catalytic co-pyrolysis of pulper rejects: …€¦ · tufan salan catalytic co-pyrolysis of pulper...
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TUFAN SALAN
CATALYTIC CO-PYROLYSIS OF PULPER REJECTS:
DETERMINATION OF SYNERGISTIC EFFECTS OF WASTE
POLYMER/CELLULOSE FIBRE MIXTURES ON PRODUCT YIELD
T.C. KAHRAMANMARAŞ SÜTÇÜ İMAM UNIVERSITY
COSTAction FP1105 Meeting: WoodCellNet Workshop
11-12 November 2014
Thessaloniki , Greece
Aim Of The Study
�Catalytic co-pyrolysis of pulper rejects such as waste paper fibers,
wood particles, elastomer, thermoset and thermoplastic polymer
wastes, which occur during the first stage of pulping process in the
waste paper recycling factory, was performed with the natural
catalysts alternative to synthetic catalyst.
Pulper Rejects
Waste Paper
Pulper
Pulper Rejects
WasteTrap
Ragger
Materials
�Pulper Rejects
Contents Amount (%)
PE (HDPE and LDPE) 21,85
OPP (Gelatin and PackingTape) 13,16
PP 10,26
Fibers 10,14
PET 8,62
Textile Material (Cotton or
Synthetic Fabric)8,57
PVC 7,24
Metals (Copper, Iron, Aluminium
etc.)3,98
Wood Particles 3,9
Rubber (Soft Rubber) 3,73
Artificial Leather (PU) 3,14
Leather (Shoes, Bags etc.) 2,56
PS 1,74
Inert materials (Sand and Glass) 1,1
�Collection and classification of waste
paper has not yet an institutional
structure.
�No good separation at source
�Collected by different people (street
collectors) and informal organizations.
�Catalysts
Zeolite: 5 M HCl Sepiolite: 2M HCl Red Mud: 2M HCl
�Catalyst were prepared from a natural mineraland clay which are zeolite (clinoptilolite) andsepiolite and aluminum factory waste red mudvia chemical and thermal activation processes.�Boiling over 100 °C for 2 h at constant stirringat a hot plate. � Filtration until pH:7 � Dried at 103 °C overnight.
The heat-treatment was carried outby heating samples at 500 °C for 2 h.
�Samples were collected from different regions 2 months .
�Dried in the air for 15 days.
�Shredding, Grinding and Sieving
�Dried in the oven overnight.
Method
� Pyrolysis Experiments
Temperature:
500 °C
Heating Rate:
10 °C/min
N2 Flow Rate:
50 mL/min
Time:
30 min
Parameters
Reference CodeParticle Size
3 mm P3
5 mm P5
7 mm P7
CatalystType and Ratio
Zeolite
5%, 10%, 15% PZ-5, PZ-10, PZ-15
Sepiolite
5%, 10%, 15% PS-5, PS-10, PZ-15
Red Mud
5%, 10%, 15% PK-5, PK-10, PK-15
Schematic Structure Experimental Setup and Pyrolysis Peactor
Before the catalytic pyrolysis processes,pulper wastes, which had a particle size of 3mm, 5 mm and 7 mm, were pyrolysed (thermaldegradation) and then catalytic pyrolysisexperiments were carried out with the sample(7 mm) which yielded maximum liquidproduct.
� TGAAnalysis ResultsZone I
Zone II
Zone III
Data
Samples
1 2 3 4 5 6 7
DegradationTemperature (°C) 245.53 245.88 246.3 241.49 241.73 242,22 241.86
Amount of Remaining Substance (%) 8.23 8.3 6.94 9.02 9.27 7.78 7.44
Data
Basic DecompositionTemperature Ranges
200-350 °C 350-600 °C 550-800 °C
Max. DrTGATemperature (°C) 291.17 480.45 690.19
Derivative (Dr) Weight Loss (%/min) 3.19 12.32 0.8
Weight Loss (%) 17.03 67.73 6.28
GreasyPhase
Water-Soluble Phase
Organic Phase
Bio-oilBio-oil
Pulper Zeolite Sepiolite Red Mud
70,58% 71,91% 67,81% 63,52%
72,55% 72,79% 68,92% 67,55%
72,85% 73,3% 69,17% 68,49%
Pyrolysis Conversion
ProductYields
0
10
20
30
40
50
60
70
80
90
100
PZ-5 PZ-10 PZ-15 P7
Yield
(%)
Products
Gas Phase
Organic Phase
Aqueous Phase
Char
Red Mud
PulperWaste Zeolite
Sepiolite
BiomassSolid+
Radicals
Radicals+Polymer
ChainScission
LightLiquids
Synergistic Effect of Plastic and Biomass
�The apparent synergistic effect leading to a high distillable liquids production.�Some preliminary considerations have to be taken into account: (N.Marin et al. 2002)
1. At the temperature of experiment (500 °C), the biomass samples, whatever theirorigins, are totally degraded. TGA analysis both of single sample or in mixture withpolymer clearly show independent thermal behaviour of biomass and demonstrate
that their degradation occurs at temperature lower than 400 °C;2. At 400 °C, solids issued from biomass pyrolysis are aliphatic oligomers with a lot ofoxygen functionalities. Slow reactions of dehydratation, dehydrogenation andpolymerization in this domain of temperature, lead progressively to a carbonaceousaromatic solid . That means, the solid in the reaction media, in our conditions, acts as atank of radicals;3. The solid provides radicals, enhancing the homolytic scission of the polyolefinicchains4. The evolution of the ratio mass of distillable liquids–initial mass of plasticsaccording to mixtures composition is almost constant for the mixtures.