speaker: ki-bum park univ. of seoul -...
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5th International Conference on
Sustainable Solid Waste Management
Speaker: Ki-Bum Park
Univ. of Seoul
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230257
279 288 299 311 322
61 65 59 59 57 59 58
2005 2007 2011 2012 2013 2014 2015
World Europe
PS;
6,9
PET,
7,1PUR,
7,5
PVC,
10,1
HDPE;
12,1LDPE,
17,3
PP,
19,1
Others;
19,9
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Pyrolysis
reactor:
Pyrolysis reactors:• Melting vessel stirred tank
• Shaft, tube reactor
• Rotary kiln, extruder
• Moving bed
• Fluidized bed
Gas
OilChar
Pyrolysis targets:• Production of oils for energy source
• Production of chemicals
BTX-aromatics
Wax
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High Cl content in oil Not acceptable in petrochemical industries
Acceptable level: < 10 ppm
Generation of chlorinated compounds during PVC thermal degradation:
Ex: HCl
Problems caused by chlorinated compounds
• Corrosion of pyrolysis process lines and equipments
• Generation of dioxins in combustion of pyrolysis oil
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Hamburg ProcessPCDD and PCDF concentration in the Pyrolysis oil
of mixed plastics with a PVC content of 13,7 % at 735 ºC.
(values in ng/g) (N.D.: Not detectable)
Results: As HCl Can be removed by water or alkaline solutions
Detection
Limit
Low
Boiling
High
Boiling
∑ TCDD 0.02 N.D. N.D.
2,3,7,8-TCDD 0.05 N.D. N.D.
∑ PeCDD 0.05 N.D. N.D.
∑ HxCDD 0.05 N.D. N.D.
∑ HpCDD 0.10 N.D. N.D.
OCDD 0.10 N.D. N.D.
∑ TCDF 0.02 N.D. N.D.
2,3,7,8-TCDF 0.02 N.D. N.D.
∑ PeCDF 0.03 N.D. N.D.
∑ HxCDF 0.03 N.D. N.D.
∑ HpCDF 0.10 N.D. N.D.
OCDF 0.10 N.D. N.D.
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1. Application of catalysts and additives
• Fe- and Ca-based catalysts (Polymer
Degradation and Stability 87 (2005) 225-
230)
• Calcium carbonate carbon composite
(Ca-C) (J. Anal. Appl. Pyrolysis 72 (2004)
27–33)
• Ca-based additives such as CaO (J. Anal.
Appl. Pyrolysis 51 (1999) 127–134)
2. Preliminary study using stepwise
pyrolysis (Fuel Processing Technology
92 (2011) 253–260)
• Not effective enough
• Catalyst deactivation
• Only conceptual
approaches: (Not
implementable in
industries)
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Proximate analysisa (wt. %) Ultimate analysis (wt. %)
Volatile matter 98.10 ± 0.26 Carbon 62.44 ± 0.25
Fixed carbon 1.84 ± 0.26 Hydrogen 8.00 ± 0.03
Ash 0.06 ± 0.01 Nitrogen 0.16 ± 0.01
Oxygen 8.75 ± 0.21
Sulfur N.D.
LHV (MJ/kg) 23.22 ± 0.44 Chlorine 20.60
N.D.: Not Detected
Proximate analysisa: ASTM D3172 method, moisture free base
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Temperature (oC)
200 400 600 800
0
6
12
18
24
30
Nor
mal
ized
mas
s to
inita
il m
ass (
wt.%
)
0
20
40
60
80
100
20 oC/min
10 oC/min
5 oC/min
Der
ivat
ive
wei
ght c
hang
e (%
)
11
Plasticizer (i.e. phthalate)
release peakChlorine release peak
Polyene degradation peak
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Two-step pyrolysis:
• 1st pyrolysis at 300-450 ℃• 2nd pyrolysis at 600-700 ℃ using the residue from the 1st pyrolysis 12
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Sample conditions
Material: soft PVC
Sample amount per experiment: 200 g
Feed material size: 3-4 mm
Fixed bed reactor conditions
Fluidizing gas: nitrogen
Flow rate: 5 ℓ/min
Run 1 Run 2 Run 3 Run 4 Run 5 Run 6
1 Step
Heating rate (oC/min) 10 10 10 10
Residue from 1st
step (400 oC)Temperature (oC) 300 350 400 450
Holding time (h) 3 3 3 3
2 Step
Heating rate (oC/min) 10 10
Temperature (oC) 600 700
Holding time (h) 2 2
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2,26
0,61 0,66
7,34 7,61
6,14
0
2
4
6
8
350 400 450
Cl co
ncentr
ation (
wt.
%)
Temperature (℃)
Residue Oil+wax
14
58,64
24,6418,25 13
27,90
38,51 48,2449,02
13,46
36,85 33,51 37,98
0
20
40
60
80
100
300 350 400 450
Pro
du
ct yie
ld (
wt.
%)
Temperature (℃)
Residue Oil+wax Product gas
Virgin PVC: 20.60
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Virgin PVC
Oil Residue Product gas
Pyrolysis oilChar+gas
Cl:100
17.73 0.53 81.73
0.220.31
1st
step
2nd
step
48,45 50,57
28,8632,01
22,6917,43
0
20
40
60
80
100
600 700
Pro
du
ct yie
ld (
wt.
%)
Temperature (℃)
Char Condensated oil Product gas
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Characteristics:
• Auger & fluidized bed reactors connected in series
• Auger pyrolyzer: slow or intermediate pyrolysis, removal of HCl
• Fluidized bed pyrolyzer: fast pyrolysis, high yield of oil
PP 61.5
PE 36
PVC 2.5
(wt. %)Feed material
Quenching system
Char
separate
system
N2 jacket
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Auger reactor
Fluidized reactor
Cyclone
Hot filter
Quenching
system
Auger
quenching system
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Reactor type Products Experiment
Auger reactor
: ~300 oC
Gases 17.80
Oil+wax 6.22
Residues 5.00
Fluidized bed reactor
: ~ 700 oC
Gases (sum) 46.59
Hydrogen 0.24
Methane 14.29
Ethane 3.61
Ethene 18.56
Propene 6.26
Butenes 1.24
1,3-butadiene 1.58
Oils (sum) 20.76
Aliphatics (sum) 0.02
Cyclooctatetraene 0.01
Other aliphatics 0.01
Aromatics (sum) 19.55
Mono aromatics (sum) 9.12
Benzene 0.06
Toluene 0.91
Ethylbenzene 0.21
o-Xylene 0.18
Styrene 2.14
Other mono aromatics 5.62
Poly aromatics (sum) 10.86
Naphthalene 4.02
Other poly aromatic compounds 5.33
Unknowns 1.19
Char 3.64
Chlorine concentration in
pyrolysis oil
: 8.07 ppm
Petrochemical industries
chlorine standard
: 10 ppm
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In TGA, chlorine as HCl was released at 280-400 °C
In the two-step pyrolysis using batch reactor,
• Pyrolysis oil from the 2nd step conducted at 700 °C contained only
0.5 wt.% of chlorine
In the two-stage pyrolysis of mixed plastic which contained 2.5 wt. % PVC,
chlorine content in oil from fluidized bed reactor was below 10 ppm (8.07 ppm)
Pyrolysis oil from fluidized bed reactor of two-stage pyrolysis process was
mainly composed of aromatic hydrocarbons (over 94 wt. %)
Yields of ethene and propene was ~25 wt. %
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Resource Recycle lab.
THE UNIVERSITY OF SEOUL5th International Conference onSustainable Solid Waste Management