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.