5-7 OCTOBERISFR2011

29

TOLEDO (SPAIN)OIL PRODUCTION BY FAST PYROLYSIS OF CELLULOSE/POLYETHYLENEMIXTURES IN METAL CHLORIDE PRESENCE
A. Solak, P. Rutkowski*
Wroclaw University of Technology, Faculty of Chemistry, Departament of Polymer and Carbonaceous Materials,
Gdanska 7/9, 50-344 Wroclaw, Polande-mail: piotr.rutkowski@pwr.wroc.pl

Abstract
Cellulose/polyethylene mixture (3:1 w/w) and Tetra Pak waste with and without metal chloride (ZnCl2, AlCl3, FeCl3)
addition were subjected to a fast pyrolysis process at 500qC and heating rate 100qC/s to evaluate the possibility of liquid
product formation with high yield. The addition of zinc, aluminum and iron chlorides has influenced the range of samples
decomposition as well as the chemical composition of resulted pyrolytic oils. It was found that a formation oflevoglucosan, main product of cellulose thermal decomposition, and phenol and its derivatives decreased in a presenceof metal chlorides. Contrarily, levoglucosenone was produced with higher yield. Fast pyrolysis of polyethylene leads tothe formation of solid long chain hydrocarbons, whereas the addition of metal chlorides promotes the formation of smallermolecules. More hydrocarbon liquid product can be ontained.

Keywords: pyrolytic oil, GC-MS, cellulose, polyethylene, Tetra Pak waste

1. Introduction
In view of co-existence of cellulose and polyolefins inpackages and other organic solid wastes, their
thermochemical co-conversion seems to be an attractive
way of use and utilization.
As it has been described in some papers, the copyrolysis process could have a potential for theenvironmentally friendly transformation of lignocellulosic
materials and plastic waste to valuable products [1-7].
Waste plastics can be converted to the fuel oil by noncatalytic or catalytic thermal processes. There weremany reports on the hydrocarbon polymers degradation
processes that led to the formation of liquid fraction [7-9].
The aim of this preliminary study was to evaluate thepossibility of catalytic fast pyrolysis application as amethod of thermochemical recycling of organic solidwastes.

2. Materials and Methods
Waste Tetra Pak (TP), commercial cellulose (Cellulose
powder, Aldrich) and powdered polyethylene (PE) wereselected for this study. Cellulose/polyethylene (CPE)
mixture in a 75:25 (w/w) ratio was prepared in a blenderfrom powdered samples. Both samples (TP and CPE)
were also mixed with 10 wt% metal chloride (ZnCl2, AlCl3,FeCl3) before pyrolysis.
Tetra Pak or CPE mixture were heated up to 500 °C withheating rate of 100qC/s under nitrogen atmosphere. The
processes were repeated under the same conditions forall samples mixed with 10 wt% of anhydrous zincchloride (p.a.), 10 wt% of aluminum chloride (p.a.) and10wt% of iron(III) chloride (p.a.).

interiores libro.indd 29

Pyrolytic oils were analyzed by GC-MS with a HP-1701
capillary column. Mass spectrometer was set at anionizing voltage of 70 eV with mass range m/z 15-450.

3. Results and Discussion
Fast pyrolysis process of cellulose/polyethylene mixture
leads to the liquids formation with high yield. A char andgaseous products are formed with a minor contribution.
Pyrolytic oils obtained from CPE mixture and Tetra Pak
are composed of three well separated phases, i.e. water,brown organic liquid and yellow wax. The metal chlorideadditives, i.e. ZnCl2, AlCl3, FeCl3 lead to the increased
formation of organic liquids instead of waxy product.
The chemical composition of resultant pyrolytic oils
clearly depends on the starting material composition andon the presence of metal chloride during the fastpyrolysis process as can be seen in Figure 1 and in
Table 1. Different compounds, i.e. levoglucosan (LG),levoglucosenone (LGon) a highly dehydrated sugar,
dianhydro-D-gluco-pyranose (DGP), phenol, phenol
derivatives and hydrocarbons (alkanes, alkenes, alkynes)
were identified in analyzed oils. Hydrocarbons weredivided into two groups, i.e. liquid (HC liq) and solid(HCsolid). It was found that the addition of metal chlorides
significantly decreases the formation of levoglucosan.
Contrarily, the increased formation of levoglucosenone
and dianhydro-D-gluco-pyranose was observed whencatalytic pyrolysis was conducted. The addition of metalchlorides enhanced the degradation of polyethylene intoa liquid product.
There are clear differences in the pyrolytic degradation ofboth materials, i.e. CPE mixture and Tetra Pak, which

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6th International Symposium on Feedstock Recycling of Polymeric Materials

must be related to the differences in their composition.
Lower proportion of levoglucosan and higher proportionof phenols were observed for Tetra Pak.
CPELG

10.00

15.00

20.00

25.00

30.00

35.00

40.00

45.00

50.00

55.00

60.00

CPE_ZnCl2

beverage package waste seems to be an alternativeroute of such material recycling.
Table 1. Distribution of different classes of compounds inpyrolytic oils obtained from CPE mixture and Tetra Pak(abbreviations are given in text)sample
CPE
CPE_ZnCl2
CPE_AlCl3
CPE_FeCl3
TP
TP_ZnCl2
TP_AlCl3
TP_FeCl3

LG
31.7
16.2
10.2
5.5
13.7
1.0
1.4
1.0

LGon
0.1
0.2
3.1
0.7
1.3
1.0
0.6
0.4

DGP
0.5
1.3
2.4
1.2
0.5
-HCliq
7.8
26.2
28.2
24.2
14.0
28.6
27.1
34.3

HCsolid
49.7
47.8
45.1
58.2
65.2
59.0
59.8
55.4

References

10.00

15.00

20.00

25.00

30.00

35.00

40.00

45.00

50.00

55.00

60.00

CPE_AlCl3
LGLGon

10.00

15.00

20.00

25.00

30.00

35.00

40.00

45.00

50.00

55.00

60.00

20.00

25.00

30.00

35.00

40.00

45.00

50.00

55.00

60.00

CPE_FeCl3

10.00

15.00

Fig. 1. GC-MS analyses of pyrolytic oils.

4. Conclusions
Fast pyrolysis of cellulose/polyethylene mixture and Tetra
Pak with and without catalyst was performed todetermine the influence of metal chloride on thechemical composition of liquid products. The use ofZnCl2, AlCl3 or FeCl3 caused a significant decrease oflevoglucosan formation and an increased degradation ofpolyethylene to liquid hydrocarbons.
These preliminary results showed that Tetra Pak ororganic wastes containing cellulose and polyolefins canbe a useful recycling resources. The fast pyrolysis ofinteriores libro.indd 30[1] E. Jakab, G. Varhegyi, O. Faix, O. Thermal
decomposition of polypropylene in the presence of woodderived materials. J. Anal. Appl. Pyrol. 56 (2000)
273285.
[2] E. Jakab, M. Blazso, O. Faix. Thermal decompositionof mixtures of vinyl polymers and lignocellulosic
materials. J. Anal. Appl. Pyrol. 58-59 (2001) 4962.
[3] V.I. Sharypov, N. Marin, N.G. Beregovtsova, S.V.
Baryshnikov, N. Kuznetsov, V.L. Cebolla, J.V. Weber,Co-pyrolysis of wood biomass and synthetic polymer
mixtures. Part I influence of experimental conditions on
the evolution of solids; liquids and gases. J. Anal. Appl.
Pyrol. 64 (2002) 1528.
[4] N. Marin, S. Collura, V.I. Sharypov, N.G.
Beregovtsova, S.V. Baryshnikov, B.N. Kuznetsov, J.V.
Weber. Copyrolysis of wood biomass and synthetic
polymer mixtures. Part II characterization of liquidphases. J. Anal. Appl. Pyrol. 65 (2002) 4155.
[5] A. Aboulkas, K. El Harfi, A. El Bouadili. Nonisothermal kinetic studies on co-processing of olive
residue and polypropylene. Energ. Convers. Manage. 49(2008) 36663671.
[6] P. Rutkowski, P and A. Kubacki. Influence ofpolystyrene addition to cellulose on chemical structure
and properties of bio-oil obtained during pyrolysis. Energ.
Convers. Manage. 47 (2006) 716731.
[7] A. Demirbas. Pyrolysis of municipal plastic wastes forrecovery of gasoline-range hydrocarbons. J. Anal. Appl.
Pyrol. 72 (2004) 97102.
[8] N. Kiran, E. Ekinci, C.E. Snape. Recycling of plastic
wastes via pyrolysis. Resour. Conserv. Recy. 29 (2000)
273-283[9] F. Pinto, P. Costa, I. Gulzurtlu, I. Cabrita. Pyrolysis ofplastic wastes. 1. Effect of plastic waste composition on
product yield. J. Anal. Appl. Pyrol. 51 (1999) 39-55.

Acknowledgement
The State Committee for Scientific Research in Poland
supported this work. Project No. N209146036.

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