Table of Contents

List of Figures ....................................................................................................................... 4 

List of Tables ......................................................................................................................... 6 

Chapter 1  The Problem and Its Scope ................................................................................ 7 

  Introduction ........................................................................................................... 7 

  Statement of the Problem ...................................................................................... 8 

  Significance of the Study ...................................................................................... 8 

  Objectives ............................................................................................................. 9 

  Scope and Limitations........................................................................................... 9 

Chapter 2  Theoretical Background .................................................................................. 11 

  Polymers and Plastic Resin Code ....................................................................... 11 

  Thermal Degradation of Plastics [18] ................................................................. 13 

  PID Temperature Controller ............................................................................... 14 

2.3.1  On/Off Operation .......................................................................................... 15 

  Pyrolysis [18] ...................................................................................................... 15 

2.4.1  Pyrolysis Products of Polyethylene [18] ....................................................... 16 

  Mass Balance for Batch Reactor [19] ................................................................. 18 

2.5.1  Oxygen balance in the Reactor...................................................................... 19 

  Energy Balance ................................................................................................... 20 

  Finite Difference Method [20] ............................................................................ 21 

  Conduction Heat Transfer [21] ........................................................................... 23 

2.8.1  Conduction through Cylindrical Shapes ....................................................... 24 

  Convection Heat Transfer ................................................................................... 25 

2.9.1
  External Natural Convection on Horizontal Walls [22] ..................................... 25 

2.9.2  External Natural Convection on Vertical Walls [22]....................................... 27 

1
 2.9.3  Internal Natural Convection – Isothermal Side Walls [22] ............................. 28 

  Radiation Heat Transfer ...................................................................................... 29 

2.10.1
  Enclosure with Gray Surfaces [21] ................................................................... 29 

2.10.2  Radiation Combined with Convection and Conduction [21]......................... 31 

Chapter 3  Review of Related Literature........................................................................... 33 

  Current state and future prospects of plastic waste as source of fuel: A review [6]
............................................................................................................................. 33 

  Co-pyrolysis of coal/waste polymer mixtures [2]................................................. 34 

  Co-pyrolysis characteristics and kinetics of coal and plastic blends [3] .............. 35 

  Influence of time and temperature on pyrolysis of plastic wastes in a semi-batch

reactor [4] ............................................................................................................. 36 

  Evaluation of pyrolysis product of virgin high density polyethylene degradation

using different process parameters in a stirred reactor. [5] .................................. 37 

  Evolution of products during the degradation of polyethylene in a batch reactor [7]

............................................................................................................................. 38 

  Reactor design and operation of small-size liquefaction plants for waste plastics
[23]
........................................................................................................................ 39 

Chapter 4  Methodology.................................................................................................... 40 

  Flow Chart .......................................................................................................... 40 

  Feedstock ............................................................................................................ 41 

4.2.1  Collection of Raw Material ........................................................................... 41 

4.2.2  Feedstock Pre-processing .............................................................................. 41 

4.2.3  Proximate Analysis ....................................................................................... 42 

  Experimental Set-up............................................................................................ 42 

4.3.1  Design of Electric Furnace ............................................................................ 43 

4.3.2  Batch Reactor ................................................................................................ 45 

2
 4.3.3  Carrier Gas .................................................................................................... 46 

4.3.4  Temperature Control ..................................................................................... 46 

4.3.5  Condenser ...................................................................................................... 47 

  Pyrolysis Experiment .......................................................................................... 48 

4.4.1  Mass loss Analysis ........................................................................................ 49 

4.4.2  Temperature Dependence of Pyrolysis Yield................................................ 50 

4.4.3  Heating Rate Dependence of Pyrolysis Yield ............................................... 50 

  Pyrolysis Oil Properties ...................................................................................... 54 

4.5.1  Physical Properties and Heating Value ......................................................... 54 

  Expected Output.................................................................................................. 55 

  Gantt Chart .......................................................................................................... 57 

APPENDIX A ..................................................................................................................... 58 

APPENDIX B...................................................................................................................... 60 

APPENDIX C...................................................................................................................... 66 

APPENDIX D ..................................................................................................................... 73 

References ........................................................................................................................... 76 

3
 List of Figures

Figure 2.1 ‐ Py‐GC/MS chromatogram of HDPE at 500 oC [18, p. 351]. ‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐17 
Figure 2.2 ‐ Simulated distillation boiling points distribution of HDPE pyrolysis condensate [18, p. 352]. ‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐17 
Figure 2.3 ‐ Approximation of derivatives. [20, p. 233] ‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐22 
Figure 2.4 ‐ Radial heat conduction through a cylindrical shell. ‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐24 
Figure 2.5 – Horizontal surfaces with plume (top row) and without plume (bottom row). [22, p. 219] ‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐25 
Figure 2.6 – Effect of the thermal boundary condition on the natural convection boundary layer along a vertical 
wall. [22, p. 200] ‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐27 
Figure 2.7 – Circulation patterns associated with regimes I –IV for the three classes of internal natural convection – 
Isothermal Surfaces. [22, p. 252] ‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐29 
Figure 2.8 ‐ Radiation exchange between two gray‐cylindrical surfaces. ‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐30 
Figure 4.1 – The Research Flow Scheme ‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐40 
Figure 4.2 ‐ Plastic waste made from plastic resin code number 2 ‐ HDPE (The PET bottles in this photo are not 
included as feedstock but the caps of the PET bottles are). ‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐41 
Figure 4.3 ‐ Buffalo 8" multifunctional heavy duty scissors used for feedstock sizing. ‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐42 
Figure 4.4 ‐ Schematic diagram of experimental set‐up. ‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐42 
Figure 4.5 ‐ Heat Balance of the system for approximating the required power input to the coil. ‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐43 
Figure 4.6 ‐ Furnace with electric resistance heating coil (Left ‐ Isometric View; Right ‐ Section View). ‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐44 
Figure 4.7 ‐ Conceptual Design of the Reactor (left ‐ showing inert gas and products flow direction; right ‐ section 
view, mounted to the furnace). ‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐45 
Figure 4.8 ‐ Rotameter (left) coupled to a pressure gage (right) use for flow control of the carrier gas. ‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐46 
Figure 4.9 ‐ Sample PID Controller (left) and Solid‐state relay (right) (Reference: https://images.google.com). ‐‐‐‐‐‐47 
Figure 4.10 ‐ Schematic diagram of initial set‐up of condensing system. ‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐48 
Figure 4.11 ‐ DefenderTM bench weighing scale manufactured by Ohaus. ‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐49 
Figure 4.12 ‐ Expected curve of the mass loss analysis experiment. ‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐55 
Figure 4.13 ‐ Expected DTA curve for the mass loss experiment. ‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐55 
Figure 4.14 ‐ Expected curve of condensed product, non‐condensable product and char yields of pyrolysis with 
respect to reactor temperature. ‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐56 
Figure 4.15 ‐ Expected curve for pyrolysis yields with varying heating rate. ‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐56 
Figure 4.16 ‐ Gantt Chart of the Project to be undertaken ‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐57 
Figure B.1 ‐ Reactor lid design and dimensions in millimeters. ‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐61 
Figure B.2 ‐ Reactor base design and dimensions in millimeters. ‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐62 
Figure B.3 ‐ Section view of furnace and reactor set‐up (1 ‐ outer surface of reactor; 2 ‐ inner suface of furnace). ‐‐64 
Figure B.4 ‐ Inner temperature trend of the polymer when subjected to a wall temperature of 807 oC. The interface 
and source code is shown in APPENDIX D. ‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐65 

4
Figure C.1 ‐ Electric Heating Furnace Dimensions. ‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐66 
Figure D.1 ‐ Visual Basic Interface for calculating the temperature distribution of a polymer in a cylindrical reactor.
 ‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐73 

5
 List of Tables

Table 2‐1 ‐ Resin Identification Code with suitability to Thermo Fuel systems. [16] [17] ‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐12 
Table 4‐1 ‐ Sample Tabulation of the Data to be recorded on the investigation of the effect of reactor temperature 
of pyrolysis yields. ‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐52 
Table 4‐2 ‐ Sample Tabulation of the data to be recorded on the investigation of the heating rate dependence of 
pyrolysis yields.‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐53 
Table A‐1 ‐ Specific Volume of HDPE (10‐3 m3/kg) at various temperatures and pressures. [15] ‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐58 
Table A‐2 – Thermodynamic Properties of Air at atmospheric pressure. [21] ‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐59 
Table A‐3 ‐ Thermodynamic Properties of Nitrogen gas at atmospheric pressure. [21] ‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐59 

6
 Chapter 1 The Problem and Its Scope

Introduction

Rapid urban development and economic growth lead to increase in the production of
commodities. The quantity of materials used for handling and transport of such commodities
should be adequate enough to accommodate the rising demand of consumer products. Plastic are
one of those materials used for handling and transport of products. To cater the increasing demands
of such commodities, generation of plastics would need to be increased which in turn increases the
plastic waste produced.

In the year 2010, in the Philippines, the total waste generation was estimated at 35 tons per
day or 13.1 million tons per year based on data provided by National Solid Waste Management
Commission (NSWMC) on their National Solid Waste Management Strategy for 2012 - 2016.
Particularly in Cebu City, projected waste disposal will amount to 195, 292 tons per year in 2016
and 217, 997 tons per year in 2020 based on a study conducted by UNEP. In the 2008 survey,
plastic waste is 12.36% of the total waste disposed, 2.64% of this waste comprises high density
polyethylene (HDPE) [1].

The local government would need to apply certain measures in order to manage the
disposal of such wastes – which is projected to increase year after year. Ways of waste disposal
generally includes the 3R (reduce, reuse, recycle) principle.

Fuel generation from biomass is an emerging alternative solution to our global dependence
on fossil fuel which is under recycling principle of waste disposal. Initiatives by researchers,
incorporate plastic waste into coal as feedstock to utilize the energy content of waste plastics for
energy production [2] [3]. Other researches utilized mixtures of virgin plastic materials extract
pyrolysis oil and non-condensable gas [4] [5]. Producing diesel fuel from waste plastic has a great
potential for resource conservation and GHG emission reduction. This resource conservation goal
is very important for most of the national and local governments, where rapid industrialization and
economic development is putting a lot of pressure on natural resources.

Worldwide research on energy generation by processing of waste plastic are being done.
These processes generally include incineration, gasification and pyrolysis. Incineration of waste
materials involves direct combustion of the waste in suitable amount of oxygen. Gasification is

7
indirect heating of the biomass in the presence of limited oxygen to primarily produce gaseous
fuels, which are also called syngas or fuel gas. Pyrolysis on the other hand, is simply describe as
thermal degradation of biomass in the absence of oxygen. Pyrolysis process will produce solid,
liquid, and gaseous fuel products namely char, tar or bio-oil, and fuel gas, respectively. Research
efforts has focused more on gasification and pyrolysis since incineration of commercial waste pose
a problem in the environmental protection scenario.

The product yields of pyrolysis greatly depends on several factors such as the temperature
range at which the feedstock is subjected, heating rate, residence time of the volatile matter, and
to a lower extent on other reactor conditions such as pressure and the type of carrier gas. In the
current context, pyrolysis of high density polyethylene (HDPE) derived from plastic bottle cap
wastes will be studied. Effect of reactor temperature and heating rate to the amount of pyrolysis
products will be investigated. It is reported that pyrolysis of HDPE produces mainly n-paraffins
and 1-olefins in liquid products [6] [7] which are can be refined to be used as a substitute for diesel
and gasoline derived from fossil fuel.

Statement of the Problem

In developing countries such as the Philippines, waste handling and management are still
considered as a continuing challenge since rapid industrialization increases waste generation.
Every year, the volume of waste that is collected locally is increasing. Ways other than landfill
disposal and recycling should be considered. One factor contributing to climate change is the
continuous dependence of the industry on fossil fuel. Alternative fuel source which is carbon
neutral is encourage globally.

Numerous research on pyrolysis of plastic has been conducted particularly high density
polyethylene (HDPE) but most of them utilized virgin raw materials instead of waste plastic
materials. Prior researches utilizing waste HDPE ( [8], [9], [10], [11], [12], [13]) didn’t investigate
HDPE specifically from plastic bottle caps, which is a very common plastic waste.

Significance of the Study

The study to be conducted benefits the following sectors of the society:

8
  The Local Community - this study would serve as a reference for the possibility of
future technological developments on plastic to oil projects for economic and
environmental benefits.
 International Research Community - the study to be conducted will contribute to the
current developments on the field of polymer pyrolysis.
 The Students - the developed pyrolysis set-up can be utilized by the students who would
conduct future pyrolysis studies.
 The University - the pyrolysis set-up will augment the current inventory of equipment
and apparatus in the Mechanical Engineering laboratory.

Objectives

The following are the objectives of the study:

1. To develop a laboratory-scale pyrolysis set-up.

2. To extract crude oil from waste HDPE by pyrolysis experiment.
3. To investigate the effect of temperature and heating rate on the pyrolysis yields of
HDPE.

Scope and Limitations

The proposed research shall include collection of waste HDPE (resin code 2) from
household waste. The used plastic will be pre-processed prior to pyrolysis. Pre-processing includes
turning the plastics into smaller pieces by cutting, washing the plastics in clean water and then
solar drying.

Characterization of the plastic material will be conducted by mass loss analysis done using
the experimental setup. This analysis will only be used to guide for the selection of temperature
range to be used on the pyrolysis proper and not to determine kinetic degradation characteristic of
HDPE (e.g. activation energy, pre-exponential factor and etc.).

Pyrolysis experiment shall be done on a laboratory-scale batch reactor. Electric heating

will be applied. A thermocouple connected to a temperature controller, which is coupled to a Solid
State Relay, will be used for temperature control. Calculated design of the condensing system will
not be made, this set-up and configuration will be based on experimentation.

9
 Heating value of the pyrolysis oil will be determined by oxygen bomb calorimeter based
on ASTM D2382-8. Physical characteristic of the oil such as viscosity, flash point and density
shall be obtained.

Since this is an experimental investigation on conversion of HDPE into pyrolysis oil, no

mathematical modelling of the kinetics and mechanism of pyrolysis process will be conducted.
Chemical analysis of the solid and liquid products of pyrolysis will not be conducted. A sample of
the non-condensable gas product will be analysed by a gas chromatography apparatus. Economic
justification of the study will not be investigated.

10
 Chapter 2 Theoretical Background

Polymers and Plastic Resin Code

A polymer is a large molecule (macromolecule) built up by the repetition of small chemical

units. To illustrate this, Eq. 2-1 shows the formation of the polymer polyethylene, with the
chemical formula (C2H4)n.

2-1

The ethylene molecule contains a double bond. Chemists have devised methods of opening
this double bond so that literally thousands of ethylene molecules become linked together. The
resulting structure, enclosed in square brackets, is the polymer polyethylene. Ethylene itself is
referred to as a monomer, which is defined as any molecule that can be converted to a polymer by
combining with other molecules of the same or different type. The unit in square brackets is called
the repeating unit. The subscript designation, n, indicates the number of repeating units strung
together in the polymer chain (molecule). This is known as the degree of polymerization (DP). It
specifies the length of the polymer molecule [14]. This can also be done by use of the term
molecular weight (MW). By definition, MW(Polymer) = DP x MW(Repeat Unit). Commercial
grade HDPE has DP in the range 10,000 to 100,000. The enthalpy melting of HDPE ranges from
192 to 218 J/g or 46 to 52 cal/g. The equilibrium melting temperature ranges from 138 – 146 oC
(the most used value is 145.5oC) [15].

The SPI resin identification coding system is a set of symbols placed on plastics to
identify the polymer type. It was develop by the Society of the Plastics Industry (SPI) in 1988 and
is used internationally. The symbols used in the code consist of arrows that cycle clockwise to
form a rounded triangle and enclosing a number, often with an acronym representing the plastic
below the triangle. The table below shows the following resin code, their properties, product
application and suitability to pyrolysis system.

11
Table 2-1 - Resin Identification Code with suitability to Thermo Fuel systems. [16] [17]

Thermo
Fuel
Resin Codes Description Properties Product Applications
system
suitability

Polyethylene • Clear and Plastic bottles for

Terephthalate optically soft drinks, water,
(PET, PETE). PET smooth juice, sports drinks, Not
is clear, tough, and surfaces for beer, mouthwash, suitable,
has good gas and oriented films catsup and salad should be
moisture barrier and bottles dressing. avoided
properties.

High Density • Excellent Bottles for milk,

Polyethylene resistance to water, juice,
(HDPE). HDPE is most solvents cosmetics, shampoo,
Very Good
used to make many dish and laundry
types of bottles. detergents, and
household cleaners.

Polyvinyl Chloride • High impact Rigid packaging

(PVC, Vinyl). In strength, applications include
Not
addition to its stable brilliant clarity, blister packs and
suitable,
physical properties, excellent clamshells.
should be
PVC has good processing
avoided
chemical resistance, performance
and weatherability.

Low Density • Excellent Bags for dry

Polyethylene resistance to cleaning,
(LDPE). LDPE is acids, bases newspapers, bread,
used predominately and vegetable frozen foods, fresh Very Good
in film applications oils produce, and
due to its toughness household garbage.
and flexibility.

12
 Polypropylene • Excellent Containers for
(PP). PP has good optical clarity yogurt, margarine,
chemical resistance, in biaxially takeout meals, and
is strong, and has a oriented films deli foods. Medicine Very Good
high melting point and stretch bottles. Bottle caps
making it good for blow molded and closures.
hot-fill liquids. containers

Polystyrene (PS). • Excellent Food service items,

PS is a versatile moisture such as cups, plates,
plastic that can be barrier for bowls, cutlery,
Very good
rigid or foamed. short shelf life hinged takeout
(gives
General purpose products containers
excellent
polystyrene is clear, • Excellent (clamshells), meat
fuel
hard and brittle. It optical clarity and poultry trays,
properties).
has a relatively low in general and rigid food
melting point. purpose form containers (e.g.,
yogurt).

Other. Use of this Dependent on Three- and five-

code indicates that a resin or gallon reusable water
package is made combination of bottles, some citrus
with a resin other resins juice and catsup Fair, Pre-
than the six listed bottles. treatment
above, or is made of Oven-baking bags, required
more than one resin barrier layers, and
and used in a multi- custom packaging.
layer combination.

Thermal Degradation of Plastics [18]

The decomposition of plastics can be considered as depolymerisation of polymer into low-

molecular product. The general reaction mechanism for the thermal degradation is described with
the following steps.

 Initiation may occur at random or end-chain positions.

 Depropagation is the release of olefinic monomeric fragments from primary radicals.
 Hydrogen chain transfer reaction, which may occur as intermolecular or intramolecular
processes, leads to the formation of olefinic species and polymeric fragments. Moreover,

13
 secondary radicals can also be formed from hydrogen abstraction through an
intermolecular transfer reaction between a primary radical and a polymeric fragment.
 Β-cleavage of secondary radicals leads to an end-chain olefinic group and a primary
radical.
 Termination takes place either in a bimolecular mode with the coupling of two primary
radicals or by disproportion of the primary macroradicals.

The decomposition of plastics depends on the plastic type. HDPE decomposition is

random-chain scission wherein the polymer is broken up randomly into smaller molecules of
varying chain lengths. Producing a volatile with or without a double bonds. Other reaction
mechanisms of plastics are end-chain scission, chain-stripping and cross-linking.

PID Temperature Controller

A control loop may consist of four or five elements and it may control in an open loop or
a closed loop form.

 Primary Element: senses the Process Variable. A thermocouple measuring

temperature is an example.
 Controller Element: may or may not be able to accept the signal from the Primary
Element without signal conditioning. If the controller element is not electrically
designed to receive the input directly, a signal Conditioner Element is needed.
 Final Control Element: the Controller Element sends the control signal to the Final
Control Element. The Final Control Element controls the Manipulated Variable
Element.

The Final Control Element may be a motor positioning valve used to control the
delivery of natural gas into a burner system, or a Solid State Relay controlling voltage
into an electric load.

 Manipulated Variable Element: the energy of the process such as Electrical Power,
Steam, Natural Gas, etc. needed by the process for the process variable to reach the set
point.

14
2.3.1 On/Off Operation

On/off control is the simplest way to control a process; a controller using on/off control
turns an ouput on or off when the process variable reaches a certain limit below or above the set
point. On/off control will cycle the process variable around the set point. The process variable
deviation from the set point is primarily due to the process dynamics rather than the controller
gain.

Controllers provide an adjustable spread or hysteresis for on/off control loops. If the spread
or hysteresis is set to 0 % and the set point is 200 oF the output will be turned off when the process
variable is equal to the set point. In most heating applications the process variable will continue
through and above the set point due to thermal dynamics. When the process variable has cycled
back down through the set point – 5 (195 oF) the output will then be turned back on. Typically, it
is more critical as to when the heat is turned back on below the set point as to how close the control
cycle will be to the set point. Occasionally, this adjustable spread or hysteresis is too narrow for
the process and an undesirable and intermittent chattering of the final control element may be
present. By monitoring the process the user can then readjust the spread or hysteresis to eliminate
this disturbance.

Pyrolysis [18]

Pyrolysis, also termed thermolysis (Greek: pur = fire; thermos = warm; luo = loosen), is a
process of chemical and thermal decomposition, generally leading to smaller molecules.
Semantically, the term thermolysis is more appropriate than pyrolysis, since fire implies the
presence of oxygen and hence of reactive and oxygen-bearing intermediates. In most pyrolysis
processes, however, air is excluded, for reasons of safety, product quality, and yield.

Pyrolysis can be conducted at various temperature levels, reaction times, pressures, and in
the presence or absence of reactive gases or liquids, and of catalysts. Plastic pyrolysis proceeds at
low (<400oC), medium (400 – 600oC) or high temperature (>600oC). The pressure is generally
atmospheric. Subatmospheric operation, whether using vacuum or diluents, e.g. steam, may be
selected if the most desirable products are thermally unstable, e. g. easily repolymerizing, as in the
pyrolysis of rubber or styrenics.

15
 The thermal decomposition of polymers yields gases, distillates and char, albeit in widely
variable relative amounts. These can be applied as fuels, petrochemicals, and monomers.
Depending on the polymers or polymer mixtures fed and the operating conditions used, yields can
vary widely. As a rule, both gaseous and liquid products are mixtures of numerous different
compounds. The problem of fractionating these effluents and upgrading to commercial
specifications, while separating undesirable impurities, must be investigated on case-by-case basis.
The char incorporates fillers pigments, and ash.

Pyrolysis processes involve breaking bonds and are often endothermic, so that ensuring a
supply of heat to the reacting material is essential and generally rate-determining. Partial oxidation
supplies such heat internally, but the pyrolysis products are diluted by oxidation or combustion
products.

2.4.1 Pyrolysis Products of Polyethylene [18]

PE pyrolysis advances at the maximal rate between 420 and 500oC leading to an imposing
series of straight-chain hydrocarbons. The yield of hydrocarbon gases and solid residue normally
stay low compared with liquid in conventional reactors. In the pyrogram of HDPE sample
displayed in Figure 2.1, the first peak (at 2 min retention time) covers C1-C5 hydrocarbons. The
next peaks from C6 to C12 include the boiling range of diesel oil (retention time 10-18 min). The
heavy oil and wax components from C20 on up to the end of the pyrogram constitute seemingly
the major part of PE pyrolysate. Because there is no control on the residence time in the batch
pyrolysis set-up, pyrolysis at higher temperature allows larger molecular weight species to leave
quickly. At low furnace temperature, the larger molecules are not vaporized, but spend longer
times in the furnace to undergo further cracking. This is shown in Figure 2.2, which shows the
simulated distillation analysis of HDPE pyrolysis products for various furnace temperatures. It is
evident that higher boiling point products desired for lube base oil are produced in greater
abundance at the higher pyrolysis temperatures (600-650oC).

16
 Figure 2.1 - Py-GC/MS chromatogram of HDPE at 500 oC [18, p. 351].

Figure 2.2 - Simulated distillation boiling points distribution of HDPE pyrolysis

condensate [18, p. 352].

17
 Mass Balance for Batch Reactor [19]

Batch reactor operation is fundamentally an unsteady state process; we expect all variables
to change with time. All materials are charged into a batch reactor at the outset and no withdrawal
is made until the reaction has reached the degree of completion desired. The mixture in the reactor
volume, VR, is generally well stirred. This means that concentrations and the temperature may be
assumed to be uniform at every point within the reactor. We will initially only consider isothermal
reactors. However, we note that, in an actual reactor, the temperature may also change with time.
The volume may be kept fixed (constant volume), or may be varied during the reaction to keep the
pressure constant.

If the reactor volume VR is filled with reactant “A”, the mass balance for component “A”
over the volume VR, over the time period t to (t + Δt) is given by:

 M A N A t   M A N A t t   M ArAVR  t 2-2

where:

NA = NA(t) = number of moles of reactant “A” within the system at time t,

MA = the molecular weight of “A”, and,

rA = rA(t) = net reation rate of component “A”.

We may divide every term by MA. Taking the limit as  t  0, we get

dN A 1 dN A
 rAVR  and rA   .
dt VR dt

This is the mass balance equation for a batch reactor expressed in terms of the
disappearance of a reactant.

A homogenous chemical reaction would be expected to proceed either (a) until equilibrium
reached, or, (b) in the case of an irreversible reaction, until the reactants are exhausted. The time
necessary for achieving a given degree of reaction, say from N AO  N A is found from integrating
the mass balance equation.

1 dN A
rA  
VR dt

18
The conversion xA at any time t is defined as:

N AO  N A dN A
xA  ; dx A   2-3
N AO N AO

We consider the case where a first order irreversible reaction, A  B , with rate expression

rA  kCA , is carried out in a batch reactor,

kN A kN AO 1  xA 
rA  kCA   2-4
VR VR

where k normally depends exponentially on the temperature:

Eo

k  koe RT 2-5

where:

ko = pre-exponential factor, /min

Eo = activation energy, kcal/mole

R = Universal gas constant, kcal/mole-K

T = temperature, K

generally referred to as Arrhenious equation.

2.5.1 Oxygen balance in the Reactor

To estimate the amount of oxygen in the reactor with respect to time, a mass balance will
be used,

m in  m out  m reactor

The mass of oxygen input, min to the reactor is zero since pure nitrogen gas is allowed to
flow. The change in mass oxygen in the reactor is a negative value since trace amounts of oxygen
will be decreasing with time as more nitrogen is inputted. The equation now becomes

m reactor  m out

19
 m  t  t   m  t   m  t 
  Q
 t  t   t V

or

dm  t   m  t 
  Q 2-6
dt V

where:

Q = volume flow rate of inert gas to the reactor, m3/s

V = remaining volume of the reactor after the polymer is melted, m3

m  t  = mass of oxygen in the reactor with time, g

After integration of Eq. 2-6 , we have

Q
 t
m  t   mo e V 2-7

Assuming that complete mixing of gasses is achieved, Eq. 2-7 is used to approximate the
amount of trace oxygen left in the reactor after purging with a flow rate, Q at a given time, t.

Energy Balance

The energy equation for the experimental model is in the form

 T T T T    2T  2T  2T 
cp  u v w   k  2  2  2   q
 t x y z   x y z 

in cylindrical coordinates (r,θ,z):

 T T v T T   1   T  1 T T
2 2

cp   vr   vz k r 
 2    q 2-8
 t r r  z   r r  r  r 
2
z 2 

The reactor design dictates all the velocity terms equal to zero. Since the temperature is assumed
to be constant with respect to θ and z, Eq. 2-8 now becomes

20
 T 1   T 
cp k r   q 2-9
t r r  r 

where:

T = polymer temperature, oK r = radius of reactor, m

ρ = polymer density, kg/m3 q’’’ = heat of reaction and volatization, J/kg

Cp = specific heat, J/kg- k = thermal conductivity, W/m-K

Equation 2-9 will be used for modelling the temperature distribution inside the reactor.

Finite Difference Method [20]

The energy balance and rate equation will be used either directly to arrive at a finite-
difference formulation (physical formulation) or to arrive at the governing differential equation.
The differential equation can then be converted into finite-difference form (mathematical
formulation).

The only new idea that is used is the approximation of derivatives in terms of differences.
Let us consider the function t(x) shown in Figure 2.3. The exact definition of the derivative at xm
is given as

21
 Figure 2.3 - Approximation of derivatives. [20, p.
233]

 dt  t  xm  x   t  xm 
 dx   lim
xm
x 0 x

As an approximation, let us not go through the limiting process. Then we could write

 dt  t  xm  x   t  xm  tm1  tm
 dx   x

x
2-10
xm

This would be an approximate expression for the derivative at xm, or more appropriately, we could
consider it to be an approximation of the derivative midway between xm and xm+1. That is,

 dt  tm 1  tm
 dx  1  x 2-11
m
2

Similarly, the slope at xm – Δx/2 may be written as

 dt  tm  tm 1
 dx  1  x 2-12
m
2

22
 The second derivative of a function is simply the rate of change of the first derivative. Thus
the second derivative at xm may be approximated as

 dt   dt 
   
d t 
2
 dx  xm x /2  dx  xm x /2
 dx 2   x
 m

Equations 2-11 and 2-12 may now be substituted into the above equation to give

tm 1  tm tm  tm 1
d t2 
 x x
 dx 2  x
 m

which reduces to

 d 2t  tm 1  2tm  tm 1
 dx 2   2-13
 x 
2
 m

Conduction Heat Transfer [21]

Whenever a temperature gradient exist in a solid medium, heat will flow from the higher-
temperature to the lower-temperature region. The rate at which heat is transferred by conduction,
qk, is proportional to the temperature gradient dT/dx times the area A through which heat is
transferred:

dT
qk  A
dx

In this relation, T(x) is the local temperature and x is the distance in the direction of the
heat flow. The actual rate of heat flow depends on the thermal conductivity k, which is a physical
property of the medium. For conduction through a homogeneous medium, the rate of heat transfer
is then

dT
qk  kA
dx

23
 The minus sign is a consequence of the second law of thermodynamics, which requires that
heat must flow in the direction from higher to lower temperature.

2.8.1 Conduction through Cylindrical Shapes

In this section we will obtain solutions to some problems in cylindrical and spherical
systems that are often encountered in practice. Probably the most common case is that of heat
transfer through a pipe with a fluid flowing inside [21]. This system can be idealized, as shown in
Figure 2.4, by radial heat flow through a cylindrical shell. Our problem is then to determine the

temperature distribution and the heat transfer rate in a hollow cylinder of length L if the inner- and
outer-surface temperatures are Ti and To, respectively, and there is no internal heat generation.
Since the temperatures at the boundaries are constant, the temperature distribution is not a function
of time and the appropriate form of the conduction equation is

d  dT 
r 0
dr  dr 

Integrating once with respect to radius gives

dT dT C1
r  C1 or 
dr dr r

A second integration gives T = C1 ln r + C2. The constants of integration can be determined

from the boundary conditions:

Ti  C1 ln ri  C2 at r  ri

Thus, C2 = Ti – C1 ln ri. Similarly, for To,

Figure 2.4 - Radial heat conduction through a

cylindrical shell.

24
 T0  C1 ln ro  Ti  C1 ln ri at r  ro

Thus, C1 = (To – Ti)/ln(ro/ri).

The temperature distribution, written in dimensionless form, is therefore

T  r   Ti ln  r / ri 

To  Ti ln  ro / ri 

The rate of heat transfer by conduction through the cylinder of length L is,

dT C T T
qk  kA  k  2 L  1  2 Lk i o 2-14
dr r ln  ro / ri 

Convection Heat Transfer

2.9.1
External Natural Convection on Horizontal Walls [22]

Two flow types are encountered in the extreme where the plane wall becomes horizontal
(Figure 2.5). When the wall is heated (and faces upward, or when it is cooled and faces downward,
the flow leaves the boundary layer as a vertical plume rooted in the central region of the wall.
When the temperature difference is sufficiently large, the heated fluid rises from all over the
surface. In cases where the surface is hot and faces downward, or when it is cold and faces upward,
the boundary layer covers the entire surface, and the flow spills over the edges. This situation is

Figure 2.5 – Horizontal surfaces with plume (top row) and without
plume (bottom row). [22, p. 219]

25
illustrated in the lower half of Figure 2.5. A two-sided plate, hot or cold, will have flow of one
type on the top side, and flow of the other type on the bottom side.

Average Nusselt number measurements for several horizontal-plate configurations have

been correlated by defining the characteristic length of the plane surface:

A
L 2-15
P

In this definition, A is the area of the plane surface and p is the perimeter of A. In the case
of a disk of diameter D, for example, L = D/4. The Nu L formulas listed below are valud for Prandtl
numbers greater than 0.5. The average Nusselt number Nu L and the Rayleigh number RaL are
both based on L.

In the case of hot surfaces facing upward, or cold surfaces facing downward (Figure 2.5,
top), the Nusselt number varies as

Nu L  0.54 Ra1/4
L (104  RaL  107 ) 2-16

Nu L  0.15Ra1/3
L (107  RaL  109 ) 2-17

where RaL is calculated using the characteristic length L and ,

g TL3 2-18
RaL 


where g = acceleration due to gravity, 9.81 m/s2

β = coefficient of thermal expansion, 1/K

ΔT = temperature difference between the two vertical walls, oK

α = thermal diffusivity, m2/s

ν = kinematic viscosity, m2/s

The convective heat transfer coefficient, hc can now be calculated by the definition of
Nusselt number,

26
 hc L
Nu L  2-19
k

Equations 2-16 to 2-18 are written for isothermal surfaces. The same correlations can be
used for uniform-flux surfaces, noting that in those cases, Nu L and RaL would be based on the L-
averaged temperature difference between the surface and the surrounding fluid.

2.9.2 External Natural Convection on Vertical Walls [22]

Consider Figure 2.6, the boundary layer flow remains laminar if y is small enough so that
Rayleigh number Ray does not exceed a certain critical value. In the laminar range, Gry < 109, a
correlation that represents the experimental data accurately is

0.67 Ra1/4
y
Nu y  0.68  4/9 2-20
1   0.492 / Pr 9/16 
 

Nu y  0.68  0.515Ra1/4
y  Pr  0.72  2-21

where the Rayleigh number is evaluated from the height of the wall to be consider.

Figure 2.6 – Effect of the thermal boundary condition on the

natural convection boundary layer along a vertical wall. [22,
p. 200]

27
2.9.3 Internal Natural Convection – Isothermal Side Walls [22]

From an engineering standpoint, a good way to use the result of heat transfer through a
two-dimensional rectangular space heated from the side is to think of three classes of possible
applications:

1. Tall enclosures (H/L > 1). The Nussel number formula recommended for this class is
Equation 2-22. This calculation procedure is applicable when  L / H  Ra1/4
H  5 , that is,

when the convective heat transfer effect is significant (Nu > 1).

q L
Nu   0.364 Ra1/4 2-22
 kH T  / L H
H

Where RaH is the Rayleigh number based on the enclosure height.

g TH 3 2-23
RaH 


where H = height of the wall, m

L = width of the enclosure, m

ν = kinematic viscosity, m2/s

2. Shallow enclosures (H/L < 1). This is another class of possible application but the
empirical correlations involved for this class of applications are not shown here since
the present study would apply tall enclosure configuration.
3. Square enclosures (H/L = 1). The empirical equations involved for this class of
applications are not shown here since the present study would apply tall enclosure
configuration.

28
 Figure 2.7 – Circulation patterns associated with regimes I –
IV for the three classes of internal natural convection –
Isothermal Surfaces. [22, p. 252]

Radiation Heat Transfer

The quantity of energy leaving a surface as radiant heat depends on the absolute
temperature and the nature of the surface. A perfect radiator, which is referred to as blackbody,
emits radiant energy from its surface at a rate as given by

q r   A1T14

The heat flow rate qr will be in watts if the surface area A, is in square meters and the surface
temperature T1 is in kelvin; σ is a dimensional constant with a value of 5.67 x 10-8 (W/m2K4) [21].

2.10.1
Enclosure with Gray Surfaces [21]

To illustrate the procedure for calculating radiation heat transfer between gray surfaces, we
will derive an expression for the rate of radiation heat transfer between two long concentric
cylinders of areas A1 and A2 and temperatures T1 and T2, respectively.

29
 Referring to Figure 2.8, the shape factor for the smaller cylinder of area A1 relative to the
larger cylinder that enclosed it, F1-2 is 1.0. From qi  j   J i  J j  Ai Fi  j   J i  J j  Aj F j i ,

Figure 2.8 - Radiation exchange between two

gray-cylindrical surfaces.
N
A1F12  A2 F21 and F21  A1 / A2 . Since surface 2 can partly view itself, from F
j 1
i j  1.0 we

Ai i  N 
have also F22  1   A1 / A2  . From qi   Ebi  J i  and qi  Ai  J i   J j Fi  j  , the net rate
1 i  j 1 
of heat loss from A1 and A2 are

A11
q1   Eb1  J1   A1  J1  J 2 
1  1

and

A2 2
q2   Eb 2  J 2   A2  J 2  J1 F21  J 2 F2 2 
1 2

Substituting the appropriate expressions for F2-1 and F2-2 yields the relation
q2  A1   J1  J 2   q2 , as expected from an overall heat balance [21]. Eliminating J2 and

substituting for J1 in the heat loss equation for A1 gives

A1  Eb1  Eb 2 
q1  2-24
1/ 1   A1 / A2  1   2  /  2 

30
where:

A1 = Surface area of inner cylinder, m2

Eb1 = Black body radiation of inner cylinder, W/m2

Eb2 = Black body radiation of outer cylinder, W/m2

ε1 = emissivity of the outer surface of inner cylinder

ε2 = emissivity of the inner surface of outer cylinder

The net rate of heat transfer in simple systems where radiation is transferred only betwwen
two gray surfaces can also be written in terms of an equivalent conductance A1 F1 2 in the form

q12  A1F12  Eb1  Eb 2  2-25

For two concentric cylinders or two concentric spheres,

1
F12  2-26
1  1  / 1   1   A1 1   2  / A2 2 

2.10.2 Radiation Combined with Convection and Conduction [21]

Energy exchange by radiation is the predominant heat-flow mechanism at high temperature

because the rate of heat flow depends on the fourth power of the absolute temperature. In many
practical problems, however, convection and conduction cannot be neglected, and in this section
we shall consider problems that involve two or all three modes of heat flow simultaneously.

To include radiation in a thermal network involving convection and conduction is it often

convenient to define a radiation heat transfer coefficient, hr as

qr   T14  T24  
hr   F1 2   2-27
A1 T1  T2   T1  T2 

where A1 = area upon which F1 2 is based, m2

T1  T2 = a reference temperature difference, in K, in which T2 may be chosen equal to T2

or any other convenient temperature in the system

31
 hr = radiation heat transfer coefficient, W/m2 K

Once a radiation heat transfer coefficient has been calculated, it can be treated similarly to
the convection heat transfer coefficient, because the rate of heat flow becomes linearly dependent
on the temperature difference and radiation can be incorporated directly in a thermal network for
which the temperature is the driving potential. Knowledge of the value of hr is also essential in

determining the overall conductance h for a surface to or from which heat flows by convection
and radiation,

h  hc  hr 2-28

32
 Chapter 3 Review of Related Literature

Current state and future prospects of plastic waste as source of fuel: A review [6]

Due to the depleting fossil fuel sources such as crude oil, natural gas, and coal, the present
rate of economic growth is unsustainable. Therefore, many sources of renewable energy have been
exploited, but the potentials of some other sources such as plastics waste are yet to be fully
developed as full scale economic activity. Development and modernization have brought about a
huge increase in the production of all kinds of plastic commodities, which directly or indirectly
generate waste due to their wide range of applications coupled with their versatility of types and
relatively low cost. The current scenario of the plastic recycling technology is reviewed in this
paper. The aim is to provide the reader with an in-depth analysis with respect to the pyrolysis of
plastic waste as obtained in the current recycling technology. As the calorific value of the plastics
is comparable to that of hydrocarbon fuel, production of fuel form plastic waste would provide a
good opportunity to utilize the waste as a better alternative to dumpsites. Different techniques of
converting plastic wastes into fuel including thermal and catalytic pyrolysis, microwave-assisted
pyrolysis and fluid catalytic cracking are discussed in detail. The co-pyrolysis of plastics waste
disposal as a partial replacement of the depleting fossil fuel with the hope of promoting a
sustainable environment.

This paper serves as a major reference for the proponent to get an overall insight of the
current technologies dedicated to pyrolysis of plastic waste. An in-depth analysis with respect to
the pyrolysis of plastic waste was obtained. Several journals publications, which focused on
pyrolysis of HDPE, cited in this paper were deemed useful.

33
 Co-pyrolysis of coal/waste polymer mixtures [2]

Mixtures of coal/waste tires, coal/waste plastics and coal/waste cotton were pyrolyzed in
the laboratory pyrolytical unit built in IRSM AS CR Prague. Non-caking hard coal (mine Lazy)
and its mixtures with some organic wastes were pyrolyzed in a quartz reactor inserted in a vertical
tube furnace. The main product yields (coke, tar, gas and reaction water) documented exhibit
entirely different influence of added waste. Results demonstrated that co-pyrolysis is meaningful
in case of waste tires and plastics. Howerver, in case of co-processing with waste cotton (natural
textile), the results are not promising.

This journal provides insights on early developments of pyrolysis of waste plastic, wherein
plastics are co-pyrolyzed with coal. The paper also provides properties of waste plastics such as
proximate analysis, density and calorific value which is useful for cross referencing with the result
that will be obtained later with HDPE plastics.

34
 Co-pyrolysis characteristics and kinetics of coal and plastic blends [3]

Co-pyrolysis behaviours of different plastics (high density polyethylene, low density

polyethylene and polypropylene), low volatile coal (LVC) and their mixtures were investigated by
TGA. Experiments were conduted under N2 atmosphere at heating rate of 20 oC.min from room
temperature to 750 oC. The results showed that the thermal degradation temperature range of
plastic was 438-521 oC, while of coal (LVC) was 174-710 oC. Plastics showed similar pyrolysis
characteristics due to similar chemical bonds in their molecular structures. The overlapping
degradation temperature interval between coal and plastic decomposition. The difference of weight
loss percent (ΔW) between experimental and theoretical ones, calculated as an algebraic sum of
those from each separted component, ΔW is 2.0-2.7 % at the pyrolysis temperature higher than 530
o
C, which indicated that the synergistic effect during pyrolysis occurs mainly in the high
temperature region. The kinetic studies were performed according to Coats and Redfern method
for first-order reaction. It was found that for plastics (HDPE, LDPE and PP), the pyrolysis process
can be described by three and four consecutive first-order reactions, respectively. The estimated
kinetic parameters viz., activation energies and pre-exponential factors for coal, plastic and their
blends, were found to be in the range of 35.7-572.8 kJ/mol and 27-1.7 x 1038 min-1, respectively.

Thermal degradation behaviour of plastic, specifically HDPE, were provided by this paper.
Thermo-gravimetric curves of individual plastics were also presented which gives insights on
expected results for thermo-gravimetric analysis of plastic caps. Tables for proximate analysis of
HDPE were also presented which can be used for cross reference. Experimental methods on
conducting thermo-gravimetric analysis were also provided.

35
 Influence of time and temperature on pyrolysis of plastic wastes in a semi-batch reactor
[4]

The objective of this work is the study of the influence of temperature and time in the
products obtained in the pyrolysis of plastic wastes. The thermal behaviour of a mixture, which
resembles municipal plastic wastes has been studied both in a thermogravimetric analyser and in
a 3.5 dm3 semi-batch reactor at atmospheric pressure in order to establish the most appropriate
time-temperature combination for plastic waste pyrolysis. It has been proved by the authors that
temperature has a strong effect in the characteristics of pyrolysis liquids and to a lesser extent in
gas and solid properties. At the lowest temperature tested (460 oC), a great proportion of extremely
viscous liquids with high content of long hydrocarbon chains are obtained, while at the highest
temperature tested (600 oC) low proportion of liquids with a high content of aromatics is produced.
The effect of time is not as strong as that of temperature except for very short reaction times (0-15
min). 15-30 min was established as the optimum reaction time range, since total conversion is
achieved and longer reaction times do not produce any effect neither in conversion nor in products
characteristics 500 oC has been found to be the most appropriate temperature for the pyrolysis of
such plastic waste in terms of both conversion and quality of the products.

The different effects of pyrolysis parameters (temperature and reaction times) on the yields
are presented on this paper, which is a good reference for the expected results for finding the
optimum condition on the study to be conducted by the proponent. Although this study utilized
mixtures of virgin plastics, it can still be used as bases since individual plastic thermal behaviour
is similar to mix plastics. A derivative thermogravimetric plot of virgin polyethylene is also
presented in this paper which provides expected similar plot on the proponents thermogravimetric
results on HDPE.

36
 Evaluation of pyrolysis product of virgin high density polyethylene degradation using

different process parameters in a stirred reactor. [5]

The yield as well as molecular weight and composition of the condensed product generated
from the HDPE was studied to gain insight into the role of temperature, equilibrium FCC catalyst,
agitator speed and carrier gas on the pyrolysis products. Pyrolysis was done in a suite stirred bucchi
stainless-steel autoclave reactor. The effect of process parameters such as degradation temperature,
catalyst/polymer ratio (%), carrier gas type and stirrer rate on the condensed product yield and
composition was determined. Reaction products were determined by GC analysis and shown to
contain naphthenes (cycloalkanes, paraffines (alkanes), olefins (alkenes) and aromatics. The
maximum “fuel like” condensed product yields were at 450 oC and 10% catalyst, respectively. The
influence of different types of carrier gassed with varied molecular weights and reactivity was
studied. Hydrogen as a reactive carrier gas increased the condensed and paraffinic product yield.
Appropriate heat transfer – by stirring – can increase the catalyst efficiency in a stirred reactor. It
is demonstrated that the use of equilibrium FCC commercial catalyst efficiency under appropriate
reaction conditions can have the ability control both the condensed yield and carbon number
distribution from HDPE degradation, and thus potentially decrease the process cost with more
valuable hydrocarbons.

The manuscript gives results on the effect of degradation temperature to the pyrolysis yield
of virgin HDPE which can be used for comparison. Data such as the relative amounts hydrocarbon
function groups are also obtained which can be used for the expected property of the pyrolysis oil.
Such property that is of use to the proponent is the boiling point of these function groups which
would be utilized in deciding the temperature to be maintained in the condenser oil outlet.

37
 Evolution of products during the degradation of polyethylene in a batch reactor [7]

The thermal degradation of two polyethylene samples (LDPE and HDPE) has been carried
out in a batch reactor under dynamic conditions. The evolution of products generated after regular
intervals of 5 min (temperature increments of approximately 25oC) has been analysed. The
behaviour of LDPE and HDPE has been compared, and no differences in the quantity and weight
fraction of the gaseous products obtained have been found. For both polymers, n-paraffins are the
major products at the very beginning of the process, while as the decomposition proceeds 1-olefins
are more abundant. The condensed fraction is much larger than the gaseous fraction and its analysis
reveals some differences between the behaviour of LDPE and HDPE at the beginning of the
degradation process. These differences disappear at higher temperatures where more similar trends
are observed. 1-Olefins, n-paraffins, dienes and olefins with wide carbon number distributions are
the most important condensed compounds obtained in the thermal degradation of both
polyethylenes. The formation of 1-olefins and n-paraffins begins at slightly lower temperatures
than for dienes and olefins. On the other hand, as the temperature increases, the amount of low and
high molecular weight compounds increases at the expense of intermediate molecular weight
products and the former become the most important by the end of the degradation process. This
behaviour could be related to the thermal cracking of waxes through secondary reactions.

The manuscript provides the different hydrocarbons expected to be produced from the
pyrolysis of HDPE at certain ranges of temperature. A curve was presented which gives the relative
amount of hydrocarbon products with different number of carbon atoms in its molecule at these
temperature ranges. The temperature range 464 – 489 oC would be expected to be inside the
temperature range to be studied by the proponent. The physical properties of the species reported
to be abundant in this temperature range will be a guide for the expected physical property of the
outgoing products from the reactor of the current study (especially boiling range and viscosity).
From these properties, the proponent expects viscous liquid to be present on the air condenser right
after the outlet of the reactor.

38
 Reactor design and operation of small-size liquefaction plants for waste plastics [23]

A small-scale fuel production is an important solution to the feedstock recycling of post-

consumer plastic wastes in terms of the costs of waste collection and transportation in current
waste treatment businesses in Japan. A tank reactor has been the major plant in the Japanese R&D
history of the small-scale production of fuel oil. The performance of a tank reactor was examined
and a new type of a flow reactor termed “moving-bed reactor” was proposed to meet the small-
scale feed stock fuel production with respect to the performance in terms of coke formation and
continuous.

The paper presented simulated heat transfer to polymer in a 1 meter diameter tank reactor.
The simulation was performed by using Equation II.7 under the assumptions similar to the current
study’s reactor design. The proponent can verify the result of the partial differential equation by
using numerical method through the result of this manuscript using the conditions stated in this
paper.

39
 Chapter 4 Methodology

Flow Chart

For completion of the proposed study, the proponent devised a flow chart of the various
activities to be undertaken. This includes the design of the set-up, fabrication of the experimental
apparatuses, at the same time collection of raw materials, pre-processing of raw materials,
equipment calibration and trial runs, data processing and analysis, and lastly conclusion and
recommendations. Before the conclusion and recommendation are made, the proponent will
resolve if the objectives are met. The flow chart is shown in Figure 4.1.

Figure 4.1 – The Research Flow Scheme

40
 Feedstock

The raw material or feedstock for the pyrolysis experiment will be those waste plastics that
has the plastic resin code number 2 encrypted in its surface - Figure 4.2. Such waste plastics
includes the product applications of HDPE as shown in Table 2-1.

Figure 4.2 - Plastic waste made from plastic resin code number 2
- HDPE (The PET bottles in this photo are not included as
feedstock but the caps of the PET bottles are).

4.2.1 Collection of Raw Material

Collection of feedstock will be done at local junkshops of Cebu City. A minimum amount
of 5 kilograms of HDPE waste will be needed for the study - 500 g for mass loss test, 2000 g for
investigation of the effect of reactor temperature, 1500 g for investigation of the effect of heating
rate, and the rest (1000 g) is for initial tests.

4.2.2 Feedstock Pre-processing

To reshape and reduce the size of the plastic caps, the raw materials will be chipped by
manual cutting using a Buffalo 8” multi-functional heavy duty scissors (Figure 4.3) into sufficient
size to enable insertion into the reactor. The resized feedstock will be washed with tap water and
the wet feedstock will be solar dried.

41
 Figure 4.3 - Buffalo 8" multifunctional heavy duty
scissors used for feedstock sizing.

4.2.3 Proximate Analysis

Fixed carbon, volatile matter, moisture and ash components of the feedstock will be
obtained by proximate analysis according to the procedures given by ASTM Standard D3172-73
(1984)

Experimental Set-up

The experimental set-up is shown in Figure 4.4.

Figure 4.4 - Schematic diagram of experimental set-up.

42
4.3.1 Design of Electric Furnace

The heat source will be from an electric heating coil insulated by ceramic material
(firebrick). The heating element material will be nichrome wire and its fabrication into the
appropriate heating coil will be done by Mega Therm Enterprise (a local fabricator of heating
elements). The minimum required temperature of the heating element and its heating capacity are
980 oK and 750 Watts. The dimension of the heating furnace and calculations are shown in
APPENDIX C.

Calculation of the required minimum capacity of electric furnace will be achieved by

summation of the following heat requirements:

1. The amount of heat needed to bring the temperature of 100 grams of polymer, at a
heating rate of 30 oC/min, from 250oC to 500 oC, QPOLYMER. The 250 oC value is chosen
since temperature control will be initiated starting with that value and 500oC is chosen
from the data of maximum degradation temperature in reference [3].

Figure 4.5 - Heat Balance of the system for approximating the required
power input to the coil.

43
 2. Heat loss from the lateral external surface of the furnace insulation, QFURNACE. This
value will be calculated by using the equations given in sections 2.8.1, 2.9.2, 2.10.1,
and 2.10.2. The dimension of insulating firebrick will also be determined.
3. Heat loss from the top of the surface of the reactor, QTOP. The equations given in
sections 2.8 and 2.9.1 will be utilized to obtain this value.
4. The amount of heat carried by the inert gas – Nitrogen gas, QCARRIER. This amount will
be approximated by doing a heat and mass balance in the part of the reactor where the
carrier will flow. This value will be the product of the mass flow rate of the carrier gas
and the difference between the output and input enthalpy.

The following heat requirements are shown schematically by doing a heat balance on the
system (Figure 4.5). The necessary properties of the different materials involved in this design is
given in APPENDIX A.

Figure 4.6 - Furnace with electric resistance heating coil (Left -

Isometric View; Right - Section View).

44
4.3.2 Batch Reactor

An unstirred 1-1/2” 304/304L schedule-40 stainless steel pipe will be used as a cylindrical
batch reactor. The inside volume capacity will be determined by approximation of the total volume
of 100 grams of feedstock from the specific volume of the polymer melt at 500oC by linear
extrapolation of Table A-1 in APPENDIX A with additional volume for the inert gas to pass
through.

A conceptual design of the reactor is shown in Figure 4.7. After an appropriate dimension
is calculated, the temperature distribution of the polymer melt with time will be calculated by
simultaneous solution of Equations 2-4, 2-5, and 2-9 using Finite Difference as discussed in section
2.7 with appropriate polymer properties in references [15] [23] [24] [25]. The exact dimension of
the reactor and the corresponding calculations are shown in APPENDIX B.

Furnace Reactor

Figure 4.7 - Conceptual Design of the Reactor (left - showing inert gas and
products flow direction; right - section view, mounted to the furnace).

45
4.3.3 Carrier Gas

Purging of oxygen inside the reactor as well as directing the flow of the products to the
condensing system will be achieved by using an inert gas as a carrier. The inert gas to be used will
be Nitrogen which will be ordered from Pryce Gas Inc. Flow control will be achieved using a
rotameter available in the Mechanical Engineering laboratory (Figure 4.8). Initially, the flow rate
will be 100 mL/min (proportionating the amount from reference [5]). The amount of trace oxygen
in the reactor is approximated by Equation 2-7.

Figure 4.8 - Rotameter (left) coupled to a

pressure gage (right) use for flow control of
the carrier gas.

4.3.4 Temperature Control

To investigate the effect of pyrolysis temperature and heating rate on the product yields,
the temperature inside the batch reactor needs to be controlled. Temperature control will be
attained using a PID controller coupled to a Solid State Relay (Figure 4.9) which will be ordered
from PMS Electronics (local supplier). The combination of these electronic components will serve
as a thermostat for the reactor.

46
 A k-type thermocouple probe will be used to measure the temperature inside the reactor
and send the input signal to the controller. The PID controller will be in on/off mode (discussed in
section 2.3.1). This mode uses a solid state relay. The solid state relay will switch the electric
heating element inside the furnace on and off in order to maintain the temperature set on the
controller; if the temperature detected by the thermocouple exceeds the pre-set value on the
controller, the solid state relay will cut the power to the heater off, and if the temperature detected
by the thermocouple is below the pre-set value on the controller, the solid state relay will turn the
power to the heater back on.

Figure 4.9 - Sample PID Controller (left) and Solid-state relay

(right) (Reference: https://images.google.com).

To achieve a specific heating rate, say 30oC/min from a reactor temperature of 250 oC until
400 oC, initially, the PID controller will be set to a temperature value of 250oC. After the process
value reaches 250oC, the set value (SV) will be changed to 280oC for 1 min. After 1 minute, the
SV will be set to 310oC for another minute. This process is repeated until it reaches 400oC.

4.3.5 Condenser

The set-up of the condensing system will be determined by experimentation (trial and
error), the basis for this set-up is from a qualitative observation of the boiling point range of the
liquid products of pyrolysis (Figure 2.2 and Figure 2.1). A calculated design of the condensing
system will not be made since the pyrolysis products are not yet identified, thus obtaining the
convective heat transfer coefficients of the flowing volatiles inside the pipes will not be possible.
The initial setup is shown in Figure 4.10. The condensing unit will mainly be composed of stainless
steel material.

47
 Using this initial design, 100 grams of feedstock will be pyrolyzed at 20 oC/min heating
rate to a reactor temperature of 500 oC. The final temperature will be held constant until no increase
in the liquid product is observed in the collectors. The temperatures at various points in the
condensing system will be observed and recorded by a temperature logger. The final temperature
of the exiting gas should be equal to the ambient temperature to collect the exact amount of oil.

The design of the condensing system for the pyrolysis experiments will be altered
accordingly depending on the temperature results. If no condensate will be present in the third
flask then the water-cooled condenser will be unnecessary. If the temperature at the exit of the air-
cooled condenser is higher than the ambient, then another condenser is needed.

Figure 4.10 - Schematic diagram of initial set-up of condensing system.

Pyrolysis Experiment

Three sets of pyrolysis experiment will be carried out for this study:

1. Mass loss analysis

2. Investigation of the effect of reactor temperature
3. Investigation of the effect of heating Rate

In order to conduct these experiments, the proponent would need to develop the systems
illustrated and discuss in the succeeding outlines with the apparatus and equipment needed.

48
4.4.1 Mass loss Analysis

The degradation temperature range of the plastic waste will be determined by conducting
a mass loss analysis. The reactor and electric furnace will be mounted on an Ohaus DefenderTM
bench scale shown in Figure 4.11. Initial weight of the plastic will be 100 grams and it will be
subjected to a heating rate of 20oC/min and the mass will be recorded every 5 secs until there is no
observed change in mass. This will be done in 5 trials. The expected result of the mass loss
experiment will be a mass loss analysis curve shown in Figure 4.12 and a differential thermal
analysis curve shown in Figure 4.13. The mass loss experiment will determine what temperature
range the raw material degrades and the critical temperature at which degradation is maximum.
Rate of weight loss will be determined by

xt  xt t
Rate of weight loss  4-1
t

Figure 4.11 - DefenderTM bench weighing scale

manufactured by Ohaus.

49
4.4.2 Temperature Dependence of Pyrolysis Yield

Initially, the mass of the reactor and all parts of the condensing system will be weighed and
recorded. The reactor and the furnace will be mounted to the bench weighing scale. 100 grams of
plastic material will be added to the reactor. Purging of oxygen inside the reactor will be done for
30 mins. After 30 mins, the heating element will be turned on and the feedstock is subjected to
uncontrolled heating until 250 oC. From 250 oC, the temperature will be increased at 20 oC/min
until the temperature reaches between the range 400 – 500 oC, depending on the results of the mass
loss analysis. Four temperatures will be used at 30 o C interval (e.g 420 o C, 450 o C, 480 o C, and
510 oC) with 5 trials every temperature value. After reaching the desired temperature, this
temperature will be kept constant until no change in mass is recorded in the bench weighing scale.
The heating element will be turned off and the whole system is allowed to cool down to
atmospheric temperature.

Final mass of the reactor and all parts of the condensing system will be recorded. The oil
yield will be collected and weighed. The amount of char left on the reactor will be determined by
getting the difference of the initial mass of the reactor and the mass of the reactor after pyrolysis.
The amount of gas will be determined by mass balance. An expected graph of the investigation of
pyrolysis yield with temperature is shown in Figure 4.14. A sample tabulation of the data expected
to be obtained in this investigation is shown in Table 4-1.

4.4.3 Heating Rate Dependence of Pyrolysis Yield

The mass of the reactor and all parts of the condensing system will be initially recorded.
The reactor and the electric furnace will be mounted on the bench weighing scale. 100 grams of
plastic material will be added to the reactor. Purging of oxygen inside the reactor will be done for
30 mins. After 30 mins, the heating element will be turned on and the feedstock is subjected to
uncontrolled heating until 250 oC. Starting at 250 oC, the heating rate will be controlled at 10
o
C/min until it reaches 550 oC. The temperature will held at 550 oC until no increase in liquid yield
is observed. The experiment will be conducted using three heating rate - 10 oC, 20 oC, and 30 oC
with 5 trials for every heating rate value.

The amount of oil, char and gas yields will be determined similarly from the pyrolysis
investigation with temperature. An expected graph of the investigation of pyrolysis yield with

50
heating rate is shown in Figure 4.15. A sample tabulation of the data expected to be obtained in
this investigation is shown in Table 4-2.

51
 52
Table 4-1 - Sample Tabulation of the Data to be recorded on the investigation of the effect of reactor temperature of pyrolysis yields.
Reactor weight Collector weight
Temperature Trial Date/Time Time Elapse, t(250)
initial, w(ri) final, w(rf) initial, w(ci) final, m(fi)
1
2
3
4
5
1
2
3
4
5
1
2
3
4
5
1
2
3
4
5
1
2
3
4
5
 53
Table 4-2 - Sample Tabulation of the data to be recorded on the investigation of the heating rate dependence of pyrolysis yields.
Reactor weight Collector weight
Heating rate Trial Date/Time Time Elapse, t(250)
initial, w(ri) final, w(rf) initial, w(ci) final, m(fi)
1
2
3
4
5
1
2
3
4
5
1
2
3
4
5
 Pyrolysis Oil Properties

The collected pyrolysis oil will be characterized by obtaining its properties. Test methods
are provided in the Mechanical Engineering laboratory manual which conforms to standard test
methods provided by the American Society of Testing and Materials.

4.5.1 Physical Properties and Heating Value

The density of the pyrolysis oil that will be obtained shall be determined by hydrometer
method according to ASTM D287 and D1250-80. Kinematic viscosity will be determined
according to test method provided in ASTM D445 and D2270. Fire point and flash point will be
determined in accordance with ASTM D92-05. Pour point of the oil will be determined using
method given in ASTM D5853-09. The heating value of the pyrolysis oil will be determined by
using an oxygen bomb calorimeter according to ASTM D4809.

54
 Expected Output

The succeeding figures show the expected graphs of the result for the pyrolysis experiment.
In Figure 4.12, the mass of the plastic waste inside the reactor is expected to decrease as the
temperature increases due to the reaction and consequent evaporation of the volatile matter. Figure
4.13 shows the rate of mass decrease with temperature. This will aid the proponent on choosing

Figure 4.12 - Expected curve of the mass loss analysis experiment.

the appropriate temperature range to do the experimental investigation on the effect of value of
temperature on the pyrolysis yields of HPDE.

Figure 4.13 - Expected DTA curve for the mass loss experiment.

55
 A maximum yield of pyrolysis oil is expected to be attained at a certain temperature with
minimum char or non-condensable product as in Figure 4.14. For the effect of heating rate, it is
reported in the prior literatures that increasing the heating rate would increase the liquid yield and
decreases the char and gas yields as shown in Figure 4.15.

Figure 4.14 - Expected curve of condensed product, non-condensable

product and char yields of pyrolysis with respect to reactor
temperature.

Figure 4.15 - Expected curve for pyrolysis yields with varying heating rate.

56
 57
Figure 4.16 - Gantt Chart of the Project to be undertaken
Gantt Chart
 APPENDIX A

Properties of Materials

Properties of the different materials that will be used for the study are given here.

The constant pressure specific heat capacity of polyethylene varies with temperature
according to the equation reported by Wunderlich and Dole [27] and is given as

 cal 
c p  t   0.545  5.3 x103 T  273 ,  
g K 

The thermal conductivity of HDPE is given in reference [24] and given as 0.46 W/m-K.
The specific volume is shown in Table A-1.

The thermodynamic properties of air and nitrogen gas at atmospheric pressure is shown in
Table A-2 and Table A-3, respectively. The thermal conductivities of stainless steel and insulating
fire brick, in reference [25], are given as 21.4 and 0.3 W/m-K, respectively.

Table A-1 - Specific Volume of HDPE (10-3 m3/kg) at various temperatures and
pressures. [15]

58
 59
Table A-2 – Thermodynamic Properties of Air at atmospheric pressure. [21]
Temperature Density, ρ Coefficient of Thermal Expansion Specific Heat, Cp Thermal Conductivity,k Thermal Diffusivity,α*10^6 Absolute Viscosity, μ x 10^6 Kinematic Viscosity, ν*10^6
K kg/m^3 β*10^3(1/K) J/kg‐K W/m‐K m^2/s N‐s/m^2 m^2/s
273 1.252 3.66 1011 0.0237 19.2 17.456 13.9
293 1.164 3.41 1012 0.0251 22 18.24 15.7
313 1.092 3.19 1014 0.0265 24.8 19.123 17.6
333 1.025 3 1017 0.0279 27.6 19.907 19.4
353 0.968 2.83 1019 0.0293 30.6 20.79 21.5
373 0.916 2.68 1022 0.0307 33.6 21.673 23.6
473 0.723 2.11 1035 0.037 49.7 25.693 35.5
573 0.596 1.75 1047 0.0429 68.9 29.322 49.2
673 0.508 1.49 1059 0.0485 89.4 32.754 64.6
773 0.442 1.29 1076 0.054 113.2 35.794 81
1273 0.268 0.79 1139 0.0762 240 48.445 181
Table A-3 - Thermodynamic Properties of Nitrogen gas at atmospheric pressure. [21]
Temperature Density, ρ Coefficient of Thermal Expansion Specific Heat, Cp Thermal Conductivity,k Thermal Diffusivity,α*10^6 Absolute Viscosity, μ x 10^6 Kinematic Viscosity, ν*10^6
K kg/m^3 β*10^3(1/K) J/kg‐K W/m‐K m^2/s N‐s/m^2 m^2/s
100 3.4808 1072 0.00945 0.0253 6.86 1.97
200 1.7108 5 1043 0.01824 0.1022 12.95 7.57
300 1.1421 3.33 1041 0.0262 0.2204 17.84 15.63
400 0.8538 2.5 1046 0.03335 0.3734 21.98 25.74
500 0.6824 2 1056 0.03984 0.553 25.7 37.66
600 0.5687 1.67 1076 0.458 0.7486 29.11 51.19
700 0.4934 1.43 1097 0.05123 0.9466 32.13 65.13
800 0.4277 1.25 1123 0.05609 1.1685 34.84 81.46
900 0.3796 1.11 1146 0.0607 1.3946 37.49 91.06
1000 0.3412 1 1168 0.06475 1.625 40 117.2
1100 0.3108 0.909 1186 0.0685 1.8591 42.28 136
1200 0.2851 0.833 1204 0.07184 2.0932 44.5 156.1
 APPENDIX B

Design of Batch Reactor

The parameters considered for selection of the size of the reactor are given below:

 Available commercial pipe size in the local market.

 Minimum inner volume required for HDPE at 500 oC.
 Temporal temperature trend at the center of the reactor should conform to 30 oC/min.

The inner volume of HPDE @ 500oC is obtained by extrapolation of Table A-1. The linear
equation for the trend line of the data is given as

m3
  1.9 x103  t  0.9268,
kg

m3
  1.9 x103   500   0.9268  1.877
kg

m3
The volume is V   x m  1.877  0.1 kg   0.1877m3 or 188 L. Additional clearance on
kg
the volume of reactor is necessary for the inert gas to pass through the top surface of the polymer
to the ¼” 40S Stainless Steel Pipe which leads to the condensing system.

The dimensions of 1-1/2” 40S Pipe is used for calculating the temperature distribution. The
design of the reactor consists of two parts – the base and the lid, and are shown on Figure B.1 and
Figure B.2. To calculate the temperature distribution of polymer melt inside the reactor, a
simultaneous solution of Equations 2-4, 2-5 and 2-9 is needed.

Let ma = raVr and Nao = 1 in Eq. 2-4 to make the degradation rate in percentage mass per
time basis.

dxa
 ma  k (1  xa )
dt

Integrating we have,

xa  Co e kt

60
 Figure B.1 - Reactor lid design and dimensions in millimeters.
where:

Co = initial mass (for percentage we can make this equal to 1)

Eo

k  ko e RT
(Eq. 2-5)

ko = 3.5 x 1030 min-1 [3]

Eo = 109.2 kcal/mol [3]

Universal Gas Constant, R = 1.987 kcal/mol-K

Thus,
Eo
 t
xa  e RT

From Equation 2-9,

T 1   T 
cp k r   q
t r r  r 

For simplicity of calculation, thermodynamic properties are assumed constant:

61
 Figure B.2 - Reactor base design and dimensions in millimeters.

 Heat loss, q is estimated to be 1.6 kJ/g [16].

 Thermal Conductivity, k = 0.46 – 0.50 W/m-K (The lower range is used) [18].
 Constant pressure specific heat, cp = 1850 J/kg-K [18].

Applying finite difference for the partial differential terms (Using Equations 2-10 and 2-13):

T ti , j 1  ti , j

r t

  T  1  
r  r t  2rti i , j  r 1 ti 1, j 
2  i  1 i 1, j
r  r  ri r  2 r
2 

The numerical equivalent of Equation 2-9 is therefore,

62
 ti , j 1  ti , j k  
cp  r t  2rti i , j  r 1 ti 1, j   q 1  xi , j 
2  i  1 i 1, j
t ri r  2 i
2 

Transposing,

 t  k  
ti , j 1   ri  1 ti 1, j  2rti i , j  ri  1 ti 1, j    t  q 1  xi , j   ti , j
 c p ri r  2 2
2 

This iterative formula is implemented in Visual Basic 6 software, the interface and
corresponding code are shown in APPENDIX D.

Solving for the temperature in the inner wall surface of the pipe, we use Equations 2-9and
2-24. For radiation between heating element and stainless steel cylinder,

A1  Eb1  Eb 2 
q1 
1/ 1   A1 / A2  1   2  /  2 

Assuming (for Figure B.3):

Emissivity of reactor surface, ε1 = 0.54 [19]

Emissivity of heating element, ε2 = 0.79 [19],

63
 Figure B.3 - Section view of furnace and reactor
set-up (1 - outer surface of reactor; 2 - inner suface
of furnace).

 48.3 

 W 

m   0.15m   5.67 x108 2 4   980  273  T1  
 1000   mK 
4

4 


530W 
1/ 0.54   48.3 / 80  1  0.79  / 0.79

Solving for T1,

T  813 oC

Calculating the temperature at the inner surface,

Ti  To
qk  2 Lk
ln  ro / ri 

Thermal conductivity, k of 304/304L stainless steel = 21.4 W/m-K [20].

 W 
2  0.15m   21.4   813  T3  K
 mK 
530W 
 24.15 
ln  
 20.46 

Solving for the inner surface temperature T3,

T3  807.4 oC

64
 Thus, the inner temperature of the reactor is 807 oC, this value is inserted on the Visual
Basic program created to get the temperature in the center of the reactor. For a heating rate of
30oC/min the temperature at r = 0 should reach, beginning at 250 oC, 600 oC in 700 sec. Putting
the appropriate values of the properties of the polymer on the program, the inner temperature after
700 sec is 607 oC as shown in the figure below

Figure B.4 - Inner temperature trend of the polymer when subjected to a wall temperature of 807
o
C. The interface and source code is shown in APPENDIX D.
Thus, the design of the reactor will be appropriate to conduct pyrolysis experiment up to a
temperature of 600 oC and a heating rate of 30 oC/min.

65
 APPENDIX C

Design of Electric Furnace

As discussed in section 4.3.1, the capacity of the heating element will be calculated from
the heat required and various heat loss of the system. Calculation of the summation of heat are –
(a) QPOLYMER, (b) QFURNACE, (c) QTOP, and (d) QCARRIER. The total heating requirement will be 530
+ 140 + 80 = 750 Watts. The minimum coil temperature is 980 K. The dimensions of the furnace
for this required temperature and heating capacity is shown in the figure below.

Figure C.1 - Electric Heating Furnace Dimensions.

66
 (a) The power calculation will be based on the amount of heat needed to raise the
temperature of 100 grams of polymer from 250 oC to 500 oC with a heating rate of 30 oC/min. The
assumption for this calculation is that the heat capacity, Cp of polyethylene varies with temperature
according to the equation reported by Wunderlich and Dole [17] is given as

 cal 
c p  t   0.545  5.3 x103 T  273 ,  
g K 

Calculating the enthalpy change,

tf
H  m c p  t  dt
ti

4.187 J 773
H  100 g  0.545  5.3x103 T  273dt  265, 089 J
1cal 523

this is the total amount of energy needed to raise the temperature of the polymer from 250 to 500
o
C. For a heating rate of 30 oC/min, the time required to achieve the temperature will be

temperature range  500  250  C

o

time   o
 8.33 min or 500sec
heating rate C
30
min

Thus the power can now be calculated,

Energy 265, 089 J

(a) Q polymer    530.2 Watts
time 500 sec

(b) Before the heat loss on the outer surface of the furnace QFurance can be calculated
the minimum temperature of the heating element should be calculated from the value obtained in
(a), let
q13 - heat required by the polymer = 530 W r2 - outer radius of reactor = 24.15 mm

T1 - temperature of polymer = 500 oC r3 - radial distance of inner surface of

insulation = 44.15 mm

L - length of reactor = 150 mm 1 - emissivity of the reactor surface = 0.54

67
 r1 - inner radius of reactor = 20.46 mm  2 - emissivity of the heating element =
0.79

r 
ln  2 
r
T2  q13  1   T1  777.507o K
2 k ss L

The minimum coil temperature is solved determining the convective and radiative heat
transfer coefficient. To solve for these, an initial assumption of the coil temperature is necessary,

983  777
Tcoil  983o K Tave   880.4o K
2

The equations below are curve fitted from the table of properties of air given in Table A-2.

979.44 Tave  1
1
1
 ,   0.001
1000 K K

W W
kair   2 x108  Tave
2
  8 x105  Tave
2
 0.004, kair  0.059
mK mK


 7 x10  T
5 2
ave  0.1091Tave  16.781 m 2
,   1.335 x10
m2 4

106 s s


 7 x10  T
5 2
ave  0.0637Tave  9.1015 m 2
,   1.012 x104 ,
m2
106 s s

Calculating the Rayleigh number with characteristic length being the height of the reactor,

g  Tcoil  T2  L3
RaL   5.72 x105


The convective resistance from Equation 2-22 is,

1 mK
R 1/4
 1.789
0.345kair RaH W

Thus the convective heat transfer coefficient in the enclosure between the reactor and the
inner surface of the furnace is,

68
 1 W
hc   2.606 2
r r  m K
2  2 3  R
 2 

Now calculating the radiative heat transfer coefficient by utilizing equations 2-25 to 2-28,

A1  2 r2 L  0.023 m 2 A2  2 r3 L  0.042 m 2

1
F12   0.501
1  1 A 1   2 
1 1
1 A2 2

  Tcoil
4
 T24   W
hr  F12    78.6 2
 Tcoil  T2  m K
 

Thus, the combined radiative and convective heat transfer coefficient and the new coil
temperature are

W
htotal  hr  hc  81.16
m K2

q12
Tnew  T2   980.4 K
 A1  A2 
htotal  
 2 

Since the new temperature is close to the initial assumed temperature, this value is the
answer. So, we can now solve for the heat loss from the external surface of the cylindrical furnace,
Qfurnace. To determining the convective heat transfer coefficient, an outer surface temperature is
initially assumed,

Let: T - ambient temperature = 25 oC

Tex - outer surface temperature of furnace – 230 oC

Tex  T
T   302  25  K
o
Tave   436.5o K
2

69
 1 W m2
  0.002 kair  0.035    4.418 x105 
K mK s
m2
   3.204 x105 
s

g  TL3
GrL   2.041x107
 2

Thus, the flow is laminar.

Pr  0.72 RaL  Pr x GrL

NuL  0.68  0.515Ra1/4

L  32.565

NuL kair W
hc   7.622 2
L m K

Solving for the heat loss,

Let, r4 - radial distance of the outer surface of furnace = 94 mm

T2  Tcoil
Tin - temperature inside the furnace =  879o K
2

Tin  T
Q furnace   140 W
 r4 
ln  
 r3   1
2 Lk firebrick 2 r4 hc L

The new Tex is given as

r 
ln  4 
Tnew  Tin   r3  q  238o C
2 Lk firebrick

Since the new temperature is close the assumed initial temperature, this value is used and
thus, QFURNACE = 140 Watts.

(c) To solve for the heat loss at the top of the reactor, QTOP, temperature of the external
surface at the top of the reactor is initially assumed.

70
Let:

Tin - temperature inside = 500oC D – diameter of the top of the reactor = 130 mm

Tout - outside surface temperature = 508 oC Area D

L 
Perimeter 4

x – thickness of the lid of reactor = 10 mm T  Tout

Tave 
2

The properties of air necessary to solve equation 2-16 to 2-18 are given below,

W W
kair  2 x108 Tave
2
 8 x105 Tave  0.004, kair  0.041
mK mK

342.1 kg kg
 ,   0.634
Tave m3 m3

J J
C p  0.1296Tave  973.81, C p  1.044 x103
kg  K kg  K

0.0317 Tave  9.8315 N  s N s

 , 2   2.693x105
106 m m2
1
979.44Tave 1 1
 3
,   0.002
10 K K

Solving for the Rayleigh number and the Nusselt number,

C p  2 g  Tout  T  L3
RaL   1.134 x105
 kar

NuL  0.54 Ra1/4

L  9.91

Thus, the convective heat transfer at the top of the reactor is

NuL kair W
hc   12.6 2
L m K

The heat loss at the top is therefore,

71
 Atop Tin  T 
QTop   80 W
x 1

kss hc

Solving for the new value of Tout,

x
kss
Tnew  Qtop  Tin  776o K
Atop

Since the new value is close to the initially assumed one, the calculation is considerable.

(d) The assumed parameters for calculating the heat carried by the nitrogen gas is shown.

Let: Q – carrier gas flow rate – 100 mL/min

TN – temperature of carrier gas inside the reactor – 500 oC

Ta – ambient temperature – 25oC

Mass flow rate of the carrier can now be calculated,

 100 m3 
101.325kPa  
PV  10002  60  s  kg
m   1.062 x106
RT 8.3143 kJ  298  773  s
 K
28 kg  K  2 

To calculate for QCARRIER, curve fitted equation of the specific heat of nitrogen gas from Table A-3
is given by,

J
C p  3x107 T 2  0.0001T  1.0494,
kg  K

Q  m  C p dT  1.062 x106    3x10 T 2  0.0001T  1.0494  dT  5.486 x104 W

TN 500  273
7
Ta 25  273

The value obtained is relatively small, so this can be neglected.

72
 APPENDIX D

Visual Basic Interface and Codes

Figure D.1 - Visual Basic Interface for calculating the temperature distribution of a polymer in a
cylindrical reactor.

Option Explicit

Dim rh As Double, cp As Double, k As Double, Hr As Double, Hv As Double, Tpoly As Single, Twall

As Single, R(0 To 99999) As Single
Dim n As Integer, m As Integer, h As Single, deltar As Single, c As Double, o As Integer, p As Integer,
mn As Integer, lm As Integer, lmm As Integer
Dim t(1 To 999999) As Double, x(1 To 999999) As Double, l As Integer, z As Integer, oo As Integer, A
As Single, u(0 To 999999) As Double
Dim deltaP(0 To 999999) As Double, kk(0 To 999999) As Double, Ea As Double, Aa As Double, pr(0
To 999999) As Double

Private Sub Clear_Click()

List1.Clear
Graph.Cls
End Sub

73
Private Sub Command1_Click()
Ea = Val(Ea1.Text)
Aa = Val(Aa1.Text)
A = Val(a1.Text)
z = Val(z1.Text)
rh = Val(rho.Text)
cp = Val(cp1.Text)
k = Val(k1.Text)
Hr = Val(Hr1.Text) * 1000 ^ 2

Tpoly = Val(Tpoly1.Text) + 273

Twall = Val(Twall1.Text) + 273
R(z * 2) = Val(r1.Text) / 100
t(1) = Val(ti.Text)
t(999999) = Val(tf.Text)

h = (t(999999) - t(1)) / Val(tss.Text)

c = k / (cp * rh)
deltar = R(z * 2) / z

x(z) = Twall
For p = 1 To z - 1
x(p) = Tpoly
Next p

For n = 0 To z * 2
R(n) = (n / (z * 2)) * R(z * 2)
Next n

For mn = 1 To Val(tss.Text)
t(mn + 1) = t(mn) + h
Next mn

Graph.DrawWidth = 1
Graph.Scale (-t(999999) / 50, Twall - 273)-(t(999999), -(Twall - 273) / 20)

74
'draw x axis
Graph.Line (-t(999999) / 50, 0)-(t(999999), 0)

'draw y axis
Graph.Line (0, Twall - 273)-(0, -(Twall - 273) / 20)

List1.Clear
Graph.DrawWidth = 3

For m = 1 To Val(tss.Text)
For oo = 1 To z - 1
kk(oo) = (Aa * (10 ^ 30) / 60) * Exp(-(Ea / (1.987 * (10 ^ -3) * x(oo))))
pr(oo) = Exp(-kk(oo) * t(m + 1))
deltaP(oo) = (1 - pr(oo))
Next oo
For l = 2 To z - 1
x(1) = ((h * c * 2) / (deltar ^ 2)) * (x(2) - x(1)) + x(1) - ((h / cp) * (Hr) * deltaP(l))
x(l) = ((h * c) / (R(l * 2) * deltar ^ 2)) * ((R((l * 2) + 1) * x(l + 1)) - (2 * R(l * 2) * x(l)) + (R((l *
2) - 1) * x(l - 1))) - ((h / cp) * (Hr) * deltaP(l)) + x(l)
List1.AddItem "" & Format(t(m + 1), "#0.00") & " " & Format(x(l) - 273, "##,##0.00000")
Next l
u(m) = x(A)
Next m

For lm = 1 To Val(tss.Text) Step Val(tss.Text) / 10

Graph.PSet (t(lm + 1), u(lm) - 273), RGB(0, 200, 0)
Next lm

End Sub

75
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