Pyrolysis of plastic wastes to fuel oil with and without catalyst Baoying Shi, Y ufeng Wang Guangdong Dongguan

Quality Supervision Testing Center DongguanChina C hengzhi Chuai School of Material Science & Chemical Engineering Tianjin Universi ty of Science & Technology Tianjin, China AbstractTwo types of waste plastics wer e used in this study: polyethylene (PE) and polypropylene (PP). This paper descr ibed pyrolysis of plastic waste materials with and without catalyst. The influen ce of the production of liquid was investigated from plastic wastes by various c atalysts. On the laboratory condition, using self-making PZSM-5 zeolite as catal yst, the yield of liquid product was highest. Key words-plastic wastes; pyrolysi s; fuel oil; catalyst I. INTRODUCTION In recent years accumulation of plastic wa stes produced all over the world has negative implications on the environment. T here can be used for ranking of different disposal processes in an environmental and resource compatible way, landfill and incineration with heat recovery. Land fill space is becoming scarce and expensive, a problem exacerbated by the fact t hat plastic waste is more voluminous than other waste type. Incineration on the other side, to recover energy, produces toxic gaseous products, which only shift s a solid waste problem to air pollution one. One possible alternative is the py rolysis of plastics, one of the principal routes for recycling plastic wastes in which both energetic and chemical value of the plastics are recovered as compar ed to incineration in which the chemical value of the polymer is completely lost . Pyrolysis of plastic waste could have an important role in converting this was te into economically valuable hydrocarbons, which can be used as fuels in the pe trochemical industry. The pyrolysis process consists of the thermal degradation of the wastes in the absence of oxygen/air. Plastics pyrolysis may provide for d isposal of plastic wastes with recovery of valuable gasoline-range hydrocarbons. In pyrolysis, the polymeric materials are heated to high temperatures, so their macromolecular structures are broken down into smaller molecules and a wide ran ge of hydrocarbons are formed. These pyrolytic products can be divided into a ga s fraction, a liquid fraction consisting of paraffins, olefins, naphthenes and a romatics, and solid residues. Pyrolysis appears to be a technique that is able t o convert waste plastics into gasoline-range hydrocarbons [1]. There are four ma jor methods for conversion of organic wastes to synthetic fuels: (1) hydrogenati on, (2) pyrolysis, (3) thermal and/or catalytic cracking, (4) gasification and b ioconversion [2, 3]. Literature reports several papers on pyrolysis of plastic w astes [4]. The decomposition of a polymer mixture over HZSM-5 modified with phos phoric acid zeolite catalysts (PZSM-5) has been comparatively studied [5]. Catal ytic decomposition increased the amount of gaseous products, lowered the condens ate, and changed their composition with respect to non-catalytic at the same pyr olysis temperature. The gaseous products contained a large C1C3 fraction, while t he liquid products contained mainly aromatic hydrocarbons. II. EXPERIMENTAL Two types of waste plastics were used in this study. Polyethylene (PE) and polypropy lene (PP) wastes were collected from landfill in the form of cattery and they we re shredded into 20mm20mm size. A schematic representation of the simplified expe rimental process used is shown in Fig.. FIG.. SIMPLIFIED EXPERIMENT PROCESS FOR PLASTIC WASTER PYROLYSIS Plastic sample s were weight for run 100.00g and pyrolyzed in the tube. Heat to tube was suppli ed from external heater and the power was adjusted to give an appropriate heat u p time. The simple thermocouple was placed directly in the pyrolysis medium. For each run, the heater was terminated when the desired temperature. The pyrolysis products were collected within three different groups as non-condensable gaseou s products, condensable as tarry liquids and solid residue. III. RESULTS AND DIS CUSSION PE and PP wastes are the main components of municipal plastic wastes. Th e behaviors of PE and PP are similar, which show that both of them have a consta nt degradation behavior at the involved temperature range. Degradation finished between for PE, and degradation temperature of PP is higher than PE, between 42 0440. The yields of liquid products increase quickly with increasing pyrolysis tim e from 30 min to 70 min. 978-1-4244-5089-3/11/$26.00 2011 IEEE

Pyrolysis of plastics has been studied extensively in the past. Kaminsky has rev iewed conversion of plastic wastes into gasoline-range hydrocarbons via pyrolysi s in the absence of a catalyst. Four types of mechanisms of plastics pyrolysis h ave been proposed: (1) End-chain scission or depolymerization, (2) Random-chain scission, (3) Chain-stripping and (4) Cross-linking[6]. The pyrolysis of PE and PP occurs through the random-chain scission mechanism and a whole spectrum of hy drocarbon products is obtained. PE thermal degradation consists of free radical formation and hydrogen abstraction steps. The results see Fig.. FIG.. CURVES FOR YIELD OF THE LIQUID PRODUCTS FROM PYROLYSIS OF PLASTIC WASTE TA BLE. THE MAIN PROPERTIES OF WASTE PE DEGRADATION TO OIL OVER CATALYSTS Catalyst Conversion (%) Yield to liquid product (%) Coke yield (%) Pyrolysis temperature () Pyrolysis time (min) No Catalyst 87.08 77.76 12.92 417~442 138 CaO 88.26 76.86 11.74 398~411 120 ZnCl2 89.92 73.94 10.08 400~405 219 Fe 85.50 71.88 14.50 400~410 151 Montmorillonite 77.50 67.30 22.50 387~398 130 PZSM-5 (original Si/Al ratio: 25) 94.12 73.30 5.88 310~365 135 PZSM-5 (original Si/Al ratio: 38) 94.24 74.04 5.76 290~369 140 PZSM-5 (original Si/Al ratio: 50) 93.84 73.08 6.16 298~375 140 Commercial cracking catalyst 88.84 75.94 11.16 360~380 146 Table I shows the overall conversion, the yield to liquid products and the coke yield of waste PE for calcium oxide (CaO), zinc chloride (ZnCl2), iron powder re duced (Fe), Montmorillonite, ZSM-5 zeolite modified with phosphoric acid (PZSM-5 ) and a commercial cracking catalysts used in this study. Experiments in the abs ence of any catalyst, pure thermal degradation of waste plastic, showed a polyme r require much higher temperatures. In such a catalytic cracking system, PZSM-5 as acidic solid catalysts increases oil conversion. All zeolite-based catalysts used showed conversion values above 90% and much lower yield to liquid products above 74%. Because of the strong zeolitic acidity and its smaller pores, severe overcracking takes place resulting into the formation of small molecules that ar e collected mainly in the gaseous fraction. ZSM-5 is well known for its slow cok ing tendency. This can be attributed to the shape selectivity properties of its relatively small pore structure that does not allow the growth of large coke mol ecules. A more detailed table of the liquid yield vs. time is used in following paragraphs to assess and compare the activity of each catalyst used. Montmorillo nite, Clay-based catalyst, have been proven less active than zeolites, but still were able to completely degrade polyethylene after a slight increase in the pro cess temperature. TABLE II. THE MAIN PROPERTIES OF WASTE PP DEGRADATION TO OIL O VER CATALYSTS Catalyst Conversion (%) Yield to liquid product (%) Coke yield (%) Pyrolysis temperature () Pyrolysis time (min) No Catalyst 84.54 75.58 15.46 398~426 156 PZSM-5 (original Si/Al ratio: 25) 95.24 73.26 21.98 332~381 140 PZSM-5 (original Si/Al ratio: 38) 95.56 73.62 21.94 340~390 150

PZSM-5 (original Si/Al ratio: 50) 94.00 72.88 21.12 351~383 154 Because of the shape selectivity properties and higher conversion of PZSM-5, the y are applied to waste PP and their results in table II. From the results, the c onversion of waste PP is similar with waste PE, but its coke yield and pyrolysis temperature are much higher than waste PE and pyrolysis product color of waste PP is harder than waste PE. FIG.. YIELD OF THE PRODUCTS OBTAINED BY PE PYROLYSIS AT DIFFERENT DOSAGE OF CATA LYST FIG.. YIELD OF THE PRODUCTS OBTAIN BY PP PYROLSIS AT DIFFERENT DOSAGE OF CATALYS T Catalyst is the most import for pyrolysis, especially the

dosage of catalyst. Figs. and show the yield distributions of the pyrolysis produ cts obtained from PE and PP wastes at different dosages of catalyst. From Figs. and , the reaction temperature decrease quickly with the dosage of the catalyst i ncrease. The yield of fuel oil is much higher with the dosage of catalyst at 8%. IV. CONCLUSION It is well known that PZSM-5 has the shape selectivity propertie s of its relatively small pore structure that does not allow the growth of large coke molecules. The liquid products from plastic wastes could be considered as a mixture of heavy naphtha, gasoline and light gas oil fractions. The gaseous pr oducts typically contain C1C4 paraffinic hydrocarbons with some olefins. As such, most of the liquid products formed would be ideally suited to further processin g in a petrochemical refinery. Currently, due to the higher oil prices, pyrolysi s process is likely to be economically competitive. Moreover, environmental cons iderations may hasten the industrial implementation of pyrolysis process in the near future. REFERENCES [1] Pinto, F.,Costa, P.,Gulyurtlu, I. Effect of plastic waste composition on product yield, Journal of Analytical and Applied Pyrolysis, 1999, 51(1):39-55 [2] Williams, Elizabeth A, Paul T. Analysis of products deriv ed from the fast pyrolysis of plastic waste Source, Journal of Analytical and Ap plied Pyrolysis, 1997, 40,347-363 [3] Demirbas A. Recent advances in biomass con version technologies, Energy Edu. Sci. Technol, 2000, 6, 77-83 [4] Miller, Steph e n J., Shah, Naresh. Conversion of waste plastic to lubricating base oil, Energ y and Fuels, 2005, 19(4), 1580-1586 [5] Williams, P.T. Recycling plastic waste b y pyrolysis, Journal of the Institute of Energy, 1998, 71, 81-93 [6] Manos G, Ga rforth A, Dwyer J. Catalytic Degradation of High Density Polyethylene over diffe rent Zeolitic structures, Ind Eng Chem Res, 2000, 39, 1198202