State of Libya

Sabratha University
Faculty of Engineering - Sabratha
Chemical Engineering Department

Process simulation and analysis of waste tire

gasification plant

The Thesis was submitted in partial fulfillment of the requirement for the
Bachelor of science in chemical engineering

Submitted by
Hamam Mohammed Farag
Mazen Farhat Alamory

Supervised by
Mr. Foad Rajab

2022 - 2023
 ‫إهدإء‬
‫ى‬
‫المصطف عليه أفضل صالة‬ ‫الحمد هلل والصالة والسالم عىل الحبيب‬
‫وسالم أما بعد‪:‬‬

‫مسيتنا الدراسية ى يف‬ ‫ى‬

‫الحمد هلل الذي وفقنا للوصول لهذه الخطوة يف ر‬
‫َّ‬
‫ومشقة‪.‬‬ ‫المرحلة الجامعية إىل نهايتها بعد تعب‬
‫همة ونشاط‪ ،‬ممت ىُّ‬
‫ني لكل من كان له‬ ‫تخرجنا بكل َّ‬
‫وها نحن نختم بحث ُّ‬
‫ر‬
‫المستني لمن كان معنا‬ ‫السية العطرة‪ ،‬والفكر‬ ‫ى‬
‫ر‬ ‫مسيتنا‪ ،‬ألصحاب ر‬
‫فضل يف ر‬
‫باليسي‪.‬‬
‫ر‬ ‫وساعدنا ولو‬

‫العاىل (والدينا األحبة)‪ ،‬أطال‬ ‫التعليم‬ ‫بلوغنا‬ ‫ف‬ ‫األول ى‬

‫لمن كان له الفضل َّ‬
‫ي‬ ‫ي‬
‫هللا ى يف ُعمرهم ورحم من فارقنا‪.‬‬

‫إىل من وضعتننا عىل طريق الحياة إىل من وضع الموىل ‪ -‬سبحانه وتعاىل ‪-‬‬
‫َّ‬
‫الجنة تحت قدميها‪ ،‬و وقرها ى يف كتابه العزيز (أمهاتنا الحبيبات)‪.‬‬

‫كثي من العقبات والصعاب‪.‬‬ ‫ى‬

‫إىل إخوتنا؛ من كان لهم بالغ األثر يف ر‬

‫صياتة؛ ممن لم يتوانوا‬ ‫ى‬

‫إىل جميع أساتذتنا الكرام يف كلية الهندسة بجامعة ر‬
‫ى يف مد يد العون‪.‬‬
‫ُّ‬
‫نجلهم ون ر‬
‫حيمهم‪.‬‬ ‫إىل كل األصدقاء والمعارف الذين‬

‫نهدي لكم بحثنا‬

 ‫شكر وتقدير‬
‫األخية ى يف الحياة الجامعية من وقفة نعود‬
‫ر‬ ‫ال بد لنا ونحن نخطو خطواتنا‬

‫إىل أعوام قضيناها ى يف رحاب الجامعة مع أساتذتنا الكرام الذين قدموا لنا‬

‫كبية ى يف بناء جيل الغد‪.‬‬ ‫الكثي ر ى‬

‫باذلي جهود ر‬ ‫ر‬

‫نقدم أسىم آيات الشكر واالمتنان والتقدير والمحبة إىل الذين حملوا‬

‫أقدس رسالة ى يف الحياة إىل الذين أناروا لنا طريق العلم والمعرفة إىل جميع‬

‫صياتة‪.‬‬
‫أساتذتنا األفاضل بكلية الهندسة بجامعة ر‬

‫نتوجه بالشكر الجزيل إىل الذين تفضلوا ر‬

‫باإلشاف عىل هذا البحث جزاهم‬

‫الخي فلهم منا كل التقدير‪.‬‬

‫هللا عنا كل ر‬

‫االستاذ‪ /‬فؤاد رجب‬

‫االستاذ‪ /‬عبدالباري الحراري‬

 Abstract

Gasification is a thermochemical pathways used to convert carbonaceous feedstock

into syngas (CO and H2) in deprived oxygen environment. The process can
accommodate conventional feedstock such as coal as well as discarded waste
including plastics, rubber, and even municipal solid waste (MSW) due to the high
reactor temperature.

The purpose of this study is to provide a modelling and simulation framework to

analyze the technical potential of treating waste tires for the syngas production and
quality. Moreover, the sensitivity analysis was conducted to investigate the effect of
the key operating parameter on the process performance. Air-gasification of wastes
tier in a gasifier was successfully modelled based on minimization of Gibbs free
energy using Aspen Hysys.

The results show that the temperature should be between 750 – 950°C, air-fuel ratio
should be between 1.35 – 1.51. Furthermore, the plant considered to be profitable,
where the capital cost was found to be 71,354 $ and the payback period is within 3
months.

I
 TABLE OF CONTENTS

Abstract I
List of Tables II
List of Figures III
Abbreviations IV
CHAPTER ONE: INTRODUCTION
1.1 Introduction 1
1.2 Problem statement 3
1.3 Objective 3
CHAPTER TWO: LITERATURE REVIEW
2.1 Waste tire problem 5
2.1.1. Waste tire generation 5
2.1.2. Disposal of waste tires 5
2.1.3. Current methods for treating waste tires and their challenges 6
2.2 Tire composition 7
3.2.1. Constituents of a tire 7
2.2.2. Characterization of a tire 11
2.3. Pyrolysis of waste tires 12
2.3.1. Definition of waste tire pyrolysis 12
2.3.2. Waste tire pyrolysis products 12
2.3.3. Valuable chemicals from pyrolysis oil 15
2.3.4. Waste tire pyrolysis economics 16
CHAPTER THREE: PROCESS DESCRIPTION & SIMULATION
SETUP
3.1 Simulation basis manager 19
3.1.1 Characteristics of waste tire 19
3.1.2 Fluid package 20
3.1.3 Reaction chemistry 20
3.2 Model construction 21
3.2.1 Assumptions 21
3.2.2 Air separation unit modelling 22
3.2.3 Pre-treatment (Grinding and Drying) Modelling 22
3.2.4 Modelling of pyrolysis and combustion zone 22
3.2.5 Modelling of gasification zone 22
3.2.6 Modelling of solid separation section 22
3.2.7 Modelling of Syngas Cooling 22
CHAPTER FOUR: RESULT AND DICUSION
4.1 Model application 26
4.1.1 Effect of gasifier temperature 26
4.1.2 Equivalence ratio (ER) 30
4.2 Hand calculation 32
4.2.1 Maas and energy balance 32
4.2.2 Design of heat exchanger 33
CHAPTER FIVE: PROJECT EVALUATION
5.1 Overview 42
5.2 Cost Estimation 42
5.3 Cost of Materials 43
5.4 Utility Costs UC 44
5.5 Fixed Operation Costs FOC 44
CHAPTER SIX: CONCLUSION RECOMMENDATIONS
6.1 Conclusion 47
6.2 Recommendation 48
References & Appendix
 List of Tables
Table 2.1: Several methods used for treating waste tires 6
Table 2.2: Typical elements of a tire and their constituent materials 7
Table 2.3: Typical composition of passenger and truck tires 9
Table 2.4: Constituents of a particular tire formulation 10
Table 2.5: Constituents of a specific tire formulation 10
Table 2.6: Typical proximate analysis of a waste tire 11
Table 2.7: Typical ultimate analysis of a waste tire 11
Table 2.8: Yield of BTX, ethylbenzene, styrene and limonene at 500 °C. 15
Table 3.1: Tire proximate and ultimate analysis 19
Table 3.2: Gasification reactions and their kinetic parameters 20
Table 4.1: Stream specifications 32
Table 4.4: Cost of raw material and products 43

II
 List of Figures
Figure 2.1: Various components that make up a tire 8
Figure 2.2: Schematic of a typical waste tire pyrolysis system 12
Figure 2.3: True boiling point curve of TDO obtained at 500 °C 14
Figure 3.1: Simplified process flow diagram of a waste-based polygeneration facility. 21
Figure 3.2: Process flow diagram of waste tire gasification using Aspen HYSYS 24
Figure 4.1: Variation of syngas yield with gasifier temperature 27
Figure 4.2: Variation of syngas composition with gasifier temperature 27
Figure 4.3: Variation of syngas LHV with gasifier temperature 29
Figure 4.4: Variation of CGE% with gasifier temperature 29
Figure 4.5: Variation of syngas composition with oxygen flowrate 30
Figure 4.6: Variation of heating value of syngas with oxygen flowrate 31

III
 ABBREVIATIONS
GHG Greenhouse gases
IGCC Integrated Gasification Combined Cycle
USA States of America
EU European Union
CB Carbon black
SBR Styrene butadiene copolymer
NR Natural rubber
PBD Polybutadiene rubber
CPR Chloroprene rubber
NTR Nitrile rubber
TT Truck tires
PCT Passenger car tires
BR Butadiene copolymer
BTX Benzene, toluene and xylene
PR Peng Robinson
WT Waste tire
ASU Air separation unit
AFR Air-fuel ratio
LHV Lower heating value
HHV Higher heating value
CGE Cold gas efficiency
ER Equivalence ratio
SBM Simulation Basis Manager

IV
CHAPTER ONE
INTRODUCTION
1.1 Introduction
Human development while sounds positive, unfortunately it comes at environmental
and ecological hurdles; augmentation and stockpile of waste, raise in CO2 and other
greenhouse gases (GHG) emission, strain in energy-water-food resources are amongst
these costs. Recycling, reusing and reducing is an early intellectual practice to lessen the
societal trans-developments impact while paying more attention to the finiteness of
resources. For example, making of the wheel have carried civilization following the
other, but less emphasis was put into its disposal until recently. Used tires besides being
unsightly and taking up valuable land space, their illegal dumps and stockpiles raise
many environmental concerns. It is estimated that annual worldwide generation of
discarded tire is over 1.2 billion with only fraction is re-treaded, granulated or subjected
to energy recovery while the majority being openly incinerated, dumped or stockpiled.
In US it is estimated that one tire is generated per capita annually (i.e. over 300M) and
the current stockpiles is estimated to be more than 1.5 billion. In Japan around 100M is
generated annually and in Australia is about 18M with over one year of stockpile for
both countries. In Europe, in a study by the European Union in 2002 an estimate of
250M tires were disposed and with over 3 billion were stockpiled. Tire is a composite
mix of many chemical components including natural rubber, polypropylene,
polystyrene, anti-oxidants, inorganic stabilizer, carbon black, silicate, fabric, nylon,
aramid, and steel in addition to the volcanizing Sulphur. Pyrolysis, following shredding
and metal stripping, into liquid oil, gas, and metal streams as well as a reasonable grade
of active carbon still facing many technical challenges. It is due to the low temperature
in which a mixed paraffin, aromatics, raisins, and asphaltine are coexist within the
liquid cuts. Also similar impurities exist within the gaseous stream with presence of
Sulphur dioxins at large proportion to syngas (CO and H2). Further distillation and gas
separation which are thermally driven processes which lowers the overall process
metrics. Alternatively gasification at higher temperature to a single stream of syngas
that ensures complete feedstock conversion and narrower syngas mix renders the
process higher metrics [1].

Gasification is a core technology that can be utilized broadly to generate energy without
polluting the environment. Because of its many applications, it is currently enjoying a
considerable renaissance. Gasification is one of a thermo-chemical conversion process

1
which can be used to produce clean fuels. Gasification is compatible with new
applications in the area of biomass conversion to produce clean energy that can be
incorporated in Integrated Gasification Combined Cycle plants (IGCC) for electricity
generation [1].

Using the gasification process, a wide range of carbonaceous material can be converted
into high value fuel. The range covers from coal, biomass and municipal / agricultural /
industrial waste including discarded tires. The product of gasification is normally
composed of syngas that is a mixture of hydrogen and carbon monoxide. The
production of syngas using gasification is a complex process that is based on several
factors including the composition of feedstock, the gasifier temperature/pressure and the
amount of oxidizer and moderator. The process of gasification utilizes the partial
combustion of feedstock by carefully controlling the amount of oxidizer. The amount of
oxidizer also controls the temperature of the gasification process that is the most
important parameter of gasifier, as reported by Walawender [3].

The chemical and physical phenomena that occur during gasification of tire crumbs are
essentially similar to a typical carbonaceous material subjected to thermal
decomposition. This includes drying, devolatilization (which includes release of volatile
flammable gases, flaming combustion of the volatiles, and glowing combustion of fixed
carbon), heat conduction, fissuring, shrinkage, and fragmentation of solid particles. The
chemical reactors used in the gasification process are distinguished by the concurrent
flow of feedstock and gasifying agent [2].

Numerical simulations are necessary to help in finding out feasible operating conditions
to achieve better process performance. In this research the simulation of waste tire
gasification process was carried out using Aspen HYSYS as a simulation tool due to its
capability on the solids handling. Moreover, it includes particular physical property
model and accurately represents the solid particle.

2
1.2 Problem statement

The rapid increase in vehicle usage since the past two decades results in the generation
of waste tires to an alarming rate. Around 2,600,000 metric tons of used tires were
produced in the European Union in the year 2000, while only a small percentage of
these waste tires goes to reuse [1]. At the moment, the most frequent option for this
waste solid removal is land filling which causes environmental and hygiene problems.
Furthermore, land filling is a potential danger because of the possibility of accidental
fires with high emissions of hazardous gases. A better alternative is their employment as
substituting fossil fuels in some industries like cement industry. But the complex nature
of the tires and the stringent environmental regulation makes it difficult to recycle
through incineration. Nowadays, gasification is a commonly used technology for
extracting the energy from solid materials like coal, coke, biomass, scrap tires, etc. This
technology can make use of the high energy content of the tires. These solid materials
are gasified to produce a gas containing mainly carbon monoxide and hydrogen. The
gases can be utilized in gas turbines of Integrated Gasification Combined Cycle (IGCC)
systems. The use of hydrogen in fuel cells is another very attractive alternate for power
production.

1.3 Objectives

The main goal in this research is to develop a model of the gasification that convert
waste tires to syngas, where the proposed model can be used to improve the
understanding of the process and can be used as a predictive tool at the optimization
stage. Validation of this model will be carried out using data available in literature.

3
CHAPTER TWO
LITERATURE REVIEW
2.1 Waste tire problem
2.1.1. Waste tire generation
Approximately 1.5 billion new tires are sold each year worldwide and just as many are
categorized as having reached their end-of-life. European regulations define end-of-life
tires as those that should either be recycled, valorized or have their usefulness extended
(if the intention is to use them again) owing to their physical state and security
regulations. The increase in population coupled with economic growth of many nations
promote the growth of the automotive industry which in turn increases the number of
tires and subsequently the number of waste tires discarded annually. In 2010, 289
million waste tires were generated in the European Union (EU); 500 million waste tires
were generated in 2007 by the United States of America (USA) and 52.5 million waste
tires were generated in Australia in the years 2007-2008. From a South African context,
it is estimated that there are 60 million waste tires disposed of across the country with
approximately 11 million waste tires added each year [3].

2.1.2. Disposal of waste tires

Most of the waste tires generated end up being dumped in stockpiles and landfills (some
illegally); it is estimated that in the developed world 1 car tire per person is discarded
each year. It is also estimated that 4 billion waste tires are currently in landfills and
stockpiles worldwide [4].

Tires are designed to withstand harsh mechanical and weather conditions (such as
ozone, light and bacteria) and their complex nature makes them difficult to recycle
and/or process further. Due to their design, waste tires resist degradation (non-
biodegradable) when in landfills and their bulky nature makes them take up a lot of
landfilling space. Waste tires dumps present a serious threat to both the environment
and human health as they promote the growth of pests and disease carrying insects.
Waste tires also pose a high risk of fires that can be difficult to extinguish and could
have environmental impacts due to uncontrolled emissions of potentially harmful
compounds into the atmosphere, soil and groundwater. Tire fires produce toxic gases
which contain carcinogenic and mutagenic chemicals, this makes the waste tire dumps
highly undesirable. Landfilling and stockpiling are thus currently the easiest forms of

4
dealing with waste tires. However, landfilling and stockpiling fail to utilize the material,
energy and chemical potential in waste tires [5].

2.1.3. Current methods for treating waste tires and their challenges

Various processes or methods have been used as alternative pathways for dealing with
the problem of waste tire generation. These pathways are: direct disposal, material
recovery and recycling and thermal treatment with energy recovery. Direct disposal
includes landfilling and stockpiling. Material recovery and recycling includes processes
such as crumbing, milling/grinding, re-treading, devulcanisation, and civil engineering
applications. Thermal treatment with energy recovery includes incineration, gasification
and pyrolysis [5].

Table 2.1 shows some of the ways which have been used to deal with waste tires in
several countries. Most of the pathways in Table 2.1 (except landfilling and stockpiling)
are aimed at reducing the amount of waste tires discarded by converting them into re-
usable products or energy [6].

Table 2.1: Several methods used for treating waste tires [6].

In this section, material recovery and recycling and thermal treatment with energy
recovery will be briefly discussed. The discussions will highlight the products from
each pathway and their common end uses. The drawbacks/limitations associated with
the processes in each pathway are highlighted as these bring about the necessity to
explore the possibility of using waste tire pyrolysis for recovery of valuable chemicals.
Materials recovery and recycling will be discussed first followed by thermal treatment

5
with energy recovery. End-of-life tires are a potential source of raw materials and as
such, several processes have been used for material recovery and recycling from waste
tires. The processes involved in material recovery and recycling ensure conversion of
waste tires into materials that can be used to produce new goods or used for utilitarian
purposes. In these processes, the waste tires can undergo size reduction to give products
that are similar to the original rubber materials or the tires can be used as whole.
Material recovery and recycle processes take advantage of the fact that used tires are
relatively similar to new tires in composition with slightly less rubber. The different
processes of material recovery and recycling are briefly discussed below [7].

2.2 Tire composition

3.2.1. Constituents of a tire

Tires contain vulcanized rubber (60-65 wt.%), carbon black (CB) (25-35 wt.%) and the
remainder comprises of accelerators, fillers, reinforcing textile cords, fabric belts, steel
wire reinforcing beads etc. that are added during the manufacturing process. These
components have varying properties and composition and are individually added to
achieve a final tire product. Each component will give a specific property to the tire or
to the tire manufacturing process. Table 2.2 shows different elements of the final tire
product and Figure 2.1 shows the different components that make up a tire [3].

Table 2.2: Typical elements of a tire and their constituent materials [3].

6
 Figure 2.1: Various components that make up a tire [3].

Different natural and synthetic rubber formulations are used for the production of
passenger and truck tire s; the tires are mainly a blend of both rubbers. The rubbers used
in tire manufacturing are thermoset polymers. The most commonly used of the synthetic
rubbers is styrene butadiene copolymer (SBR) with a styrene content of about 25 wt.%.
Other rubbers used in tire manufacturing are natural rubber (NR) (polyisoprene),
polybutadiene rubber (PBD), nitrile rubber (NTR) and chloroprene rubber (CPR). The
different rubbers used yield different compounds as degradation products. Isoprene and
dipentene (limonene) are the main degradation products of natural rubber whereas
styrene, 4- vinylcyclohexene, ethylbenzene and cumene are main degradation products
of styrene-butadiene rubber. It can then be concluded that tire formulations that have a
high content of natural rubber are desirable for pyrolysis if limonene is to be targeted as
a compound of interest. Truck tires (TT) generally contain more natural rubber content
than passenger car tires (PCT) and the amount of each component added varies from
region to region as shown in Table 2.3 [8].

Carbon black is an amorphous carbon of quasi-graphitic structure and is used in tire

manufacturing to provide strength and aid abrasion resistance of the rubber in the tire. It
is primarily produced by partial combustion of fossil hydrocarbons like petroleum
residue [8].

7
 Table 2.3: Typical composition of passenger and truck tires [8].

An extender oil (a mixture of aromatic hydrocarbons) is added to the tire during

manufacturing to soften and improve workability of the rubber. The amount of extender
oils added depends on the tire formulation as shown in Table 2.4 and Table 2.5. The
constituents (and composition) shown in Table 2.4 and Table 2.5 represent just two
particular formulations out of a variety of formulations used in tire manufacturing. It
can then be concluded that the amount of extender oil in tire formulation will have an
effect on the quantities of potentially valuable chemicals obtained from pyrolysis as the
oil decomposes during pyrolysis [8].

An accelerator (typically an organo-sulphur compound) is added as a catalyst for the

vulcanisation process. Typically, zinc oxide and stearic acid are also added as these
compounds control the vulcanisation process and enhance the physical properties of the
rubber. The different additives can be a variety of compounds as shown in Table 2.4 and
Table 2.5, however, they still fulfil the same purpose.

Sulphur is added to the tire to form cross-links between the rubber polymer chains thus
also hardening the rubber to prevent excessive deformation at elevated temperatures
The cross-linking of the elastomers gives the rubber materials their thermoset
characteristics; the Sulphur content is normally up to 1.5 wt.%.

8
Table 2.4: Constituents of a particular tire formulation [9].

Table 2.5: Constituents of a specific tire formulation [9].

9
2.2.2. Characterization of a tire

In literature, tire is normally characterized using the proximate and ultimate (elemental)
analyses. Depending on the intention of the specific literature, calorific values of the tire
can also be included [9].

Table 2.6 and Table 2.7 show the proximate and ultimate analyses of some tires in
literature. It can be seen that the characterization will depend on the type of tire material
evaluated. The variation in the different components is also a result of different tire
formulation from various tire brands. A tire with a high volatile matter content is
desirable for pyrolysis processes aiming to recover valuable chemicals from waste tires.
For this study, the importance of tire characterization is for tire definition purposes in
Aspen Hysys simulation as will be explained in later in chapter 3 [9].

Table 2.6: Typical proximate analysis of a waste tire.

Table 2.7: Typical ultimate analysis of a waste tire.

10
2.3. Pyrolysis of waste tires

2.3.1. Definition of waste tire pyrolysis

Pyrolysis is a thermal process that decomposes an organic material into low molecular
weight compounds under inert conditions. Pyrolysis breaks down the organic part of a
tire into a gas product, a liquid product and a solid product. Figure 2.1 shows a
schematic of a typical waste tire pyrolysis system [10].

Figure 2.2: Schematic of a typical waste tire pyrolysis system.

In the typical waste tire pyrolysis system shown in Figure 2.2, the tires (typically in a
size-reduced form) are pyrolysis in a reactor (at a specific temperature and pressure)
where vapor and solid products are obtained. The vapor product from the reactor is
condensed to yield a (non-condensable) gas and a liquid product fraction [10].

2.3.2. Waste tire pyrolysis products

 Gas product

The gas fraction is the gas remaining after condensation of the vapors from the reactor
(for liquid recovery) during pyrolysis and it is called pyrolysis gas or pyro-gas. The gas
is typically composed of paraffinic and olefin compounds that range from C1 to C5, with
hydrogen, carbon monoxide, carbon dioxide, , with some low concentrations of sulphur
and nitrogen compounds. The presence of C4 compounds is mainly attributed to the

11
thermal degradation of the rubber as tires typically contain a mixture of both natural and
synthetic rubber of which the latter is mainly SBR or BR [11].

The gas produces is normally used as fuel for the pyrolysis process, where its calorific
values is 29.9 – 42.1 MJ/m3 depending on the tire brands used in the process [12].

 Liquid product

The liquid product (TDO) has a complex composition consisting of both short and long
chain carbon molecules and single and multiple ring structures. The proportion of
aliphatic and aromatics vary with pyrolysis conditions. Alkylated derivatives of single
and multiple ring aromatics are also present in. TDO is a dark brown/black colored
liquid of medium viscosity and has a Sulphur/aromatic smell due to the presence of
sulphur containing compounds. TDO is a combination of the processing oils and
organic additives in the original tires and the products of decomposition of the different
rubbers. The composition TDO varies with reactor conditions i.e. temperature, pressure
and volatile residence time [13].

The oil product has high calorific values (around 40 MJ/kg) and can be used as fuel.
TDO has a wide boiling point range (about 50 °C to above 350 °C) as shown in Figure
2.3 from. The wide boiling point range would require a lot of effort to convert the oil to
traditional liquid fuels or make it difficult for its direct application as fuel (Martinez et
al., 2013). TDO can be blended with diesel fuel if it is to be used as automotive fuel but
only in small proportions to not greatly affect the performance and emissions of
standard automotive diesel engines. Direct use of TDO as engine fuel can only be in
diesel engines that are less fuel-quality demanding and have less stringent emission
regulations such as stationary engines and marine propulsion engines [14].

Upgrading of TDO to meet specific fuel requirements is required due to the high
contents of aromatics and Sulphur and a high viscosity. Depending on the final use of
TDO as fuel, different upgrading techniques may be required. The poor fuel-quality
characteristics of TDO oil results in limited application and low selling prices for the oil
as compared to traditional fuels from crude oil [15].

12
 Figure 2.3: True boiling point curve of TDO obtained at 500 °C [15].

TDO can also be used as a source of chemical feedstock due to its various constituent
compounds. The limited application of TDO as fuel (in its crude form), potentially
expensive investment for upgrading TDO to match diesel fuel and consequent low
selling price of the oil present an opportunity for converting waste tires into the high
value chemicals found in the oil.

 Solid product

The solid product is called pyrolysis char; it contains the inorganic matter of the tire
(ash, zinc oxide, steel, silicates etc.) and the non-volatile carbon black added during tire
manufacture. Sulphur from vulcanization is mainly retained in this product fraction.
Tire composition and pyrolysis conditions determine the composition of the char
product. Coking or the deposition of degraded tire material on the carbon black can also
form part of the char product, this would be indicated by an amount of char higher than
the sum of the carbon black and inorganics in the original tire. The quality of char
obtained under vacuum is better than that under atmospheric conditions due to vacuum
minimizing coking that would block the pores of the char thus minimizing its surface
area [11].

The char product obtained can be upgraded for use as activated carbon for different
applications, as a solid fuel or re-used as carbon black in the tire manufacturing process.
The char product however needs upgrading to increase surface area, reduce the ash and
Sulphur contents for use in these applications [11].

13
2.3.3. Valuable chemicals from pyrolysis oil
TDO is a potential source of chemical feedstock as it contains valuable chemicals like
benzene, toluene and xylene (BTX), styrene, ethylbenzene and limonene. These are
chemicals that have wide industrial applications. The yields of these chemicals depend
on reactor conditions and the type of tire used as different studies used different tire
types. Table 2.8 and Table 2.9 show the yields (based on tire feed) of BTX,
ethylbenzene, styrene and limonene at 500 °C and 600 °C from different literature
sources [13].

Table 2.8: Yield of BTX, ethylbenzene, styrene and limonene at 500 °C.

As can be seen from Table 2.8 and Table 2.9, the potentially valuable chemicals are
present in TDO in sufficient quantities given the wide variety of compounds that are
present in TDO. About 1999, 6.9 Mt of benzene, 2.3 Mt of toluene and 1.9 Mt of
xylenes were produced in Western Europe, and looked at ways of converting BTX into
valuable products. BTX compounds are a high value feedstock for the plastic/polymer
industry, and the demand for xylene in the industry is growing [16].

Another valuable chemical from waste tire pyrolysis is limonene, and it is the target
chemical in this study. Limonene is a monoterpene that is a dimer of isoprene molecules
and can be obtained from the thermal decomposition of the poly-isoprene contained in
the tire. The poly-isoprene could either be from natural or synthetic rubber. Limonene is
a major component of TDO with common yields of between 2.5 and 5 wt.% on the
basis of a steel-free tire although yields as high as 27 wt.% have been reported.
Limonene has wide industrial applications and has been used in the formulation of

14
industrial solvents, terpene resins and adhesives, as a cleaning agent, as a dispersing
agent for pigment and in the manufacturing of flavoring agents, fragrances and
pesticides [8].

The current demand for limonene is mostly catered for by citrus-derived limonene. The
global production of citrus limonene was estimated at over 70 000 tons in 2013, with
both the demand and supply expected to increase constantly in future. Citrus harvest is a
seasonal activity and as such, a drop in supply of citrus-derived limonene can be
expected when the citrus season ends. The supply of citrus limonene is subject to
agricultural vulnerabilities, which could bring volatility to the price of limonene.
Production and recovery of tire -derived limonene then become vital to close the
potential limonene supply gap given the wide industrial use of limonene [8].

The price of citrus limonene can range between 8 and 25 US$ per kilogram based on
purity. To this author’s knowledge, there currently is no information available on the
price of tire-derived limonene. Impurities in tire-derived limonene include light
aromatics and undesirable Sulphur containing compounds such as thiophene and
benzothiazole. As such, it is necessary to obtain sufficient purity for tire-derived
limonene to minimize the undesirable impurities and to attain a high selling price [8].

The yields of the valuable chemicals discussed above vary with pyrolysis conditions
and the tire material used. Therefore, it is necessary to optimize the reactor conditions
depending on the type of chemical desired [8].

2.3.4. Waste tire pyrolysis economics

A preliminary economic feasibility study was performed for converting waste tires into
carbon black by partial combustion of the oil produced from pyrolysis. The study
reported that major pyrolysis projects have failed to gain commercial success due to the
low market value of the pyrolysis oil and char produced. Therefore, deemed it necessary
to produce carbon black which had a higher market value than pyrolysis oil in order to
improve the economics of their process. The preliminary feasibility study was using a
tire flow rate of 100 tons/day and found that the process was economical over a 5-year
project life. The process yielded 20% gas, 35% char and 45% oil. The saleable products
were carbon black, activated char and Boudard carbon with a tipping fee also adding to

15
the revenue stream, the study concluded that waste tire pyrolysis processes are only
economical if high value products are produced and recommended recovery of valuable
chemicals as a pathway to make waste tire pyrolysis economically feasible [17].

Shelly and El-Halwagi (1999) conducted an economic feasibility study for a waste tire
pyrolysis process that converts the pyrolysis oil into a synthetic crude product. The
pyrolysis oil obtained was upgraded (hydrotreating and hydrocracking) to produce the
synthetic crude product. The study by found that the process considered was economical
having used a tire feed rate of 100 tons/day. The saleable products from the process
were synthetic crude, carbon black and steel; a tipping fee also contributed to the
revenue stream. No information was provided about the yields of the different products
that were sold. It was however noted that a tire feed rate of 100 tons/day could be
difficult to obtain due to transportation costs and/or scheduling conflicts. There is
therefore a need to look at waste tire pyrolysis economic feasibility at lower tire feed
rates. Higher feed rates might have more costs savings due to the effect of economies of
scale, however, more realistic flow rates need to be used. The study also highlighted the
need for upgrading pyrolysis primary products in order to improve process economics
[18].

Pilusa et al. (2014) conducted a preliminary economic feasibility study for conversion
of waste tires into fuel in South Africa over a 5 year project life, assumed a constant
supply of waste tires from REDISA. The pyrolysis oil obtained was fractionated to
produce tire -derived fuel and heavy fuel oil. The process yielded 10% steel, 45 % oil,
37% char and 8% gas. The saleable products from the process were light diesel-
equivalent fuel, refined carbon black, steel and sodium sulphite (a product of scrubbing
the flue gases generated in the process using sodium hydroxide solution). The process
used a tire feed rate of 30 tons/day and it was found to be economically feasible. The
study highlighted the necessity for upgrading of the pyrolysis primary products to more
valuable products in order to achieve economic feasibility for waste tire pyrolysis
processes. The study also concluded that a continuous product market demand is
required for economic success of pyrolysis processes [15].

The economic studies evaluated in this section have highlighted the need for waste tire
pyrolysis processes that are focused on production of high value products as opposed to

16
selling the primary products. The economic evaluation of the current study is therefore
focused on the feasibility of recovering valuable products from waste tires [15].

17
 CHAPTER THREE
PROCESS DESCRIPTION & SIMULATION
SETUP
3.1 Simulation basis manager

Simulation Basis Manager (SBM) is the welcome interface for a simulation project in
Aspen Hysys and helps mainly in selecting and defining pure components, assigning a
property package for carrying out flash and physical properties calculations

3.1.1 Characteristics of waste tire

To establish the theoretical framework for gasification of the tire, both the thermal
properties and chemical composition are determined. Thermo-gravimetric is used to
determine the proximate composition of tire in terms of its moisture, volatile, fixed
carbon, and ash fractions. The analysis is based upon measurements of the mass change
of the sample as a function of a controlled/specified temperature profile [2].

Thermo-scientific is used to evaluate the elemental composition of tire by analysing the

combusted stream while passed through appropriate thermally conductive detection
column. Also, the Bomb calorimeter is used to find out the heating value of tire. The
result of proximate, ultimate and heating value analysis are given in table 3.1 [2].

The composition is normalized for one mole of carbon on dry basis which lead to the unit
composition formula for the tire of CH1.1057O0.0915N0.0035S0.0066, and this chemical formula
is used as an input to Aspen Hysys as hypothetical solid component to define the waste
tier [2].
Table 3.1: Tire proximate and ultimate analysis [2].
Proximate (Wt.%)
Moisture 1
Volatile Matter 68
Fixed Carbon 23.2
Ash (dry) 8.8
Ultimate (Wt.%) (dry)
C 73.8
H 6.8
N 0.3
S 1.3
O 9
Ash 8.8
HHV (MJ/kg) 36
MW (kg/kmole) 14.83

18
3.1.2 Fluid package

Selecting the appropriate proper property method is important as it is crucial to the

outcomes from the simulation. From reviewed literature, different property methods were
chosen to estimate physical properties of conventional components. Many property
methods were selected by various researchers. Hence, Peng Robinson (PR), is selected
and used, where its result is validated with previous experimental study and it was in a
good agreement [19].

3.1.3 Reaction chemistry

The gasification of WT involves a series of physical and chemical processes, including

drying, pyrolysis or devolatilization, oxidation, and finally char reduction. As soon as the
material enters the gasifier, it is rapidly dried to remove the bounded moisture. The
complex material then starts to devolatilize and yields volatile matter and residual
amounts of char. The char present in the gas phase is reformed into a combustible gas
mixture H2, CO, CO2, CH4, small hydrocarbons via reactions with steam, air, and carbon
dioxide according to the environment and kinetic mechanism. While the main reduction
reactions are assumed to be initiated in the reactive zone (bed), other processes continue
to occur at the freeboard region of the gasifier [20].

The chemical reactions depicting the char oxidation and gasification along with the
kinetic parameters are shown in Table 3.2. The most widely referenced kinetic data have
been considered in this work [20].

Table 3.2: Gasification reactions and their kinetic parameters [20].

ΔHr (MJ/mol) Reaction
Reaction
@ 25 °C Number
C + 0.5O2 CO -111 (R2)
C + CO2 2CO 172 (R3)
C + H2O CO + H2 131 (R4)
C + 2H2 CH4 -75 (R5)
CO + 0.5O2 CO2 -283 (R6)
H2 + 0.5 O2 H2O -242 (R7)
CO + H2O CO2 + H2 -41 (R8)
CH4 + H2O CO + 3H2 206 (R9)
H2 + S H2 S -300 (R10)
0.5 N2 + 1.5H2 NH3 -91 (R11)

19
3.2 Model construction

This section describes the modelling and simulation approach used for the waste tier
gasification-based polygene ration process, where the block flow diagram is shown in
figure 3.1.

3.2.1 Assumptions

The simulations were based on the following assumptions:

1. The gasification zone is isothermal and operates at a steady state.

2. The gasification reaction occurs at constant atmospheric pressure (1 bar).
3. Pressure drops are neglected.
4. The solid char is 100% carbon.
5. Drying and pyrolysis are instantaneous and occur simultaneously.
6. Tar formation was neglected.
7. Heat losses from the gasifiers were neglected.
8. Chemical and phase equilibriums were achieved.

Figure 3.1: Simplified process flow diagram of a waste-based polygene ration facility.

20
3.2.2 Air separation unit modelling

The ASU was considered for the reactor; it was not modelled in detail in this study.
Instead, the component splitter block of Aspen Hysys was used to separate oxygen and
nitrogen. The power consumed by the ASU was estimated as 0.4 kWhe/m3 oxygen [21].

3.2.3 Pre-treatment (Grinding and Drying) Modelling

The waste tier pre-treatment including the drying and Size reduction of waste up to 2 mm
to make it suitable for gasification is necessary step in the practical process, but in this
model is not considered because it is a mechanical process [21].

3.2.4 Modelling of pyrolysis and combustion zone

Breakdown of WT was simulated in conversion reactor “Pyrolysis”. WT breakdown

closely represent a pyrolysis process in gasifier. Biomass breakdown into its constituting
conventional elements of Carbon (C), Hydrogen (H), Nitrogen (N), Oxygen (O), and
Sulphur (S). Pyrolysis reaction involved was R1. Char from WT breakdown consist of a
pure carbon, it was simulated as bottom products of conversion reactor “Pyrolysis”.
Bottom product as a solid contains char and sulphur. Tee-101 block simulating carbon
separation, whereas 96% of carbon was converted, while remaining 4% unconverted and
circulated on cyclone separator. The sulphur was reacting with hydrogen and modelled as
separate conversion reaction. The sulphur split from carbon on X-101 component splitter
block.

C4.306 H6.176 O2.587 N0.048 S0.003 4.306C + 3.088H2 + 1.2935O2 + 0.024N2 + 0.003S (R1)

3.2.5 Modelling of gasification zone

The product of conversion reactor “Pyrolysis”, which is conventional elements reacted

with oxygen and steam at gasifier. The product streams of conversion reactor “Pyrolysis”
are volatiles and carbon to gasifier. Streams “volatile” and “carbon to gasifier” connected
to a feed of “gasifier-A”. The mechanism of gasification involves complex collection of
various reaction during real gasification process, however the gasification reactions were
simplified into major reactions as listed on table 3.2. Reaction R2 until R7 occurred on
“gasifier-A” and modelled as equilibrium reaction in Gibbs reactor. The reactions using

21
Gibbs free energy minimisation method to find equilibrium constant. Equilibrium
constant through Gibbs free energy minimisation was calculated by Aspen Hysys.
Reactions R8 and R9 occurred on “gasifier-B” as equilibrium reaction, where default data
of equilibrium constant vs temperature was provided by Aspen Hysys. Gasification
process modelled on both “gasifier-A” and “gasifier-B” as a set of equilibrium reactions.
The gasification on “gasifier-A” modelling the pyrolysis and char combustion. Reaction
on “gasifier-B” modelling CO shift conversion and Steam CH4 reforming reaction using
equilibrium method in equilibrium reactor. The entire streams outlet “gasifier-B”, which
are stream “6” and “7” passed through “HS-reactor” which models the conversion of
solid sulphur into hydrogen sulphide (H2S) with a conversion reactor assuming complete
conversion, since sulphur does not have equilibrium constant embedded in Aspen Hysys
and the reaction itself is non-equilibrium.

3.2.6 Modelling of solid separation section

Products from “H2S reactors” on stream “8” and “9” passed cyclone separator “X-101” to
separate unconverted solid carbon with 85% efficiency. Bottom outlet of “X-101”
contains solid only, went to “X-102” that split solid stream into recycle stream that was
sent back to the “gasifier A”, and another stream named “carbon loss” was the loss of the
solid carbon. Top outlet of “X-101” is the raw syngas product.

3.2.7 Modelling of Syngas Cooling

The raw syngas produced is wet and contains a fine particles of solid carbon that cannot
be separated in cyclone, so the gas is cooled in a shell and tube heat exchanger using a
cooling water, to 35 0C, where the water and solid particles are condensed and separated
in two phase separator.

22
23
Figure 3.2: Process flow diagram of waste tire gasification using Aspen HYSYS
CHAPTER FOUR
RESULT AND DISCUSION
4.1 Model application

The developed model was used to investigate how variations in temperature, air-fuel ratio
(AFR) would affect syngas quality (in terms of composition and LHV).

4.1.1 Effect of gasifier temperature

Figure 4.1, 4.2 and 4.3 show the influence of gasifier temperature on yield, composition
and heating value of syngas, where the gasifier temperature was varied from 500 to
1500°C, at an increment of 100°C.

The syngas yield is used to quantify the rate of conversion of gaseous species from the
simulation. It can be computed by dividing the volumetric flow rate of gaseous species by
the mass flow rate of the feed as shown in bellow [22].

̇
𝑉𝑔
𝑌𝑔 = 4.1
𝑚̇𝑓

where Yg is the syngas yield in the unit of Nm3/kg, Vg is the volumetric flow rate of
syngas products at the standard state of 1 atm and 25 ℃ in Nm3/h, mf is the mass flow
rate of feedstock in kg/h [22].

Figure 4.1 indicates that as the gasifier temperature increases from 500°C to 1500°C, the
syngas yield is increased until reach the maximum at around 900 oC.

24
 Figure 4.1: Variation of syngas yield with gasifier temperature.

Figure 4.2: Variation of syngas composition with gasifier temperature.

25
Figure 4.2 indicates that as the gasifier temperature increases from 500°C to 1500°C, H2
content increased initially and attained a maximum value at 750°C, then decreased
continuously until 1500°C. CO content increased with increase in temperature until
1500°C, while CO2 and CH4 concentrations decreased with increase in temperature. N2
decreased with increase in temperature until 900℃ and then maintained a constant level
until 1500°C. These trends result from the various reactions taking place during the
gasification process. At low temperatures, a huge percentage of carbon in the feedstock is
unutilized resulting in low syngas yield. However, as temperature increases more carbon
is oxidized, increasing its conversion rate into CO, while methane is converted to
hydrogen by steam reforming reaction. These result in increase in the gasifier
temperature, which favors the production of H2 and CO, consequently improving the
energy content of the syngas.

The lower heating value of syngas depends on the content of the combustible gases (CO,
H2 and CH4) in the syngas and could be computed using. [23]

LHVg=(xCO∗LHVCO)+(xH2∗ LHVH2)+ (xCO2∗ LHVCO2) 4.2

Where, x = mole fraction of gas constituents, LHVg = lower heating value of syngas

Figure 4.3 shows the variation of syngas lower heating value (LHV) with gasifier
temperature, which indicates that the syngas LHV experienced a sharp rise as gasifier
temperature increased from 500℃ to 900℃. It however, experienced slight increase until
1050℃. Ramzan et al, and Puig-Arnavat et al reported similar variations [23].

26
 Figure 4.3: Variation of syngas LHV with gasifier temperature.

The cold gas efficiency produced at the end of the gasification stage were computed with
the formulas below [24].

𝐿𝐻𝑉𝑠𝑦𝑛𝑔𝑎𝑠
𝐶𝐺𝐸(%) = × 100 4.3
𝐿𝐻𝑉𝑤𝑎𝑠𝑡𝑒 𝑓𝑒𝑒𝑑

The effect of gasifier temperature on the CGE% is shown in figure 4.4, where it can be
seen that it is increased with temperature to and attained a maximum value at 900°C.

Figure 4.4: Variation of CGE% with gasifier temperature.

27
4.1.2 Equivalence ratio (ER)

is a measure of the amount of air used for gasification in relative to complete combustion
It is defined as the ratio of air/fuel ratio supplied to the stoichiometric air/fuel ratio
needed for complete combustion of carbon and hydrogen present in the fuel [24].

Oxygen
( )
fuel used
ER = Oxygen 4.4
( )
fuel stoichiometric

Since the denominator always constant, and for simplicity we use the molar flow of
oxygen instead of equivalence ratio, the result of oxygen flowrate on syngas composition
and LHV are shown in figures 4.5 and 4.6.

Figure 4.5 shows that increase in air flowrate increases the content of CO2 and N2 but
decreases that of H2, CH4 and CO. This is because the process shift towards combustion
with increasing air-fuel ratio.

Figure 4.5: Variation of syngas composition with oxygen flowrate.

28
As observed from Figure 4.6 syngas LHV constantly dropped in value with increase in
air-flowrate. This is as an obvious consequence of decrease in mole fractions of the
combustible gases (H2, CH4 and CO) as the air-fuel ratio increases that high air-fuel ratio
decreases the content of H2 and CO as well as the LHV, while CO2 content would
increase.

Figure 4.6: Variation of heating value of syngas with oxygen flowrate.

29
4.2 Hand calculation
Hand calculation around heat exchanger (E-100) including mass and energy balance,
equipment design and sizing is performed as a sample of calculation.

4.2.1 Maas and energy balance

Heat exchanger E-100 is utilizing cooling water to cool down the syngas from 800 C to
around 500 C, the specification of inlet and outlet streams are shown in table 4.1.

Table 4.1: Stream specifications.

Shell side Tube side
F9 F10 F7 F8
Fluid water Syngas
Flow rate (kg/h) 2857.141 1318.914
Inlet 25 800
Temperature (oC)
Outlet 98.55 500
Specific heat capacity Cp (kJ/kg.K) 4.18 2.22

Applying mass and energy balance around the exchanger based on the fooling formula:

Energy in (Gas) + Energy in (Water) = Energy out (Gas) + Energy out (Water

Where it can be written in the following mathematical form,

(F7×Cps×T7) + (F9×Cpw×T9) = (F8×Cps×T8) + (F10×Cpw×T10)

30
As F7 = F8 = 1318.914 kg/h and

F9 = F10 = X kg/h

So the equation can be written as

(F7×Cps×T7) + (F9×Cpw×T9) = (F7×Cps×T8) + (F9×Cpw×T10)

And simplified and rearranged to the following form

F7 × Cps × (T7 – T8) = F9 ×[Cpw × (T10 – T9)]

Putting the values, and solving for X

1318.914 × 2.22 × (1073 – 773) = x × [4.18 × (371.55 – 298)]

X = 2857.141 kg/h  F9 = F10 = 2857.141 kg/h

4.2.2 Design of heat exchanger

1. Fluid allocation and thermos-physical properties

Water is placed on the tube side, while the syngas is on the shell side.

The given data and operating condition are shown in table 4.1, where the thermos-
physical properties are calculated at mean average temperature [26].

Mean shell side temp = (98.55+25)/2 = 61.77°C

Density (𝜌𝑤 ) = 1000 kg/m3

Viscosity (μw) = 0.8904x103 N.s/m2

Specific heat capacity of water (Cpw) = 4.18 kJ/ kg-ᵒC

Thermal conductivity (k) = 0.66 W/m.°C

Mean shell side temp = (800+500)/2 = 650 °C

31
Viscosity of syngas = μg = 0.02257m Ns/m2

Specific heat capacity of syngas (Cpg) = 4.569 kJ/ kg-ᵒC

Thermal conductivity = kf = 0.2501 W/m.°C

2. Calculation of Heat Load

Q = m*Cp*ΔT = m Cp (T2-T1)

= 1318.914 × 4.569 × (800 – 500)

= 1.774*106 kJ/h = 492.77 kW

3. Log mean temperature difference LMTD

Counter current flow is selected due to its high performance and better heat transfer

(𝑇ℎ,𝑖 − 𝑇c,o )−(𝑇ℎ,𝑜 − 𝑇c,i )

𝑀𝑇𝐷 = (𝑇ℎ,𝑖 𝑇c,o )
ln −
(𝑇ℎ,𝑜 𝑇c,i )
−

(800−98.55)−(500−25)
𝑀𝑇𝐷 = (800−98.55) = 580.723 ℃
ln
(500−25)

for one shell pass and two tube passes and using the chart below, the temperature
correction factor Ft is calculated

(𝑇1 −𝑇2 ) (800−500)

𝑅= = (98.55−25) = 4.08
(𝑡2 −𝑡1 )

32
 (𝑡 −𝑡 ) (98.55−25)
𝑆 = (𝑇2 −𝑡1 ) = = 0.09
1 1 (800−25)

So, Ft = 0.989

Using MTD and Ft, the corrected MTD (ΔTlm) is calculated as following

Corrected MTD = ΔTlm = ΔTm × Ft

= 580.723 × 0.989

ΔTlm = 574.335 ᵒC

4. Calculation of the provisional area

𝑘𝐽
Initial guess of overall heat transfer coefficient is 61.51 𝑚2 .ℎ𝑟.℃.

Using the heat load and overall heat transfer coefficient, and ΔTlm the provisional area is
calculated

𝑞 1.774 ∗ 106 𝑊
𝐴= = = 50.27 𝑚2
𝑈 × ∆𝑇𝑚 61.51 k𝐽
.× 574.335 ℃
𝑚2 . ℎ𝑟℃

33
 5. Number of tubes needed is calculated

Tube Specifications used for the first trail is as following

o Tube outer diameter = do = 20mm = 0.02m

o Tube inner diameter = di = 16mm = 0.016m
o Tube thickness = 2mm = 0.002m
o Tube length = L = 5m
o Material of construction is carbon steel with thermal conductivity (k) equal to 45
W
m2 .℃

A 50.27
𝑁𝑡 = = ≈ 160 𝑡𝑢𝑏𝑒𝑠
π × d0 × L π × 0.02 × 5

6. Shell diameter and baffle spacing

Since the shell fluid is relatively clean, the triangular 1.25do arrangement is selected

= 1.25𝑑0 = 1.25(0.02) = 0.025 𝑚 ≈ 25 𝑚𝑚

1
𝑁
Bundle diameter  𝐷𝑏 = 𝑑0 (𝑘 𝑡 )𝑛1
1

For triangular pitch and two tubes passes K1 and n1 can be found from the following table

1 1
𝑁 160
So, Bundle diameter 𝐷𝑏 = 𝑑0 (𝑘 𝑡 )𝑛1 = (0.02) ( )2.207 = 0.374 m = 374 𝑚𝑚
1 0.24

For fixed and U- tube heat exchanger with bundle diameter ≈ 0.374 𝑚, the Bundle
Diameter Clearance (DBC) is found from the chart below

DBC = 12 mm

34
Shell diameter (Ds)= bundle diameter (Db)+ Bundle Diameter Clearance (BDC)

Ds = 0.374+0.012 = 0.386 m = 386 mm

1
Baffle spacing (𝐵𝑠 )= 5 x shell diameter (Ds) = 0.0772 m = 77.2 mm

7. Shell side heat transfer coefficient (hs)

(𝑝𝑡−𝑑0 )𝐷𝑠 ×𝐵𝑠 (0.025−0.02)0.386×0.0772

Cross flow area (As) = = = 0.005 𝑚2
𝑝𝑡 0.025

𝑘𝑔
𝑠ℎ𝑒𝑙𝑙 𝑠𝑖𝑑𝑒 𝑓𝑙𝑜𝑟𝑎𝑡𝑒 ( ) 2083.773
ℎ𝑟
Shell - side mass velocity (Gs) = = 3600 X 0.005
𝐴𝑠

kg
= 115.77
𝑚2 𝑠

Shell equivalent diameter for a triangular pitch arrangement

1.10
𝑑𝑒 = (𝑝𝑡2 − 0.917𝑑02 ) = 14.201 𝑚𝑚 = 0.014201 𝑚
𝑑0

𝐺𝑠 ×𝑑𝑒
Shell side Reynolds number Re = 𝜇𝑤

35
 kg
115.77 ×0.014201 𝑚
𝑚2 𝑠
= 𝑘𝑔 = 1846
0.08904𝑥10−3
𝑚,𝑠

Prandtle number

𝐽 𝑘𝑔
𝐶𝑝𝑤 ×𝜇𝑤 4.18𝑥103 ×0.8904𝑥10−3
𝑘𝑔.𝐶 𝑚.𝑠
Pr = = 𝑊 = 5.64
𝑘𝑤 0.66
𝑚.𝐶

For 25% of baffle cuts and Re, 𝐽ℎ is found from chart below  𝐽ℎ = 1.7x10−2

1 1
𝑘𝑓 𝑗ℎ 𝑅𝑒 𝑃𝑟 3 (0.66)(1.7x10−2 )(1846)(5.64)3 𝑊
ℎ𝑠 = = = 2596.16 2
𝑑𝑒 0.014201 𝑚 .𝐶

8. Tube side heat transfer coefficient (hi)

𝑘𝑓 𝜇
ℎ𝑠 = 𝑗ℎ 𝑅𝑒 𝑃𝑟 0.33 ( )𝟎.𝟏𝟒
𝑑𝑖 𝜇𝑤

Re = 16225.78

𝐽 𝑘𝑔
𝐶𝑝𝑔 ×𝜇𝑔 4.569𝑥103 ×0.02857𝑥10−3
𝑘𝑔.𝐶 𝑚.𝑠
Pr = = 𝑊 = 0.522
𝑘𝑔 0.2501
𝑚.𝐶

𝜇
Neglect (𝜇 )
𝑤

36
 5
L/di = = = 312.5
16𝑥10−3

Using graph  Jh = 4×10-3

0.2501
hi = 16𝑥10−3 × 4×10-3 × 16225.78 × (0.412)0.33

hi = 818.635 W/m.oC

9. Overall heat transfer coefficient (Uo)

Overall heat transfer coefficient is calculated based on inside and outside tube flow

1 𝑊
𝑈𝑜 = = 474.87
𝑑 𝑚2 ℃
1 1 𝑑𝑜 ln( 𝑜⁄𝑑 ) 𝑑 𝑑
𝑖
+ + + 𝑜 + 𝑜
ℎ𝑜 ℎ𝑑𝑜 2𝑘𝑤 𝑑𝑖 ℎ𝑜 𝑑𝑖 ℎ𝑑𝑖

Well above assumed value 61.51 W/m2.oC, so the design is acceptable

10. Pressure drop in the shell side

𝐷 𝐿 𝜌𝑢𝑠2 𝜇
∆𝑃𝑠 = 8𝑗𝑓 (𝑑𝑠 )(𝑙 )( )(𝜇 )−0.14 / 𝑙𝐵 𝑖𝑠 𝑏𝑎𝑓𝑓𝑙𝑒 𝑠𝑝𝑎𝑐𝑖𝑛𝑔
𝑒 𝐵 2 𝑤

𝑘𝑔
𝐺𝑠 115.77 2
𝑚 ,𝑠
Where, 𝑢𝑠 = = 𝑘𝑔 = 0.1157 𝑚/𝑠 and 𝜇 = 𝜇𝑤
𝜌 1000 3
𝑚

For 25% of baffle cuts and Re , jf is calculated from the following chart

 Jf = 6x10-2

37
 386 5 1000(0.1157)2
∆𝑃𝑠 = 8(0.06) ( )( )( ) = 5.7𝑘𝑃𝑎
14.201 77.2𝑥10−3 2

11. Tube side pressure drop

Re = 16225.73  Using chart  Jf = 0.0042

8 𝑗𝑓 𝐿 𝜇 −𝑚 𝜌 𝑣 2
∆𝑃 = 𝑁𝑡 [2.5 + + (𝜇 ) ] 𝑖2 / 𝑎𝑠𝑠𝑢𝑚𝑖𝑛𝑔 𝑡ℎ𝑎𝑡 𝜇 = 𝜇𝑤
𝑑𝑖 𝑤

8 (0.0042) (5) (0.1081)(13.16)2

∆𝑃 = 2 [2.5 + ][ ]
0.016 2

∆𝑃 = 40.5 𝑘𝑃𝑎

The pressure drop in the tube side and shell side are acceptable.

38
CHAPTER FIVE
PROJECT EVALUATION
5.1 Overview
The capital cost of the project is performed based on the real time price that have
obtained from the international company that manufacturing this kind of processes.
We have contacted with many companies such as MINGJIE GROUP, HUAYIN
GROUP.

The technical information and feasibility provided by HUAYIN GROUP study related
to the 10 ton/day machine is available in the appendix, where it is used as a base line
for the project evaluation.

5.2 Cost Estimation

The equipment cost base on the HUAYIN GROUP supplier is around 30,000
USD.[25] Since the price is in 2022, the cost escalation will be considering only the
location factor (LFA) as a following:

𝐶𝑜𝑠𝑡 𝑖𝑛 𝑦𝑒𝑎𝑟 𝐴 = 𝑐𝑜𝑠𝑡 𝑜𝑓 𝑝𝑙𝑎𝑛𝑡 𝑜𝑛 𝑈𝑆𝐺𝐶 ∗ 𝐿𝐹𝐴

𝐿𝐹𝐴 for middle east = 1.07

The exchange rate in 2003 averaged about 1 LYD = 0.799 $

The exchange rate in 2022 it averaged about 1 LYD = 0.256 $

0.256
The location factor for Middle East is thus: 1.07 ∗ 0.799 = 0.3428

∴ 𝐶𝑜𝑠𝑡 𝑖𝑛 𝑚𝑖𝑑𝑑𝑙𝑒 𝑒𝑎𝑠𝑡 = (30,000 ∗ 0.3428) + 30,000 = 40.284 𝑀$

The Outside battery limit OSBL capital cost is estimated as 40% of Inside battery limit ISBL
cost. The engineering cost and contingency are estimated as 10% and 15% of the sum (ISBL
+ OSBL) cost, respectively.

𝑂𝑆𝐵𝐿 = 0.4 ∗ 40.284 = 16.12 𝑀$

𝐸𝐶 = 0.1 ∗ (40.284 + 16.12) = 5.64 𝑀$

𝐶𝑜𝑛𝑡𝑖𝑛𝑔𝑒𝑛𝑐𝑦 = 0.15 ∗ (54.045 + 21.62 + 7.57) = 9.31 𝑀$

 Total Fixed Capital Cost TFCC

𝑇𝐹𝐶𝐶 = 40.284 + 16.12 + 5.64 + 9.31 = 71.354 𝑀$

39
5.3 Cost of Materials

The cost of raw material and products are shown in table below, where all data have
been taken from ALIBABA website [27]

Table 4.4: Cost of raw material and products [27]

Material Price
Waste tire 100 $/ton
water 0.00015 $/ton
Fuel oil 560 $/ton
Carbon black 100 $/ton
Steel wire 400 $/ton

 Product Material Cost PMC

The All products including fuel oil (FO), carbon black (CB), and steel wire (SW) are
considered as a valuable and sealable product, except fuel gas which is used as a heating
source for the plat operation. Since the process is batch process, the plant capacity was
selected to around 10 tons per day.

Fuel oil (40%-45%)

𝑡𝑜𝑛 $ $
10 x 40% x 560 = 2240
𝑑𝑎𝑦 𝑇𝑜𝑛 𝑑𝑎𝑦

Carbon black (30% – 35%)

𝑡𝑜𝑛 $ $
10 𝑑𝑎𝑦
x 30% x 100 𝑇𝑜𝑛 = 300 𝑑𝑎𝑦

Steel wire (10%-15%)

𝑡𝑜𝑛 $ $
10 x 10% x 400 = 400
𝑑𝑎𝑦 𝑇𝑜𝑛 𝑑𝑎𝑦

Total cost of product material PMC

$
= 2940
𝑑𝑎𝑦

 Raw Material Cost RMC

Waste tire (10 ton/day)

𝑡𝑜𝑛 $ $
10 x 100 = 1000
𝑑𝑎𝑦 𝑇𝑜𝑛 𝑑𝑎𝑦

Fuel oil (0.3 ton/day)

40
 𝑡𝑜𝑛 $ $
0.3 x 560 = 168
𝑑𝑎𝑦 𝑇𝑜𝑛 𝑑𝑎𝑦

Total cost of raw material RMC

$
= 1168 𝑑𝑎𝑦

5.4 Utility Costs UC

Cooling water (1 ton/hr)

𝑡𝑜𝑛 $ 24 ℎ𝑟 $
4 x 0.15 x = 14.4
𝑑𝑎𝑦 𝑇𝑜𝑛 𝑑𝑎𝑦 𝑑𝑎𝑦

Electricista (5.5 kWh)

𝑡𝑜𝑛 $ 24 ℎ𝑟 $
5.5 𝑑𝑎𝑦
x 0.15 𝑇𝑜𝑛 x 𝑑𝑎𝑦
= 19.8 𝑑𝑎𝑦

Total cost of utility TCU

$
= 34.2 𝑑𝑎𝑦

5.5 Fixed Operation Costs FOC

 Labor
From the obtained data, two operators per shift position and 2 shift positions per day
is assumed. Operator salaries vary by region and experience level.

For initial estimates, an average value of $50 per shift position per day, and the
working days is 20 days/month.

$ $
𝐶𝑜𝑠𝑡 𝑜𝑓 𝐿𝑎𝑏𝑜𝑟 = 2 × 2 × 50 = 200
𝑑𝑎𝑦 𝑑𝑎𝑦

 Maintenance
Maintenance which includes both materials and labor, and is typically estimated as 3 to 5% of
total fixed capital cost (TFCC) per month, depending on the expected plant reliability plants
with more moving equipment or more solids handling usually require higher maintenance.

𝑀$ $
= 0.03 × 𝑇𝐹𝐶𝐶 = 0.03 ∗ 71.354 = 2.14 = 107
𝑚𝑜𝑛𝑡ℎ 𝑑𝑎𝑦

41
  Overhead Expense OE
Is typically estimated as 65% of maintenance and labor costs.
= 0.65 × (𝑀𝑎𝑖𝑛𝑡𝑒𝑛𝑎𝑛𝑐𝑒 + 𝑙𝑎𝑏𝑜𝑟)

$
= 0.65 ∗ (200 + 107) = 200
𝑑𝑎𝑦

Total fixed operation costs TFOC is a sum of (Labor + Maintenance + OE)

$
TFOC = 507 𝑑𝑎𝑦

 Gross margin GM

GM = PMC – RMC - UC - TFOC = 2940 - 1168 - 34.2 – 507 = 1231 $/day = 24620 $/month

 Simple Pay-Back Time

A simple method for estimating the payback time is to divide the total investment by the
Gross margin.
𝑇𝑜𝑡𝑎𝑙 𝐹𝑖𝑥𝑒𝑑 𝐶𝑎𝑝𝑖𝑡𝑎𝑙 𝐶𝑜𝑠𝑡 𝑇𝐹𝐶𝐶
𝑆𝑖𝑚𝑝𝑙𝑒 𝑃𝑎𝑦 − 𝐵𝑎𝑐𝑘 𝑇𝑖𝑚𝑒 =
𝐺𝑟𝑜𝑠𝑠 𝑚𝑎𝑟𝑔𝑖𝑛 𝐺𝑀

71,354 $
𝑆𝑖𝑚𝑝𝑙𝑒 𝑃𝑎𝑦 − 𝐵𝑎𝑐𝑘 𝑇𝑖𝑚𝑒 = $
= 2.89 ≅ 3 𝑚𝑜𝑛𝑡ℎ𝑠
24,620 𝑚𝑜𝑛𝑡ℎ

This means that the project is strongly profitable and has a high income rate as
mentioned by the supplier.

42
 CHAPTER SIX
CONCLUSIO & RECOMMENDATIONS
6.1 Conclusion

Going by the obtained results, it can be concluded that:

 Air-gasification of wastes tier in a gasifier was successfully modelled based on

minimization of Gibbs free energy using Aspen Hysys.
 Sensitivity analysis revealed that gasification temperature, air-fuel ratio had
significant effects on syngas quality.
 From the Aspen Hysys model sensitivity analysis, it is recommended that to
obtain syngas of good quality from the downdraft gasifier system, temperature
should be between 750 – 950°C, air-fuel ratio should be between 1.35 – 1.51.
 The plant considered to be profitable, where the capital cost was found to be
71,354 $ and the payback period is within 3 months.

43
6.2 Recommendations

1. Applying this kind of processes to reduce the waste tire landfilling in Libya,
and take advantage of energy production.
2. Study the use of other type of wastes such as MSW in gasification process.
3. Include for the experimental work for waste tire pyrolysis mad gasification.

44
REFFERANCE
[1] Departement of Engineering (DOE), Gasification World Database 2007
(Current Industry Status Report)”, Office of Fossil Energy National Energy
Technology Laboratory (NETL) 2007.
[2] Isam Janajreh, Gasification of Waste Tires, Conference Paper · June 2014,
ResearchGate.
[3] Hita, I., Arabiourrutia, M., Olazar, M., Bilbao, J., Arandes, J.M. and
Sánchez, P.C. 2016. Opportunities and barriers for producing high quality
fuels from the pyrolysis of scrap tires. Renewable and Sustainable Energy
Reviews, 56, pp.745-759.
[4] Martínez, J.D., Murillo, R., García, T. and Veses, A. 2013. Demonstration of
the waste tire pyrolysis process on pilot scale in a continuous auger reactor.
Journal of hazardous materials, 261, pp.637-645.
[5] Pilusa, J., Shukla, M. & Muzenda, E., 2014. Economic Assessment of Waste
Tyres Pyrolysis Technology : A Case study for Gauteng Province, South
Africa. International Journal of Research in Chemical, Metallurgical and
Civil Engineering, 1(1), pp.41–49.
[6] Adhikari, B., De, D. and Maiti, S. 2000. Reclamation and recycling of waste
rubber. Progress in Polymer Science (Oxford), 25(7), pp.909–948.
[7] Dabić-Ostojić, S. et al., 2014. Applying a mathematical approach to improve
the tire retreading process. Resources, Conservation and Recycling, 86,
pp.107–117.
[8] Danon, B., Van Der Gryp, P., Schwarz, C.E. and Görgens, J.F. 2015. A
review of dipentene (dl-limonene) production from waste tire pyrolysis.
Journal of Analytical and Applied Pyrolysis, 112, pp.1-13.
[9] Kar, Y. 2011. Catalytic pyrolysis of car tire waste using expanded perlite.
Waste Management, 31(8), pp.1772–1782.
[10] Wang, W.C., Bai, C.J., Lin, C.T. and Prakash, S. 2016. Alternative fuel
produced from thermal pyrolysis of waste tires and its use in a DI diesel
engine. Applied Thermal Engineering, 93, pp.330-338.
[11] Martínez, J.D., Puy, N., Murillo, R., García, T., Navarro, M.V. and Mastral,
A.M. 2013. Waste tyre pyrolysis–a review. Renewable and Sustainable
Energy Reviews, 23, pp.179-213.
[12] Williams, P.T. 2013. Pyrolysis of waste tyres: A review. Waste
Management, 33(8), pp.1714–1728.

45
[13] Choi, G.G., Jung, S.H., Oh, S.J. and Kim, J.S., 2014. Total utilization of
waste tire rubber through pyrolysis to obtain oils and CO 2 activation of
pyrolysis char. Fuel Processing Technology, 123, pp.57- 64.
[14] Frigo, S., Seggiani, M., Puccini, M. and Vitolo, S. 2014. Liquid fuel
production from waste tyre pyrolysis and its utilisation in a Diesel engine.
Fuel, 116, pp.399-408.
[15] Pilusa, J., Shukla, M. & Muzenda, E., 2014. Economic Assessment of Waste
Tyres Pyrolysis Technology : A Case study for Gauteng Province, South
Africa. International Journal of Research in Chemical, Metallurgical and
Civil Engineering, 1(1), pp.41–49.
[16] Weitkamp, J., Raichle, A. and Traa, Y. 2001. Novel zeolite catalysis to
create value from surplus aromatics: Preparation of C2+-n-alkanes, a high-
quality synthetic steamcracker feedstock. Applied Catalysis A: General,
222(1–2), pp.277–297.
[17] Wojtowicz, M.A. and Serio, M.A. 1996. Pyrolysis of scrap tires: Can it be
profitable?. Chemtech- Washington DC-, 26, pp.48-53.
[18] Shelley, M.D. and El-Halwagi, M.M., 1999. Journal of Elastomers and
Plastics. Journal of Elastomers and Plastics, 31, pp.232–254.
[19] Peter Akhator , Jude Asibor, Simulation of Air‐Gasification of Wood Wastes
Using Aspen Plus, International Journal of Engineering Science and
Application Akhator and Asibor., Vol.5, No.3, 2021.
[20] P. Kannan, A. Al Shoaibi & C. Srinivasakannan, Process simulation and
sensitivity analysis of waste plastics gasification in a fluidized bed reactor,
WIT Transactions on Ecology and The Environment, Vol 163, 2012.
[21] Chaudhary Awais Salman, Ch Bilal Omer. Process Modelling and
Simulation ofWaste Gasification-Based Flexible Polygeneration Facilities
for Power, Heat and Biofuels Production. MDPI, Basel, Switzerland, 2020.
[22] Lanrewaju I. Fajimi, Bilainu O. Oboirien , Thomas A. Adams II. Simulation
studies on the co-production of syngas and activated carbon from waste tyre
gasification using different reactor configurations. Energy Conversion and
Management: X 11 100105. 2021.
[23] Peter Akhator, Jude Asibor. Simulation of Air‐Gasification of Wood Wastes
Using Aspen Plus. International Journal of Engineering Science and
Application. Vol.5, No.3, 2021.

46
[24] Chaudhary Awais Salman, Ch Bilal Omer. Process Modelling and
Simulation of Waste Gasification-Based Flexible Polygeneration Facilities
for Power, Heat and Biofuels Production. Energies, Published: 18 August
2020.
[25] HUAYIN GROUP for machine manufacturing, China, available at
https://www.oilpyrolysis.net/equipment/Waste-Tire-Recycle-to-Fuel-Oil-
Project.html.
[26] Chen, C.C. and Mathias, P.M. 2002. Applied thermodynamics for process
modeling. AIChE Journal, 48(2), pp.194-200.
[27] Alibaba Group ®.2023. [Online] Available from http://www.alibaba.com/.
[Accessed on: 22 Jan 2023].

47