MARMARA UNIVERSITY

INSTITUTE FOR GRADUATE STUDIES

IN PURE AND APPLIED SCIENCES

THEORETICAL AND EXPERIMENTAL

INVESTIGATION OF CO-GASIFICATION AND
CATALYTIC GASIFICATION
BEYZANUR ÖZTÜRK

MASTER THESIS
Department of Chemical Engineering

Thesis Supervisor

Asst. Prof. Dr. Uğur ÖZVEREN

ISTANBUL, 2020
 MARMARA UNIVERSITY
INSTITUTE FOR GRADUATE STUDIES
IN PURE AND APPLIED SCIENCES

THEORETICAL AND EXPERIMENTAL

INVESTIGATION OF CO-GASIFICATION AND
CATALYTIC GASIFICATION
BEYZANUR ÖZTÜRK
524516013

MASTER THESIS
Department of Chemical Engineering

Thesis Supervisor

Asst. Prof. Dr. Uğur ÖZVEREN

ISTANBUL, 2020
 INSTITUTE FOR GRADUATE STUDIES IN PURE AND APPLIED
SCIENCES

Beyzanur ÖZTÜRK, a Master of Science student of Marmara University Institute for Graduate
Studies in Pure and Applied Sciences, defended her thesis entitled “Theoretical and
Experimental Investigation of Co-Gasification and Catalytic Gasification”,
on………………2020 and has been found to be satisfactory by the jury members.

Jury Members
Assist.Prof. Dr. Uğur ÖZVEREN (Advisor)
Marmara University ............................................................................. (SIGN) ................

Doç.Dr. Özge Kerkez Kuyumcu (Jury Member)

Marmara Üniversitesi ........................................................................... (SIGN) ................

Assist.Prof. Ömer Faruk Dilmaç (Jury Member)

Marmara Üniversitesi ........................................................................... (SIGN) ................

A P PR O V A L
Marmara University Institute for Graduate Studies in Pure and Applied Sciences Executive
Committee approves that Beyzanur ÖZTÜRK be granted the degree of Master of Science in
Faculty of Engineering, Chemical Engineering Program on ……………….2020.

Director of the Institute

Prof. Dr. Bülent EKİCİ

ACKNOWLEDGEMENT

I would like to express my sincere gratitude to Asst. Prof. Dr. Uğur ÖZVEREN for his
constant patience, guidance, and very warm encourage through my graduate studies at the
Marmara University. Without his encouragement, understanding, and support during
working on my thesis, I would never be able to accomplish my research work.

I would like to acknowledge the Department of Chemical Engineer fellow graduate and
undergraduate students of our laboratory especially Furkan KARTAL and Mehmet
AYDEMİR.

Finally, I would like to thank my family and all my friends especially my mother and my
grandmother for their support and motivation for me throughout my study.

January, 2020 Beyzanur ÖZTÜRK

i
TABLE OF CONTENTS
CONTENT Page
ACKNOWLEDGEMENT ................................................................................................. i
TABLE OF CONTENTS ..................................................................................................... ii
ÖZET ................................................................................................................................ iv
ABSTRACT ..................................................................................................................... v
SYMBOLS ...................................................................................................................... vi
ABBREVIATIONS ........................................................................................................ vii
LIST OF FIGURES ...................................................................................................... iviii
LIST OF TABLES ................................................................................................................ x
1. INTRODUCTION ..................................................................................................... 1
1.1. Energy ................................................................................................................ 1
1.2. Biomass .............................................................................................................. 4
1.3. Coal .................................................................................................................... 6
1.4. Utilization of Coal and Biomass ........................................................................ 9
1.5. Gasification ...................................................................................................... 12
1.6. Co- gasification Technology ............................................................................ 18
1.7. Catalytic Gasification ....................................................................................... 19
1.8. Gasifier Types .................................................................................................. 21
1.8.1. Fixed Bed .................................................................................................. 21
1.8.2. Fluidized Bed Gasifiers............................................................................. 23
1.8.3. Entrained Flow Gasifier ............................................................................ 26
2. MATERIAL AND METHODS .............................................................................. 27
2.1. Sample Characterization .................................................................................. 27
2.1.1. Elemental Analysis ................................................................................... 27
2.1.2. Proximate Analysis ................................................................................... 27
2.2. Thermal Analysis ............................................................................................. 27
2.3. Kinetic Analysis ............................................................................................... 29
2.3.1. Model Fitting Approach............................................................................ 30
2.3.2. Model Free Approach ............................................................................... 31
2.4. Aspen Modelling.............................................................................................. 33
3.1. RESULTS AND DISCUSSION .......................................................................... 33
3.1. Fuel Characterization ....................................................................................... 34

ii
 3.2. Thermal Analysis ............................................................................................. 35
3.3. Kinetic Analysis ............................................................................................... 41
3.4. Gasifier Modelling with ASPEN Plus ............................................................. 51
3.4.1. Assumptions ................................................................................................. 51
4. CONCLUSION ....................................................................................................... 68
REFERENCES................................................................................................................... 71

iii
ÖZET

KATALİTİK VE BİRLİKTE GAZLAŞTIRMANIN DENEYSEL VE TEORİK İNCELENMESİ

Birlikte gazlaştırma ve katalitik gazlaştırma işlemi, reaksiyon hızını arttırıp çalışma

sıcaklığını düşürürerek genel sistemin enerji verimliliğini arttırmak için uygundur.
Bununla birlikte, bir termal dönüşüm olarak birlikte gazlaştırma ve katalitik gazlaştırma,
fiziksel özelliklerin değiştiği, ısı ve kütle transferi gibi çeşitli kimyasal ve fiziksel
süreçleri içeren karmaşık işlemler olarak düşünülmektedir.

Bu tez, biyokütle, kömür ve bunların karışımları için birlikte gazlaştırma ve katalitik

gazlaştırmanın sinerjik etkileşimlerinin teorik ve deneysel olarak belirlenmesini
amaçlamaktadır. Bu çalışmada Fındık Çotanağı, Çan Kömürü ile bunların karışımları,
NETZSCH 449 Jüpiter F3 termogravimetrik analiz cihazı ile katalitik ve katalitik
olmayan koşullar altında CO2 gazlaştırma kullanılarak gazlaştırıldı. Termogravimetrik
analiz verileri yardımıyla, izotermal olmayan kinetik analizler, sırasıyla Friedman ve
Flynn-Wall-Ozawa (FWO) diferansiyel ve integral eş dönüşüm yöntemleri kullanılarak
gerçekleştirildi. Kinetik sonuçlar katalitik etkinin belirlenmesi için kullanıldı. Ayrıca,
sinerjistik etkileşimlerin belirlenmesi için, Aspen Plus® yazılımında geliştirilen akışkan
yataklı gazlaştırıcı kullanılarak teorik çalışma yapıldı. Aspen Plus®'taki
simülasyonlardan elde edilen sonuçlar ile literatürden elde edilen deneysel sonuçların iyi
bir uyum içinde olduğu doğrulandı ve bu nedenle Aspen Plus®'taki modelin, singazın
bileşimini ve ekserji değerini doğru olarak tahmin etmek için kullanılabileceğini gösterdi.

Anahtar Kelimeler: Termal Analiz, Kinetik, Akışkan Yatak Gazlaştırıcı, Aspen Plus®,
Birlite Gazlaştırma, Katalitik Gazlaştırma

iv
ABSTRACT

THEORETICAL AND EXPERIMENTAL INVESTIGATION OF CO-GASIFICATION AND

CATALYTIC GASIFICATION

Co-gasification and catalytic gasification are suitable to enhance overall system energy
efficiency by increasing reaction rates and reducing operating temperature. However, co-
gasification and catalytic gasification as a thermal conversion is thought of complex
phenomena that involve several chemical and physical processes like alteration of
physical properties and chemical reactions including heat and mass transfer.

This dissertation aims to investigate theoretical and experimental determination of

synergistic interactions of co-gasification and catalytic gasification for biomass, coal and
their blends. Therefore, in this study, hazelnut husk, Çan lignite and their blend were
gasified in NETZSCH 449 Jupiter F3 thermogravimetric analyzer under catalytic and
non-catalytic conditions by CO2 gasification. By the aid of thermogravimetric analyzer
data, the non-isothermal kinetic analysis was conducted by using differential and integral
isoconversional methods; Friedman and Flynn-Wall-Ozawa (FWO) method,
respectively. The kinetic results were used for determination of catalytic effect.
Furthermore, theoretical study was performed by using fluidized-bed gasifier in the
Aspen Plus® software to determinate synergistic interactions. The validation results
obtained from simulations in Aspen Plus® depicted a good agreement with the
experimental results from literature, so the demonstration of the model in Aspen Plus®
can be employed to predict the composition and exergy value of syngas accurately.

Keywords: Thermal Analysis, Kinetics, Fluidized-bed gasifier, Aspen Plus®, Co-

gasification, Catalytic Gasification

v
SYMBOLS

α : Degree of conversion

C : Carbon

Ea : Activation energy (kJ/mol)

GJ : Giga Joule

f(α) : The reaction model ( function of conversion)

H : Hydrogen

kg : Kilogram

mg : Miligram

Mt : Megaton (1000000 tons)

n : Degree of reaction

MJ : Mega Joule

N : Nitrogen

O : Oxygen

R : Boltzmann gas constant (8.314 J mol−1 K−1)

S :Sulphur

t : Time (s)

T : Temperature (°C)

vi
ABBREVIATIONS
A : Ash

ASTM : American Society for Testing and Materials

CFB : Circulating Fluidized Bed

ETC : Et Cetera

EÜAŞ : Electric Generation Corporation

EPDK : Energy Market Regulatory Authority

FC : Fixed Carbon

FWO : Flynn Wall Ozawa

IEA :International Energy Agency

MTA : Mineral Research and Exploration Institute

MTOE : Millions of Tonnes of Oil Equilavent

M : Moisture

Min : Minute

TFC : Total Final Consumption

TG : Thermogravimetry

TGA : Thermogravimetric Analysis

TKİ : Turkey Coal Institution

TTK : Turkish Hard Coal Enterprise Intstitution

VM : Volatile Matter

WT. % : Percentage (Weight Basis)

vii
LIST OF FIGURES

Figure 1.1 Classification of energy resources 2

Figure 1.2 Electricity TFC from 1971 to 2015 by sector (Mtoe) 3
Figure 1.3 The electricity consumption of the world 3
Figure 1.4 Bio-based product flowchart for biomass feedstocks 5
Figure 1.5 The breakdown products of cellulose 6
Figure 1.6 The estimated and used coal reserve percentages of the world for each
8
coal rank
Figure 1.7 2015 source of primary energy production quantities worldwide 10
Figure 1.8 The rate of primary energy consumption worldwide by the end of 2016 11
Figure 1.9 Gasification process reactions 14
Figure 1.10 Fixed bed gasifier 22
Figure 1.11 Circulating fluidized fed gasifier 25
Figure 1.12 Bubbling fluidized bed gasifier 26
Figure 1.13 Entrained flow gasifier 26
Figure 2.1 TGA device 28
Figure 3.1 TGA and DTG curves of hazelnut husk at 5 °C/min 36
Figure 3.2 TGA and DTG curves of Çan Lignite at 5 °C/min 38
Figure 3.3 TGA and DTG curves of Co-gasification hazelnut husk blend and Çan
39
Lignite at 5 °C/min
Figure 3.4 TGA and DTG curves of catalytic co-gasification of Çan Lignite and
40
hazelnut husk at 5 °C/min
Figure 3.5 The iso-conversional curves of Friedman method for hazelnut husk 41
Figure 3.6 The iso-conversional curves of FWO method for hazelnut husk (a),(b) 43
Figure 3.7 The iso-conversional curves of Friedman method for Çan Lignite 44
Figure 3.8 The iso-conversional curves of FWO method Çan Lignite (a), (b) 45
Figure 3.9 The iso-conversional curves of Friedman method for co-gasification of
46
blend
Figure 3.10 The iso-conversional curves of FWO method for co-gasification of
48
blend (a), (b)

viii
Figure 3.11 The iso-conversional curves of Friedman method for catalytic co-
49
gasification of blend

Figure 3.12 The iso-conversional curves of FWO method for catalytic co-
50
gasification of blend

Figure 3.13 The model flowsheet of developed circulating fluidized bed gasifier 52
Figure 3.14 The effect of gasifier temperature on syngas composition; (a)
58
hazelnut husk (b) Çan Lignite (c) hazelnut husk & Çan Lignite Blend
Figure 3.15 Gasifier pressure influence on syngas composition a) hazelnut husk
60
(b) Çan Lignite (c) hazelnut husk & Çan Lignite blend
Figure 3.16. The effect of CO2/fuel ratio on syngas composition; (a) hazelnut
62
husk (b) Çan Lignite (c) hazelnut husk & Çan Lignite blend
Figure 3.17 Temperature effect on syngas composition in catalytic gasification;
64
(a) hazelnut husk (b) Çan Lignite (c) hazelnut husk & Çan Lignite blend
Figure 3.18 The effect of CaO/fuel ratio on syngas composition; (a) hazelnut
66
husk (b) Çan Lignite (c) hazelnut husk & Çan Lignite blend

ix
LIST OF TABLES

Table 1.1 The generation of notable agricultural residues in Turkey, (2006) 11

Table 1.2 Public coal reserve and production information by the end of 2016 12
Table 1.3 Stage depending on temperature in gasification 14
Table 3.1 The results of proximate analysis for hazelnut husk and Çan Lignite 34
Table 3.2 The results of elemental analysis for hazelnut husk and Çan Lignite 34
Table 3.3 Experimental studies 36
Table 3.4 Friedman Method for hazelnut husk gasification 42
Table 3.5 FWO Method for hazelnut husk gasification 43
Table 3.6 Friedman Method for Çan Lignite gasification 44
Table 3.7 FWO Method for Çan Lignite gasification 46
Table 3.8 Friedman Method for co-gasification of blend 47
Table 3.9 FWO Method co-gasification of blend 48
Table 3.10 Friedman Method for catalytic co-gasification of blend 49
Table 3.11 FWO method for catalytic co-gasification of blend 51
Table 3.12 Definition of blocks in the CFB gasifier model 53
Table 3.13 The comparison of the experimental studies from the new developed
54
model and the literature for coal
Table 3.14 The investigation of the experimental studies from the new developed
55
model and the literature for biomass
Table 3.15 The investigation of the experimental studies from the new
55
developed model and the literature for biomass & coal mixture
Table 3.16 The investigation of the experimental studies from the literature and
56
the new developed model for catalytic gasification

x
1. INTRODUCTION

Energy is a significant factor considering improvement of living standards and countries

economic and social development. While there are major developments and alterations in
the industrial field in the world, the increase in the population on the other hand increases
the energy demand.
Blends of coal and biomass for co-gasification is considered as a promising method from
the point of improved efficiency, environmental and economic benefits [1]. CO2 assisted
gasification increases the product gas lower heating value. Furthermore, the utilization of
catalytic properties of compounds, that naturally exists in biomass, affecting the CO2
gasification process and can even promote higher thermochemical reactivity in biomass
blended coal compared to solely coal [1, 2]. Recently, important researches related to co-
gasification of various coal and biomass blends are performed [3]. Extensive studies on
co-gasification are available in the literature [4]. However, there are limited studies have
been reported on catalytic and non-catalytic co-gasification of blended coal and biomass
under CO2 atmosphere.
The objective of this study is to investigate catalytic and non-catalytic CO2 assisted co-
gasification of Çan lignite and hazelnut husk by using thermal analysis to determine the
underlying kinetics in comparison to the parent lignite and biomass. Moreover, this study
presents the novelty of simulating catalytic and non-catalytic co-gasification under CO2
atmosphere for determination of synergistic interactions, sensitivity analysis was
conducted by using fluidized-bed gasifier generated by using Aspen Plus® software.

1.1. Energy

After the industrial revolution with developing industry, energy has been used in all areas
of life. Deficiency of energy in the world means low living standards for developed
countries and poverty for developing countries. Therefore, alternative energy resources
and new technologies to use energy resources efficiently have been investigated due to
high energy consumption in 20th century.

The growth in world population with increasing urbanization, and industrialization have
made energy technology more critical in all areas of human life such as industry,
residantal, commercial and public services, transport etc. Because of exhausting energy

1
resources, foreign dependency and environmental effects, producing safe, adequate, cheap
and clean energy is among the main economic and social problems of the countries.

Energy resources can be classified into nonrenewable and renewable. Nonrenewable

energy resources, like coal, natural gas, and petroleum (oil), are found in limited amounts
in environment. Renewable resources such as water (hydro), wind, geothermal, solar and
biomass, are regenerated over relatively short periods of time naturally ( Figure 1.1) [5].

Figure 1.1 Classification of energy resources [5]

According to International Energy Agency (IEA 2017), data’s Electricity TFC (Total Final
Consumption) from 1971 to 2015 by sector is given in Figure 1.2.

Shares of world electricity consumption between the years 1973 and 2015 are given in
Figure 1.3. In 1973, while the share of the industry sector was 53.5 % of total 440 Mtoe
energy consumption, the shares of residential sector, transport sector, public and
commercial services, and other sectors were 23.0 % , 2.4 % , 15.2% , and 5.9%
respectively [6].

2
 1
.Includes agriculture, fishing and non-specified other.

Figure 1.2 Electricity TFC from 1971 to 2015 by sector (Mtoe) [6].
When 2015 year is considered, world electricity consumption was 1737 Mtoe. Most of the
share was industry sector with 42.0 %, followed by residential with 27.1%. Commercial
and public services accounted for 22.2% and while transport sector had a share of 2.1%
other sector constituted 6.6% (Figure 1.3) [6].

Figure 1.3 The electricity consumption of the world [6]

Utilization of energy generated with high efficiency is of significance to assess potential

of alternative and renewable energy sources in addition to the available energy resources.

Particularly in recent years, studies have been focused on clean and environmentally
friendly liquid fuels, various chemicals and electrical energy generation from advanced
fuels rather than conventional systems from carbonaceous fuels. In this field, gasification

3
process stands out as an alternative technology that enables the production of clean gas
products that can be used in many fields such as internal combustion engine, fuel cell,
liquid fuel production. Gasification process has become attractive owing to worldwide
increasing environmental sensitivity and restrictions on carbon emissions against global
warming.

The conversion of our low-heating value lignite and biomass resources into liquid fuels
and various chemicals with gasification technology is an extremely important issue in
terms of the use of our local energy resources and ensuring energy security to meet
Turkey's growing energy needs.

1.2. Biomass

By comparison with other resources of renewable energy, biomass such as plant, food,
animal and urban wastes and forest by-products, is considered the most abundant in nature.
Biomass is becoming increasingly important, because fossil fuel resources are limited and
affect environment negatively. Biomass is carbon-based renewable resource that does not
cause environmental pollution. Additionally, biomass as the fuel it is more difficult to
transmit than liquid fuels, and has lower heating value than coal [7]. Biomass energy is
defined as any kind of fuel obtained from biofuels and living organisms. Biomass is widely
utilized in the world as an energy source obtained by direct processing of animal and plant
wastes and provides significant contributions to the world economy [8].

Biomass has three advantageous factors in its use as fuel. Firstly; It is a carbon-neutral
renewable resource and can be improved in sustainable bioenergy production. As the
second; eco-friendly. It does not conduce to greenhouse gas emissions and reduces the
amount of NOx and SOx by replacing fossil fuels. Thirdly; Despite the fluctuation of fossil
fuel prices, it has economic potential. Because of the biomass resources distribution all
over the world, it creates opportunities such as the development of bio-based economy as
well as energy security [9].

Plant biomass is made up of cellulose, lignin and hemicellulose, and slightly amounts of
extractives such as lipids and proteins [10].

4
 Figure 1.4 Bio-based product flowchart for biomass feedstocks [11]
Plants use solar energy, and carbon dioxide and as outcome of the reaction, oxygen and
monosaccharid ((CH2O) n)are formed (1.1). The sugar polymeric structure, cellulose, is
stored in the form of starch or hemicellulose. 75% by weight of most biomass is sugar
polymer [12].

nCO2 + nH2O + light+ chloropyl → (CH2O)n + nO2 (1.1)

Cellulosic biomass includes three main organic compounds; cellulose, hemicellulose and
lignin. Respectively, cellulosic biomass 25-35% hemicellulose, 40-45% cellulose, 15-30%
lignin and up to 10% other components [13] . Cereals, potatoes have a starch content of
approximately 50% [14].

Cellulose, a biopolymer, is a polysaccharide composed by the binding of D-glucose by β-

glyosidic bonds and its molecular formula (C6H12O6). Cellulose is composed of strong
intramolecular and intermolecular hydrogen bonds. Due to its straight chain structure, it
has a high degree of crystal structure. It is resistant to enzymes and insoluble in water. On
the other hand, it undergoes rapid hydrolysis under subcritical conditions [15]. The
breakdown products of cellulose are given in Figure 1.5.

5
 Figure 1.5 The breakdown products of cellulose [15]

Hemicellulose, composed of mixed polysaccharides, is an important carbohydrate fraction

of plants, and forms polysaccharide microfibrils by attaching to cellulose with hydrogen
bonds. On the contrary cellulose, it consists of side chains.
Biomass contains structures called extractives, inorganic components that form water and
ash in addition to components like hemicellulose, lignin and cellulose. The extractant is
comprise of phenolic compound, aliphatic acid, alcohol, sugar, amine, ether and it is
solvable in polar or non-polar solvers [16, 17].

Biomass is an eco-friendly and clean energy source. Even though carbon dioxide is
released as biomass is burned, the use of carbon dioxide by green plants during
photosynthesis protects the environment from the greenhouse effect. In other words,
biomass energy can be said to be piece of the natural carbon cycle. Biomass fuels contain
negligible sulphur and do not produce sulphur dioxide, which causes acid rain when
burned. By burning biomass, smaller amount of ash is obtained than the ash obtained in
consequence of the coal combustion, that can be used as an additive in soil for agricultural
purposes [18].

1.3. Coal

Coal is a significant energy resource that widely used in the energy sector throughout the
world. Although it was the most utilized feed stock in the production of energy from the
Industrial Revolution to the mid twentieth century, it has been replaced by natural gas and
petroleum since 1960s. Petroleum (oil) crisis in 1973 with decrease in petroleum

6
production and the rise in petroleum prices led human beings to renewable natural
resources.

Coal is an important resource because it is abundant and widespread throughout the world
and is a safe and economical fuel [19]. Coal formation takes place millions of years by
accumulation of vegetation in low swamp layers of the earth. Anaerobic bacteria degrade
organic materials in oxygen free medium causing the organic material to lose part of its
water and under harsh environment. Sediment layer covers it over the years. Coal is a
solid, rich in carbon and combustible gases and comprise of inorganic and organic
materials [20]. Mainly, coal comprised of carbon, hydrogen, nitrogen, mineral material
(inclusive of components of silicon, aluminum, iron and the others). Its formation process
varies greatly in terms of geological, petrographic, physical, chemical and thermal
properties. Coals are divided into two classes as hard and brown coals depending on
calorific value, volatile matter, constant carbon content, coking and caking properties.
[19].

There are various compositional distinctions among the coals mined in the world. Different
coal types are generally categorized by rank that resides on the conversion degree from the
original source. While the gradual conversion process continued, the fixed carbon content
and the heating value of the coal increases and the volatile material amount in the coal
reduces. The sorting coals method utilized in Canada and the United States has been
improved by ASTM and is depend on a range of parameters acquired by different tests.
These parameters are given below.

 Volatile matter: The part of a coal sample which is released as a gas when heated without
air under the detected conditions is volatile matter. Volatile matter includes volatile
organic and inorganic gases like nitrogen, carbon dioxide and sulfur [21].
 Fixed carbon: It is the combustible solid waste which remains after the coal sample is
heated and the volatile matter is removed [21]. It consists primarily of carbon containing
less hydrogen, nitrogen and sulfur.
 Ash: The inorganic substances left after complete combustion, such as silica, aluminum
and potassium.
 Moisture: The water in the coal in case of natural accumulation in the coal. The moisture
of a coal sample is measured as the released amount of water when heated under the

7
projected conditions
 Heating value: When coal (or any other substance) starts to burn totally with oxygen,
the energy that is released as heat is called heating value.

Anthracitic coals have the highest fixed carbon components and the lowest volatile content
with the highest rank. However, the Lignite coals, have the lowest fixed carbon content
and the highest volatile content, thus they are in low rank. The predicted coal percentage
of the world for all coal rank is given in Figure 1.6. [22]

In summary, Lignite coal has the lowest heating value while Anthracite coal has the highest
heating value.

Figure 1.6 The estimated and used coal reserve percentages of the world for each coal
rank [22]
Coal is generally used by burning in thermal power plants. As a result of coal burning,
some harmful gas emissions such as SOx, NOx and COx are formed [23]. Coal can also
be used for domestic, industry, transportation and heating purposes [24]. In 2017, 33% of
electricity production in Turkey was covered by coal [25]. According to the BP (2018)
report, the world coal reserve is reported to be 1,035 trillion tons. The total coal resources
of Turkey is reported to be around 17.25 billion tons [26].

8
Turkish lignite is generally known to have low heating values. Besides, Turkish lignite is
low rank coals because of Turkish lignite’s high ash and humidity and low carbon and
energy content [27].

Coal is mainly utilized in power plants to produce electricity. It can be also used to generate
energy gas, hydrogen, through gasification process since it is not freely found in nature
but in the form of compound on the earth crust [28]. Hydrogen has the highest energy
content per unit mass; Combustion of 1 kg of hydrogen provides energy equivalent to that
of given off by 2,8 kg of oil or 2,1 kg of natural gas. Hydrogen is a very clean fuel. In
systems where hydrogen is utilized as fuel, the residual gas is exhausted as just water or
water vapor. Hydrogen can be used directly as a fuel in internal combustion engines and
for flameless combustion on catalytic surfaces. It is about 33% more efficient than fossil
fuels [29].

When hydrogen energy is compared to primary energy sources, it has features such as
being portable, abundant in nature, renewable and being able to be stored. It is thought that
fossil energy systems will be replaced by hydrogen energy systems [30]. There are many
ways to obtain hydrogen. The world's hydrogen demand is met approximately 50% by
natural gas, 30% by oil, 18% by coal, 3.9% by water, and 0.1% by other sources [31, 32].
The amount of hydrogen currently produced in the world is approximately 0.1 Gt [33]. To
produce hydrogen from coal is by the gasification. Gasification is the method including
the conversion of any carbon-containing fuel to a product gas with an available heating
value [34]. Carbon-containing fuel in a reactor with high temperature, high pressure and
oxygen, the solid fuel undergoes a chemical conversion into gas. [31, 35, 36] This product
is called synthesis gas, and it can produce electricity, heat, hydrogen or liquid synthetic
fuels [34, 37].

1.4. Utilization of Coal and Biomass

World primary energy production was calculated as 13.790 Mtoe in 2015. Increased by
0.6 % compared to 2014 [38]. In 2015, primary energy production amounts in terms of
global resources are shown in Figure 1.7. The major share of this primary energy
production is petroleum (4416.26 Mtoe), coal (3871.53 Mtoe) and natural gas (2975.71
Mtoe) from fossil fuels [6].

9
 Figure 1.7 2015 source of primary energy production quantities worldwide [6]

Nuclear energy increased by 1.4% and reached 670 Mtoe. Other renewable energy sources
such as solar, wind, geothermal and hydraulic have also accelerated compared to previous
years [38]. When the energy resources are analyzed, as of the end of 2016, the amount of
global energy use is calculated as 13,147 Billion of tonnes of oil. Turkey covers the top
1% of world energy consumption and the amount of 126.9 Mtoe [39]. As of 2016, various
energy resources have been used in the world, and they are used in natural gas, petroleum
and coal etc. with 85.5%. fossil resources. (Figure 1.8.). According to the information
obtained in 2016; petroleum is the highest in energy consumption worldwide with 33.3%.
Following petroleum, coal ranked second in energy consumption, 28.1% in natural gas,
24.1% in natural gas, 6.9% in hydraulic, 4.5% in nuclear power, and finally in renewable
energy sources 3.2% are consumed (Figure 1.8) [40].

10
 Figure 1.8 The rate of primary energy consumption worldwide by the end of 2016 [40]

Turkey has biomass different agricultural residues. In Table 1.1 is shown the generation
of Turkey’s fruit and fruit tree residues and their estimated energy value [41].

Table 1.1 The generation of notable agricultural residues in Turkey, (2006)

Residue Heating Total Available Theoretical Actual

Value Heating Residue(tons) Production(tons) Production(tons)

(MJ/kg) Value
(x105 GJ)
Apricots Tree 19.3 13.4 69,571 1,328,846 86,964
prunning

Olive Tree 18.1 39.9 220,627 - 441,254

prunning

Pistachio Tree 19.0 31.9 167,88 - 209,611

prunning

Walnut Tree 19.0 4.8 25,240 - 50,480

prunning

Almond Tree 18.4 4.2 22,800 13,076 28,500

prunning

Shell 19.38 4.6 23,205 44,366 25,784

Hazelnut Shell 19.3 87.5 453,510 698,499 566,437

Tree 19.1 332.2 1,742,389 - 2,177,986

prunning

11
As of the end of 2016, it is seen in Table 1.2 that the lignite reserve is 12.712 million tons
(Mt) and the hard coal reserve is 1.297 million tons. As of the end of 2016, 1,5 Mt hard
coal and and 27 Mt lignite were generated. [42]

Table 1.2 Public coal reserve and production information by the end of 2016

Institution Reserv (million Production(million

tone) tone)

TKİ 3.646 13,7

EÜAŞ 8.502 13,3

Lignite MTA 564 -

Total 12.712 27.0

Hard Coal TTK 1.297 1,5

1.5. Gasification

Thermochemical processes are categorized as pyrolysis, gasification and combustion.

Various reactor types, working conditions and outcome products are subjects in all thermal
processes.

The commercial applications of gasification technologies and the production of fuels and
chemicals in this way have a history of over 100 years. With the increase in
industrialization and population growth, the increase in energy demand has led to the
research for alternative technologies. Therefore, gasification technology has rapidly
developed and gained importance as one of the alternative systems where energy can be
obtained. Synthesis gas obtained in gasification reactors (syngas) has reached a different
dimension in both fuel and chemical production [43].

The most important advantages of gasification are:

 Generation of electricity, production of basic substances used in chemical
production and production of liquid fuel,
 Presence of different types of feedstocks such as coal, large molecular oils,
petroleum coke, biomass and agricultural waste,
 Removal of pollutants in feedstock and production of clean synthesis gas,
 Converting wastes and low-value materials into valuable products,
 To contribute for the decrease of solid waste amount disposed of in landfills.

12
Gasification can be defined as the process in which carbonaceous materials are converted
into combustible, synthetic gas. CO, CO2, CH4 and H2 in the synthetic gas are of great
importance for the process. In general, gasification efficiency depends on the reaction
parameters such as, carbon content of the fuel, gasifier type, and the gasifier agents such
as oxygen, air, steam, CO2 or a blend of them at temperatures of about 700°C (1300°F) or
higher. As a result of these reactions, the evaluation of synthetic gas and liquid fuels are
utilized in both electricity and heat generation [44].

When the carbonaceous substances are heated directly or indirectly in proper gasification
conditions, they are pyrolyzed in the first place. During pyrolysis, hydrogen-rich, volatile
carbons begin to decompose and release tar, phenols and hydrocarbon gases, as well as a
gas product containing a higher proportion of H2 than the original feed material.
In the gasification process, the feed material becomes saturated with hydrogen. This is
explained in two ways.
In the gasification process, the feed material becomes saturated with hydrogen. This is
explained in two ways.
 Hydrogen is added directly or indirectly to the system.
 The feed material is pyrolyzed to obtain a product with an H / C ratio greater than
the original.

These processes may be carried out separately or simultaneously. If excess hydrogen is

added to the system or excess carbon is removed, the final synthetic gas production
efficiency of the system is reduced. Catalytic gasification is one example of an indirect
hydrogenation process currently under development. In that process, gasification is
accelerated with the aid of a catalyst, resulting in hydrogen and carbon monoxide. This
process performs at relatively low temperatures and allows the production of CH4 in the
same reactor. Catalyst deactivation and costs are considered as an obstacle to the
commercialization of the system in question.

Gasification is carried out in reactors in an environment where solid

carbonaceous fuels will come into contact with oxidants (oxygen, air, water vapor or
mixtures thereof in various proportions). Many reactions occur in different phases in
gasification processes. Figure 1.9 shows the thermal transformation of coal and biomass
into the resulting products.

13
 Figure 1.9 Gasification process reactions [34]

In general gasification systems have different physicochemical reactions depending on the

temperature. Since the chemical structures of coal and biomass vary, their realization
levels vary during the gasification process. These reactions and the temperature range of
the reactions can be seen in Table 1.3 [45].

Table 1.3 Stage depending on temperature in gasification

Stage Temperature

Drying >150°C
Pyrolysis 150-700°C
Combustion 700-1500°C
Reduction 800-1100°C

Drying

The first process for heating of the solid fuel is drying is. The fuel is heated from ambient
to 150 ºC in the atmospheric pressure. Despite it looks like easy, the drying process has
three complicated stages [46].

In the first stage, the temperature of the particle increases rapidly, and then water starts to
separate first. The drying speed increases significantly in the second stage. The secondly
stage is where water is collected on the solid surface and evaporation occurs from the
surface. If the solid particle is sufficiently wet, water is transported to the surface in some
form as a liquid and forms a thin layer on the surface At this stage, drying takes place at

14
a rate determined by environmental conditions, regardless of the structure of the solid
particle. The drying rate at this stage remains constant if the surface remains wet and the
environmental conditions do not change. The concentration difference among the water
on the solid surface and the water in the surrounding environment and the temperature
discrepancy between the solid surface input the system and the surrounding environment
ensure a high rate of drying at this stage. In the third stage, water is separated from the
solid by evaporation beneath the surface. When the liquid water layer on the surface is
exhausted, the heat transfer causes the water in the pores beneath the surface to evaporate.
Evaporated water reaches the surface between the layers of the solid pieces and is
separated from the solid pieces. . For this reason, mass and heat transfer resistance in the
solid particle remarkably affects the drying rate and drying rate reduces as the thickness
of the drying layer increases [47].

Pyrolysis

The pyrolysis phase is a complicated phase in which inorganic and organic compounds are
emitted from particle to the nature through diversified reactions by means of heat and mass
transfer mechanisms. [47].

There are three kinds of product formation observed in the biomass and coal pyrolysis
stage

Formation of light gases: In this phase, gases like CO, H2, H2O, CO2 and CH4 are
removed.

Tar formation: Tar is a black and very heavy, organic and inorganic molecule which is
usually emitted from solid particles in gaseous smoke from the liquid part.

Char formation: The solid phase remainder is defined as char. In various types of coals
and in almost all biomass, volatile substances constitute an important part of the
carbonaceous structure. Particularly in operation, the gases and liquids released during
pyrolysis are extremely important because they form a combustible environment around
the particle. Pyrolysis is also important in gasification systems as it is a stage that produces
product gas.

15
Combustion

Most of the drying, gasification and pyrolysis reactions are endothermic and should be
supported by an external heat source or this heat should be acquired by combustion
reactions with an amount of oxygen to be fed in [34].

Because combustion reactions are extremely fast and almost complete reactions, it can be
assumed that almost all of the O2 sent to the gasifier is spent in these reactions. The zone
where these reactions occur most in most gasifiers is the zone where O2 is fed into the
system. Therefore, a high temperature profile can be observed in these regions [47].
According to the reactions, carbon and hydrogen are oxidized to produce heat energy.
These reactions are exothermic reactions where the temperature is released. They are
converted into carbon dioxide and water vapor, respectively. These products decrease the
char and pyrolysis products connection. Ash which contains inorganic minerals that do not
burn as a result of combustion is also exposed [45, 48].

C+O2 → CO2 + 393,77 kJ/kmol Carbon (1.2)

H2+1/2O2→ H2O+742 kJ/kmol Hyrdogen (1.3)

Gasification

Gasification means that the solid fuel is partially or completely converted into gas. The
conversion can take place by thermal action or by chemical reactions, or both. When
evaluated within this scope, pyrolysis and heterogeneous combustion reactions (between
solid and gas) can be considered as gasification. However, in the heat science literature,
gasification reactions refer to reactions with gases other than oxygen. Combustion is
therefore considered a separate stage. . Gasification reactions are described in two ways
with the distinction of homogeneous and heterogeneous reactions. Although gas-gas
reactions are homogeneous, they are considered as continuation of heterogeneous
reactions.

Gasification is the conversion rate determination stage where the slowest reactions take
place. Carbon-containing heterogeneous reactions are Boudouard, Water-gas, and
hydrogenation reactions [34].

The Water-gas reaction is a heterogeneous reaction. Carbon monoxide and hydrogen are
formed with the same molar ratio as a result of this reaction.

16
Water-gas reaction; C+ H2O +131 MJ/kmol ↔ CO + H2 (1.4)

The Boudouard reaction is endothermic and the carbon dioxide in the reactor reacts via
char to produce CO with this reaction.

The Boudouard reaction; C+ CO2 + 172 MJ/ kmol ↔ 2CO (1.5)

The methanation reaction is a heterogeneous phase.

The methanation ; C+2H2 ↔ CH4 ΔH= +75 MJ/kmol (1.6)

Water-gas shift reaction is an exothermic reaction in which carbon monoxide in the reactor
reacts with water vapor to form hydrogen and carbon dioxide.

Water-gas shift reaction; CO+ H2O ↔ CO2+H2 ΔH= +42 MJ/kmol (1.7)

Fuel Selection for Gasification Systems

Coal, heavy petroleum products, domestic waste and biomass gasification are used in the
process. In order to provide the necessary hydrodynamic conditions when designing
gasification systems and to ensure the optimum operation of the system; the particle size,
elemental properties and heating value of the coal or biomass to be used; calculations
should be made according these properties.

The main considerations in coal selection can be summarized as reactivity of coal, volatile
matter ratio, mineral content, mineral composition, moisture content, heating value and
ash melting temperature. The selection criteria for coal also apply to biomass. In addition,
the other important parameters in terms of biomass density of the biomass, particle size
should be considered.

In summary, in the design of gasification systems, some physical and chemical properties
of carboneous material should be determined very well [34]. These properties are;

• Thermal value,

• Moisture content,

• Partical size and distribution,

• Compressed density,

• Volatile matter content,

• Constant carbon content,

17
• Ash content,

• Fuel reactivity,

• Elemental analysis values,

• Pollutant emissions [49].

1.6. Co- gasification Technology

Co-gasification of biomass in combination with other fuels like coal is thought a

convenient technology to reduce CO2 emission [50-56]. The advantages of biomass-coal
co-gasification technology are as follows:

• Stabilization of the quality of the feedstock,

• Development of “economic flexibility” of the system,

• Blend of coal and biomass instead of individual use creates a new type of renewable
energy source by lowering environmental impact.

• Environmental benefits, such as decreased sulfur and nitrogen emissions by adding

biomass to the fuel in the co-gasification.

Biomass is significant, affordable, and eco-friendly. Very few studies include co-
gasification of coal with biomass in the world at an industrial scale [57, 58].

Adding a certain amount of biomass to coal provides control of friction and contamination
problems leading to substances with high alkali content such as sodium and potassium.
Coal and biomass mixtures produce synergistic reactions with high thermal efficiency with
lower power output [59].
Co-gasification of coal and biomass can be carried out between the temperature range of
800 °C and 1000 °C (usually higher than 800 ° C) in gasifier using gasification agents like
steam, air, nitrogen, oxygen, carbon dioxide, or combining them by direct or indirect
heating [60].
The larger molecules of biomass (lignin and cellulose) are separated into lighter molecules,
which then turn into lighter molecules such as CO, H2, CH4 in combined gasification of
biomass and coal. During these transformations, ash, tar, coal and some polluting gases
are released. Mass loss in co-gasification was initially determined as; drying of biomass
and coal below 125 °C occurring in three stages active pyrolysis between 125 °C and 500

18
°C and passive pyrolysis above 500 °C [61]. During drying process, the volatiles and most
of the moisture are removed. In active pyrolysis stage, while some of the hemicellulose,
cellulose and lignin molecules break down, lignin breaks down completely in the passive
pyrolysis stage [62]. Above 500 °C, the fixed carbon fraction in coal and biomass causes
oxidation and gasification reactions. In particular, water-gas and water-gas exchange
reactions between 600 and 700 °C are effective. Above 750 °C, Boudouard reactions are
effective.

The experimental study for gasification was realized by Velez et al.[63]. Various mixtures
of Colombian coal gasification were investigated experimentally with this study. Rice
shells, coffee cups and sawdust were used as biomass. Gasification was conducted in
atmospheric ambients by introducing air - water vapor mixture. In the experiments, the
synthesis gas composition obtained by changing the air/fuel ratio among 2-3 kg/ kg and
steam/fuel ratio among 0.1 - 0.8 kg/kg were examined. The temperature of the steam and
air supplied to the system was increased to 350 ºC by preheating. The reactor used was
coated with 10 cm thick refractory material via 22 cm inner diameter, and was made of
310 stainless steel at a height of 4 m. The spreader plate used was selected with 142 holes
and a hole diameter of 1 mm. A propane-powered burner was used to provide initial
ignition in the system.

The syngas obtained was investigated by gas chromatography and the gas composition
was analyzed. Since the gas analyzer could not measure methane, the methane amount in
the gas obtained from the system could not be found. It was stated that at the end of the
experimental study, the gasification of biomass with coal increases the amount of H2 in
the gas mixture obtained, but this effect is small, it is a small effect and it is emphasized
that biomass which is a renewable energy source will be beneficial in reducing CO2
emissions.

1.7. Catalytic Gasification

Catalytic gasification of blend (biomass and coal) is very attractive method because of the
higher reaction rate at lower reaction temperature.

19
Catalyst:

Catalysts are added to the reaction ambient externally, modifying the reaction rate and
come out of the reaction without deteriorating its chemical structure. Mainly, three types
of catalysis, rely on the state of the material are:

-Heterogeneous,

-Homogeneous,

-Enzyme catalysis.

In heterogeneous catalysis; the reagents, and the catalyst are in various phases In general,
the catalyst has solid phase, and the reagents are gas or liquid. Heterogeneous catalysts are
significant catalysts used in the chemical industry, particularly in the synthesis of very
important basic chemicals type.

In homogeneous catalysis; the reactants are in the same physical state with the catalyst and
it is generally liquid. Acid and base catalysis can be given as an example to homogeneous
liquid catalysis. In recent years, researchers have worked to prepare a new class of metallic
compounds that will serve as homogeneous catalysts. Many of the reactions they catalyze
are organic. As homogeneous catalysis occurs mostly under atmospheric conditions, it
reduces the cost of production. They can also be designed to be selective for a reaction and
cost less than precious metals (Pt, Au, Ru etc.) used in heterogeneous catalysis.

Supported catalysts comprise catalytically active materials, the majority of which are
metals. These catalysts may be granular, pelleted, extruded and annular. The supports
alone are inert substances which do not have catalytic activity and are a dispersing agent
of the active phase. Their effect on catalytic activity depends on the reaction and reaction
conditions. They are especially used to improve mechanical strength in weak catalysts.
The supports also help the stability of the active structure [64].

Heterogeneous catalysts are classified as synthetic catalysts and natural minerals [65-67].
Synthetic heterogeneous catalysts are categorized transition metal (Ni, Pt and Rh based)
and alkaline earth.

Alkali metals belong to the IA group (Li, Na, etc.), are considered to only increase biomass
gasification reactions, and are not convenient for direct use as a catalyst for tar reform [68].

20
CO2 in the syngas obtained from gasification process can be absorbed by using suitable
absorbents, so the H2 component in the syngas can be enhanced [69]. Calcium oxide (CaO)
is an effective and economic material as an absorbent. The addition of CaO to the
gasification is an approach used to reduce the amount of CO2 and tar simultaneously,
because CaO is a catalyst that breaks down the tar and absorbs CO2 gas. The regenerated
CaO is then recycled to be used as the CO2 absorber. It is known that utilization of CaO as
a CO2 absorber in an enhanced high temperature gasification can decrease the quantity of
tar in the syngas [70].

1.8. Gasifier Types

Depending on the type of reactor selected, carbon conversion, temperature distributions

throughout the reactor, the amount of particles in the product gas will vary, as well as the
composition and thermal values of the final products to be directly affected by the reactor
type. The reactor types are mainly categorized into three types as fixed bed gasifiers,
fluidized bed gasifiers and entrained flow gasifiers [71].

1.8.1. Fixed Bed Gasifier

Fixed bed gasifiers are historically the oldest type of gasification and are appropriate for
small and medium-sized plant. It is not preferred in large-scale plants because the content
of the synthesized gas exported as the product is unpredictable. Fuel is also typically fed
from above and moves downwards under the influence of gravity in the fixed bed gasifier
[72]. As the fuel moves downward, it undergoes drying, thermal decomposition and
gasification. Fixed bed gasifiers are divided into drying and de-vaporizing, reduction,
combustion and ash zone. The required amount of heat for the gasifier is supplied by
burning some coal in the combustion zone. Syngas from fixed bed gasifier reactors
includes hydrocarbon, water and tar. Solid particles of coal and biomass remain in the
gasifier reactor for several hours, while the syngas generated in consequence of
gasification is extracted from the system in a few minutes. It is preferred that the particle
size to be around 6-50 mm. In addition, the outlet temperature of the synthesis gas varies
between 425 °C and 650 °C [34].

21
The fixed bed types are sorted as updraft, downdraft and crossdraft gasifiers in accordance
with the flowing direction of air and gas.

Figure 1.10 Fixed bed gasifier [68]

Updraft Gasifier

Updraft gasifiers have high efficiency as hot gases pass through the fuel column and leave
the gasifier at a relatively low temperature. The airflow is provided opposite to the fuel
flow and as low as possible of the gas generator. The gas produced is taken from the top
of the gasifier. The sensible heat taken from the gas is utilized to and preheat and dry the
fuel. Distillation and drying products that occur in the region; water, tar and oil vapors,
which do not pass into the oxidation zone. Therefore, if gasification of high volatile fuels
is carried out in these gasifiers, the gas produced will contain a high proportion of tar.
Many manufacturers use moist air to improve the quality of the gas and keep the
temperature below the ash melting point. The most important design parameters are: the
method of air loading, the gas outlet situation, the size and type of the grate, the average
amount of evaporating water for the introduction of humid air, the interior of the firebox
[73].

Downdraft Gasifier

Since the gas produced in the updraft gasifier includes a high percentage of tar, it is
difficult to use in internal combustion engines. Downdraft gasifiers have been developed
to eliminate this problem. In this type, the air delivered is in the same direction as the fuel,

22
downwards, and the gas is ejected from the bottom of the gasifier. The basic assessment is
as follows: Tar, oils and vapors released in the distillation zone do not have high
temperatures. They must also go through the partial combustion zone to pass through the
gas outlet. Here, they pass into high temperatures and break into gas. Thus, very low tar
remains in the gas mixture. The most important design parameters are; combustion zone
design, air delivery, grill design, throat design. A downdraft type gasifier has a narrowed
rectangular cross section on the air inlet portion. This is called the throat, which provides
a homogeneous thickness of the hot carbon and permits the passage of distillation gases.
Therefore, it is an important parameter in design. Downdraft type gasifiers are not
appropriate for gasification of fuels with high content of ash and moisture or high slag. If
the humidity exceeds 20 %, this fuel will not be suitable for this system. If the fuel ash
content is high, then the grill will have to be rotating. The maximum recommended ash
content for this gasifier is around 5 %. Moisture in the fuel and air is sufficient for
hydrogen production [74].

Crossdraft Gasifier

Crossdraft gasifiers are not preferred much despite their advantages over downdraft and
updraft gasifiers. The major disadvantages of this type of gasifier are; gas outlet
temperature is high, high gas velocity, CO2 reduction is weak. Gas output in crossdraft
gasifiers is also different from other types. In many cases, unlike other gasifiers, the ash,
ignition and reduction zones are not separated by a grid [74].

1.8.2. Fluidized Bed Gasifiers

In fluidized bed gasifiers, the fuel which is forming to the convenient particle size is
gasified by fluidizing in the appropriate gasification environment. Such systems are
suitable for gasification of biomass and coal particles between 0.5–5 mm. Sand, lime stone
or fuel ash can be used as the bed material. If limestone is added, some of the sulphur is
retained in the reactor. During gasification of biomass, silica sand is also utilized as inert
bed material. The mixture increases homogeneous temperature distribution and high heat
transfer throughout the reactor is obtained in such systems when the fluidization rate is
exceeded [45].

23
One of the major factors to be considered when working the reactor is that the bed
temperature does not reach the ash melting temperature. Otherwise, the ash may melt and
cause slag formation. The resulting slag bed may clog the fluidization. This phenomenon
is also referred to as bed tying. For this reason, fluidized bed systems must always be
operated below the ash melting temperature. This value is between 800 - 950 ºC in biomass
systems and 950 - 1100 ºC in coal gasifiers.

In fluidized-bed systems, it is extremely important for the gasifier to be supplied to the

reactor to be homogeneous and that no dead zones occur in the reactor in terms of
hydrodynamics of the reactor. Additionally, the diffuser plates prevent solid particles from
entering the duct where air, water vapor or oxygen is supplied to the system. For this
reason, various types of distributor plates are used in the gasification reactors. Fluidized
bed systems are divided into circulating and bubbling fluidized bed system [45].

Circulating Fluidized Bed Gasifier

In circulating fluidized bed (CFB), fuel and bed material are mixed in a hot environment.
Pyrolysis, drying, reduction and oxidation reactions occur in different regions of the
reactor due to the intensive solid - gas mixture in such systems. The gassing medium gases
fed to the reactor are fed to the system via a distributor plate. Therefore, homogeneous
mixture is ensuring. We can say that the temperature distribution throughout the reactor is
more homogeneous in circulating fluidized bed systems since the bed substance is present
throughout the entire reactor. The fluidization rate is in the order of 5-10 m/s which can
remove the bed material from the reactor. CFB is given below in Figure 1.11.

24
 Figure 1.11 Circulating fluidized bed gasifier [75]

Due to high velocity of the gasification medium in the circulating fluidized-bed systems,
the reaction time of the fuel fed is shorter than that of the bubbling fluidized-bed systems.
This may result in lower reaction efficiency. Thus, the fuel to be fed to the reactor should
be smaller in such systems. Furthermore, the bed temperature can be easily controlled and
air/fuel ratio can be easily changed compared to fixed bed gasifiers [45].

Bubbling Fluidized Bed Gasifier

In bubbling fluidized bed systems, the rate of gasification medium must be at a certain
level in order to begin to fluidize of fuel fed to the bed. The velocity at this point is called
the minimum fluidization rate. The fluidization rate in this type of reactor is kept at the
order of 2-3 m/s. At higher velocity, the bed expands, causing the bed material to exit the
reactor and accumulate in the cyclone. For this reason, high speeds are avoided in bubbling
fluidized bed gasifiers [45].

25
 Figure 1.12 Bubbling fluidized bed gasifier [76]
1.8.3. Entrained Flow Gasifier
Entrained flow gasifiers are generally preferred gasifiers in the gasification of coals. In this
type of systems, bed temperatures are in the order of 1000 - 1600 ºC, the ash in the bed is
removed from the system as molten. Because of the high bed temperatures, almost all of
the undesirable tar in the product gas is decomposed and the production of clean synthesis
gas without tar can be realized in such gasifiers. Carbon conversion is 99% in such
systems. The majority of commercially available entrained flow gasifiers with a successful
operation between 20 and 70 bar pressure were established after the 1950s [35].

Figure 1.13 Entrained flow gasifier [75]

26
Entrained flow gasifiers are mostly used in gasification integrated combined cycle power
plants for gasification of high energy coals. Coal feeding systems can be found dry coal
feed or coal water mixture form [35].

2. MATERIAL AND METHODS

2.1. Sample Characterization

2.1.1. Elemental Analysis

Elemental analysis is made to obtain the relative proportions of the five elements (C, N, S,
O, and H) that constitute the organic structure of fuel to a great extent. In elemental
analysis of coal, trace elements like F and Cl can also found the elemental analysis [77].

2.1.2. Proximate Analysis

In proximate analysis of the fuel, the moisture, fixed carbon, and volatile matter content
with ash are determined.

Proximate analysis was developed for the analysis of charcoal as the method of the
American Test and Materials Association (ASTM) D1762-84. It is used in the analysis of
many hydrocarbon-based solid fuels, particularly coal [78]. According to the ASTM
method, the short analysis requires that the crucible containing the fuel is heated to 750 °
C, cooled and weighed before being used for proximate analysis. In this method the
moisture content is calculated as a percentage of the mass loss of samples drying in an
inert atmosphere. Volatile compounds of solid fuels are present as a percentage of the
mass lost in the range from 105 °C and 950 °C. The ash percentage is the mass remaining
as a result of combustion of solid fuel at 750 °C for 6 hours. Short analysis is used in the
characterization of the solid fuel composition as a measure of the combustion quality of
the solid fuel. When the fixed carbon value of the fuel content is high, the thermal value
of the fuel increases; when the ash percentage in the fuel rises, the thermal value of the
fuel decreases. Turkish coals generally consist of young coals. Therefore, when the
proximate analysis values of Turkish coals are investigated, it is seen that the moisture
and ash percentages are high whereas the fixed carbon percentages are low.

27
2.2. Thermal Analysis

Thermogravimetric Analysis (TGA) shows how mass changes as a function of temperature

or time under a certain condition. This method tells about sample composition, and thermal
behavior of the sample as it undergoes gasification or any kind of process at specified
circumstances. Thermogravimetric analysis is a convenient method for monitoring the
thermal and kinetic behavior of solid fuels. It is cheap, fast, and easy technique to
determinate composition of solid fuels. In this study, NETZSCH 449 Jupiter F3 was used
as thermagravimetry analyzer. ( Figure 2.1)

The NETZSCH 449 Jupiter F3 consists of mainly three parts; carrier system and furnace,
and balance that measures mass change. Thermagravimetric analyzer NETZSCH 449
Jupiter F3 as a complement to the heater and pressure regulator is used as support
equipment. The temperature go up to 1250°C, and can be up to 1600 °C performed
studies with normal gas. Protective gas represents the gas to the balance. The gas to the
balance should always be inert. The balance should not go into a corrosive substance and
the scale should not come into contact with a corrosive substance, in order not to erosion.
Purge gases represent the gas leading to the furnace.

Support equipments of TGA device are heat exchanger, pressure regulator, water
circulator. The water circulator is used to keep stable the temperature of the balance.

Figure 2.1 TGA device

28
Heat exchanger is the heating collar and the transfer line. The use of heater exchanger is
to prevent condensation of CO2 or gases. If condensation occurs, the scale of the balance
and the system may be corrupted. Purge gas (CO2) comes from the line and after the
pressure is set, it moves to the collar.

The NETZSCH 449 Jupiter F3 device can be used as gasifier in different atmospheres. In
this experimental, gasification process was performed under 100 % CO2 atmosphere.

2.3. Kinetic Analysis

Thermogravimetric methods can examine the kinetics of solid phase degradation reactions.
Aim of kinetic analysis is to specify the kinetic parameter effect on the conversion (α).

The method of thermogravimetric analysis includes techniques in which the mass change
is recorded as a function of temperature and time if the sample to be examined is heated
or cooled in a environment. Depending on the study it can be applied in three different
ways [79, 80].

1. “Isothermal thermogravimetry” where the mass of the sample is recorded as a

function of time at constant temperature ( Model fitting Approach).

2. “Quasi-isothermal thermogravimetry” is the method that the sample is heated until

its mass remains constant at each of increasing temperature series ( Model Free
Approach).

3. "Dynamic thermogravimetry" in which the change in the mass of the material is

recorded in an environment where the temperature is changed at a predetermined
speed ( Nonlinear Regression Analysis Approach).

Different computer programs have been developed to perform kinetic analysis with the
data obtained from TG analysis. Malek [81], initiated studies to develop computer
programs to operate the kinetic analysis of non-isothermal TG data of solid phase
degradation reactions. Perrenot and Widman [82], developed program using the Sestak-
Berggran equation and Mettler software language. Elder [83], using Fortran programming
language has created an algorithm for the nth order reactions. Malek [81] developed this
program for sequential reactions. Mitilky and Sestak[84], generalized the program in
question. Flynn [85], determined Arrhenius parameters (E (activation energy) and k0

29
(frequency factor)) using integral equation. Additionally, Dollimore and colleagues [86]
developed another computer program.

In this dissertation, FWO and Friedman method which are model free approaches have
been used to kinetic analysis for each gasification experiment.

2.3.1. Model Fitting Approach

2.3.1.1. Coats-Redfern method

Coats-Redfern (1964) kinetic model is based on the integral form of the reaction model.
In this integral method [87];

a.A (s) ↔ b.B (s) + c.C (g) (2.1)

In a solid phase degradation reaction according to the equation, the decomposition rate of
the substance A is expressed by the kinetic equation (2.2).
𝑑𝛼
= 𝑘. (1 − 𝛼)𝑛 (2.2)
𝑑𝑡

𝑓(𝛼) = (1 − 𝛼)𝑛 (2.3)

n= Degree of reaction

(2.2) by taking the integral of the equation linearization, kinetic variables are derived from
the equation is calculated. These equations:

1. for n≠1 ;

1−(1−𝛼)1−𝑛 𝑘 R
𝛼 𝐸𝑎
𝑙𝑜𝑔 ( (1−𝑛).(𝑇)2
) = 𝑙𝑜𝑔 (𝑏𝐸𝑎 ) − (𝑅T) (2.4)

By selecting the appropriate “n” value, log A (log𝑘𝛼 ) and Ea can be calculated from the
1−(1−𝛼)1−𝑛
slope of the line obtained by plotting 𝑙𝑜𝑔 ( (1−𝑛).(𝑇)2
) versus 1/T.

2. for n=1 ;
(1−𝑎) 𝑘 R
𝛼 𝐸𝑎
𝑙𝑜𝑔 (−𝑙𝑜𝑔 ) = 𝑙𝑜𝑔 (𝑏𝐸𝑎 ) − (2.303𝑅T) (2.5)
(𝑇)2

Kinetic variations can be computed from the slope of the line obtained by plotting
(1−𝑎)
𝑙𝑜𝑔 (−𝑙𝑜𝑔 ) versus 1/T.
(𝑇)2

30
2.3.2. Model Free Approach

Generally, the shape of the TG curves will be a function of the reaction kinetics; therefore,
it is known that kinetic variables can be calculated from TG curves. Diverse methods
developed for this purpose are sorted by Flynn and Wall [88], as follows:

1. “Integral methods” in which weight change with temperature is used directly,

2. “Differential methods” using weight change rate,
3. “Difference differential methods” which take into account the second differences in
the rate of weight change,
4. Special methods applicable to initial velocity,
5. Methods using non-linear heating rate.

Solid state decomposition processes may be presented by the following Equation;

𝑑𝛼 𝐸𝑎
= 𝑘0 exp (− 𝑅𝑇) 𝑓(𝛼) (2.6)
𝑑𝑡

α: degree of conversion

f(α): the reaction model which is a function of conversion

R: Boltzmann gas constant (8.314 J mol−1 K−1)

k0: Arrhenius pre-exponential factor

Ea: Activation energy (kJ/mol)

The conversion is expressed as:

𝑚𝑖 −𝑚𝑡
𝛼= (2.7)
𝑚𝑖 −𝑚∞

𝑚𝑖 : Initial mass of sample

𝑚𝑡 : Mass of the sample at time t

𝑚∞ : Final mass of the sample

For dynamic studies of non-isothermal data a term β as the heating rate (in K/min) is
presented the following equation can be obtained[89]:
𝑑𝛼 𝑘0 𝐸𝑎
= exp (− 𝑅𝑇) 𝑓(𝛼) (2.8)
𝑑𝑡 𝛽

31
Iso-conversional methods can be categorized as integral and differential analysis
methods. Differential methods utilize the mainly solid state equation Eq. (2.6), although
the integral methods are propped up the integral form of the non-isothermal rate law as
the following expression [89],
𝛼 𝑑𝛼 𝑘0 𝑇 𝐸𝑎
∫0 = 𝑔(𝛼) = ∫𝑇 exp (− 𝑅𝑇) 𝑑𝑇 (2.9)
𝑓(𝛼) 𝛽 0

where g(α) is the integrated form of the conversion dependence function. If we define x
= Ea/RT, Eq. (2.9) can be stated as follows;
𝑘0 𝐸𝑎
𝑔(𝛼) = ( ) 𝑝(𝑥) (2.10)
𝛽𝑅

The term p(x) is known as the temperature integral and it has no exact analytical solution
[90].

2.3.2.1. Friedman method

The Friedman method is a differential iso-conversional approach that can be given as

written below:

𝑑𝛼 𝐸𝑎
ln [𝛽𝑖 (𝑑𝑇 ) ] = 𝑙𝑛[𝑘𝛼 𝑓(𝛼)] − 𝑅𝑇𝛼 (2.11)
𝛼,𝑖 𝛼

Activation energy (Ea) can be found from the slope of the plotting curve of ln
(βi(dα/dT)α,i) versus 1/Tα, at a constant α value. Subscript i is the ordinal number for an
experiment performed at a given heating rate [91].

2.3.2.2. The Flynn–Wall–Ozawa (FWO) method

The FWO method developed by Ozawa (Ozawa, 1965) and Flynn-Wall [92] is another
integral method for calculating non-isothermal data.

The Flynn–Wall–Ozawa (FWO) technique utilizes the Doyle approximation [93] for the
temperature integral:

ln 𝑝(𝑥) ≅ −5.331 − 1.052𝑥 (2.12)

Taking logarithm of Eq. (2.9) and combining with Eq. (2.10) gives the FWO expression
in Eq. (1.35).

32
 𝑘 𝐸𝑎
𝛼 𝛼 𝐸𝑎
𝑙𝑛𝛽𝑖 = 𝑙𝑛 ( 𝑅𝑔(𝛼) ) − 5.331 − 1.052 𝑅𝑇𝛼 (2.13)
𝛼

Activation energy (Ea) is acquired from a plot of ln(βi), versus 1000/Tα,i, that symbolizes
the linear relationship with a given conversion value at different heating rates [94].

2.4. Aspen Modelling

Aspen Plus is a thermodynamic simulation program for physical, chemical and biological
applications. Aspen Plus is one of the most preferred programs for overcoming complex
situations and simplifying the design of the process. The Aspen Plus program has been
and continues to be preferred by many researchers for thermodynamic simulations of
solid fuel gasification processes. For example, they modeled the fluidized bed gasification
of wood samples by using Aspen Plus. The simulation model is designed to minimize
Gibbs free energy and is subdivided into thermodynamic simulations of combustion,
pyrolysis, Boudouard reaction and other gasification reactions. The researchers also
conducted the sensitivity analysis for the model; examined the effects of air temperature,
oxygen factor, gasifier pressure, oxygen content in the air, and superheated steam on
gasification performance.

The choice of the reactor generally depends on the size, the type of fuel fed, the
composition of the output product, the moisture content, and the vapor/oxygen/air content
of the gasifying agent used. Simulation approach is very beneficial because it allows the
sensitivity analysis of a process to be performed without operating experimental work.
The selection of the appropriate affinity model has helped to attain an optimized process
that can decrease costs and the time including experimental studies. The Aspen Plus
simulation software used in the modeling of combustion and coal gasification process in
combination with integrated biomass and coal gasification to estimate synthesis gas,
synthetic natural gas (SNG) and energy generation.

33
3.1. RESULTS AND DISCUSSION

3.1. Fuel Characterization

Hazelnut husk sample used in the study was supplied from Düzce city of Turkey while
Çan Lignite from Çanakkale by Turkish Coal Enterprises Institution. Biomass and coal
were pulverized with the shredder “IKA M20 Universal Mill” and sieved to under 250
µm particle size via “Mortar Grinder Retsch RM 200”.

Proximate analysis was performed using ASTM standard testing method 5142-04
standards by using “Netzsch 409 PC” TGA device. The results of proximate analysis for
biomass and coal can be seen in the Table 3.1.

Table 3.1 The results of proximate analysis for hazelnut husk and Çan Lignite

Hazelnut Husk (wt %) Çan Lignite (wt %)

M 4,03 3,48
VM 64,30 30,44
FC 22,97 26,14
A 8,70 39,94

M: Moisture, VM: Volatile Matter, FC: Fixed Carbon, A: Ash,

Ultimate analysis was performed using LECO Truspec CHN-S analysis. Table 3.2
demonstrates the ultimate analysis values of coal and biomass.

Table 3.2 The results of elemental analysis for hazelnut husk and Çan Lignite

Hazelnut Husk (wt %) Çan Lignite (wt %)

C 39,75 32,74
H 5,06 3,00
O 52,30 56,99
N 0,82 0,77
S 2,07 6,50

S: Sulphur N: Nitrogen O: Oxygen H: Hydrogen C: Carbon

34
3.2.Thermal Analysis

The experiments were performed under 100% CO2 atmosphere non-isothermally. It was
seen that all of CO2 gasification processes included three subsequent reaction regions
which were associated with first pyrolysis, second pyrolysis and gasification stages
respectively when the results of TG analyses were investigated.

3.2.1. Experimental Study

All weighted samples (15.0±1.0 mg and < 250µm) was placed in an Al2O3 crucible.
Samples underwent gasification process in 100% CO2 atmosphere temperature from 110
C up to the 1100 °C in 5, 10 and 15 oC/min heating rates.
0

In TGA experimental system; purge CO2 gas, and argon protective gas flow rates were
adjusted to 20 mL/min and 15 ml/min respectively. The reaction starting temperature was
110 °C, and the final temperature was 1100 °C with 5, 10 and 15 oC/min heating rates.

Correction Experimental Study:

In the beginning of the gasification experiment, the density of the air reduces causing the
mass to behave as if it was increasing due to the dominant effect of decrease in the density
of the air when the temperature increases.

Correction was required to eliminate any mistake caused mass loss except only by the
reactions. In performed experimental studies, the procedure was the same throughout all
the heating rates. For all three heating rates correction experiments were performed with
empty crucible. (5, 10 and 15 oC/min).

Correction of TGA measurements are performed by making the experiment with an

empty crucible to avoid any interference due to buoyancy effect. The blank curve
obtained serves as baseline and subtracted from the sample measurement curve.

The experimental studies were performed in different conditions. The measurements in

100 % CO2 atmosphere with the conditions are in Table 3.3.

35
Table 3.3. Experimental studies

Heating Rate Sample

1. Hazelnut Husk
2. Çan Lignite
5 °C/ min 3. 50% Çan Lignite + 50% Hazelnut Husk
4. 40% Hazelnut Husk+ 40% Çan Lignite + 20% CaO

5. Hazelnut Husk
6. Çan Lignite
10 °C/ min 7. 50% Çan Lignite + 50% Hazelnut Husk
8. 40% Hazelnut Husk+ 40% Çan Lignite + 20% CaO

9. Hazelnut Husk
10. Çan Lignite
15 °C/ min
11. 50% Çan Lignite + 50% Hazelnut Husk
12. 40% Hazelnut Husk+ 40% Çan Lignite + 20% CaO

3.2.2. CO2 Gasification of Hazelnut Husk

TG and DTG curves of hazelnut husk gasification profile given in Figure 3.1 shows how
mass loss varies with increasing temperature from 110 oC up to 1100 oC at 5 °C/min under
CO2 gasification atmosphere.

Figure 3.1 TGA and DTG curves of hazelnut husk at 5 °C/min

In DTG curves, the peaks reveal the highest mass change during the process generally
arouse from the biomass components decomposition; hemicellulose, lignin and cellulose.

36
Cellulose and hemicellulose decompose the first since they contain high amount of
oxygen. Volatiles from cellulose and hemicellulose are released by the temperature
increasing after the moisture evolved. The thermal degradation can be considered as the
removal of hemicellulose, cellulose, and lignin parts after moisture release. The
dissociation of the cellulose and hemicellulose constituents of hazelnut husk can also be
named as the primary pyrolysis zone when the lignin component decompose slowly in
the secondary pyrolysis zone.

In Figure 3.1, the gasification reaction took place in 3 steps based on TG and DTG curves.
These steps are in the temperature range of 150 °C - 365 °C, 365°C - 600 °C and 600 °C
- 1100 °C in the order.

51.74 % of the initial mass loss took place in the first stage mentioned as primary
pyrolysis with the maximum loss of 2.13 %/min at 280.7 °C then it was followed by the
secondary pyrolysis stage with the mass loss of 28.41 %. In the last stage known as
gasification, 14.37 % mass decrease happened with a small peak at 680.7 °C. The
maximum loss in that stage was detected as 0.47 %. The residual mass was found to be
3.61 % which can be considered as ash at the end of the gasification. In this last stage
most of the fixed carbon separated in the hazelnut husk. Gasification range was observed
from 600 ºC to 1100 ºC. The lower temperature peak stands for the hemicellulose
component degradation, which happened via a maximum mass loss rate of 2.13 %/min.
The degradation proceeds up to a temperature of approximately 380°C. The slow
decomposition rate of the lignin ingredient starts continuing up to a temperature of about
600 °C beyond that a small mass change was observed above 380°C [95]. The mass loss
of 51.74% indicates that volatile matter is removed from the hazelnut husk. The mass loss
of 28.41% indicates that fixed carbon is removed from the hazelnut husk.

3.2.3. CO2 Gasification of Çan Lignite

TG and DTG curves of Çan lignite gasification profile in Figure 3.2 indicates the mass
loss profile against temperature which started from 110 oC up to 1100 oC at 5 °C/min
under CO2 gasification atmosphere.

37
 Figure 3.2 TGA and DTG curves of Çan Lignite at 5 °C/min
As shown in Figure 3.2., the zones were stated n the basis of slope changes found in TG
curve which were also supported by DTG curve peaks. The TGA curves for Çan lignite
under CO2 gasification atmosphere showed mainly three steps located between 150 °C
and 530°C for the first step and between 530 °C and 725 °C for the second step, and the
last gasification step between 725 °C and 1000 °C.

The TGA thermogram of Çan lignite under CO2 atmosphere is in Figure 3.2. The
observed thermal changes can be categorized into three temperature ranges. Between the
temperature range of 150 °C–530 °C, primary and secondary devolatilization occurs
during the thermal process [96]. Over 530 °C, formation and the gasification processes of
the char happen. The maximum gasification temperature is found to be ≥ 900°C for Çan
Lignite sample.

32.56 % mass loss was detected in the first stage pyrolysis. The mass loss of 32.56 %
indicates that volatile matters and other components were removed from Çan lignite. At
460.1 °C, the maximum mass loss (0.84%) of the first pyrolysis fraction occurred. 16.06
% mass loss was in the second pyrolysis stage. It is a gasification zone between 725 °C
and 1000 °C. 11.59 % of the mass loss in the last stage refers to the fixed carbon separated
in the Çan lignite, while at 802.5 °C, 0.35% to the fixed carbon loss at most. Residual
mass can be considered 38.38% as ash content.

38
3.2.4. Co-Gasification of Çan Lignite and Hazelnut Husk

TG and DTG curves of co-gasification of Çan lignite and hazelnut husk profile given in
Figure 3.3 shows how mass loss varies with increasing temperature from 110 oC up to
1100 oC at 5 °C/min under CO2 gasification atmosphere.

Figure 3.3 TGA and DTG curves of co-gasification hazelnut husk and Çan Lignite at 5
°C/min.
The TGA curves for the blend of Can lignite and hazelnut husk under CO2 gasification
atmosphere showed mainly three steps located between 150 °C and 365°C for the first
step, between 365 and 750 °C for the second step. The last step occurred between 750 °C
and 955 °C.

There are mainly three stages observed in gasification; dehydration, devolatilization and
char oxidation. The first is considered as moisture removal stage. In the second one, most
of the mass loss is caused devolatilisation of hemicellulose and cellulose resulting in char
formation. In the third stage gasification is favored by char oxidation reactions. All stages
are characterized with mass loss rate as can be detected in TG and DTG curves. 27.36 %
mass loss was in the primary pyrolysis stage. At 288.0°C, the highest mass loss
percentage (1.07%) of the primary pyrolysis occurred and this peak was originated from
the removed volatile matters of biomass sample in the blend. 34.73% mass loss was in
the secondary pyrolysis stage. At 460.1°C, the highest mass loss (0.62%) of the secondary

39
pyrolysis occurred and that expresses the removed volatile matters of coal sample in the
blend. It is a gasification zone between 750 °C - 955 °C. 15.14% mass loss in that stage
refers to the fixed carbon separated in the blend while 0.51 % maximum mass loss at
886.1 °C refers to the removal of biomass and coal fixed carbon at most . Residual mass
can be considered 21.71% as ash content.

3.2.5. Catalytic Co-Gasification of the Blend

TG and DTG curves of catalytic co-gasification of Çan lignite and hazelnut husk blend
profile given in Figure 3.4 shows how mass loss varies with increasing temperature from
110 °C up to 1100 oC at 5 °C/min under CO2 gasification atmosphere.

Figure 3.4. TGA and DTG curves of catalytic co-gasification of Çan lignite and
hazelnut husk blend at 5 °C/min
The TGA curves for catalytic co-gasification of the blend under CO2 gasification
atmosphere showed mainly four steps located between 150 °C and 360 °C for the first
step, 360 °C and 675°C for the second one, and the next between 675 °C and 805 °C. The
last step occurred between 805 °C and 905 °C.

Primary pyrolysis stage between the temperature of 150 °C and 360 °C resulted in 21.30
% mass loss with volatile decomposition. At 286.2 °C, the maximum mass loss (0.89%)
was detected. In the secondary pyrolysis stage, 24.30 % (360 °C -675 °C) of the mass was
lost since the decomposition of lignin and cellulose components of hazelnut husk at

40
459.4°C, mass loss reached to its maximum rate of 0.57 %. The mass loss of the third
stage was 4.30 %. At 726.7 °C, the highest percentage of mass loss (0.22%) of the
gasification step where fixed carbon underwent a reaction to produce syngas took place.
In the last stage, 6.93 % loss resulted mostly from the decomposition of CaCO3 which
could be attributed to the CO2 released by decomposition of CaCO3. At 876.1 °C it
reached to maximum loss with 1.38%. Residual mass of the process can be considered
42.58% as ash content.

3.3. Kinetic Analysis

The mass loss curves examined at different heating rates are thermogravimetrically
analyzed to specify the kinetic parameters effect on the conversion (α).
The non-isothermal kinetics of mass loss during the gasification of hazelnut husk, Turkish
lignite, blend of hazelnut husk with Turkish lignite and catalytic co-gasification in CO2
environment between the temperature range of 600 °C - 960 °C were assessed by using
FWO method by using the thermokinetic software (Kinetix.3) combined with the
instrument.

3.3.1. CO2 Gasification of Hazelnut Husk

3.3.1.1.Friedman Method

Figure 3.5 shows Friedman iso-conversional curves for CO2 Gasification of hazelnut husk.

Figure 3.5 The iso-conversional curves of Friedman method for hazelnut husk

41
The corresponding activation energy versus fractional mass loss values are listed in Table
3.4.

Table 3.4. Friedman Method for hazelnut husk gasification

Fraction Mass loss Activation Energy(kj/mol)
0.10 334.76
0.20 279.45
0.30 260.24
0.40 249.38
0.50 158.09
0.60 62.96
0.70 20.95
0.80 36.51
0.90 112.67

The results of Friedman method for hazelnut husk gasification were studied in three
stages. The first stage average activation energy from 0.10 to 0.50 fraction mass loss is
about 256.38 kJ/mol, where primary pyrolysis takes place. In the second stage, which is
considered secondary pyrolysis, the average activation energy is 41.96 kJ/mol, where the
conversion factor is from 0.60 to 0.70. In the final stage, referred as gasification reaction,
the average activation energy for conversion factor from 0.80 to 0.90 is about 74.59
kJ/mol.

3.3.1.2.Flynn Wall Ozawa Method

Figure 3.6 shows FWO iso-conversional curves for CO2 Gasification of hazelnut husk.

(a)

42
 (b)
Figure 3.6 The iso-conversional curves of FWO method for hazelnut husk (a), (b)

The corresponding activation energy versus fractional mass loss values are listed in Table
3.5.

Table 3.5 FWO Method for Hazelnut Husk gasification

Fraction Mass loss Activation Energy(kj/mol)
0.10 251.72
0.20 207.23
0.30 198.60
0.40 198.72
0.50 153.21
0.60 78.84
0.70 44.56
0.80 33.23
0.90 53.32

The results of FWO method for hazelnut husk gasification were studied in three stages.
The corresponding average activation energy in the first primary pyrolysis stage for the
conversion factors from 0.10 to 0.50 is about 201.89 kJ/mol. In the second stage, which
is considered secondary pyrolysis from 0.60 to 0.70 conversion factor, the average
activation energy is 61.70 kJ/mol. In the final stage, where gasification reactions take
place, the average activation energy for conversion factor from 0.80 to 0.90 is about 43.28
kJ/mol.

43
3.3.2. CO2 Gasification of Çan Lignite
3.3.2.1.Friedman Method

Figure 3.7 shows Friedman iso-conversional curves for CO2 Gasification of Çan Lignite.

Figure 3.7 The iso-conversional curves of Friedman method for Çan Lignite

Table 3.6 reveals the corresponding activation energy versus fractional mass loss values.

Table 3.6 Friedman Method for Çan Lignite gasification

Fraction Mass loss Activation Energy(kj/mol)
0.10 116.19
0.20 72.08
0.30 73.35
0.40 3.33
0.50 3.68
0.60 8.93
0.70 36.89
0.80 72.11
0.90 112.33

There have been three stages for Çan lignite gasification process with Friedman kinetic
method. Average activation energy was computed as 87.20 kJ/mol for conversion factors
from 0.10 to 0.30 of the first primary pyrolysis. This value in the second stage, where the
conversion factor is from 0.40 to 0.50, average activation energy is 3.51 kJ/mol. In the
gasification stage, the average activation energy for conversion factor from 0.60 to 0.90
is about 57.57 kJ/mol.

44
3.3.2.2.Flynn Wall Ozawa Method

Figure 3.8 shows FWO iso-conversional curves for CO2 Gasification of Çan Lignite

(a)

(b)
Figure 3.8 The iso-conversional curves of FWO method for Çan Lignite (a), (b)

The corresponding activation energy versus fractional mass loss values are listed in Table
3.7.

45
Table 3.7. FWO Method for Çan Lignite gasification
Fraction Mass loss Activation Energy(kj/mol)
0.10 116.80
0.20 86.04
0.30 79.77
0.40 54.01
0.50 32.35
0.60 24.20
0.70 27.80
0.80 40.14
0.90 64.99

The results of FWO method for Çan lignite were studied in three stages. The first stage
conversion fraction range is from 0.10 to 0.30, and the average activation energy is about
94.20 kJ/mol, Second stage average activation energy is 43.18 kJ/mol for the conversion
factor from 0.40 to 0.50. In the final stage, mass loss fraction starts from 0.60 and the
average activation energy is about 39.28 kJ/mol.

3.3.3. CO-Gasification of Çan Lignite and Hazelnut Husk

3.3.3.1.Friedman Method

Figure 3.9 shows Friedman iso-conversional curves for the Co-gasification of Çan
Lignite and Hazelnut Husk.

Figure 3.9 The iso-conversional curves of Friedman method for co-gasification of blend

The corresponding activation energy versus fractional mass loss values are listed in
Table 3.8.

46
Table 3.8. Friedman Method for co-gasification of blend
Fraction Mass loss Activation Energy(kj/mol)
0.10 304.92
0.20 296.29
0.30 182.14
0.40 94.14
0.50 28.55
0.60 19.35
0.70 40.16
0.80 97.35
0.90 138.62

The results of Friedman method for co-gasification of blend have been studied in three
stages. The kinetic parameters, the average activation energy for the first stage where
mass conversion fraction is from 0.10 to 0.30, are about 261.11 kJ/mol. In the secondary
pyrolysis stage, the average activation energy is 47.34 kJ/mol, between the selected
conversion range of 0.40 and 0.60. In the final stage, the average activation energy for
conversion factor from 0.70 to 0.90 is about 92.04 kJ/mol.

3.3.3.2.Flyn Wall Ozawa Method

Figure 3.10 shows FWO iso-conversional curves for the CO-Gasification of Çan Lignite
and Hazelnut Husk.

(a)

47
 (b)

Figure 3.10 The iso-conversional curves of FWO method for co-gasification of blend
(a), (b)

The corresponding activation energy versus fractional mass loss values are listed in Table
3.9.

Table 3.9. FWO Method for co-gasification of blend

Fraçction Mass Activation Energy(kj/mol)
loss
0.10 244.29
0.20 240.41
0.30 186.39
0.40 108.42
0.50 68.38
0.60 38.80
0.70 34.73
0.80 52.56
0.90 85.78

The results of FWO method for co-gasification of blend have been studied in three stages.
The first stage, where primary pyrolysis takes place, the average activation energy for
conversion factor from 0.10 to 0.30 is about 223.69 kJ/mol. In the second stage, which is
considered secondary pyrolysis, where the conversion factor is from 0.40 to 0.60, the
average activation energy is 71.86 kJ/mol. In the final stage, where gasification reactions
take place, this value from conversion factor from 0.70 to 0.90 is about 57.79 kJ/mol.

48
3.3.4. Catalytic CO-Gasification of the Blend
3.3.4.1.Friedman Method

Figure 3.11 shows Friedman iso-conversional curves for the catalytic co-gasification of
the blend

Figure 3.11 The iso-conversional curves of Friedman method for catalytic co-
gasification of blend

The corresponding activation energy versus fractional mass loss values are listed in
Table 3.10.

Table 3.10 Friedman Method for catalytic co-gasification of blend

Fraction Mass loss Activation Energy(kj/mol)
0.10 162.65
0.20 121.18
0.30 70.73
0.40 35.19
0.50 22.23
0.60 15.42
0.70 17.09
0.80 32.00
0.90 413.00

The results of Friedman method for catalytic co-gasification of the blend have been
studied in four stages. The first stage, where primary pyrolysis takes place, the average
activation energy for conversion factors from 0.10 to 0.20 is about 141.92 kJ/mol, while
for the secondary pyrolysis stage, it is 42.71 kJ/mol for the conversion factor from 0.30

49
to 0.50. For the third stage, where first of gasification process takes place, 15.42 kJ/mol
average activation energy is calculated for the conversion factor of 0.60. In the final
gasification stage, the average activation energy for conversion factor from 0.70 to 0.90
is about 154.03 kJ/mol.

3.3.4.2.Flyn Wall Ozawa Method

Figure 3.12 shows FWO iso-conversional curves for the catalytic co-gasification of blend.

(a)

(b)
Figure 3.12 The iso-conversional curves of FWO method for catalytic co-gasification of
blend

50
The corresponding activation energy versus fractional mass loss values are listed in
Table 3.11.
Table 3.11 FWO Method for catalytic co-gasification of blend
Fraction Mass loss Activation Energy(kj/mol)
0.10 164.01
0.20 122.31
0.30 71.52
0.40 35.55
0.50 22.45
0.60 15.50
0.70 17.20
0.80 32.59
0.90 426.86

The results of FWO method for catalytic co-gasification of the blend have been studied
in four stages. The first stage, where primary pyrolysis takes place, the average activation
energy for conversion factors from 0.10 to 0.20 is about 143.16 kJ/mol, while for the
secondary pyrolysis stage, it is 43.17 kJ/mol for the conversion factor from 0.30 to 0.50.
For the third stage, where first of gasification process takes place, 15.50 kJ/mol average
activation energy value is calculated for the conversion factor of 0.60. In the final
gasification stage, the average activation energy for conversion factor from 0.70 to 0.90
is about 158.88 kJ/mol.

3.4. Gasifier Modelling with ASPEN Plus

3.4.1. Assumptions

In this study, CFB gasifier model was operated in Aspen Plus programme. The
gasification is depend upon minimizing Gibbs free energy. The process is thought to reach
chemical equilibrium from the point of thermodynamics as the Gibbs minimization. The
assumptions about the gasification process are given as:

 Steady state and isothermal

 Thermolysis reactions reach the chemical equilibrium quickly.
 Ash doesn’t take place in reactions.
 Char includes carbon and ash.
 Heavy hydrocarbons and tar are neglected.
 Feedstock devolatilization products mainly involve CH4, CO, H2O, H2 and CO2,

51
3.4.2. Fluidized Bed Gasifier Model Development
The steady-state simulation of the catalytic gasification process in the CFB gasifier was
executed in Aspen Plus® V11. Besides, the Soave-Redlich-Kwong (SRK) state equation
was chosen with STEAMNBS as the free-water method. The Aspen Plus simulation
design for the catalytic gasification process in CFB gasifier is demonstrated in Fig. 3.13.

Figure 3.13 The model flowsheet of developed circulating fluidized bed gasifier
The gasification process mainly splitted into three zones that are pyrolysis, gasification,
and combustion. The “CANCOAL” and “HAZLHUSK” streams identify the “non-
conventional solid” coal and biomass feed. Elemental and proximate analysis for biomass
and coal are utilized as feedstock. The mixer was used fort the feding of feedstock
streams. The characterized coal and biomass feed enter the yield reactor called
"DECOMP" and converts into conventional volatile matters (H2, CO2, CO, H2O, tar and
CH4,) and solids (carbon and ash). This reactor may be considered to represent the
primary pyrolysis of carbon-based fuel. The fuel gives a reaction by the gasifying agent
(CO2) that comes from the separator “CO2SPLT” stream in the “RGibbs” reactors
“GSFR1” and “GSFR2“. It can be assumed that secondary pyrolysis occurs in the reactor
"GSFR1" after the "DECOMP" reactor. The “GSFR2” block is an “RGibbs” reactor,
where the gasification reactions of volatile matters and solids are dominant. However, it
should be noted that for “RGibbs” reactors, these reactors determine the products to be
released with minimization of Gibbs free energy using the reactants at the specified

52
temperature and pressure. The reason for saying that they represent pyrolysis or
gasification zones is that we can manipulate the composition of the products to be formed
by adjusting the temperature of the reactors and the feed rate of gasification agent. Ash
and unburned carbon sent to combustion reaction while the “RGibbs” reactor that named
as “COMBUSTR”. Solid particles are holded, and the gas is separated in the cyclone. The
first reactor products are splitted into a certain rate and prevented from feding into the
second reactor in the “SEP1” separator. In the “SEP2” separator, ash and unconverted
carbon are separated and fed into the reactor for combustion. The outlet gas, which is
substantially free of solid particles in the cyclone, proceeds to the separator called
"WATSEP". Table 3.12 gives a brief clarification about the blocks.

Table 3.12 Definition of blocks in the CFB gasifier model

Block Name Aspen Plus® ID Description

Decomposes unconventional
solid feedstock into
DECOMP RYIELD
conventional components by
using the calculator block

GSFR1 Minimizes the Gibbs free

RGIBBS energy and simulates whole
GSFR2
gasification reactions

Minimizes the Gibbs free

COMBUSTR RGIBBS energy and simulates
combustion reactions

CO2SPLT Dispenses streams

FSPLIT homogenously into desired
SPLIT1
blocks

Combines streams into a single

MIXFEED MIXER
stream

Removes solid particles from

CYCLONE CYCLONE
gas

Separator of the CO (100 %),

SEP1 SEP
CO2 (60 %) and CH4 (85 %)

Separator of the solid particles

SEP2 SEP
(C and Ash)

WATSEP SEP Separator of the H2O (100 %)

53
3.4.3. Model Validation
3.4.3.1. Validation OF Fluidized Bed Gasifier

Different experimental studies in the literatüre were taken from like input variables,
operating conditions and synthesis gas compositions to validate the developed model. A
comparison of syngas compositions in experimental studies and simulation results is
given in Table 3.13, Table 3.14, Table 3.15 and Table 3.16.

Table 3.13 The comparison of the experimental studies from the new developed model
and the literature for coal [97] , [98]

54
Table 3.14 The investigation of the experimental studies from the new developed model
and the literature for biomass[99] , [100]

Table 3.15 The investigation of the experimental studies from the new developed model
and the literature for biomass & coal mixture [101] , [102]

55
Table 3.16 The investigation of the experimental studies from the literature and the new
developed model for catalytic gasification [103] [104]

The results for the model effectively show resemblance with the studies from literature
as can be seen in tables. The Gibbs reactors used in the simulation program assume that
reactions happen fast and reach chemical equilibrium conditions, whereas, in
experimental studies, conversion rates of reactions vary depending on the residence time.
Therefore, CH4 may be various in some experiments since the reaction times are not
enough for reaching equilibrium conditions in experimental works. The model results are
acceptable to apply in fluidized bed gasification processes.

3.4.4. Parametric Study

The gasifier pressure and temperature effects as well as the influence of CO2/fuel ratio on
the syngas composition have been researched by parametric studies to evaluate the
gasification characteristic properties of hazelnut husk and Çan lignite in the CFB gasifier.
Çan lignite and hazelnut husk and were given individually to the gasifier as feedstock and
optimal conditions were assigned for each of them. Then, the fuels (50% hazelnut husk,
50% Çan lignite) were fed at the same time for co-gasification and lastly the same
processes were done again with CaO catalysis.

56
3.4.4.1. Effect of Gasifier Temperature on Syngas Composition

The gasifier temperature influence on the syngas composition for hazelnut husk, Çan
lignite and its blend are shown in Figure 3.14. The temperature of gasifier is between 600
°C - 1100 °C, the CO2 / fuel ratios are 0.65 for hazelnut husk, 0.25 for Çan lignite and
0.45 for their blend and the gasifier pressure is 3 bars.

(a)

(b)

57
 (c)

Figure 3.14 The effect of gasifier temperature on syngas composition; (a) hazelnut husk
(b) Çan Lignite (c) hazelnut husk & Çan Lignite Blend

One of the behaviors clearly seen in the Figure 3.14 is that when the gasifier temperature
enhances, the CO composition rises, and the CO2 composition reduces. This can be
explained by the driving forward of the Boudouard reaction. However, when the gasifier
temperature reaches at a certain point syngas composition change rate by temperature
decreases. These temperatures were 760 °C for hazelnut husk, 720 °C for Çan lignite and
750 °C for the blend.

3.4.4.2. Effect of Gasifier Pressure on Syngas Composition

The pressure of the gasifier has major effect on the syngas composition change. The
pressure was changed from 1 bar to 20 bar to analyze the gasifier pressure effect on the
syngas composition. The temperature in the gasifier is constant at 760 °C for hazelnut
husk and 720 °C for Çan lignite and 750 °C for the blend. The gasifier pressure effect on
the syngas composition can be seen in Figure 3.15.

58
(a)

(b)

59
 (c)

Figure 3.15 Gasifier pressure influence on syngas composition a) hazelnut husk (b) Çan
Lignite (c) hazelnut husk & Çan Lignite blend

When a dynamic equilibrium is varied with a disturbing factor in accordance with the Le
Chatelier principle, the system goes to the direction for minimizing this effect. The
gasifier pressure changes the reactions direction and changes the syngas composition,
because gasification reactions are also equilibrium reactions. When the gasifier pressure
increasing, the amounts of H2 and CO gases reduces and the amounts of CO2 and CH4
gases rises. The decrease in H2 gas concentration and the increase in CH4 gas
concentration is based on the methane formation reactions, and the reduction in CO gas
composition and enhancement in CO2 composition can be clarified by Boudouard
reaction. Only CH4 composition improves the valuable chemicals at high pressure, thus
the system pressure is needed to be setted with this factor is considered.

3.4.4.3. Effect of CO2/Fuel Ratio on Syngas Composition

The determination of the CO2/fuel ratio is significant to obtain CO efficiently in the last
of the gasification process. The influence of CO2/fuel ratio on syngas composition can be
seen in Figure 3.16. The ratio ranges from 0.1 to 2 and the pressure of the gasifier is
constant at 3 bars and the temperature of the gasifier is constant at 760 °C for hazelnut
husk, 720 °C for Çan lignite and 750 °C the blend.

60
(a)

(b)

61
 (c)

Figure 3.16. The effect of CO2/fuel ratio on syngas composition; (a) hazelnut husk (b)
Çan Lignite (c) hazelnut husk & Çan Lignite blend

The decreasing behaviour of H2 concentration as the CO2 / fuel ratio increases can be
expressed by the water gas shift reaction driving in the reverse direction due to the
increased amount of carbon dioxide. Moreover, the increase in CO fraction until the CO2
/ fuel ratio reaches a certain point can also be associated with the water gas reaction. This
ratio was 0.45 for hazelnut husk, 0.2 for Çan lignite and 0.35 for the blend. On the
contrary, the concentration of the components in the syngas cannot be explained only by
the reactions. The concentration of CO2 in the syngas rises as the amount of CO2 fed into
the reactor enhances.

3.4.4.4. Effect of Temperature on Syngas Composition in Catalytic Gasification

The catalyst effect on the syngas composition is given in Figure 3.17. The ratio of
CaO/fuel is 0.25 for hazelnut husk, 0.5 for Çan lignite and 0.35 for the blend, and the
temperature of the gasifier ranges from 600 °C to 1100 °C and pressure of the gasifier is
constant at 3 bars.

62
(a)

(b)

63
 (c)

Figure 3.17 Temperature effect on syngas composition in catalytic gasification; (a)

hazelnut husk (b) Çan Lignite (c) hazelnut husk & Çan Lignite blend

The H2 composition is found higher between the 600 °C - 800 °C when the catalyst is fed
into the gasifier. In the utilization of CaO catalyst for gasification, H2 formation at
temperatures lower than 800 °C indicates a great enhancement. The reactions occurred
for increasing the concentration of H2 gas due to the adsorption characteristic properties
of the CaO catalyst on the CO2. However, the H2 gas concentration depicts an important
reduce, because CaO, that holds the CO2 and turns into CaCO3, decomposes at high
temperatures and emittes CO2 gas into the gasifier when the temperature enhances,
especially after 800 °C. H2 gas generation at gasification temperatures lower than 800 °C
shows a large improvement in the utilization of CaO catalyst. Because of the adsorption
characteristics of the CaO catalyst on the CO2 gas, the reactions occur in order to enhance
the H2 gas concentration. Nevertheless, the H2 gas concentration indicates an important
decrease with the temperature increases, especially after 800 °C, since CaO, which holds
the CO2 gas and turns into CaCO3 form, breaks down at high temperature and releases
CO2 gas into the gasifier backwardly. CaO catalyst does not contain any side effect at
high temperatures. The fast increase observed by CO and CO2 gases can be elucidated by

64
the complex reactions series in the gasifier with ignoring the catalytic effect. CaO catalyst
has no effect at high temperatures.

3.4.4.5. Effect of CaO/Fuel Ratio on Syngas Composition

The CaO amount affects the cost and thermodynamic properties in the gasification
operation. Parametric study was conducted for finding the ideal CaO/fuel ratio. Gasifier
pressure is fixed at 3 bar, CO2/fuel ratio and temperature are at maximum CO fraction for
all fuels.

(a)

65
 (b)

(c)

Figure 3.18 The effect of CaO/fuel ratio on syngas composition; (a) hazelnut husk (b)
Çan Lignite (c) hazelnut husk & Çan Lignite blend

It was concluded that the enhancement of the CaO / fuel ratio from 0.05 to 1.25 enhanced
the H2 gas composition in the synthesis gas. There was not observed any important rise

66
in composition of H2 after then the CaO / fuel ratio overran a certain point. This ratio was
0.25 for hazelnut husk, 0.5 for Çan lignite and 0.35 for the blend.

67
4. CONCLUSION

In this thesis, the assessment of the theoretical and experimental investigation co-
gasification and catalytic co-gasification are discussed, and operating conditions effect
on gas composition was investigated. In accordance with the data acquired:

 Thermogravimetric analysis is useful to produce data that contributes to the

interpretation of the gasification reactions and to study the characteristics of
biomass gasification, coal gasification and co-gasification of blend and catalytic
co-gasification of blend samples.
 Biomass sample (hazelnut husk) has much higher volatile matter and much lower
fixed carbon and mineral matter content compared to coal sample (Çan Lignite)
resulting in different thermolysis behavior of the latter.

 TG and DTG profiles of hazelnut husk gasification, Çan Lignite gasification, co-
gasification of blend and catalytic co-gasification of blend were examined in the
thermal analysis results, it was observed that the catalytic co-gasification process
consisted of four stages, while the other gasification processes show three stage.
 The FWO method kinetic analyses by using corresponding activation energy and
against fractional mass loss indicate similar kinetic trends with and Friedman
method investigation despite some variations in apparent activation.
 The highest Ea was calculated in the first stage of co-gasification of blend by both
Friedman and FWO methods, while the lowest Ea value was observed by
Friedman and FWO method in the second and third stage, respectively.
 The highest Ea was calculated in the fourth stage of catalytic co-gasification of
blend by both Friedman and FWO methods, while the lowest Ea value was
observed in the third stage.
 Modeling-based techniques ensure cost-effective and alternative access by
comparison with the experimental studies to design and optimize to any complex
system. Aspen plus process simulation software is beneficial for designing and
optimization of system parameters.
 In this study, Aspen Plus simulation is thought to arrive chemical equilibrium
with regards to thermodynamic approach.

68
 Methane formation reactions do not reach equilibrium in real processes, but the
model reach equilibrium rapidly.
 When the gasifier temperature and the CO composition enhances, and the CO2
composition reduces, the gasifier temperature ranges from 600 °C to 1100 °C.
This can be clarified by the driving forward of the Boudouard reaction. However,
when the gasifier temperature reaches at a certain point syngas composition
change rate by temperature decreases. These temperatures were 760 °C for
hazelnut husk, 720 °C for Çan lignite and 750 °C for the blend.
 The pressure values were changed between 1 bar and 20 bar. The concentrations
of H2 and CO gases reduce and CH4 and CO2 compositions enhance while the
gasifier pressure rises. As a result, it was seen that operating at lower pressures
was more suitable.

 The decreasing behaviour of H2 concentration as the CO2 / fuel ratio increases

can be explained by the water gas shift reaction driving in the reverse direction
due to the increased amount of carbon dioxide. It was determined that this ratio
was 0.45 for hazelnut husk, 0.2 for Çan lignite and 0.35 for the blend. As the
amount of CO2 fed into the reactor increases, the concentration of CO2 in the
syngas increases.

 The H2 formation in the system reaches the highest level between 600 °C to 800
°C in presence of catalysts. The rapid increase of CO and CO2 concentrations can
be elucidated by the lost catalytic effect and the complex reactions.
 It was observed that H2 gas concentration in the synthesis gas increased when the
CaO/fuel ratio enhanced from 0.05 to 1.25, the. After the CaO/fuel ratio exceeded
a certain point, significant rise in H2 gas concentration was not observed. This
ratio was 0.25 for hazelnut husk, 0.5 for Çan lignite and 0.35 for the blend.

69
CURRICULUM VITAE

Name Surname :Beyzanur ÖZTÜRK

Place of Birth :Akyazı, SAKARYA

Date of Birth :26.07.1994

Education

High School :2007-2011, Adapazarı Anadolu İmam-Hatip High School

Bachelor :2011-2015 Selcuk University Chemical Engineering

Department

Foreign Language :English.

Work Experience

2018 - ……. : Quality Assurance Assisant Specialist – Neutec Inhaler İlaç

San.Tic.A.Ş.

70
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