MICROWAVE PYROLYSIS OF PLASTIC

WASTES FOR PRODUCTION OF FUEL

AND OTHER CHEMICALS
Elham Khaghani
Professor M. M. Farid
Professor A. Williamson

Department of Chemical and Materials Engineering

1
 Presentation outline
2

  Introduction
  Research objectives
  Pyrolysis background
  Thermalpyrolysis
  Microwave pyrolysis

  Experimental thermal pyrolysis setup

  Results and discussions

  Proposed microwave induced pyrolysis setup

  Conclusions

  Future work
 Research objectives Introduction
3

  Comprehensive literature review

  Conducting thermal pyrolysis experiments

  Developing the ASTMS method

  Analysing the products using GC/FID

  Designing the microwave heating system

 Presentation outline
4

  Introduction
  Research objectives
  Pyrolysis background
  Thermal pyrolysis
  Microwave pyrolysis

  Experimental thermal pyrolysis setup

  Results and discussions
  Proposed microwave induced pyrolysis setup
  Conclusions
  Future work
 Introduction
5

  Definition of pyrolysis:
Pyrolysis can be described as the thermal decomposition of organic components in
an oxygen-free atmosphere to yield char, oil and gas
  Key parameters in pyrolysis reaction
reactor type
pyrolysis temperature
heating rate
pyrolysis time
operating pressure
chemical composition of resins
 Introduction
6

  Types of pyrolysis
Pyrolysis  Hea,ng rate  Residence  Temperature  Reac,on  Pressure  Major 
,me  (°C)  environment  (bar)  product 

Carboniza,on  Very slow  Hrs‐days  400  Combus4on   1  Charcoal 

Conven,onal  10‐100 °C/ 10s‐10min  <600  Primary / 1  Gas, 

min  Secondary   Liquid,  
Char 
Fast/Flash  Up to  <1s  <600  Primary / 1  Liquid 
1000°C/s  Secondary 
>700  Primary  1  Gas 
Ultra  Very high  <0.5s  1000  Primary  1  Gas 
Vacuum  Medium  2‐30s  400  Primary   <0.1  Liquid 
 Introduction
7

• Candidates for pyrolysis

Fraction %
PE PP PVC PS Expanded PS ( fast food packagin) Others

3%
7%

9%

11%
55%

15%
 Industrial process for pyrolysis Introduction
8

  Fuji fixed-bed pyrolysis process

  Hamburg university process

  VEBA pyrolysis process

  BASF process

  BP recycling plant
 Fuji fixed-bed pyrolysis process Introduction
9

  Zeolite – based ZSM-5 catalysts

60%
gasoline
20%
Maximum 80% oil
capacity 5000 kerosene
tonne/year
plastic wastes 15% gas 20% diesel
 Hamburg university process Introduction
10

Maximum capacity 50 kg/h

25-45% gas 30-50% liquid

 VEBA pyrolysis process
Synthetic oil produced by rotary kiln reactor at 650°C
11

Maximum capacity 40000 tonne/year

80% high quality liquid 10%methane-butane 10%hydrogenation

products gas and further residues

VCC Veba Combi Cracking

LPH Liquid Phase hydrogenation
GPH gas Phase hydrogenation
 BASF process Introduction
12

Maximum capacity 150000 tonne/year

20-30% gas 60-70% liquid

 BP recycling plant Introduction
13

•  Nominal capacity 50 kg/h

•  80%efficiency in converting plastic wastes into petrochemical
•  The gas contains high content of ethylene and propylene
 Why thermal pyrolysis? Introduction
14

  Limited supply of natural resources (crude oil and gas)

  Fluctuation of high price and availability of crude
  Decreasing toxic air emissions and reducing greenhouse gases
  Recycle some of the stored energy within the waste plastics
  Diminishing imports of crude oil Sample Calorific value (MJ kg-1)
Polyethylene 46.50
Polypropylene 46.50
Polystyrene 41.90

Kerosene 46.50
Gas Oil 45.20
Heavy Oil 42.50
 Pyrolysis products Introduction
15

• Gas products
Hydrogen Methane Ethane Ethene Propane Propene Butane Butene CO CO2 HCL
HDPE 0.12 1.9 2.21 6.08 1.31 4.56 0.22 0.36 0 0 0.00
LDPE 0.05 1.14 1.67 4.00 1.33 4.00 0.32 2.00 0 0 0.00
PS 0.04 0.53 0.08 0.26 0.02 0.05 0.00 0.06 0 0 0.00
PP 0.05 0.93 1.45 3.52 1.00 3.53 0.23 1.29 0 0 0.00
PET 0.31 0.71 0.03 1.41 0.13 0.09 0.00 0.00 13.29 22.71 0.00
PVC 0.12 0.77 0.47 0.15 0.24 0.19 0.11 0.15 0 0 52.93
• Oil/wax products (C6-C60)
HDPE, LDPE and PP : mainly saturated alkane and alkene group liquids
PVC :combination of alkane, alkene and aromatic compounds
PS : aromatic compound generated from benzene ring
PET : aldehydes, ketones, carboxylic acids, alcohols and aromatic compounds

PE PP PS PVC PET

• Solid products: the major element is carbon

 Why microwave pyrolysis ? Introduction
16

  MW technology is environmentally friendly

(is produced from electricity)
  Volumetric heating leads to produce uniform

microstructure materials
  The high heating rate

  Quick respond to changes in process parameters

  The nature of microwave heating is also much more

efficient compared to resistance heating
 Microwave pyrolysis Introduction
17

Reflection Conductor
Interaction of
electromagnetic Transmission Insulation
radiation with
materials
Absorption Dielectrics
 Microwave pyrolysis Introduction
18

Types of cavities

Single mode Multimode

 Microwave pyrolysis Introduction
19

Dielectric theory

D=f (Temperature, ion concentration, ion size, dielectric constant,

microwave frequency, viscosity of reacting medium)
 Microwave pyrolysis Introduction
20

Dielectric mechanisms
 Microwave pyrolysis Introduction
21

Electromagnetic wave propagation

(Reflected and transmitted signals)
Microwave pyrolysis Introduction

Available technologies
 Semi batch reactor
Ludlow Palafox et al. (2001)
 Continues conveyor belt type reactor
Charles L.Emery (1993)
 Continues screw type reactor (under design)
Petter Heyerdahl and Geoffrey Gilpin
 Continues type reactor
James S. Klepfer (1999)  

22
 Schematic drawing of the microwave-induced pyrolysis of HDPE

23
Ludlow Palafox et al. (2001)
 Schematic drawing of the microwave-induced pyrolysis

24
Charles L.Emery (1993)
 Schematic diagram of the microwave-assisted pyrolysis
system under design P. Heyerdahl and G. Gilpin (Norwegian Uni.)
25
Schematic diagram of the microwave pyrolysis of organic
waste materials James S. Klepfer (1999)
26
 Presentation outline
27

  Introduction
  Research objectives
  Pyrolysis background
  Thermal pyrolysis
  Microwave pyrolysis

  Experimental thermal pyrolysis setup

  Results and discussions
  Proposed microwave induced pyrolysis setup
  Conclusions
  Future work
 Thermal pyrolysis setup
28
 Presentation outline
29

  Introduction
  Research objectives
  Pyrolysis background
  Thermal pyrolysis
  Microwave pyrolysis

  Experimental thermal pyrolysis setup

  Results and discussions
  Proposed microwave induced pyrolysis setup
  Conclusions
  Future work
 Results of thermal pyrolysis
30

  Effect of temperature
500°C  525°C  575°C 
PLASTIC  Oil/wax  Gas  Residue  Oil/wax  Gas  Residue  Oil/wax  Gas  Residue 
HDPE  74.04  25.96  0  73.30  26.7  0  73.20  26.8  0 
LDPE  73.92  26.08  0  72.74  27.26  0  69.62  30.38  0 
PP  77.30  22.70  0  77.20  22.80  0  75.76  24.24  0 
 Product analysis
31
Gas Chromatograph –Flame
Ionisation Detector (GC/FID)
  Shimadzu GC 2010 with FID
  FORTEHT-5 column
  (25 m×0.22mm×0.10um)
  0.1gr sample dissolved in 5 ml
carbon disulfide
  Internal standard: C15 and C23
  Standard mixture: D2887 (C6-
C44)
  1 µl injected into column
  Oven temperature:
start: 80°C followed by ramp 15°C/min to
160°C ,then ramp 30°C/min to 380°C (15 min)
  FID temperature: 400°C
  Helium used as carrier gas
 Pyrolytic oil/wax composition of HDPE at 500°C
32 Alkene
  GC/FID chromatogram
Alkane

Diene
 Carbon number distribution for the pyrolysis of HDPE
33

(a) 500 °C (b) 525 °C 0.1 (c) 575 °C

0.1 0.1
0.08
0.08 0.08
0.06

TIC%
TIC%

0.06

TIC%
0.06
0.04
0.04 0.04
0.02
0.02
0.02
0 0
0
8 13 18 23 28 33 38 43 8 13 18 23 28 33 38 43
8 13 18 23 28 33 38 43

*(c) 500 °C *(d) 600 °C *(e) 700 °C

*Obtained by Carlos Ludlow-Palafox and Howard A. Chase (2001)

 Comparison of HDPE at 500°C, 525°C & 575°C
34

0.1
HDPE-500
0.08

0.06 HDPE-525
TIC%

0.04 HDPE-575

0.02

0
8 10 12
14 16 18
20 22 24
26 28 30
32 34 36
38 40 42
44
Carbon Number
 Comparison of LDPE at 500°C, 525°C, 575°C
35

0.12
LDPE-500
0.1

0.08 LDPE-525
TIC%

0.06 LDPE-575
0.04

0.02

0
8 10 12
14 16 18
20 22 24
26 28 30
32 34 36
38 40 42 44
Carbon Number
 Comparison of PP at 500°C, 525°C, 575°C
36

0.16
0.14
PP-500
0.12
PP-525
0.1
TIC%

0.08 PP-575
0.06
0.04
0.02
0
8 10 12
14 16 18
20 22 24
26 28 30
32 34 36
38 40 42 44
Carbon Number
 Comparison of HDPE-LDPE-PP at 575 °C
37

0.14

0.12
HDPE-575
0.1
LDPE-575
0.08
TIC%

0.06 PP-575

0.04

0.02

0
8 10 12 14 16 18 20 22 24 26 28 30 32 34 36 38 40 42 44
Carbon Number
 Evolution of diene compounds (C10-C22)
38

0.06
HDPE500
0.05 HDPE525

HDPE575
Alkadiene TIC%

0.04

0.03

0.02

0.01

0
10 11 13 15 17 20 22
Carbon number
 Evolution of alkene and alkane compounds
39

0.06 0.05
HDPE500 HDPE500
0.05

Alkane TIC%
0.04
Alkene TIC%

HDPE525 HDPE525
0.04 HDPE575 HDPE 575
0.03
0.03
0.02
0.02

0.01 0.01

0 0
8 15 26 31 36 39 44 10 20 29 36 41
Carbon number Carbon number
 Presentation outline
40

  Introduction
  Research objectives
  Pyrolysis background
  Thermal pyrolysis
  Microwave pyrolysis

  Experimental thermal pyrolysis setup

  Results and discussions
  Proposed microwave induced pyrolysis setup
  Conclusions
  Future work
 Proposed microwave induced pyrolysis setup
41

Schematic of the microwave pyrolysis of plastic apparatus: 1) Generator, 2) Isolator (Circulator +

Dummy load), 3) Directional coupler, 4) 3-stub tuner, 5) Quartz reactor, 6) Nitrogen inlet, 7) Seal, 8)
Bearing, 9) Gear transition, 10) Adjustable speed electrical machinery,11) Applicator (rotary kiln
reactor), 12) Optical pyrometer, 13) Feed inlet, 14) Condenser, and 15) Product container.
 Presentation outline
42

  Introduction
  Research objectives
  Pyrolysis background
  Thermal pyrolysis
  Microwave pyrolysis

  Experimental thermal pyrolysis setup

  Results and discussions
  Proposed microwave induced pyrolysis setup
  Conclusions
  Future work
 Conclusions
43

  Thermal pyrolysis of polyolefines yielded mainly oil/wax

  The maximum yield of oil/waxes (500°C to 575°C)
77.3% for PP>74.04% for HDPE> 73.92% for LDPE
  The yield of oil/waxes decreased with the increase in temperature
  GC chromatogram shows a homologous series of triplets (diene,
alkene, alkane)
  The main chemical components of the oil/wax :
alkenes > alkanes > diene
  The maximum yields of diene were observed at 525°C and for
alkenes and alkanes were recorded at 500 °C.
 Conclusions
44

  The Maximum yields for carbon number distribution was

  C10 to C15 for HDPE and LDPE
  C8, C11, C15 and C16 for PP
  Concentration of aliphatic species above C32 were greatly reduced
  The higher temperature favours of formation of higher yield of
heavier compounds between 500°C and 575°C
  The average quantitative ratio of
alkane: alkene: diene at 500°C
1:1.61: 0.36 for HDPE
1:1.54: 0.29 for LDPE
 Future Work
45

  Conduct microwave pyrolysis experiment using rotary kiln reactor

  Simulate the electromagnetic field distribution
  Mathematical modelling
  Examine the effect of processing parameters
  Characterise the oil/wax fraction using GC/FID
  Kinetic study to investigate the effect of microwave on reaction rate
  Convert batch process to continuous process
  Construct the pilot scale reactor
 Thank you
46

Questions?