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Kultur Dokumente
Abstract
This paper describes non-catalytic pyrolysis of plastic waste materials. Three types of waste plastics were used in this study: polystyrene (PS),
polyethylene (PE) and polypropylene (PP). Under pyrolysis conditions, plastic wastes can be decomposed into three fractions: gas, liquid
and solid residue. The liquid products are usually composed of higher boiling point hydrocarbons. In order to obtain useful gasoline-range
hydrocarbons from the pyrolytic oil, fractional distillation is preferred for product separation. More valuable chemical raw materials including
benzene, toluene and other condensed aromatic hydrocarbons may be obtained by refining the pyrolytic oil. The results showed that waste PS
yielded higher liquid, and waste PE and PP yielded higher gaseous products. The dominant pyrolytic liquid product of PS waste was styrene.
© 2004 Elsevier B.V. All rights reserved.
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doi:10.1016/j.jaap.2004.03.001
98 A. Demirbas / J. Anal. Appl. Pyrolysis 72 (2004) 97–102
Fig. 1. Simplified experimental device for plastic waste pyrolysis. (1) Digital balance, (2) temperature transmitter, (3) thermocouple, (4) external heater,
(5) steel reaction vessel, (6) ice baths, and (7) collection vessels for liquid products.
A. Demirbas / J. Anal. Appl. Pyrolysis 72 (2004) 97–102 99
pyrolyzed in the tube. Heat to tube was supplied from exter- Table 2
nal heater and the power was adjusted to give an appropriate Product distribution in plastic pyrolysis (wt.% of waste)
heat up time. The simple thermocouple (NiCr–Constantan) Waste Pyrolysis Gas Oil Residue Other
was placed directly in the pyrolysis medium. For each run, temperature
the heater was started at 298 K and terminated when the de- (K)
sired temperature. Polyethylene (PE) 1033 55.8 42.4 1.8 –
Polypropylene (PP) 1013 49.6 48.8 1.6 –
The pyrolysis products were collected within three dif-
Polystyrene (PS) 854 9.9 24.6 0.6 64.9 styrene
ferent groups as non-condensable gaseous products, con- Mixture PE/PP/PS 1023 52.0 46.6 1.4 –
densables as tarry liquids and wax degradation products and
Source: Ref. [23].
solid residue. The products were analyzed mainly in liquid
state using a Fisons Ins. gas chromatograph (model GC
8000) equipped with a flame ionization detector, 30 m long, proposed [21]:
and 0.25 i.d. ZB-625 capillary column. Some chromato-
graphic analysis of the gaseous products was also made. (1) End-chain scission or depolymerization.
(2) Random-chain scission.
(3) Chain-stripping.
(4) Cross-linking.
3. Results and discussion
Different mechanisms are to some extent related to bond
PE and PP are the main components of MPWs. The ther- dissociation energies, the chain defects of the polymers, and
mogravimetric (TG) curves for PE, PP and PS wastes are the aromaticity degrees, as well as the presence of halogen
depicted in Fig. 2. The TG behaviors of PE and PP are sim- and other hetero-atoms in the polymer chains [1]. The py-
ilar, but PS is different. The behavior of PE or PP and PS rolysis of PS occurs by both end-chain and random chain
shows one main distinct weight loss step, which show that scission and the monomer recovery is only some 45% [22].
both of them have a constant degradation behavior at the PS thermal degradation is a radical chain process including
involved temperature range. Degradation finished between initiation, transfer and termination steps [8]. The product
720 and 760 K for the plastic wastes. The differences in TG distribution from PS pyrolysis depends on initial molecular
curves could obviously be attributed to the macromolecular weight (MW) of the PS sample [9]. While initial MW in-
structure and pyrolysis mechanism. creases from 2200 to 50,000 the yield of styrene increases
Pyrolysis of plastics has been studied extensively from 67 to 78 wt.%. The pyrolysis of PE and PP occurs
in the past [17,18]. Conversion of plastic wastes into through the random-chain scission mechanism and a whole
gasoline-range hydrocarbons via pyrolysis in the absence spectrum of hydrocarbon products is obtained [17]. PE
of a catalyst has been reviewed by Kaminsky [19,20]. thermal degradation consists of free radical formation and
Four types of mechanisms of plastics pyrolysis have been hydrogen abstraction steps [8]. Table 2 shows the product
Fig. 3. Curves for yield distributions of pyrolytic products from municipal solid waste. Heating rate: 10 K/s.
distribution in plastic pyrolysis [23]. The residual products Fig. 5, the yields of gaseous products increase from 12.3 to
from plastic pyrolysis are very low. 42.4 wt.% with increasing pyrolysis temperature from 550
The yield distributions of the pyrolytic products from mu- to 900 K. The yields of liquid products increase with in-
nicipal solid waste are given in Fig. 3. From Fig. 3, the creasing pyrolysis temperature up to 750 K and then slightly
yields of gaseous products increase with increasing pyrolysis decrease with temperature increasing from 750 to 900 K.
temperature. The yields of liquid products increase with in- The yield distributions of the pyrolytic products obtained
creasing pyrolysis temperature up to 675 K and then slightly from PS at different temperatures are shown in Table 3. From
decrease from 675 to 850 K. Fig. 4 shows the yields of the Table 3, the yields of styrene increase from 56 to 64% with
gaseous products from pyrolysis of municipal solid waste. increasing pyrolysis temperature from 650 to 750 K and then
Individual yield of each gas product with increasing pyrol- decrease from 64 to 49.6% with increasing pyrolysis tem-
ysis temperature is irregular. perature from 650 to 875 K. While pyrolysis temperature in-
The yield distributions of the pyrolytic products from creases from 650 to 875 K the yield of C2 –C4 hydrocarbons
municipal plastic waste are given in Fig. 5. As seen from increases from 3.8 to 22.5 wt.%.
Fig. 4. Curves for yields of the gaseous products from pyrolysis of municipal solid waste.
A. Demirbas / J. Anal. Appl. Pyrolysis 72 (2004) 97–102 101
Table 3
Yields of the products obtained by PS pyrolysis at different temperatures (K)
Compound 650 675 700 725 750 800 875
Table 5
Yields of the products obtained by PP pyrolysis at different temperatures
(K)
Fraction 675 725 800 875
Total-paraffin 30.4 28.2 24.9 29.6
Total-olefin 44.7 42.1 39.5 35.5
Naphthene 21.5 22.8 24.4 23.5
Aromatics 1.4 4.5 8.6 10.2
Others 2.0 2.4 2.6 1.2
Table 4 Table 6
Yields of the products obtained by PE pyrolysis at different temperatures Yields of the products obtained by municipal plastic waste pyrolysis at
(K) different temperatures (K)
Fraction 675 725 800 875 Fraction 675 725 800 875
Total-paraffin 35.6 39.8 43.7 44.2 Total-paraffin 32.5 31.4 31.1 33.2
Total-olefin 42.6 38.9 34.8 32.6 Total-olefin 37.3 33.6 32.3 31.6
Naphthene 19.6 18.5 17.6 17.2 Naphthene 20.7 21.5 23.0 22.7
Aromatics 5.8 1.7 3.5 5.8 Aromatics 7.9 13.6 12.5 11.6
Others 1.4 1.1 0.4 0.2 Others 1.6 1.9 1.1 0.9
102 A. Demirbas / J. Anal. Appl. Pyrolysis 72 (2004) 97–102