gas. 2011.
[74] M. Williams and R. Minjares, “A t echnical s ummary of Euro 6 / VI v ehicle e mission s tandards,”
no. June, 2016.
[75] M. Sadeqzadeh et al., “Mechanistic modeling of cobalt based catalyst sintering in a fixed bed
reactor under different conditions of fischer-tropsch synthesis,” Ind. Eng. Chem. Res., vol. 51, no.
37, pp. 11955–11964, 2012.
[76] C. Boyer et al., “Development of the Fischer-Tropsch Process: From the Reaction Concept to the
Process Book,” Oil Gas Sci. Technol., vol. 71, no. 3, 2016.
[77] D. Merino, O. Sanz, and M. Montes, “Effect of the thermal conductivity and catalyst layer
thickness on the Fischer-Tropsch synthesis selectivity using structured catalysts,” Chem. Eng. J.,
vol. 327, pp. 1033–1042, 2017.
[78] B. Jager and R. Espinoza, “Advances in low temperature Fischer-Tropsch synthesis,” Catal. Today,

111 | P a g e
 vol. 23, no. 1, pp. 17–28, 1995.
[79] C. G. Visconti et al., “An experimental investigation of Fischer-Tropsch synthesis over washcoated
metallic structured supports,” Appl. Catal. A Gen., vol. 370, no. 1–2, pp. 93–101, 2009.
[80] L. Fratalocchi, C. G. Visconti, L. Lietti, E. Tronconi, and S. Rossini, “Exploiting the effects of mass
transfer to boost the performances of Co/γ-Al2O3 eggshell catalysts for the Fischer-Tropsch
synthesis,” Appl. Catal. A Gen., vol. 512, pp. 36–42, 2016.
[81] D. Mamabolo, B. A., Nkazi, “MODELLING OF A SLURRY BUBBLE COLUMN REACTOR FOR
FISCHERTROPSCH SYNTHESIS,” 2018.
[82] A. P. Steynberg, R. L. Espinoza, B. Jager, and A. C. Vosloo, “High temperature Fischer – Tropsch
synthesis in commercial practice,” vol. 186, pp. 41–54, 1999.
[83] R. Rauch, H. Hofbauer, and A. Chiru, “FROM GASIFICATION TO SYNTHETIC FUELS VIA FISCHER-
TROPSCH SYNTHESIS,” vol. 3, no. 52, 2020.
[84] H. Jahangiri, J. Bennett, P. Mahjoubi, K. Wilson, and S. Gu, “A review of advanced catalyst
development for Fischer-Tropsch synthesis of hydrocarbons from biomass derived syn-gas,”
Catal. Sci. Technol., vol. 4, no. 8, pp. 2210–2229, 2014.
[85] A. Egana, O. Sanz, D. Merino, X. Moriones, and M. Montes, “Fischer-Tropsch Synthesis
Intensification in Foam Structures,” Ind. Eng. Chem. Res., vol. 57, no. 31, pp. 10187–10197, 2018.
[86] C. G. Visconti et al., “Monolithic catalysts with high thermal conductivity for the Fischer – Tropsch
synthesis in tubular reactors,” Chem. Eng. J., vol. 171, no. 3, pp. 1294–1307, 2011.
[87] L. Fratalocchi, C. G. Visconti, G. Groppi, L. Lietti, and E. Tronconi, “Intensifying heat transfer in
Fischer-Tropsch tubular reactors through the adoption of conductive packed foams,” Chem. Eng.
J., vol. 349, no. May, pp. 829–837, 2018.
[88] T. T. R. Guttel, “Reactors for Fischer-Tropsch Synthesis,” Chem. Eng. Technol., no. 5, pp. 746–754,
2008.
[89] S. Leviness, S. R. Deshmukh, L. A. Richard, and H. J. Robota, “Velocys Fischer – Tropsch Synthesis
Technology — New Advances on State-of-the-Art,” pp. 518–525, 2014.
[90] C. Hopper and C. Compactgtl, “Modular Syncrude Conversion Drives Oilfield GTL Solution for
Associated Gas,” no. February, 2009.
[91] E. Tronconi, G. Groppi, and C. G. Visconti, “Structured catalysts for non-adiabatic applications,”
Curr. Opin. Chem. Eng., vol. 5, pp. 55–67, 2014.
[92] L. C. Almeida et al., “Fischer-Tropsch synthesis in microchannels,” Chem. Eng. J., vol. 167, no. 2–3,
pp. 536–544, 2011.
[93] E. Bianchi, T. Heidig, C. G. Visconti, G. Groppi, H. Freund, and E. Tronconi, “Heat transfer
properties of metal foam supports for structured catalysts: Wall heat transfer coefficient,” Catal.
Today, vol. 216, pp. 121–134, 2013.
[94] C. G. Visconti, R. Mussi, E. Tronconi, L. Fratalocchi, G. Groppi, L. Lietti, “Intensification of the
Fischer-Tropsch process through the adoption of the packed-foam reactor configuration and the
management of the catalyst activation conditions Candidato : Roberto Mussi,” 2018.

112 | P a g e
[95] C. G. Visconti, G. Groppi, and E. Tronconi, “Highly conductive ‘packed foams’: A new concept for
the intensification of strongly endo- and exo-thermic catalytic processes in compact tubular
reactors,” Catal. Today, vol. 273, pp. 178–186, 2016.
[96] J. Banhart, “Manufacture, characterization and application of cellular metals and metal foams,”
Prog. Mater. Sci., no. 46, pp. 559–632, 2001.
[97] C. G. V. M. Giuliani, “Fischer-Tropsch synthesis over structured catalyst based on washcoated
open-cell metal foams, Master Thesis Politecnico di Milano,” 2011.
[98] E. Bianchi, T. Heidig, C. G. Visconti, G. Groppi, H. Freund, and E. Tronconi, “An appraisal of the
heat transfer properties of metallic open-cell foams for strongly exo-/endo-thermic catalytic
processes in tubular reactors,” Chem. Eng. J., vol. 198–199, pp. 512–528, 2012.
[99] R. Philippe et al., “Effect of structure and thermal properties of a Fischer-Tropsch catalyst in a
fixed bed,” Catal. Today, vol. 147, no. SUPPL., 2009.
[100] I. C. Yates and C. N. Satterfield, “Intrinsic Kinetics of the Fischer-Tropsch Synthesis Cobalt
Catalyst,” no. 7, pp. 168–173, 1991.
[101] D.E. Mears, “D.E. Mears, J. Catal. 20 (1971) 127–131.,” J. Catal., no. 20, pp. 127–131, 1971.
[102] D. W. J. Froment G. F, Bischoff K. B., Chemical Reactor Analysis and Design, John Wiley. 2009.
[103] S. Ergun, “Fluid flow through packed columns,” Chem. Eng. Prog., no. 48, 1952.
[104] B. P. et Al., The Properties of Gases and Liquids. McGraw-Hill.
[105] N.-J. Chase, M.W., Jr., Themochemical Tables, Fourth Edi. .
[106] D. W. Green, Perry R.H., Perry’s Chemical Engineers’ Handbook, 7th editio. McGraw-Hill, 1997.
[107] P. Wilke, C. R. , Chang, “Correlation of Diffusion Coefficients in Dilute Solutions,” AICHE, vol. 1,
pp. 264–270, 1995.
[108] Eurokin, “EUROKIN spreadsheet on requirements for measurement of intrinsic kinetics in the gas-
solid fixed-bed reactor.”
[109] S. S. Specchia V., Baldi G., “Heat transfer in paced bed reactors with one phase flow,” Chem. Eng.
Commun., vol. 4, p. 361, 1980.
[110] T. S. Giorgio Valtulini, Enrico Tronconi, “MODELING STUDY OF A PACKED-FOAM REACTOR FOR
METHANE STEAM REFORMING, Master Thesis Politecnico di Milano,” 2018.
[111] T. S. Teguh Imam BURHANUDIN, Carlo Visconti, “Intensifying Heat Transfer in Fischer-Tropsch
Synthesis on Multi-Tubular Reactors Loaded with Washcoated and Packed Conductive Foams,
Master Thesis Politecnico di Milano,” 2018.
[112] P. Chaumette, “Influence of the hydrocarbons distribution on the heat produced during Fischer-
Tropsch synthesis,” Top. Catal., vol. 2, pp. 301–311, 1995.
[113] D. Wu, J., Zhang, H., Ying, W., and Fang, “Chem. Eng. Technol.,” Chem. Eng. Technol., vol. 33, p.
1083, 2010.
[114] X. Zhu, X. Lu, X. Liu, D. Hildebrandt, and D. Glasser, “Heat transfer study with and without

113 | P a g e
 Fischer-Tropsch reaction in a fixed bed reactor with TiO2, SiO2, and SiC supported cobalt
catalysts,” Chem. Eng. J., vol. 247, pp. 75–84, 2014.
[115] R. B. Anderson, “Catalysis, Vol. 4, ed. P.H. Emmett (Rheinhold, New York, 1956) ch. 2.”
[116] J. M. P. and T. K. S. R.C. Reid, The Properties of Gases and Liquids, 3rd ed. New York: Mc Graw Hill,
1977.
[117] R. Zennaro, M. Tagliabue, and C. H. Bartholomew, “Kinetics of Fischer-Tropsch synthesis on
titania-supported cobalt,” Catal. Today, vol. 58, no. 4, pp. 309–319, 2000.
[118] T. E. Bracconi M., Ambrosetti M., Maestri M., Groppi G., “A fundamental analysis of the influence
of the geometrical properties on the effective thermal conductivity of open-cell foams,” Chem.
Eng. Process., no. 129, pp. 181–189, 2018.
[119] T. E. Ambrosetti M., Bracconi M., Groppi G., “Analytical Geometrical model of open cell foams
with detailed description of strut-node intersection,” Chemie Ing. Tech., vol. 7, pp. 915–925,
2017.
[120] D. A. G., “An improved equation for the overall heat transfer coefficient in packed beds,” Chem.
Eng. Process., vol. 35, pp. 323–331, 1996.
[121] N. A. Mamonov, L. M. Kustov, S. A. Alkhimov, and M. N. Mikhailov, “One-dimensional
heterogeneous model of a fischer-tropsch synthesis reactor with a fixed catalyst bed in the
isothermal granules approximation,” Catal. Ind., vol. 5, no. 3, pp. 223–231, 2013.
[122] E. N. Fuller, P. D. Schettler, and J. C. Giddings, “A new method for prediction of binary gas-phase
diffusion coefficients,” Ind. Eng. Chem., vol. 58, no. 5, pp. 18–27, 1966.
[123] E. ToolBox, “Thermal Conductivity of common Materials and Gases,” 2003. [Online]. Available:
https://www.engineeringtoolbox.com/thermal-conductivity-d_429.html.
[124] C. A. Chanenchuk, I. C. Yates, and C. N. Satterfield, “The Fischer-Tropsch Synthesis with a
Mechanical Mixture of a Cobalt Catalyst and a Copper-Based Water Gas Shift Catalyst,” Energy
and Fuels, vol. 5, no. 6, pp. 847–855, 1991.
[125] S. L. S. E. Iglesia, S.C. Reyes, R.J. Madon, “Selectivity Control and Catalyst Design in the Fischer-
Tropsch Synthesis: Sites, Pellets, and Reactors,” Adv. Catal., vol. 39, pp. 221–302, 1993.
[126] J. K. Murray Barr, Barr’s the Human Nervous System: An Anatomical Viewpoint. LWW; Ninth,
North American edition, 2009.
[127] M. A. Nielsen, Neural Networks and Deep Learning. Determination Press, 2015.
[128] O. D. J. Martin T. Hagan, Howard B. Demuth, Mark Hudson Beale, Neural Network Design, 2nd
ed. 2014.
[129] BruceBlaus, “Anatomy of a multipolar neuron,” 2013. [Online]. Available:
https://en.wikipedia.org/wiki/Neural_circuit#/media/File:Blausen_0657_MultipolarNeuron.png.
[130] V. K. Ojha, A. Abraham, and V. Snášel, “Metaheuristic design of feedforward neural networks: A
review of two decades of research,” Eng. Appl. Artif. Intell., vol. 60, no. December 2016, pp. 97–
116, 2017.
[131] M. Azzam, N. A. K. Aramouni, M. N. Ahmad, M. Awad, W. Kwapinski, and J. Zeaiter, “Dynamic

114 | P a g e
 optimization of dry reformer under catalyst sintering using neural networks,” Energy Convers.
Manag., vol. 157, no. December 2017, pp. 146–156, 2018.
[132] B. V. Ayodele and C. K. Cheng, “Modelling and optimization of syngas production from methane
dry reforming over ceria-supported cobalt catalyst using artificial neural networks and Box-
Behnken design,” J. Ind. Eng. Chem., vol. 32, pp. 246–258, 2015.
[133] H. Li, Z. Zhang, and Z. Liu, “Application of artificial neural networks for catalysis: A review,”
Catalysts, vol. 7, no. 10, 2017.
[134] D. Kriesel, Neural networks - a brief introduction. 2007.
[135] D. Pedamonti, “Comparison of non-linear activation functions for deep neural networks on
MNIST classification task,” 2018.
[136] S. I. Amari, “Natural Gradient Works Efficiently in Learning,” Neural Comput., vol. 10, no. 2, pp.
251–276, 1998.
[137] D.-A. Clevert, T. Unterthiner, and S. Hochreiter, “Fast and Accurate Deep Network Learning,”
2016.
[138] A. Ng, “Machine Learning.” [Online]. Available: https://www.coursera.org/learn/machine-
learning.
[139] I. A. Saleh, “Conjugate Gradient Back-propagation with Modified Polack –Rebier updates for
training feed forward neural network,” Iraqi J. Stat. Sci., no. 20, pp. 164–173, 2011.
[140] G. R. E. Polack, “Note sur la convergence de méthodes de directions conjuguées,” Rev.
FRANÇAISE D’INFORMATIQUE Rech. OPÉRATIONNELLE. SÉRIE ROUGE, no. 3, p. 35-43, 1969.
[141] A. Iscen, G. Tolias, Y. Avrithis, and O. Chum, “Dropout: A Simple Way to Prevent Neural Networks
from Over tting,” J. Mach. Learn. Res., vol. 15, pp. 1929–1958, 2018.
[142] A. C. Ian Goodfellow, Yoshua Bengio, Deep Learning. 2016.
[143] S. S. Azzam, “Overfitting and Regularization.” [Online]. Available:
https://machinelearningmedium.com/2017/09/08/overfitting-and-regularization/.
[144] J. Brownlee, “How to use Learning Curves to Diagnose Machine Learning Model Performance,”
2019. [Online]. Available: https://machinelearningmastery.com/learning-curves-for-diagnosing-
machine-learning-model-performance/.
[145] S. Curteanu and H. Cartwright, “Neural networks applied in chemistry . I . Determination of the
optimal topology of multilayer perceptron neural networks,” no. 71, pp. 527–549, 2011.
[146] “How the Genetic Algorithm Works.” [Online]. Available:
https://it.mathworks.com/help/gads/how-the-genetic-algorithm-works.html.
[147] M. Mitchell, An introduction to genetic algorithms. MIT Press, 1999.
[148] M. Rocha and J. Neves, “Preventing premature convergence to local optima in genetic algorithms
via random offspring generation,” Lect. Notes Comput. Sci. (including Subser. Lect. Notes Artif.
Intell. Lect. Notes Bioinformatics), vol. 1611, pp. 127–136, 1999.
[149] G. E. P. Box, “Science and Statistics,” J. Am. Stat. Assoc., vol. 71, no. 356, p. 791, 1976.

115 | P a g e
Appendix A: Physical and Transport Properties

List of physical and transport for various case studies.

Case Base ε=0.3 ε=0.46 𝜀𝑓 =0.85 𝜀𝑓 =0.95 𝑑𝑐𝑒𝑙𝑙 =0.001 𝑑𝑐𝑒𝑙𝑙 = 0.003
Property case [m] [m]
𝑅𝑒𝑑𝑝 0.1523 0.1523 0.1522 0.1526 0.1512 0.1532 0.1511
5
𝑈𝑜𝑣 [𝑚2 𝐾/𝑊] 382.87 420.25 346.62 382.64 383.62 673.3 266.28
ℎ𝑤𝑎𝑙𝑙,𝑒𝑞 1764.48 1873.78 1655.30 1762.98 1769.4 2031.03 1519.69
[𝑊/𝑚2 /𝐾] 4
Bi 11.57 11.11 12.08 11.56 11.58 6.67 14.9
𝑒𝑓𝑓 0.305 0.337 0.274 0.305 0.306 0.304 0.306
𝑘𝑟,𝑒𝑞 [W/m/K]
0
ℎ𝑤 [𝑊/𝑚2 /𝐾] 439.79 371.38 494.61 432.00 436.06 430.43 436.37
𝑐𝑜𝑛𝑣
ℎ𝑤 6.85 6.85 6.85 6.85 6.85 6.84 6.86
2
[𝑊/𝑚 /𝐾]
ℎ𝑤 [𝑊/𝑚2 /𝐾] 439.79 378.23 501.45 438.85 442.92 437.28 443.23
ℎ𝑤𝑎𝑙𝑙,𝑓𝑜𝑎𝑚 491.73 491.62 491.91 490.66 495.30 976.03 330.95
[𝑊/𝑚2 /𝐾]
𝑒𝑓𝑓 0.305 0.338 0.274 0.305 0.306 0.305 0.306
𝑘𝑟 [𝑊/𝑚/𝐾]
𝑘𝑒𝑓𝑓 [𝑊/𝑚/𝐾] 7.445 7.445 7.445 13 3.667 7.445 7.445
𝑆𝑣 [𝑚2 /𝑚3 ] 1119.21 1119.21 1119.21 1307.23 852.24 2238.42 746.14
ℎ𝑒𝑞 [𝑊/𝑚2 /𝐾] 931.52 869.85 993.37 929.50 938.22 1413.31 774.18
𝑅𝑓𝑙𝑢𝑖𝑑 0.0148 0.0134 0.0165 0.0149 0.0149 0.0149 0.0148
[𝑚2 𝐾/𝑊]
𝑅𝑓𝑜𝑎𝑚 0.00094 0.00091 0.00098 0.00064 0.0016 0.00071 0.0013
[𝑚2 𝐾/𝑊] 8
𝑅𝑒𝑞 [𝑚2 𝐾/𝑊] 0.00089 0.00086 0.00093 0.00061 0.0015 0.00067 0.00122
1
𝑈𝑜𝑣𝑒𝑟𝑎𝑙𝑙 0.00196 0.0020 0.00193 0.00168 0.0025 0.00138 0.00252
[𝑊/𝑚2 /𝐾]

Case 𝑑𝑝 =200 𝑑𝑝 =400 0.8ℎ𝑤 1.2ℎ𝑤 0.8ℎ𝑤𝑎𝑙𝑙,𝑓𝑜𝑎𝑚 1.2ℎ𝑤𝑎𝑙𝑙,𝑓𝑜𝑎𝑚

Property [nm] [nm] [𝑊/𝑚2 / [𝑊/𝑚2 /𝐾] [𝑊/𝑚2 /𝐾] [𝑊/𝑚2 /𝐾]
𝐾]

116 | P a g e
 𝑅𝑒𝑑𝑝 0.1016 0.2029 0.1522 0.1523 0.1520 0.1525
𝑈𝑜𝑣 [𝑚2 𝐾/𝑊] 398.08 367.38 382.91 382.84 383.06 382.73
ℎ𝑤𝑎𝑙𝑙,𝑒𝑞 2266.43 1427.23 1764.73 1764.30 1765.72 1763.59
[𝑊/𝑚2 /𝐾]
Bi 14.87 9.35 11.57 11.57 11.57 11.57
𝑒𝑓𝑓 0.305 0.305 0.305 0.305 0.305 0.305
𝑘𝑟,𝑒𝑞 [W/m/K]
0
ℎ𝑤 [𝑊/𝑚2 /𝐾] 588.6902 359.8316 346.4741 519.3947 433.7129 432.3823
𝑐𝑜𝑛𝑣
ℎ𝑤 7.10 6.67 5.48 8.22 6.85 6.85
2
[𝑊/𝑚 /𝐾]
ℎ𝑤 [𝑊/𝑚2 /𝐾] 595.79 366.50 351.95 527.61 440.56 439.23
ℎ𝑤𝑎𝑙𝑙,𝑓𝑜𝑎𝑚 491.48 491.93 491.91 491.60 394.09 589.31
[𝑊/𝑚2 /𝐾]
𝑒𝑓𝑓 0.305 0.306 0.305 0.305 0.305 0.305
𝑘𝑟 [𝑊/𝑚/𝐾]
𝑘𝑒𝑓𝑓 [𝑊/𝑚/𝐾] 7.445 7.445 7.445 7.445 7.445 7.445
𝑆𝑣 [𝑚2 /𝑚3 ] 1119.21 1119.21 1119.21 1119.21 1119.21 1119.21
ℎ𝑒𝑞 [𝑊/𝑚2 /𝐾] 1087.27 858.43 843.86 1019.22 834.66 1028.54
𝑅𝑓𝑙𝑢𝑖𝑑 0.0149 0.0148 0.0148 0.0148 0.0148 0.0149
[𝑚2 𝐾/𝑊]
𝑅𝑓𝑜𝑎𝑚 0.00093 0.00096 0.00095 0.00095 0.00095 0.00095
[𝑚2 𝐾/𝑊]
𝑅𝑒𝑞 [𝑚2 𝐾/𝑊] 0.00088 0.00090 0.00089 0.00089 0.00089 0.00090
𝑈𝑜𝑣𝑒𝑟𝑎𝑙𝑙 0.00179 0.00207 0.00207 0.00187 0.00209 0.00186
[𝑊/𝑚2 /𝐾]

Case 0.8𝑈𝑜𝑣 1.2𝑈𝑜𝑣 𝑘𝑠𝑜𝑙𝑖𝑑 =100 𝑘𝑠𝑜𝑙𝑖𝑑 =400 2𝑘𝑟𝑒𝑓𝑓 𝑒𝑓𝑓

3𝑘𝑟
Property [𝑚2 𝐾 [𝑚2 𝐾/𝑊] [W/m/K] [W/m/K] [W/m/K] [W/m/K]
/𝑊]
𝑅𝑒𝑑𝑝 0.1521 0.1524 0.1515 0.1526 0.1525 0.1526
𝑈𝑜𝑣 [𝑚2 𝐾/𝑊] 306.36 459.38 383.46 382.65 382.72 382.63
ℎ𝑤𝑎𝑙𝑙,𝑒𝑞 1765 1764.15 1768.37 1763.06 1763.48 1762.91
[𝑊/𝑚2 /𝐾]
Bi 11.57 11.57 11.58 11.56 11.57 11.56
𝑒𝑓𝑓 0.305 0.305 0.305 0.305 0.305 0.305
𝑘𝑟,𝑒𝑞 [W/m/K]
0
ℎ𝑤 [𝑊/𝑚2 /𝐾] 433.27 432.73 435.39 432.05 432.31 431.96
𝑐𝑜𝑛𝑣
ℎ𝑤 6.85 6.85 6.85 6.85 6.85 6.85
2
[𝑊/𝑚 /𝐾]
ℎ𝑤 [𝑊/𝑚2 /𝐾] 440.12 439.58 442.24 438.90 439.16 438.81
ℎ𝑤𝑎𝑙𝑙,𝑓𝑜𝑎𝑚 492.10 491.49 494.53 490.72 491.02 490.61
[𝑊/𝑚2 /𝐾]
𝑒𝑓𝑓 0.305 0.305 0.306 0.305 0.610 0.915
𝑘𝑟 [𝑊/𝑚/𝐾]
𝑘𝑒𝑓𝑓 [𝑊/𝑚/𝐾] 7.445 7.445 3.722 14.90 7.445 7.445
𝑆𝑣 [𝑚2 /𝑚3 ] 1119.21 1119.21 1119.21 1119.21 1119.21 1119.21
ℎ𝑒𝑞 [𝑊/𝑚2 /𝐾] 932.22 931.07 936.77 929.62 930.18 929.42

117 | P a g e
 𝑅𝑓𝑙𝑢𝑖𝑑 0.0149 0.0149 0.0148 0.0149 0.0074 0.0045
[𝑚2 𝐾/𝑊]
𝑅𝑓𝑜𝑎𝑚 0.0010 0.00089 0.00155 0.00064 0.00095 0.00095
[𝑚2 𝐾/𝑊]
𝑅𝑒𝑞 [𝑚2 𝐾/𝑊] 0.00096 0.00084 0.00141 0.000614 0.00084 0.00079
𝑈𝑜𝑣𝑒𝑟𝑎𝑙𝑙 0.00204 0.00191 0.00247 0.00169 0.00191 0.00187
[𝑊/𝑚2 /𝐾]

𝑻𝒐𝒑𝒆𝒓 [ ͦ𝑪]

Appendix B: Artificial Neural Networks part

Parameters of GA

Case Population size Fraction kept Mutation rate Generations Fitness

limit
ANN 120 0.8 0.1 100 10−4
parameters
Operating 100 0.8 0.1 100 1
Conditions

Figure 1 Evolution of population fitness and best individual fitness during the optimiztion of operating conditions

118 | P a g e