Catalytic stepwise pyrolysis of packaging plastic waste

In this paper the combination of catalytic and stepwise pyrolysis is explored. A mixture of polyethylene (PE), polypropylene (PP), polystyrene (PS), poly(ethylene terephthalate) (PET) and poly(vinyl chloride) (PVC), which resembles real municipal plastic waste, has been pyrolyzed in a 3.5 dm3 semi-batch reactor at 440 C for 30 min using a ZSM-5 zeolite as catalyst. A low temperature (300 C) dechlorination step has been carried out both with and without catalyst. It has been proved that the application of such dechlorination step gives rise to a 75 wt% reduction of chlorine in the liquid fraction. However, such step has a negative influence on the catalyst, which loses some catalytic activity. The optimum procedure in terms of quality and chlorine content of the products is the combination of first a low temperature step without catalyst, and second the catalytic pyrolysis step.

Pyrolysis of plastic packaging waste: A comparison of plastic residuals from material recovery facilities with simulated plastic waste

Pyrolysis may be an alternative for the reclamation of rejected streams of waste from sorting plants where packing and packaging plastic waste is separated and classified. These rejected streams consist of many different materials (e.g., polyethylene (PE), polypropylene (PP), polystyrene (PS), polyvinyl chloride (PVC), polyethylene terephthalate (PET), acrylonitrile butadiene styrene (ABS), aluminum, tetra-brik, and film) for which an attempt at complete separation is not technically possible or economically viable, and they are typically sent to landfills or incinerators. For this study, a simulated plastic mixture and a real waste sample from a sorting plant were pyrolyzed using a non-stirred semi-batch reactor. Red mud, a byproduct of the aluminum industry, was used as a catalyst. Despite the fact that the samples had a similar volume of material, there were noteworthy differences in the pyrolysis yields. The real waste sample resulted, after pyrolysis, in higher gas and solid yields and consequently produced less liquid. There were also significant differences noted in the compositions of the compared pyrolysis products.

Kinetic study of low-temperature conversion of plastic mixtures to value added products Batch-mode pyrolysis of 200.0 g samples of polymers was studied at low temperature. The cracking reaction was carried out in a stainless-steel autoclave with reaction temperatures of 360, 380, 400 and 420 C, initial pressure of 6.325 kPa (absolute pressure) and reaction times of 0240 min. Based on the experimental results, a four-lump kinetic model has been developed to describe the production distribution of the light fractions, middle distillates and heavy fraction. This model reasonably fitted the results in each reaction of operation conditions. It was also found that the pyrolysis kinetics of separated plastic, mixed plastic and mixed plastic containing additives can be described by the same kinetic model. The plastic additives have not had a great influence on the product distribution and kinetics of the mixed plastic pyrolysis. Finally, the optimum conditions of lowtemperature conversion of plastic mixtures to value-added products were established. The formation of heavy fractions from HDPE was as high as 70 wt% at 380 C at a reaction time of 250 min. During the thermal degradation of plastic mixtures, the heavy fractions yielded up 50 wt% for 30 min reaction time at 400 C. The total activation energies for the conversion of HDPE and the plastic mixtures were estimated to be 217.66 kJ mol1 and 178.49 kJ mol1, respectively. Pyrolysis of waste polypropylene for the synthesis of carbon nanotubes Waste polypropylene (PP) is used as precursor for synthesizing multi-walled carbon nanotubes (MWCNTs) by single stage chemical vapor deposition (CVD) method using nickel as catalyst. The pyrolytic degradation of PP to MWCNT was achieved by exposing the catalyst and precursor to temperature 600,700 and 800C under argon and hydrogen atmosphere for an hour. The resultant carbon was purified and characterized by XRD, Raman scattering, SEM, TEM and HRTEM. All the analysis confirmed the graphitic nature and multi-walled morphology of the CNT. Moreover the MWCNT was found to exhibit high transmittance to visible light up to 85% at 550nm, comparable to that of typical ITO films (90%), suggesting that MWCNTs can be used for optoelectronic devices. The present work could be employed for synthesizing CNTs, having wide range of applications, and for environment protection as well since waste plastic is being used.

Pyrolysis of waste materials using TGA-MS and TGA-FTIR as complementary characterization techniques Pyrolysis of waste materials, biomass wood waste, waste tyre, refuse derived fuel (RDF) and waste plastic was performed using two thermo gravimetric analyzers (TGA). One TGA was coupled to a mass spectrometer (MS) and the other to an infrared spectrometer (FTIR). The kinetic parameters of the pyrolysed waste materials obtained for TGA-MS and TGA-FTIR were compared using a model based on first-order reactions with a distribution of the activation energies. A further comparison of the volatile species evolved by thermal degradation (TGA) and the subsequent characterization by the MS and FTIR spectra was performed. The firstorder reaction pathways and subsequent activation energies calculated from the differential TGA data presented good repeatability between the TGA-MS and TGA-FTIR. The TGA-MS and TGA-FTIR produced a broad spectrum of qualitative data characterizing the volatile gaseous fraction of the waste materials pyrolysed. TGAMS and TGA-FTIR are shown to be valuable techniques in corroborating the respective thermo grams and spectrograms of the volatile species evolved during the pyrolysis of waste materials. However both techniques are prone to interference and careful interpretation of the spectra produced is required. Characterization of the waxes obtained by the pyrolysis of polyolefin plastics in a conical spouted bed reactor The thermal pyrolysis of three different polyolefin plastics (HDPE, LDPE and PP) has been carried out in a conical spouted bed reactor. This technology is especially interesting because of the high selectivity to waxes due to the low residence times and high heating rates that reduce secondary reactions and increase the yield of primary pyrolysis products (waxes). These have been obtained operating at 450, 500 and 600C and a complete characterization has been carried out using different techniques, such as gel permeation chromatography (GPC), Fourier transform infrared (FTIR) spectrophotometery, simulated distillation and the measurement of heating value and melting point. Operating conditions and feed type have been observed to have a significant effect on the properties of the different waxes. The characterization has been carried out bearing in mind the potential use of waste plastic-derived waxes as a feedstock for cracking units. Deactivation and regeneration of ZSM-5 zeolite in catalytic pyrolysis of plastic wastes In this work, a study of the regeneration and reuse of ZSM-5 zeolite in the pyrolysis of a plastic mixture has been carried out in a semi-batch reactor at 440 C. The results have been compared with those obtained with fresh-catalyst and in non-catalytic experiments with the same conditions. The use of fresh catalyst produces a significant change in both the pyrolysis yields and the properties of the liquids and gases obtained. Gases more rich in C3C4 and H2 are produced, as well as lower quantities of aromatic liquids if compared with those obtained in thermal decomposition. The authors have proved that after one pyrolysis experiment the zeolite loses quite a lot of its activity, which is reflected in both the yields and the products quality; however, this deactivation was found to be reversible since after regeneration heating at 550 C in oxygen atmosphere, this catalyst recovered its initial activity, generating similar products and in equivalent proportions as those obtained with fresh catalyst. Influence of time and temperature on pyrolysis of plastic wastes in a semi-batch reactor The objective of this work is the study of the influence of temperature and time in the products obtained in the pyrolysis of plastic wastes. The thermal behavior of a mixture, which resembles municipal plastic wastes, has been studied both in a thermo gravimetric analyzer and in a 3.5 dm3 semi-batch reactor at atmospheric pressure in order to establish the most appropriate timetemperature combination for plastic waste pyrolysis. It has been proved by the authors that temperature has a strong effect in the characteristics of pyrolysis liquids and to a lesser extent in gas and solid properties. At the lowest temperature tested (460 C), a great proportion of extremely viscous liquids with high content of long hydrocarbon chains are obtained, while at the highest temperature tested (600 C) low proportion of liquids with a high content of aromatics is produced. The effect of time is not as strong as that of temperature except for very short reaction times (015 min). 1530 min was established as the optimum reaction time range, since total conversion is achieved and longer reaction times do not produce any effect neither in conversion nor in products characteristics. 500 C has been found to be the most appropriate temperature for the pyrolysis of such plastic waste in terms of both conversion and quality of the products.

Catalytic pyrolysis of plastic wastes with two different types of catalysts: ZSM-5 zeolite and Red Mud The influence of ZSM-5 zeolite and Red Mud in the pyrolysis of plastic wastes has been studied. Both catalysts have been thoroughly characterized; the zeolite shows weak and strong acid sites and great BET surface area (412.0m2 g1), while Red Mud contains lower acidity, with also weak and strong acid sites, meso-macropores and BET surface area of 27.49m2 g1. Both catalysts have been tested in pyrolysis of a mixture of plastics which resembles municipal plastic wastes, at 440 and 500 C in a 3.5dm3 semi batch reactor. The results have been compared with those of the thermal process. It has been proved that ZSM-5 zeolite has a strong effect in the characteristics and distribution of pyrolysis products. It generates at both temperatures a greater proportion of gases and liquids with a higher content of aromatics than without catalyst. Red Mud needs higher temperatures than ZSM-5 zeolite to exert a catalytic effect in pyrolysis, since similar results to those obtained without catalyst are obtained at 440 C, while at 500 C a higher yield of gases and a greater proportion of aromatics in the liquids are obtained. Study of the pyrolysis of municipal solid waste for the production of valuable products To obtain information on the potential of thermal conversion (pyrolysis) of municipal solid waste (MSW), a thermo gravimetric study (TGA) is performed in a stream of nitrogen. Based on TGA results, pyrolysis experiments are carried out in a semi-batch reactor under inert nitrogen atmosphere. Slow pyrolysis is performed up to 550 C (heating rate of 4 C/min). Fast pyrolysis is performed at 450, 480, 510 and 550 C and different input transfer rates (12 or 24 g material/min). The pyrolysis products are studied on composition and yield/distribution and investigated for their use as valuable product. The liquid obtained by slow pyrolysis separates spontaneously in a water rich product and an oily product. For all fast pyrolysis conditions, viscous, brown oil which contains a poly (ethylene-co-propylene) wax is obtained. Composition analyses by GC/MS of the oil products (slow/fast pyrolysis) show that aliphatic hydrocarbons are the major compounds. The pyrolysis oils have high calorific value (between 35 and 44 MJ/kg), low wt% of water (around 6 wt %) and a low O/C value (between 0.2 and 0.3). The presence of waxy material is probably due to incomplete breakdown of poly (ethylene-co-propylene) present in MSW under study. The optimal pyrolysis conditions, regarding to oil yield, fuel properties, and wax yield is fast pyrolysis at 510 C with 24 g material/min input transfer rate. The fast pyrolysis gases contain mainly hydrocarbons and have an averaged LHV around 20 MJ/Nm3. ICP-AES analyses of pyrolysis products reveal that almost none of the metals present in MSW are distributed within the liquid fractions. Hydrogen-rich gas production from waste plastics by pyrolysis and low-temperature steam reforming over a ruthenium catalyst Operating conditions for low-temperature pyrolysis and steam reforming of plastics over a ruthenium catalyst were investigated. In the range studied, the highest gas and lowest coke fractions for polystyrene (PS) with a 60 g h_1 scale, continuous-feed, two-stage gasifier were obtained with a pyrolyzer temperature of 673 K, steam reforming temperature of 903 K, and weight hourly space velocity (WHSV) of 0.10 g-sample g-catalyst_1 h_1. These operating conditions are consistent with optimum conditions reported previously for polypropylene. Our results indicate that at around 903 K, the activity of the ruthenium catalyst was high enough to minimize the difference between the rates of the steam reforming reactions of the pyrolysates from polystyrene and polypropylene. The proposed system thus has the flexibility to compensate for differences in chemical structures of municipal waste plastics. In addition, the steam reforming temperature was about 200 K lower than the temperature used in a conventional Ni-catalyzed process for the production of hydrogen. Low-temperature steam reforming allows for lower thermal input to the steam reformer, which results in an increase in thermal efficiency in the proposed process employing a Ru catalyst. Because low temperature steam reforming can be also expected to reduce thermal degradation rates of the catalyst, the pyrolysis-steam reforming process with a Ru catalyst has the potential for use in small-scale production of hydrogen-rich gas from waste plastics that can be used for power generation. Multiple use of waste catalysts with and without regeneration for waste polymer cracking Waste plastics contain a substantial number of valuable chemicals. The wastes from post-consumer as well as from industrial production can be recycled to valuable chemical feedstock, which can be used in refineries and/or petrochemical industries. This chemical recycling process is an ideal approach in recycling the waste for a better environment. Polymer cracking using a laboratory fluidized bed reactor concentrated on the used highly

contaminated catalyst, E-Cat 2. Even though E-Cat 2 had low activity due to fewer acid sites, the products yielded were similar with amorphous ASA and were far better than thermal cracking. The high levels of heavy metals, namely nickel and vanadium, deposited during their lifetime as an FCC catalyst, did not greatly affect on the catalyst activity. It was also shown that E-Cat 2 could be used with and without regeneration. Although there was more deactivation when there was no regeneration step, the yield of gases (C2C7) remained fairly constant. For the first time, these results indicate that waste FCC catalyst (E-Cat) is a good candidate for future feedstock recycling of polymer waste. The major benefits of using E-Cat are a low market price, the ability to tolerate reuse and regeneration capacity.

CONVERSION OF WASTE PLASTICS (POLYETHYLENE) TO FUEL BY MEANS OF PYROLYSIS There is an increase in the production and consumption of plastics as the day goes by. All plastics need to be disposed after their usefulness, as waste. The needs to manage this waste from plastic become more apparent. This leads to pyrolysis, which is a way of making these wastes to become very useful to us by recycling them to produce fuel oil. In this study, plastic wastes (polyethylene) were used for the pyrolysis to get fuel oil that has the same physical properties as the fuel used in aviation industry (JP-4). The experiment was carried out in two ways, first, thermal pyrolysis (without the aid of a catalyst) and second, catalytic pyrolysis (with the aid of a catalyst). The catalyst used for the experiment was silica-alumina. Pyrolysis runs without oxygen and in high temperature of about 430C, which is why a reactor was constructed for the reaction and a furnace designed to provide the required temperature. This study shows that the pyrolysis of polyethylene requires a temperature of about 550C and catalyst to waste ratio of 1:4 for it to yield the highest quantity of hydrocarbon. Catalytic co-processing of coal and petroleum residues with waste plastics to produce transportation fuels Coprocessing reactions with waste plastics, petroleum residues and coal were performed to determine the individual and blended behavior of these materials using lower pressure and cheaper catalysts. The plastic used in this study was polypropylene. The thermodegradative behavior of polypropylene (PP) and PP/ petroleum residues/coal blends were investigated in the presence of solid hydrocracking (HC) catalysts. A comparison among various catalysts has been performed on the basis of observed temperatures. The higher temperatures of initial weight loss of PP shifted to lower values by the addition of petroleum residues and coal. The catalysts were also tested in a fixed-bed micro reactor for the pyrolysis of polypropylene, petroleum residues and coal, alone and blended together in nitrogen and hydrogen atmosphere. High yields of liquid fuels in the boiling range 100480 C and gases were obtained along with a small amount of heavy oils and insoluble material such as gums and coke. The results obtained on the co-processing of polypropylene with coal and petroleum residues are very encouraging as this method appears to be quite feasible to convert plastic materials into liquefied coal products and to upgrade the petroleum residues and waste plastics. CATALYTIC THERMAL DECOMPOSITION OF POLYETHYLENE BY PYROLYSIS GAS CHROMATOGRAPHY An experimental study of the thermal decomposition of polyethylene in an inert atmosphere has been carried out in the temperature range 300-800C using Shimadzu PYR-2A pyrolyzer for heating the sample. The method allows the accurate control and measurement of the pyrolysis temperature. The production of hydrocarbons and the corresponding monomers of these polymeric systems were monitored. The effects of variation of temperature, sample size, pyrolysis atmosphere, residence time and catalyst on the distribution of these products were studied. As the carrier gas rapidly swept the primary products from the hot zone into the chromatographic column, so the secondary decomposition is largely eliminated and the pyrolysis products give accurate information about the nature, composition and structure of the pyrolysis material. Pyrolysis of municipal plastic wastes: Influence of raw material composition The objective of this work is the study of pyrolysis as a feedstock recycling process, for valorizing the rejected streams that come from industrial plants, where packing and packaging wastes are classified and separated for their subsequent mechanical recycling. Four real samples collected from an industrial plant at four different times of the year, have been pyrolysed under nitrogen in a 3.5 dm3 autoclave at 500 C for 30 min. Pyrolysis liquids are a complex mixture of organic compounds containing valuable chemicals as styrene, ethyl-benzene, toluene, etc. Pyrolysis solids are composed of the inorganic material contained in the raw materials, as well as of

some char formed in the pyrolysis process, and pyrolysis gases are mainly composed of hydrocarbons together with some CO and CO2, and have very high gross calorific values (GCV). It has been proved by the authors that the composition of the raw material (paper, film, and metals contents) plays a significant role in the characteristics of pyrolysis products. High paper content yields water in the pyrolysis liquids, and CO and CO2 in the gases, high PE film content gives rise to high viscosity liquids, and high metals content yields more aromatics in the liquid products, which may be attributed to the metals catalytic effect. Pyrolysisgasification of plastics, mixed plastics and real-world plastic waste with and without NiMgAl catalyst Polypropylene, polystyrene, high density polyethylene and their mixtures and real-world plastic waste were investigated for the production of hydrogen in a two-stage pyrolysisgasification reactor. The experiments were carried out at gasification temperatures of 800 or 850 C with or without a NiMg Al catalyst. The influence of plastic type on the product distribution and hydrogen production in relation to process conditions were investigated. The reacted NiMgAl catalysts were analyzed by temperature programmed oxidation and scanning electron microscopy. The results showed that lower gas yield (11.2 wt.% related to the mass of plastic) was obtained for the non-catalytic non-steam pyrolysisgasification of polystyrene at the gasification temperature of 800 C, compared with the polypropylene (59.6 wt.%) and high density polyethylene (53.5 wt.%) and waste plastic (45.5 wt.%). In addition, the largest oil product was observed for the non-catalytic pyrolysisgasification of polystyrene. The presence of the NiMg Al catalyst greatly improved the steam pyrolysisgasification of plastics for hydrogen production. The steam catalytic pyrolysisgasification of polystyrene presented the lowest hydrogen production of 0.155 and 0.196 (g H 2/g polystyrene) at the gasification temperatures of 800 and 850 C, respectively. More coke was deposited on the catalyst for the pyrolysisgasification of polypropylene and waste plastic compared with steam catalytic pyrolysisgasification of polystyrene and high density polyethylene. Filamentous carbons were observed for the used NiMgAl catalysts from the pyrolysisgasification of polypropylene, high density polyethylene, waste plastic and mixed plastics. However, the formation of filamentous carbons on the coked catalyst from the pyrolysisgasification of polystyrene was low. Operating Conditions for the Pyrolysis of Poly-(ethylene terephthalate) in a Conical Spouted-Bed Reactor Continuous pyrolysis of poly-(ethylene terephthalate) (PET) was performed in a conical spouted-bed reactor. This reactor is especially suitable for this process, because of its excellent hydrodynamic behavior and its versatility. An optimization of the operating conditions has been performed to avoid particle agglomeration and defluidization, given that these are serious problems that hinder plastic waste pyrolysis. Moreover, the influence of temperature in the pyrolysis product distribution was studied in the range of 500600 C. PET pyrolysis led to a high yield of gas fraction, a low amount of liquids, a significant yield of solid fraction, and a solid residue that remained in the reactor coating sand particles. The main products obtained are carbon monoxide, carbon dioxide, benzoic acid, and acetaldehyde. Pyrolysis of Mixed Plastic Wastes for the Recovery of Benzene, Toluene, and Xylene (BTX) Aromatics in a Fluidized Bed and Chlorine Removal by Applying Various Additives Mixed plastic wastes are very difficult to mechanically recycle into new products because of their nonhomogeneity. Therefore, pyrolysis and gasification seem to be very effective in the extraction of energy from mixed plastic wastes in the form of oil and gas. In this study, a fraction of mixed plastic wastes was pyrolyzed in a bench-scale plant equipped with a fluidized-bed reactor and a char removal system. This study has two aims. The first is to find out the optimum reaction temperature for a high yield of benzene, toluene, and xylene (BTX) aromatics. The second is to find out the best additive for chlorine removal. To find out the optimum reaction temperature for the maximum BTX content, experiments at a temperature range of 660780 C were carried out. The pyrolysis oils that were obtained from the experiments were composed of aliphatics and mono- and polyaromatic compounds. The reaction temperature had a positive effect on the BTX aromatics yield. The maximum BTX aromatics yield was obtained at 719 C, with a value of 18 wt % of the organic product. The pyrolysis oils had almost no metal content. The metals that were present in the feed material were concentrated in the solid product, the char. It seems that the char removal system, which was composed of a cyclone and a hot filter, almost perfectly removed the char particles. Besides the pyrolysis oil, a combustible gas was also obtained. The main components of the gas were CH4, C2H4, C3H6, C4H6, and C4H10. The higher heating value of the product gas was about 50 MJ/kg. To absorb the hydrogen chloride that was formed from the degradation of the polyvinyl chloride (PVC) in the mixed plastic wastes, additives (calcium oxide, calcium hydroxide, crushed

oyster shells, and rice straw) were added to a fraction of the mixed plastic wastes. In the experiments without any additive, the chlorine contents of the pyrolysis oils were 350500 ppm. When the additives, especially calcium oxide, calcium hydroxide, and crushed oyster shells, were applied, the chlorine content of the pyrolysis oils significantly decreased to 50 ppm. The results of this study suggest that the use of oyster shells as a HCl absorbent can stimulate the recycling of waste oyster shells, which are abundant in Korea. Catalytic pyrolysis of HDPE in continuous mode over zeolite catalysts in a conical spouted bed reactor A study has been carried out using HZSM-5, HY and H zeolite-based catalysts in the pyrolysis of high density polyethylene (HDPE) continuously fed into a conical spouted bed reactor (CSBR) at 500 C and atmospheric pressure, with the aim being to assess the yields and composition of the main products (both light olefins and automotive fuel hydrocarbons). Product streams have been grouped into seven lumps: light olefins (C2C4) and light alkanes (<C4) in the gas fraction, the liquid fraction consisting of three lumps (non-aromatic C5C11 compounds, single-ring aromatics and C11+ hydrocarbons), wax and coke. The results are compared with those already obtained in thermal pyrolysis in a CSBR and with those obtained in the literature using catalysts in bubbling fluidized beds. HZSM-5 zeolite-based catalyst is very selective to light olefins, 58 wt% once equilibrated; whereas high yields of non-aromatic C5C11 products (around 45 wt %) are obtained with H and HY zeolite-based catalysts. Wax yield increases as reactions proceed, especially with HY and H zeolite-based catalysts, due to catalyst deactivation by coke formation. Product distribution with the different catalysts and their evolution throughout continuous operation by feeding HDPE is explained according to the different properties of the zeolites used. Pyrolysis of mixed plastics for the recovery of useful products Thermal and catalytic pyrolysis of polystyrene (PS) with low-density polyethylene (LDPE), high-density polyethylene (HDPE), polypropylene (PP), poly-ethylene terephthalate (PET) plastics were carried out in a 25 cm3 stainless steel micro reactor at around 430440 C under 5.56.0 MPa of N2 gas pressure for 1 h. Three reactions of each plastic with PS were conducted in the ratio of 1:1, 1:2 and 1:3. The amount of PS was varied to explore its role and reactivity. In all co processing reactions, ratio 1:1 afforded the best yields in the form pyrolytic oils. SIM distillation of hexane soluble portion showed that the low boiling fractions were not found and fractions were obtained only after 96 C+ boiling point. It could be due to the vaporization of high volatile components. In most of the binary pyrolysis, light cycle oil (LCO) fractions have low recovery than heavy cycle oil (HCO). GC identified some very important chemical compounds present in the liquid products obtained from the pyrolysis of mixed plastics. The results obtained from this study have shown usefulness and feasibility of the pyrolysis process of the mixed plastics as an alternative approach to feedstock recycling. Thermal and catalytic degradation of pyrolytic oil from pyrolysis of municipal plastic wastes Thermal and catalytic degradation of pyrolytic oil obtained from the commercial rotary kiln pyrolysis plant for municipal plastic waste was studied by using fluid catalytic cracking (FCC) catalyst in a bench scale reactor. The characteristics of raw pyrolytic oil and also thermal and catalytic degradation of pyrolytic oil using FCC catalyst (fresh and spent FCC catalyst) under rising temperature programming was examined. The experiments were conducted by temperature programming with 10 C/min of heating rate up to 420 C and then holding time of 5 h. During this programming, the sampling of product oil was conducted at a different degradation temperature and also different holding time. The raw pyrolytic oil showed a wide retention time distribution in GC analysis, from 5 of carbon number to about 25, and also different product characteristics with a comparison of those of commercial oils (gasoline, kerosene and diesel). In thermal degradation, the characteristics of product oils obtained were influenced by reaction temperature under temperature programming and holding time in the reactor at 420 C. The addition of FCC catalyst in degradation process showed the improvement of liquid and gas yield, and also high fraction of heavy hydrocarbons in oil product due to more cracking of residue. Moreover, the characteristic of oil product in catalytic degradation using both spent and fresh FCC catalysts were similar, but a relatively good effect of spent FCC catalyst was observed. Conversion of hazardous plastic wastes into useful chemical products Azoisobutylnitrile (AIBN) initiator was used in the treatment of most widely used domestic plastics in lieu of catalysts. The pyrolysis of low-density polyethylene (LDPE), high-density polyethylene (HDPE), polypropylene (PP), poly-ethylene terephthalate (PET) and polystyrene (PS) plastics with azoisobutylnitrile was carried out

individually under nitrogen atmosphere. A series of single (plastic/AIBN) and binary (mixed plastics/AIBN) reactions were carried out in a 25-cm3 micro-autoclave reactor. The optimum conditions selected for this study were: 5% AIBN by weight of total plastics, 60 min, 650 psi and 420 C. It was found that HDPE, LDPE, PP underwent to a maximum cracking and produced highest amounts of liquid and gaseous products. Pyrolysis of PET and PS plastics with AIBN afforded comparatively significant amount of insoluble organic materials. In other reactions, fixed ratios of mixed plastics were pyrolyzed with AIBN that afforded excellent yields of liquid hydrocarbons. This result shows a very significant increase in the liquid portions of the products on using AIBN in the pyrolysis of plastics. The use of AIBN in the pyrolysis of plastics is seems to be feasible and an environmental friendly alternative to catalytic process for maximizing the liquid fuels or chemical feed stocks in higher amounts. Pyrolysis of the rejects of a waste packaging separation and classification plant Plastic wastes coming from a waste packaging separation and classification plant have been pyrolysed in a semibatch nonstirred autoclave, swept by a continuous flow of N2. The plastic waste contains 39.5% PE, 34.2% PP, 16.2% PS and EPS, and some other minor materials. Temperatures in the range 400600 C have been explored, and it has been found that over 460 C total thermal decomposition of the waste plastics takes place. Three catalysts have been tested: HZSM-5, red mud and AlCl3. Solid yields about 57%, liquid yields in the range 4070% and gas yields in the range 1224% were obtained. The liquid products were a mixture of C 5C20 compounds with a very high proportion of aromatics (>70%). Such liquids contain significant amounts of valuable chemicals such as styrene (2040%), toluene (915%) and ethylbenzene (716%) and have rather high GCV (4043 MJ kg -1). Thermal pyrolysis oils were a wax-like product which solidified at room temperature, whereas the oils obtained with any of the catalysts were less viscous and maintained in liquid state at room temperature. HZSM-5 favored gas production and, increased the aromaticity and decreased the carbon number of the oils. AlCl3 did not modify pyrolysis yields but gave rise to lighter liquids. Red mud produced higher liquid yields and the liquids were less viscous, but it was not observed a clear effect on the carbon number of the oils. Fuels by pyrolysis of waste plastics from Agricultural and Packaging sectors in a pilot scale Reactor The pyrolysis of waste plastics (so called chemical recycling) is one perspective way of their utilizations, but the end product properties are a key point of the industrial leading of processes. In this paper a pilot scale pyrolysis process has been investigated. Waste plastics were decomposed in a tube reactor at 520 C, using hourly feed rate of 9.0 kg. Raw materials were selectively collected wastes from agricultural and packaging industry. For supporting the more intensive cracking of C\C bonds of main polymer structure a commercial ZSM-5 catalyst was tested in concentration of 5.0%. Products were separated into gases, gasoline, light and heavy oil by distillation. Plastic wastes could be converted into gasoline and light oil with yields of 2048% and 1736% depending on the used parameters. The gas and liquid products had significant content of unsaturated hydrocarbons, principally olefins. In the presence of ZSM-5 catalyst the yields of lighter fractions (especially gasoline) could be considerably increased and the average molecular weight of each fraction has decreased. Gasoline had C5C15 hydrocarbons, while light oil had C12C28. The used catalyst has promoted the formation of i-butane in gases and affected the composition of both gasoline and light oil. Properties of products are advantageous for fuel-like applications, and they are able to increase the productivity of refinery. On the other hand the possibility for further utilization of products from pyrolysis basically was affected by the source and the properties of raw materials. Waste polyethylene from agricultural consisted of some elements from fertilizers (N, S, P and Ca), which could not be removed from the surfaces of raw materials by pre-treatment (e.g. washing). In that case significant concentration of N, S, P and Ca can be measured in all products, but the catalyst has decreased the concentration of impurities. Gasoline, light oil and heavy oil were nitrogen free and sulphur content was below 12 mg/kg in hydrocarbons obtained by the pyrolysis of polypropylene waste from packaging. Catalytic degradation of plastic waste into petrochemicals using Ga-ZSM-5 Catalytic degradation of polyolefin has been carried out using Ga-ZSM-5 in a pilot plant (10 kg/h), with continuous feeding of polyolefin pellets from industrial plastic waste (IPW) and pellets of plastic waste as stipulated in the Containers and Packaging Recycling Law (RLW). As regards the product resulting from the degradation of IPW pellets, liquid compounds accounted for more than 50%. More than 80% of the liquid consisted of aromatics, with more than 90% being benzene, toluene, o-xylene, m-xylene, and p-xylene (BTX). Hydrogen was produced at a level of 3%, this value corresponding to 60% of the total gas volume. It has been confirmed that degradation took place over a period of 460 h, with catalytic cracking under conditions of

alternating degradation and regeneration. The liquid yield was more than half of the total product throughout the process of degradation. During degradation, the amount of BTX was observed to decrease slightly, while the amounts of other aromatics and liquids were seen to increase. With RLW pellets, aromatic yields, including those of BTX, decreased, while those of other liquids, gases, and residues increased beyond the values noted for IPW pellets. Due to the undesirable accumulation of residue on the inner walls of the kiln, the process could only be carried out for up to 170 h. Analysis of products from the pyrolysis and liquefaction of single plastics and waste plastic mixtures Waste plastics in the form of two examples of real world municipal solid waste plastics and a simulated mixture of municipal waste plastics were pyrolyzed and liquefied under moderate temperature and pressure in a batch autoclave reactor. In addition, the five main polymers which constitute the majority of plastics occurring in European municipal solid waste comprising, polyethylene, polypropylene, polystyrene, polyethylene terephthalate and polyvinyl chloride were also reacted. The plastics were reacted under both a nitrogen (pyrolysis) and hydrogen pressure (liquefaction) and the yield and composition of products are reported. The hydrocarbon gases produced were mainly methane, ethane, propane and lower concentrations of alkene gases. A mainly oil product was produced with the mixed plastic waste with significant concentrations of aromatic compounds, including single ring aromatic compounds. The composition of the oils and gases suggested that there was significant interaction of the plastics when they were pyrolyze and liquefied as a mixture compared to the results expected from reactions of the single plastics. Pyrolysis of municipal plastic wastes separated by difference of specific gravity Municipal plastic wastes (MPWs) generated in Korea were separated by the difference of specific gravity (SG), and were classified as those with less than 1 SG (low MPW), 11.1 SG (medium MPW) and 1.11.2 SG (high MPW). These were well degraded into mainly liquid products in a stirred semi-batch reactor in the absence of oxygen at 400 C. In these types of MPWs, the order of liquid yield was medium MPW (about 90%) > low MPW (about 81%) > high MPW (76%). The medium MPW showed highest liquid yield, but lowest gas and residue yields. The physicochemical properties of the liquid products of the three types of MPWs were compared. The liquid products obtained were described by a cumulative amount as a function of lapse time of reaction and also by paraffin, olefin, naphthene and aromatic (PONA) products distribution as a function of carbon number. Three MPWs showed similarly short carbon number distribution consisting of mainly light liquid products, whereas the fraction of liquid PONA products, etc., was clearly different in the MPW types. For main liquid products, the case of low MPW was olefin components (>75%), medium MPW was aromatic components (>95%) and high MPW was methylmethacrylate (>55%), then aromatic (>20%) and phenol components (>15%). It is concluded that the different characteristics of liquid products of each MPW stem from different chemical nature and structure of plastic types contained in MPWs. Chemical recycling of plastic wastes made from polyethylene (LDPE and HDPE) and polypropylene (PP) The recycling of either model polymers or waste products based on low-density polyethylene (LDPE), highdensity polyethylene (HDPE) or polypropylene (PP) is examined using the dissolution/reprecipitation method, as well as pyrolysis. In the first technique, different solvents/non-solvents was examined at different weight percent amounts and temperatures using as raw material both model polymers and commercial products (packaging film, bags, pipes, food-retail outlets). The recovery of polymer in every case was greater than 90%. FT-IR spectra and tensile mechanical properties of the samples before and after recycling were measured. Furthermore, catalytic pyrolysis was carried out in a laboratory fixed bed reactor with an FCC catalyst using again model polymers and waste products as raw materials. Analysis of the derived gases and oils showed that pyrolysis gave a mainly aliphatic composition consisting of a series of hydrocarbons (alkanes and alkenes), with a great potential to be recycled back into the petrochemical industry as a feedstock for the production of new plastics or refined fuels. Characteristics of liquid product from the pyrolysis of waste plastic mixture at low and high temperatures: Influence of lapse time of reaction Pyrolysis of a waste plastic mixture (high-density polyethylene: low-density polyethylene: polypropylene: polystyrene = 3:2:3:1) into a liquid product was carried out in a stirred semi-batch reactor at low (350 C) and high (400 C) temperatures. The effect of lapse time of reaction in the reactor and also degradation temperature

on the characteristics of the liquid product from pyrolysis of the mixture was investigated. Liquid products were described by cumulative amount distribution, paraffin, olefin, naphthene and aromatic (PONA) distribution and molecular weight distribution. Their characteristic was quite differed with a lapse time of reaction and also at low and high degradation temperatures, because of the different physicochemical properties of the plastic types in the mixture. With increase of lapse time of reaction, the order for the main products in PONA components obtained at 350 C was firstly aromatic products and then olefin products, while at 400 C the order was firstly aromatic products, then olefin products and finally paraffin products. The experiments also showed from the molecular weight distribution of liquid PONA components that the paraffin and olefin products had a wide distribution by mainly random scission of polymer, but in the case of olefin products were produced by an endchain scission mechanism as well as random scission mechanism, as evidenced by much more light olefin products. This phenomenon was evident at a higher degradation temperature. Also, both the light olefin and naphthene products with a molecular weight of around 120, as a main product, showed a similar trend as a function of lapse time, which had a maximum fraction at 343 min (at 350 C) and 83 min (at 400 C). Among PONA components, the highest concentrations of aromatic products were obtained with a molecular weight of around 100 at the fastest lapse time of reaction, regardless of degradation temperature. It was concluded that the characteristics of liquid product on the pyrolysis of plastic mixtures were strongly influenced by lapse time of reaction and degradation temperature. Catalytic Pyrolysis of Low Density Polyethylene over H- , H-Y, H-Mordenite, and H-Ferrierite Zeolite Catalysts: Influence of Acidity and Structures1 Low-density polyethylene (LDPE) catalytic pyrolysis was investigated over H--25, H--150, H--300, H-Y12, H-Mordenite-20, and H-Ferrierite-20 zeolite catalysts. The numbers denote the SiO2/Al2O3 molar ratios. The influence of the zeolites acidity on the transformation of LDPE was studied by varying the SiO 2/Al2O3 molar ratios of the zeolite. The influence of the zeolite structure was investigated by using the proton forms of Y, , Mordenite, and Ferrierite zeolites. The catalysts were characterized using X-ray powder diffraction patterns, nitrogen adsorption, and FTIR spectroscopy with pyridine as the probe molecule. The large pore and least acidic H--300 catalyst showed the lowest activity in the catalytic pyrolysis of LDPE. The H--25 catalyst, with higher acidity than H--300, showed higher activity for LDPE pyrolysis than H--300, indicating the importance of strong acid sites for this reaction. The H-Ferrierite and H-Mordenite catalysts, with small pores, showed the lowest effect on LDPE pyrolysis, although the catalysts were more acidic than H--25and H--150, indicating that not only acidity but also the structure and pore size of zeolites are important for pyrolysis of LDPE. However, the H-Y zeolite catalyst with large pores and cavities is not suitable for this reaction because of rapid deactivation due to coke formation. Catalytic pyrolysis of high density polyethylene in a conical spouted bed reactor The catalytic pyrolysis of high density polyethylene (HDPE) on a HY zeolite catalyst has been carried out in a conical spouted bed reactor (CSBR) at 500 C, and individual products have been monitored with the aim of obtaining product distribution data. The CSBR does not have defluidization problems in the pyrolysis of plastics. The 69 wt% of the product stream corresponds to the gasoline fraction (C 5C10). It is noteworthy that this fraction fulfils European Union requirements for commercial gasoline and its RON index, 96.5, is of the same order as standard automotive fuel. The remaining products are mainly gases, especially propylene and butenes, although there is also a heavy fraction consisting of aromatics with more than one ring and unreacted waxes. Waste catalysts for waste polymer Catalytic cracking of high-density polyethylene (HDPE) over fluid catalytic cracking (FCC) catalysts (1:6 ratio) was carried out using a laboratory fluidized bed reactor operating at 450 C. Two fresh and two steam deactivated commercial FCC catalysts with different levels of rare earth oxide (REO) were compared as well as two used FCC catalysts (E-Cats) with different levels of metal poisoning. Also, inert microspheres (MS3) were used as a fluidizing agent to compare with thermal cracking process at BP pilot plant at Grange mouth, Scotland, which used sand as its fluidizing agent. The results of HDPE degradation in terms of yield of volatile hydrocarbon product are fresh FCC catalysts steamed FCC catalysts used FCC catalysts. The thermal cracking process using MS3 showed that at 450 C, the product distribution gave 46 wt% wax, 14% hydrocarbon gases, 8% gasoline, 0.1% coke and 32% nonvolatile product. In general, the product yields from HDPE cracking showed that the level of metal contamination (nickel and vanadium) did not affect the product

stream generated from polymer cracking. This study gives promising results as an alternative technique for the cracking and recycling of polymer waste. Kinetic Evaluation of the Pyrolysis of Polyethylene Waste The main aim of this study was the identification of possible routes for reaction mechanism for the pyrolysis of polyethylene. In this paper, a kinetic study of the pyrolysis of polyethylene is presented. The pyrolysis reactions were carried out in a six autoclave system using different temperatures and reaction times. It was analyzed if the direct conversion of plastic wastes into gaseous, liquid, and solid products was favored or if parallel reactions and/or reversible elementary steps should be considered. A theoretical model has been ajusted to experimental data. The kinetic parameters of polyethylene pyrolysis were estimated. Fast Pyrolysis of Halogenated Plastics Recovered from Waste Computers The disposal of waste computers is an issue that is gaining increasing interest around the world. In this paper, results from the fast pyrolysis in a fluidized bed reactor of three different waste computer monitor casings composed of mainly acrylonitrile-butadiene-styrene (ABS) copolymer and two different waste computer body casings composed of mostly poly(vinyl chloride) (PVC) type polymers are presented. Preliminary characterization of the waste plastics was investigated using coupled thermo gravimetric analysis-Fourier transform infrared spectrometry (TGA-FT-IR). The results showed that the plastics decomposed in two stages. For the ABS-containing monitor casings, aromatic and aliphatic material was released in the first and second stages. The PVC-containing computer body casing samples showed a first-stage evolution of HCl and a second stage evolution of aromatic and aliphatic material and further HCl. In addition, each of the five plastics was fastpyrolyzed in a laboratory-scale fluidized bed reactor at 500 C. The fluidized bed pyrolysis led to the conversion of most of the plastics to pyrolysis oil, although the two PVC computer body cases produced large quantities of HCl. The pyrolysis oils were characterized by GC-MS and it was found that they were chemically very heterogeneous and contained a wide range of aliphatic, aromatic, halogenated, oxygenated, and nitrogenated compounds. Production of Hydrogen from Plastic by Pyrolysis and Catalytic Steam Reform Thermal decomposition of the most common plastics such as polyethylene and polypropylene produces a mixture of many different hydrocarbons that can be used as a feedstock for producing hydrogen. The proposed process includes two steps: pyrolysis of plastics and catalytic steam reforming of pyrolysis gases and vapors. This research provides a proof of concept supported by experiments on selected polymers performed using a microscale reactor system interfaced with a molecular beam mass spectrometer and demonstrates process performance using a two-reactor bench-scale system. From 60 g/h polypropylene fed to the system 20.5 g/h hydrogen was produced, which corresponds to 80% of the theoretical potential. Pyrolysis of some whole plastics and plasticscoal mixtures This paper demonstrates the thermal and catalytic pyrolysis of some whole plastics and plasticcoal mixtures with and without solvent in an inert atmosphere of N2 using a micro autoclave. The temperature was varied between 300 and 400C. The effect of some catalysts, i.e., AlCl 3 and CoMo, on the liquid yield was also studied. The results demonstrate that temperature has a promising effect on the yield; however high temperature, as well as high catalyst loading, caused a decline in liquid yield. The effect of the solvent was found to be significant. None of the catalysts show an impressive effect on the yield of the desired products. Among the plastics studied, high density polyethylene (HDPE) and polypropylene (PP) gave high yields even in the absence of a solvent and catalyst. The results are quite promising in terms of resource recovery, both from coal as well as plastics. The idea will also help in combating the environmental problems associated with plastics and coal. Pyrolysis of low-density polyethylene using synthetic catalysts produced from fly ash Catalytic pyrolysis of low-density polyethylene (LDPE) was investigated using various fly ash-derived silica alumina catalysts (FSAs). FSAs were prepared by a simple activation method that basically includes NaOH treatment of fly ash by a fusion method, followed by an aging process. A series of LDPE pyrolysis experiments was conducted and the catalytic performance of FSAs was assessed in terms of the degradation temperature and the simulated boiling point distribution of the liquid products. The effects of synthesis conditions such as NaOH/fly ash weight ratio and aging time were examined by X-ray diffractometer (XRD), Brunauer-Emmett-

Teller (BET) surface area analyzer, and scanning electron microscope to clarify the controlling factors affecting the catalytic activity. To obtain catalyst with high activity, it is necessary to produce sufficient silica and alumina species that can be easily co-precipitated into solid acid catalyst by destruction of the fly ash structure and to optimize the activation time for catalyst synthesis to prevent the transformation into inactive phases. The catalytic performance of FSA obtained from optimal conditions was equivalent to that of commercial catalysts, demonstrating the effectiveness of the catalyst. Conversion of Waste Plastic to Lubricating Base Oil A new process has been developed for the conversion of waste plastic to lubricating base oil. It has also been demonstrated that waste plastic and Fischer-Tropsch (FT) wax can be co-processed to produce lube range molecules. The process uses a thermal, non-catalytic, atmospheric pressure pyrolysis process that converts highmolecular-weight molecules to lower-molecular-weight molecules in the lube oil range. Hydroisomerization is then used to convert this product to low-pour-point oils of unconventional base oil (UCBO) quality. The major byproduct is diesel, with little production of C4- gas. Initial experiments in bench-scale laboratory pyrolysis units were followed by tests in a 1 gal/day pilot plant. The feedstock's that were tested consisted of polyethylene (PE), 96% PE-4% poly (ethylene terephthalate) (PET), FT wax, and a 50/50 mixture of PE and FT wax. The product distribution and lube quality showed surprisingly little variation for these feedstock's. The pyrolysis yields of 385 C+ product were in the range of 37-57 wt %, whereas the potential lube yields were 60-70 wt %, assuming all the olefins (almost all 1-olefins) could be upgraded to lube by oligomerization. Hydroisomerization of the pyrolysis bottoms yielded oil with a viscosity of 3.4-5.4 cSt, pour points between -13 to -37 C, and a viscosity index in the range of 150-160. Removal of nitrogen, bromine, and chlorine from PP/PE/PS/PVC/ABS-Br pyrolysis liquid products using Fe- and Ca-based catalysts. The thermal and catalytic degradation of a complex polymer mixture was performed at 450 C at atmospheric pressure in a batch process. The mixture contained polyethylene (PE), polypropylene (PP), polystyrene (PS), acrylonitrile-butadiene-styrene copolymer with a brominated flame retardant and antimony oxide synergist (ABS-Br) and poly(vinyl chloride) (PVC), in a 3/3/ 2/1/1 weight ratio. The effect of iron (FeOOH and Fe-C composite) and calcium (CaCO3 and Ca-C composite) based catalysts for removal of heteroatom- (nitrogen, bromine, and chlorine) containing compounds in oil products was studied. Changes in the amount and distribution of heteroatoms were described using NP gram curves. Iron catalysts give best results for bromine removal from decomposition oil while calcium catalysts have high efficiency for chlorine removal; however, both Fe- and Ca-catalysts have low effect in nitrogen removal. Carbon composite catalysts give three times less chlorine but they produce higher amounts of nitrogen in degradation oils than the corresponding Fe and Ca pure compounds. In bromine removal Ca-C composite shows higher effect compared to CaCO3 while Fe-C composite has slightly worse effect than FeOOH. Pyrolysis of municipal plastic wastes for recovery of gasoline-range hydrocarbons 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. Thermal degradation of PE and PS mixed with ABS-Br and debromination of pyrolysis oil by Fe- and Ca-based catalysts Polymer mixtures were containing 8g of high density polyethylene (PE) or polystyrene (PS) and 2 g of acrylonitrile-butadiene-styrene copolymer containing a polybrominated epoxy type flame retardant (ABS-Br) were thermally degraded at 450 C. FeOOH and two carbon composites based on iron (Fe-C) and calcium (CaC) were used for catalytic decomposition and their effect on the bromine and nitrogen amount and distribution in pyrolysis oil was determined by GC-AED analysis. It was found that iron-based catalysts removed bromine

from pyrolysis oil and decreased the nitrogen amount converting nitrile compounds into ammonia. Calcium carbon composite had lower effect especially on the pyrolysis of PS/ABS-Br mixture. These liquid products can be used as fuel oil or feedstock in petroleum refinery. Investigation of catalytic degradation of high density polyethylene by hydrocarbon group type analysis Catalytic degradation of waste high-density polyethylene (HDPE) to hydrocarbons by ZSM-5, zeolite-Y, mordenite and amorphous silica-alumina were carried out in a batch reactor to investigate the cracking efficiency of catalysts by analyzing the oily products including paraffins, olefins, naphthenes and aromatics with gas chromatography/mass spectrometry (GC/MS). Catalytic degradation of HDPE with zeolite-Y, mordenite and amorphous silica-alumina yielded 71-82 wt.% oil fraction, which mostly consisted of C6-C12 hydrocarbons, whereas ZSM-5 yielded much lower 35% oil fraction, which mostly consisted of C 6-C12 hydrocarbons. Both all zeolites and silica-alumina increased olefin content in oil products, and ZSM-5 and zeolite-Y particularly enhanced the formation of aromatics and branched hydrocarbons. ZSM-5 among zeolites showed the greatest catalytic activity on cracking waste HDPE to light hydrocarbons, whereas mordenite produced the greatest amount of coke. Amorphous silica-alumina also showed a great activity on cracking HDPE to lighter olefins in high yield, but no activity on aromatic formation. Chlorinated pyrolysis products of co-pyrolysis of poly (vinyl chloride) and poly (ethylene terephthalate)

The influence of poly (vinyl chloride) on poly (ethylene terephthalate) pyrolysis was investigated. Products of degradation of this two-polymer mixture were separated by gas chromatography and chloro-organic components were identified. Chloro-esters of terephthalic and benzoic acids were found. Mass spectra and fragmentation pattern for identified compounds have been shown. The signals from two fragments at m/z 211 and 213 were proposed to be used for a fast identification of such compounds.

Characterization of Styrene Recovery from the Pyrolysis of Waste Expandable Polystyrene Catalytic and thermal degradation of waste expandable polystyrene (WEPS) have been studied in a semi-batch reactor with continuous flow of nitrogen to achieve greater oil yield and maximize styrene monomer recovery. Effect of temperature, nature of catalyst and its size, reaction time of catalytic pyrolysis, and effect of repyrolysis have been also investigated. Higher reaction temperature favors the oil yield and also decreases the reaction time with maximum styrene selectivity (76.31 wt %) at 450 C. Among the catalysts studied, solid base BaO is found to be the most efficient and increases the styrene selectivity (84.29 wt %) significantly at a reaction temperature of 350 C in comparison to thermal and acid catalytic degradation. Modified catalyst FeA/Al (A = basic material) also shows better activity than Fe 2O3 or Fe/Al. Increase in the size of the catalyst and repyrolysis decrease the oil yield, and styrene production also decreases on repyrolysis.

Characterization of Styrene Recovery from the Pyrolysis of Waste Expandable Polystyrene Catalytic and thermal degradation of waste expandable polystyrene (WEPS) have been studied in a semi-batch reactor with continuous flow of nitrogen to achieve greater oil yield and maximize styrene monomer recovery. Effect of temperature, nature of catalyst and its size, reaction time of catalytic pyrolysis, and effect of repyrolysis have been also investigated. Higher reaction temperature favors the oil yield and also decreases the reaction time with maximum styrene selectivity (76.31 wt %) at 450 C. Among the catalysts studied, solid base BaO is found to be the most efficient and increases the styrene selectivity (84.29 wt %) significantly at a reaction temperature of 350 C in comparison to thermal and acid catalytic degradation. Modified catalyst FeA/Al (A = basic material) also shows better activity than Fe 2O3 or Fe/Al. Increase in the size of the catalyst and re-pyrolysis decrease the oil yield, and styrene production also decreases on re-pyrolysis. Fluidized bed pyrolysis of a recycled polyethylene Fluidized bed pyrolysis is a special class of feedstock recycling processes for plastics recycling which provides for a rather uniform spectrum of products, reduces the maintenance time and cost and gives the possibility to apply the process even on a relatively small scale. The present study describes investigations carried out by injecting recycled polyethylene in a laboratory scale fluidized bed reactor, batchwise or continuously operated.

The batchwise experiments allowed to investigate the polymer-to-particles interactions inside the fluidized bed reactor, which strongly affect the phenomenology and the rate of polymer degradation. The continuous experiments indicated how the yield and the composition of products are affected by two key operating variables of the process: the bed temperature and the residence time in the reactor. Catalytic pyrolysis of polyethylene The influence of zeolite catalytic upgrading of the pyrolysis gases derived from the pyrolysis of polyethylene has been investigated. The yield and composition of the derived hydrocarbon gases and oils have been investigated in terms of the temperature of the catalyst. Polyethylene was pyrolysed in a fixed bed reactor and the pyrolysis gases passed to a secondary reactor containing Y-zeolite or zeolite ZSM-5 catalyst. The polyethylene was pyrolysed at 500C and the temperature of the catalyst bed was 400, 450, 500, 550 or 600C. The oils consisted of mainly aliphatic compounds represented by alkadiene, alkene and alkane hydrocarbons and their branched chain derivatives. The uncatalysed pyrolysis oil also contained low concentrations of aromatic hydrocarbons. After catalysis there was a marked increase in the concentration of aromatic compounds in the oil, which further increased in concentration as the temperature of catalysis was raised. The single ring compounds consisted of mainly toluene, ethylbenzene and xylenes and the two and three ring compounds were mainly, naphthalene and phenanthrene and their methyl derivatives. The Y-zeolite produced significantly greater concentration of aromatic hydrocarbons in the derived oils compared to when zeolite ZSM-5 catalyst was used. Study of the Low Temperature Pyrolysis of PVC The characteristics of PVC pyrolysis dechlorination has been studied in a fixed bed reactor under different operating conditions such as temperature, time, heating rate. It is found that about 90% chlorine in PVC can be effectively removed within 3 h with heating rate of 5 /min at temperature 300 C, with 10% chlorine remaining in volatile gas and residue. The yield of combustible gas increases and the yield of tar as well as residue decreases with the increasing of the pyrolysis temperature. Thermogravimetric technique was used to investigate the weight-loss curves of PVC pyrolysis process; elemental analysis and FTIR were conducted to analyze the functional-group composition of products. The results showed that the PVC pyrolysis is a two-step process. The first step is mainly a dechlorination process which, accompanied by depolymerization and this reaction, can be seen as a first-order reaction: apparent energy activation is about 130 kJ/mol. The second step is a further cracking process of the residue which produces low molecular hydrocarbons including alkene and aromatic compounds. Microwave-Induced Pyrolysis of Plastic Wastes The performance of a novel microwave-induced pyrolysis process was evaluated by studying the degradation of high-density polyethylene and aluminum/polymer laminates in a semi batch bench-scale apparatus. The results showed that the new process has the same general features as other, more traditional, pyrolytic processes but with the advantage that it is able to deal with problematic wastes such as laminates. Degradation experiments were performed between 500 and 700 C and the relationship between temperature, residence time of the pyrolytic products in the reactor, and the chemical composition of the hydrocarbon fraction produced was investigated. Toothpaste tubing was used as an example of a laminated material to be treated with the novel process. Clean aluminum was recovered together with hydrocarbons and the trial proved that the process has excellent potential for the treatment of plastic wastes on a commercial scale. Tertiary Resource Recovery from Waste Polymers via Pyrolysis: Neat and Binary Mixture Reactions of Polypropylene and Polystyrene Batch pyrolysis of polypropylene, polystyrene, and their binary mixture was carried out at temperatures of 350 and 420 C. Two different loadings were also studied for neat polypropylene and polystyrene to assess the impact of total pressure, which was also a function of reaction time and temperature. For neat polypropylene pyrolysis, total conversion was an order of magnitude higher at 420 C than at 350 C. For neat polystyrene pyrolysis, conversion reached approximately 75% at 350 C, whereas at 420 C, the conversion reached a maximum of approximately 90% after 10 min of reaction and decreased to approximately 70% after 180 min. For binary mixture pyrolysis, the overall conversion was higher than the average of the conversions for the two neat cases. The conversion of polystyrene remained the same, but significant enhancement of the polypropylene conversion was observed. These results suggest that the more facile degradation of polystyrene helped to initiate the less reactive polypropylene.

Recyling of plastic wastes via pyrolysis Pyrolysis for the simultaneous generation of oils and gases can be convenient to obtain hydrocarbons and even to recover crude petrochemicals or to generate energy from waste plastics. A GrayKing apparatus has been used to pyrolyze waste polyethylene (PE), polystyrene (PS), both separately and with different compositions. Thermo gravimetric analysis of waste plastics indicated the critical temperatures, which should be effective for pyrolysis. The chosen heating rate was low in order to achieve higher liquid yields. The results showed that waste PS yielded higher liquid, and waste PE yielded higher gaseous products. The dominant liquid product of PS waste was styrene whereas for waste PE, prophenylbenzene was the dominant pyrolysis product. Conversion of Waste Plastic to Oil: Direct Liquefaction versus Pyrolysis and Hydroprocessing Two approaches for the conversion of waste post consumer plastic (PCP) into oil have been investigated: (1) direct liquefaction and (2) pyrolysis followed by hydprocessing of the pyrolysis liquids. The PCPs investigated were a washed PCP provided by the American Plastic Council (APC) and a PCP prepared by dry preparation methods provided by the Duales System Deutschland (DSD). The DSD plastic contained significantly more ash, paper, dirt, and chlorine than the APC plastic and is considered to be more representative of true waste PCP. Direct liquefaction of both plastics was investigated using small additions (1-5 wt %) of a number of different solid acid catalysts. At 445 C, the catalytic effect on oil yields was negligible for both plastics. Several catalysts had a significant effect on the boiling point distribution for the APC plastic, producing lighter products, but had little or no effect for the DSD plastic. An alternative approach of pyrolysis followed by hydprocessing the pyrolysis liquids were investigated for the DSD plastic. Pyrolysis yields of 75-80% of relatively heavy liquids were achieved at 600 C. Addition of Na2CO3 to the pyrolysis reactor decreased the chlorine content of the pyrolysis liquids to ~50 ppm. The boiling point distribution of the pyrolysis liquid was substantially improved (55-65% gasoline fraction) by either thermal or catalytic hydroprocessing (450 C, 200 psig initial H 2 pressure). The effect of adding 1-5% of several catalysts was relatively small, increasing the gasoline fraction over that obtained by thermal hydroprocessing by 5-10%. Addition of Na2CO3 to the hydroprocessing reactor decreases the chlorine content of the final product to a few ppm. These results indicate that pyrolysis followed by hydprocessing of the pyrolysis liquids is a good approach for true PCP that contains a significant amount of chlorine, paper and inorganic material. Pyrolysis of plastic wastes. 1. Effect of plastic waste composition on product yield Accumulation of enormous amounts of plastic waste produced all over the world has negative implications on the environment. Pyrolysis of plastic waste could have an important role in converting this waste into economically valuable hydrocarbons, which can be used either as fuels or as feed stock in the petrochemical industry. End product yields and properties depend on the plastic waste composition. The presence of PE (polyethylene) increased alkane content, whilst PS (polystyrene) led to higher aromatic content in the end product. The presence of PP (polypropylene) favored alkenes' formation. Therefore, both PS and PP increased the octane number of end product. Therefore, the desired end product can be obtained by adequate blending of plastic wastes. Pyrolysis of plastic wastes 2. Effect of catalyst on product yield Thermolysis of plastic waste may have an important role in dealing with the enormous amounts of plastic waste produced all over the world, by decreasing their negative impact on the environment. This waste may be converted into economically valuable hydrocarbons, which can be used both as fuels and as feed stock in the petrochemical industry. End product yields and properties depend on the plastic waste composition. The presence of PE (polyethylene) increases alkane content, whilst PS (polystyrene) leads to higher aromatic content in the end product. The alkenes' formation benefited from the presence of PP (polypropylene). Although, the desired end products can be obtained by adequate blending of plastic wastes, it is not always technically or economically possible to obtain the quality required. The addition of a catalyst could not only improve the quality of products obtained, but could also enable the selectivity of a certain product to be achieved. To study the influence of several catalysts on product distribution, the average plastic waste composition existing in Portuguese municipal solid wastes (68% PE, 16% PP and 16% PS) was chosen. Unfortunately, the catalysts studied in this work, led to results similar to those obtained in their absence.

Catalytic degradation of polyethylene over solid acid catalysts In this study we investigated the catalytic degradation of polyethylene (PE) in a fixed-bed reactor composed of a melter and a catalytic cracking bed. Solid acid catalysts, silica-alumina and zeolites [HZSM-5, natural zeolite (NZ), Y zeolite, etc.] were screened for polyethylene degradation in the range of 450-500C. The degradation products of PE, especially a liquid fraction, formed over solid acid catalysts, were analyzed by gas chromatography-mass spectroscopy (GC-MS). Compared with those obtained by thermal degradation, the catalytic degradation products are distributed in a narrow range of carbon numbers. The liquid fraction contained large amounts of iso-paraffins and aromatics, as are present in the gasoline fraction of petroleum. The NZ catalyst (clinoptilolite structure, occurring in the Youngil area of Korea) was an efficient catalyst for the PE degradation. The acidity and characteristic pore structure of zeolites appear to be responsible for the good performance. The effects of temperature, contact time, and the presence of nickel metal on the product distribution in PE degradation are also discussed in this work. Interaction of Plastic in Mixed-Plastic Pyrolysis The pyrolysis of mixed-plastic waste has been proposed as a means of recycling to produce petrochemical feedstock. The interaction of the main plastic types in plastic mixtures is significant in predicting the likely yield and composition of products from different plastic mixtures. The six main plastics in municipal solid waste are high-density polyethylene (HDPE), low-density polyethylene (LDPE), polypropylene (PP), polystyrene (PS), poly(vinyl chloride) (PVC), and poly(ethylene terephthalate) (PET). Each of the plastics was pyrolyzed individually in a fixed-bed reactor heated at 25 C min-1 to a final temperature of 700 C. Polystyrene was then mixed with each of the other five plastics in a ratio of 1:1 and pyrolyzed in the fixed-bed reactor under the same pyrolysis conditions. The yield and composition of the derived oil/wax and gases was determined. The main gases produced from the individual plastics were hydrogen, methane, ethane, ethene, propane, propene, butane, and butene and for the PET plastic carbon dioxide and carbon monoxide. Hydrogen chloride was also produced with PVC. Analysis of the oil/wax showed that the polyalkene plastics, HDPE, LDPE, and PP, gave a mainly aliphatic composition consisting of a series of alkanes, alkenes, and alkadienes. PVC gave a mainly aromatic oil, and PS and PET, which have aromatic groups in their structures, also showed a more aromatic composition. There was a higher gas yield from the mixtures of the plastics with PS than would be expected from the pyrolysis of the individual plastics, coupled with a reduction in the oil/wax phase. The average molecular weight of the oil/wax from the mixed plastics was less than expected from the individual molecular weights. Compositional analysis of the oil/wax showed that changes in the concentration of aromatic hydrocarbons and polycyclic aromatic hydrocarbons were produced with the mixture compared to that expected from the individual plastics. Conversion of Waste Plastic to Oil: Direct Liquefaction versus Pyrolysis and Hydroprocessing. Two approaches for the conversion of waste post-consumer plastic (PCP) into oil have been investigated: (1) direct liquefaction and (2) pyrolysis followed by hydprocessing of the pyrolysis liquids. The PCPs investigated were a washed PCP provided by the American Plastic Council (APC) and a PCP prepared by dry preparation methods provided by the Duales System Deutschland (DSD). The DSD plastic contained significantly more ash, paper, dirt, and chlorine than the APC plastic and is considered to be more representative of true waste PCP. Direct liquefaction of both plastics was investigated using small additions (15 wt %) of a number of different solid acid catalysts. At 445 C, the catalytic effect on oil yields was negligible for both plastics. Several catalysts had a significant effect on the boiling point distribution for the APC plastic, producing lighter products, but had little or no effect for the DSD plastic. An alternative approach of pyrolysis followed by hydprocessing the pyrolysis liquids was investigated for the DSD plastic. Pyrolysis yields of 7580% of relatively heavy liquids were achieved at 600 C. Addition of Na2CO3 to the pyrolysis reactor decreased the chlorine content of the pyrolysis liquids to 50 ppm. The boiling point distribution of the pyrolysis liquid was substantially improved (5565% gasoline fraction) by either thermal or catalytic hydroprocessing (450 C, 200 psig initial H 2 pressure). The effect of adding 15% of several catalysts was relatively small, increasing the gasoline fraction over that obtained by thermal hydroprocessing by 510%. Addition of Na 2CO3 to the hydroprocessing reactor decreases the chlorine content of the final product to a few ppm. These results indicate that pyrolysis followed by hydprocessing of the pyrolysis liquids is a good approach for true PCP that contains a significant amount of chlorine, paper and inorganic material.

Stepwise pyrolysis for raw material recovery from plastic Waste High costs of pollution control for incinerators, the high energy content of plastics as well as the chemical composition of plastics are demanding for alternative treatment of plastic refuses where plastic waste is considered as a resource of energy and as chemical raw material. One possible alternative is the pyrolysis of plastics. Kinetic data obtained from micro thermogravimetry and well stirred type reactor experiments confirm that different molecular structures of commodity plastics bring about different reaction mechanisms of thermal decomposition, different reaction rates, and different temperature dependencies of the decomposition rates. From that, stepwise pyrolysis of mixtures of plastics seems to be reasonable where the different components are pyrolyzed at different temperatures. This work aims at a stepwise pyrolysis procedure where the thermal decomposition of different components of a mixture of plastics is performed consecutively at different temperatures. For a continuous process a cascade of well stirred reactors has been developed where mixing of the reactor contents occurs by circulating of stainless steel spheres. Examples for the separation of single plastics by thermal decomposition of mixtures of poly(vinyl chloride), polystyrene and polyethylene and polystyrene, polyamide 6 and polyethylene, respectively, are presented. In a first step hydrogen chloride from poly(vinyl chloride) is obtained, in the second step the monomer of polystyrene and: or polyamide 6 is formed and in the third step aliphatic compounds from polyethylene decomposition are trapped. Catalytic plastics cracking for recovery of gasoline-range hydrocarbons from municipal plastic wastes This paper reviews recent developments in plastics cracking, a process developed to recycle plastic wastes into useful petrochemical materials. Under thermal cracking 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. By adopting customary fluid cracking catalysts and reforming catalysts, more aromatics and naphthenes in the C6C8 range can be produced, which are valuable gasoline-range hydrocarbons. More tests are, however, needed to verify the pyrolysis process in a pilot scale particularly for treatment of mixtures of bulk plastics. Plastics cracking are only an elementary conversion technology; its application has to be combined with other technologies such as municipal solid waste collection, classification and pretreatment at the front end, as well as hydrocarbon distillation and purification at the back end. Social, environmental and economic factors are also important in industrial implementation of the technology.

Classification of Volatile Products from the Temperature-Programmed Pyrolysis of Low- and HighDensity Polyethylene

A fixed bed reactor under argon flow was used to pyrolyze small samples of low- (LDPE) and highdensity (HDPE) polyethylene. A special gas-phase sampling technique was used to determine the composition of products eluted from the reactor as a function of temperature and time. Capillary gas chromatography was used to determine the total volatile product evolution rate. The maximum volatile product evolution temperature was 425 C for LDPE and 430 C for HDPE. The distribution of n-paraffins and 1-olefins was determined. The hydrocarbon fraction from LDPE contained 47.2 wt % n-paraffins at the maximum product evolution temperature; the weight percentages were 6.6 gaseous n-paraffins, 9.1 C5C9, 23.7 C10C15, and 60.6 C16. The yield and distribution of hydrocarbons from pyrolysis of HDPE at the maximum product evolution temperature of 430 C were similar to that found for LDPE. n-Paraffins constituted 48.8 wt %, of which 5.5 wt % were gaseous nparaffins, 9.4 wt % C5C9, 23.5 wt % C10C15, and 61.6 wt % C16+. 1-Olefin products were also grouped by carbon number. Pyrolysis of LDPE produced 14 wt % of 1-olefins at the maximum product evolution temperature; weight percentages were 20.7 1-olefins gases, 22.8 C5C9, 26.4 C10C15, and the 30.1 C16+. Pyrolysis of HDPE produced 14.4 wt % of 1-olefins, of which 33.3 wt % were 1-olefin gases, 40.9 wt % C5C9, 17.3 wt % C10C15, and 8.5 wt % C16+.
Analysis of products derived from the fast pyrolysis of Plastic waste Plastic Waste has become an increased problem in many industrialized countries. Concern over the volumes king created has lead to a number of governments introducing new legislation for its recovery as a resource. Traditional recovery methods have gem concentrated on recycling of materials or Incineration for energy. The majority of polymers in waste is mainly hydrocarbon in nature and so can be used as a feedstock for the chemical industries or as a fuel. Pyrolysis is a tertiary recycling process and has an ability to provide three end

products: a gas, oil and a char which all have the potential to be further utilized. It is anticipated that if waste recovery targets currently being set are to be met then methods, such as pyrolysis, will have to be closely examined. The pyrolysis of a plastic mixture in a fluidized bed reactor was studied. The mixture was a simulated fraction of that found in municipal solid waste in Europe. The reactor was constructed of stainless steel and was 70 cm high x 10 cm diameter, with a 17 cm high x 20 cm diameter expander section. The sample was introduced batch wise into the bed. The influence of temperature on product yield and composition was studied. Pyrolysis was carried out at temperatures between 500 and 700C. This gave widely differing product yields of between 9.79 and 88.76% gas and between 18.44 and 57.1 f % oil. The oils were analyzed for their functional groups using Fourier transform infrared spectroscopy. The molecular weight distribution was also determined using size exclusion chromatography. It was found that as temperature was increased the amount of aromatic compounds in the oil increased. The molecular weight range was also affected. Potential applications for the oils were also investigated. Pyrolysis of a fraction of mixed plastic wastes depleted in PVC A fraction of plastic wastes from DSD (Duales System Deutschland) which is depleted in polyvinylchloride (PVC) was pyrolyzed at 638, 690 and 735C in a technical-scale fluidized bed reactor. At 638C over 50 wt. % of the pyrolysis product was oil with a boiling point less than 295C; this can be used as feedstock in a steam cracker. The experiment at 690C yielded about 40 wt. % of an oil, about the half of which consists of benzene, toluene and xylene (BTX-aromatics). At the highest reaction temperature of 735C, the main product was highly aromatized oil; the BTX-aromatics content is about 20 wt. % of the pyrolysis product. Transformation of Several Plastic Wastes into Fuels by Catalytic Cracking The thermal and catalytic cracking of several plastic wastes (polypropylene, polystyrene, and polystyrenepolybutadiene) dissolved in refinery LCO has been studied in a riser simulator, under operating conditions (catalyst, temperature, contact time, C/O ratio) that are similar to commercial FCC units. The results of the product distribution show the interest of this strategy, which may be integrated into refinery operation for largescale tertiary exploitation of plastic wastes. Ultra pyrolytic Upgrading of Plastic Wastes and Plastic/Heavy Oil Mixtures to Valuable Light Gas Products Viable operating conditions were identified experimentally for maximizing the production of high-value products such as ethylene, propylene, styrene, and benzene, from the ultrapyrolysis of waste plastics. Using both a batch micro reactor and a pilot-plant-sized reactor, the key operating variables considered were pyrolysis temperature, product reaction time, and quench time. In the micro reactor experiments, polystyrene (PS), a significant component of waste plastics, was pyrolyzed at temperatures ranging from 800 to 965 C, with total reaction times ranging from 500 to 1000 ms. At a temperature of 965 C and 500 ms, the yields of styrene plus benzene were greater than 95 wt %. In the pilot-plant experiments, our recently patented internally circulating fluidized bed (ICFB) reactor (Milne et al., U.S. Patent No. 5,370,789, 1994b) was used to ultra-pyrolyze lowdensity polyethylene (LDPE) in addition to LDPE (5% by weight)/heavy oil mixtures at a residence time of 600 ms. Both experiments produced light olefin yields greater than 55 wt % at temperatures above 830 C. High-temperature liquefaction of waste plastics High-temperature liquefaction of commingled post-consumer plastics obtained from the American Plastics Council was studied. The liquefaction reaction was carried out in a tubing bomb micro-reactor with operating temperatures of ~5OOC, hydrogen pressures of ~790 kPa cold and reaction times of O-30 min. These high temperatures were used to reduce the residence time required for liquefaction. Reactions were carried out in the absence of catalysts. Total conversion and conversions to asphaltenes, oil, gas and coke were monitored. Total conversion as high as 100% was achieved. Gas yields up to 70% and oil yields as high as 60% were obtained. The kinetics of liquefaction of these waste materials was studied. Maximum yield of liquid product was obtained at ~500C and ~5-10 min reaction time.

Conversion of Polyethylene to Transportation Fuels through Pyrolysis and Catalytic Cracking A high-density polyethylene was thermally cracked in both a closed tubing-bomb reactor at 450-500 C and an open system using the same reactor at 480 C. In the closed system, distillate yield increased at a higher temperature which also accelerated the formation of gases and coke. Secondary reactions such as saturation, isomerization, cyclization, and aromatization were found at high severity. In contrast, the open system produced less naphtha but more gas oil. Compositionally, the distillates contained more olefins, less saturates, and very little aromatics, compared with those from the closed system. Pyrolytic waxy products from polyethylene were catalytically cracked in a fixed-bed reactor at 470 and 510 C, respectively. High yields of gasoline of improved quality and liquefied petroleum gas were obtained along with a small amount of low-value products such as dry gas, heavy cycle oil and coke. Fast Pyrolysis of Plastic Wastes Preliminary results using an atmospheric-pressure fluidized-bed fast pyrolysis process have been obtained for the fast pyrolysis of commercial grades of polystyrene, poly (viny1 chloride), and polyethylene. On the basis of these tests, polyethylene was selected for detailed study because of the difficulty in regenerating the monomer in good yields and because of its abundance as a waste material-about 70% of all plastic waste. A test program was undertaken to attempt to produce higher value products from polyethylene, rather than monomer. This approach not only disposes of the waste but also offers the possibility of cost return. Both thermal and catalytic pyrolysis tests have been done in an atmospheric-pressure fluidized-bed reactor. Initial results suggest that catalytic pyrolysis can give promising yields of a liquid hydrocarbon product that could be refined to yield a transportation fuel. Product composition from the pyrolysis of polyethylene can be controlled over a wide range by a suitable combination of type of catalyst, temperature, and particle size.