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plastic pyrolysis process diagram

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Physico-chemical characterization of chars produced in the co-pyrolysis of wastes and possible routes of valorization, in Chemical Engineering (Lisboa: Universidade Nova de Lisboa), 2736. doi: 10.1179/1743967112Z.00000000029, Thilakaratne, R., Tessonnier, J. P., and Brown, R. C. (2016). Steam activation of pyrolytic tyre char at different temperatures. Technol. Aguado et al. Front. Catalytic and thermal depolymerization of low value post-consumer high density polyethylene plastic. The use of synthetic catalysts enhanced the overall pyrolysis process and improved the quality of produced liquid oil. Miskolczi et al. (2002) reported that PP degradation produces maximum gas in the presence of acid catalysts. The liquid oil produced from the catalytic pyrolysis of PP/PE was 44 and 40% from TA-NZ and AA-NZ catalysts, respectively. J. Anal. Catalytic recycling of the mixture of polypropylene and polystyrene. Therefore, it has the potential to be used in various energy and transportation applications after further treatment and refining. The functional groups in pyrolysis oil was analyzed by a FT-IR, Perkin Elmer's, UK instrument. doi: 10.1016/j.jaap.2014.06.013, Aguado, J., Sotelo, J. L., Serrano, D. P., Calles, J. Stab. Kinetics of the thermal and thermo-oxidative degradation of polystyrene, polyethylene and poly (propylene). Fuel Process. This material can block the flow line and make difficult the continuous control of unit process. Catalysts have a very critical role in promoting process efficiency, targeting the specific reaction and reducing the process temperature and time (Serrano et al., 2012; Ratnasari et al., 2017). Cross-link network of polydimethylsiloxane via addition and condensation (RTV) mechanisms. B:Environ. The catalytic pyrolysis of PS produced the highest liquid oil (70 and 60%) compared to PP (40 and 54%) and PE (40 and 42%), using the TA-NZ and AA-NZ catalysts, respectively. (2001). Catalytic degradation of polyethylene over mesoporous molecular sieve MCM-41 modified with heteropoly compounds. However, microporous catalysts hinder the entrance of larger molecules and thus higher carbon chain compounds are produced from catalytic pyrolysis of PE with microporous catalysts. Also, the impact on the environment in the pyrolysis of waste plastics must be taken into consideration. (2011) and Seo et al. The next step is the melting system, where the solid plastic is changed to a low-viscosity melt. doi: 10.1002/1521-3935(20010301)202:6<775::AID-MACP775>3.0.CO;2-G, Ramli, M. R., Othman, M. B. H., Arifin, A., and Ahmad, Z. Effect of polyethylene terephthalate on the catalytic pyrolysis of polystyrene: Investigation of the liquid products. A process study on the pyrolysis of waste polyethylene.

Fuel Process. Furthermore, the addition of PET with PS, PE and PP (20/40/20/20% ratio) reduced the liquid oil yields down to 28 and 30% overall, using TA-NZ and AA-NZ catalysts, respectively, with higher fractions of char and gas. Miandad, R., Rehan, M., Nizami, A. S., Barakat, M. A. E. F., and Ismail, I. M. (2016c). doi: 10.9790/1684-11214751. Energy. The catalytic pyrolysis of PS produced a higher liquid oil (70 and 60%) than PP (40 and 54%) and PE (40 and 42%), using TA-NZ and AA-NZ catalysts, respectively. (2014). (2011). Fixed-bed pyrolysis-catalytic cracking process for oil recovery of waste plastic is in use at several commercial processes. A capillary GC 30 m long and 0.25 mm wide column coated with a 0.25 m thick film of 5% phenyl-methylpolysiloxane (HP-5) was used. Stab. Polym. This is required to be a compact process that can be controlled in a stable and continuous way, because of movement of the high-viscosity material for each unit system in the process. Eng. A., and Dwyer, J.

doi: 10.1016/0141-3910(91)90119-C, McNeill, I. C., Zulfiqar, M., and Kousar, T. (1990). This is an open-access article distributed under the terms of the Creative Commons Attribution License (CC BY). The increase in cracking, in the presence of a high acidic catalyst, promotes the production of gases (Miandad et al., 2016b, 2017a).

ThermalCatalytic cracking of real MSW into Bio-Crude Oil. Developing advanced catalysts for the conversion of polyolefinic waste plastics into fuels and chemicals.

doi: 10.1016/j.joei.2016.11.005, Gebreslassie, B. H., Slivinsky, M., Wang, B., and You, F. (2013). In addition, due to rapid urbanization, the land available for landfills, especially in cities, is reducing. The catalytic pyrolysis of PP produced a complex mixture of liquid oil containing aromatics, olefins and naphthalene compounds. Figure 5. Proc. doi: 10.1016/j.polymdegradstab.2004.06.001, Zeaiter, J. polyethylene Moreover, formation of carbocation during PP degradation, due to the presence of tertiary carbon in its carbon chain, may also favor gas production (Jung et al., 2010). Miandad et al. The catalytic pyrolysis was carried out using an individual or mixture of these plastic wastes in different ratios (Table 1). The gas chromatography-mass spectrometry (GC-MS) analysis of oil showed a mixture of aromatics, aliphatic and other hydrocarbon compounds. Other important point is that if there is trouble in a continuous automatic feeding system, it can be quickly transferred to a manual system. doi: 10.1016/j.jaap.2004.03.001, Dimitrov, N., Krehula, L. K., Siroi, A. P., and Hrnjak-Murgi, Z. (2004). Polym. In order to obtain an oil product in the pyrolysis of waste plastics, the major steps for waste plastics that are derived from the household, industry, etc. Appl. Resour. Furthermore, various researchers utilized the produced liquid oil as transportation fuel after blending with conventional diesel at different ratios. Nileshkumar et al. Overall, in the presence of catalysts, PE and PP follow the Random-chain scission mechanism, while PS follows the unzipping or end chain scission mechanism (Cullis and Hirschler, 1981; Peterson et al., 2001). FT-IR analysis of liquid oil produced from catalytic pyrolysis with TA-NZ. The liquid oil produced from catalytic pyrolysis of PS, with both activated catalysts, mainly contains aromatic hydrocarbons with some paraffins, naphthalene and olefin compounds (Rehan et al., 2017). Eng. J. Appl. Furthermore, catalytic pyrolysis of PP and PE carried out individually with PS, mainly produced aromatic compounds due to the presence of PS. The gases produced from pyrolysis of some plastic waste such as PVC are toxic, and therefore pyrolysis emission treatment technology has to be further refined to achieve maximum environmental benefits. The authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest.

(2015) and Rehan et al. doi: 10.1016/j.wasman.2017.08.032, PubMed Abstract | CrossRef Full Text | Google Scholar, Miandad, R., Kumar, R., Barakat, M. A., Basheer, C., Aburiazaiza, A. S., Nizami, A. S., et al. The activation process increased the BET surface area and reduced the pore size of the char (Lopez et al., 2009). doi: 10.1016/j.energy.2015.07.030, Nizami, A. S., Rehan, M., Waqas, M., Naqvi, M., Ouda, O. K. M., Shahzad, K., et al. The LCA can analyze the environmental impact of the biorefinery and all products by conducting detailed energy and material balances of all life stages including raw material extraction and processing, manufacturing, product distribution, use, maintenance, and disposal/recycling. The produced liquid oil was collected from the oil collection tank, and further characterization was carried out to uncover its chemical composition and characteristics for other potential applications. Stab. According to Lee (2012) and Williams (2006), PE has a long chain carbon structure, and its degradation occurs randomly into smaller chain molecules via random chain scission, which may promote gas production. However thermal pyrolysis of the only PE without a catalyst converted it into wax instead of liquid oil due to its strong long chain branched structure (Lee, 2012; Miandad et al., 2016b). The studies were carried out to explore the potential of produced liquid oil in the context of engine performance and vehicle exhaust emission. Manag. Catal. 17, 2535. Authors are also thankful to Deanship of Scientific Research (DSR) at KAU for their financial and technical support to CEES. The market for pyrolysis based biorefinery products should be created/ expanded to attract further interest and funding, in order to make this concept more practical and successful. However, the use of synthetic catalysts increased the cost of the pyrolysis process. The obtained data revealed the presence of aromatics and aliphatic functional groups in the oil (Figures 6, 7). doi: 10.1016/j.jtice.2015.01.015, Siddiqui, M. N., and Redhwi, H. H. (2009). Miandad et al. Furthermore, Bernando (2011) upgraded the plastic char with biomaterial and carried out the adsorption (3.622.2 mg/g) of methylene blue dye from wastewater. doi: 10.1016/j.fuel.2013.08.044. Macromol. Figure 4. (2006). (2013). Waste Manag. MR and ASA have analyzed the data and written parts of the manuscript. Moreover, cross-linking reaction was favored by strong Bronsted acidic sites and when this reaction occurred the completing cracking may decrease to some extent and enhance the production of char (Serrano et al., 2000). The produced liquid oil characterization was carried out to investigate the effect of feedstock composition on the quality of liquid oil produced in the presence of modified NZ. TA-NZ and AA-NZ contain a high amount of alumina and silica that leads to the hydrogenation of styrene to its derivate, resulting in the production of styrene monomers instead of styrene. 50, 7191. In the third step, the separated plastics are delivered by the feeding system such as the conveyer, hopper and extruder, etc. Eng. A Gen. 278, 3743. Pyrolysis 72, 97102. Municipal Solid Waste: Turning a Problem Into Resourceewaste: The Challenges Facing Developing Countries, Urban Specialist. 5. 119, 162175. A continuous condensation system using a water bath and ACDelco Classic coolant was used to ensure the condensation temperature was kept below 10C, and to ensure the maximum condensation of vapor to liquid oil. PEs initial degradation started at 270C and propagated slowly but gradually until the temperature reached 385C. The liquid oil produced from the catalytic pyrolysis of PE, when using both catalysts, produced mainly Naphthalene, Phenanthrene, Naphthalene, 2-ethenyl-, 1-Pentadecene, Anthracene, 2-methyl-, Hexadecane and so on (Figures 4A, 5A). Stab. doi: 10.1016/j.fuel.2010.05.032, Wu, J., Chen, T., Luo, X., Han, D., Wang, Z., and Wu, J. Thermal properties of bio-flour-filled polyolefin composites with different compatibilizing agent type and content. Literature reports that the presence of these volatile impurities further promotes the degradation process of polymers (McNeill and Bounekhel, 1991; Dziecio and Trzeszczynski, 2000). (2014) modified NZ from Sukabumi, Indonesia by depositing transitional metals such as Ni, Co, and Mo and carried out pyrolysis of low-density polyethylene (LDPE). Furthermore, liquid oil produced from different types of plastic waste had higher heating values (HHV) in the range of 41.744.2 MJ/kg similar to that of conventional diesel. Lee (2012) reported that PS degradation occurred via both random-chain and end chain scissions, thus leading to the production of the stable benzene ring structure, which enhances further cracking and may increase liquid oil production. PS and PP showed single step decomposition, while PE and PET showed a two-stage decomposition under controlled conditions. Thilakaratne et al. London: Oxford University Press. Basically, waste plastics are melted to materials of low viscosity and then the liquefied reactant is thermally decomposed to low-molecular-weight hydrocarbons in the pyrolysis reactor. Gandidi et al.

doi: 10.1016/j.jcis.2017.10.029, Miandad, R., Nizami, A. S., Rehan, M., Barakat, M. A., Khan, M. I., Mustafa, A., et al. Stud. In this study, modified NZ catalysts were added in the reactor with the feedstock. Waste Manag. Plastic waste recycling is carried out in different ways, but in most developing countries, open or landfill disposal is a common practice for plastic waste management (Gandidi et al., 2018). (2004) reported highly reactive olefin production, as intermediate products during the catalytic pyrolysis of PE, that may favor the production of paraffin and aromatic compounds in produced liquid oil. Change 2, 218220. doi: 10.1016/j.wasman.2013.12.005, Xue, Y., Johnston, P., and Bai, X. (2014) carried out TGA of PS with PE and observed two peaks, the first one for PS at a low temperature, followed by PE degradation at a high temperature. (2003) reported that a catalyst with high acidity promotes the cracking process and produces maximum gas production. In addition, Lopez et al. Pyrolysis is the thermal degradation of plastic waste at different temperatures (300900C), in the absence of oxygen, to produced liquid oil (Rehan et al., 2017). Dawood, A., and Miura, K. (2002). Copyright 2019 Miandad, Rehan, Barakat, Aburiazaiza, Khan, Ismail, Dhavamani, Gardy, Hassanpour and Nizami. (2011) also reported the production of olefins, naphthalene with aromatic compounds from catalytic pyrolysis of PS with Al2O3, supported with Cd and Sn catalysts. Lopez et al.

The pyrolysis oil obtained from various plastic types need to be cleaned significantly before it is used in any application, to ensure minimal environmental impact. Catalytic thermal cracking of postconsumer waste plastics to fuels. For the processes of different reactor types, kiln and retort pyrolysis processes are characterized by a relatively low capital investment. (2016). doi: 10.1016/j.fuproc.2014.06.018, Inman, M. (2012). The chemical composition of the pyrolysis oil was analyzed using GC-MS, and it was found that most of the liquid oil produced a high aromatic content with some aliphatic and other hydrocarbon compounds. (1982) carried out pyrolysis of PS with the alumina-silica catalyst at 300C and found the hydrogenation of styrene to its derivate. The presence of PS with PE promotes the degradation process due to the production of an active stable benzene ring from PS (Miandad et al., 2016b).

The major compounds found were; benzene, 1,1-(1,3-propanediyl)bis-, mono(2-ethylhexyl) ester, 1,2-benzenedicarboxylic acid, anthracene, pentadecane, phenanthrene, 2-phenylnaphthalene and so on (Figures 4B, 5B). Catalytic pyrolysis of waste plastics using staged catalysis for production of gasoline range hydrocarbon oils. (2000) carried out pyrolysis of PS with PE at different ratios and reported that an increase in the concentration of PE decreased the liquid oil concentration with the increase in gas. Sci. Res. doi: 10.1016/S0921-3449(00)00052-5, Kunwar, B., Moser, B. R., Chandrasekaran, S. R., Rajagopalan, N., and Sharma, B. K. (2016). To overcome these process energy requirements, more advanced technologies can be developed using the integration of renewable energies such as solar or hydro with pyrolysis-based biorefineries, to achieve maximum economic and environmental benefits. Bomb Calorimeter and TGA (Mettler Toledo TGA/SDTA851) by adopting the standard ASTM methods. (2014). Furthermore, they generate substantial economic benefits and can help achieve a circular economy in any country. The composition of oil from the catalytic pyrolysis of PP with PE contains compounds found in the oil from both individual plastic type feedstocks. Jung et al. The Combustion of Organic Polymers. Pyrol. 1000 g of feedstock was used, with 100 g of catalyst in each experiment. (2017b).

(2000) reported that hydrogenation of styrene increased with the increase of the reaction temperature. The high production of gas may be due to the presence of PP. Kiran et al. Moreover, the presence of a high acidic site on catalysts enhanced the oligomerization, aromatization and deoxygenation mechanism that led to the production of poly-aromatic and naphthalene compounds. doi: 10.1016/j.tca.2006.09.013, Kim, J. R., Yoon, J. H., and Park, D. W. (2002). 31, 19731983. The disposal of plastic waste in landfills provide habitat for insects and rodents, that may cause different types of diseases (Alexandra, 2012). 241, 11011117. Appl. Pyrol. Wu et al. The end-chain scission results in monomer production while random chain scission produces oligomers and monomers (Peterson et al., 2001). 70, 383398. Thus, it may be the reason that styrene was not found in the liquid oil, however, its derivate was detected at high quantities (Lee et al., 2001). 29, 273283. PP degradation started at a very low temperature (240C) compared to other feedstocks. 142, 441451. Pyrolytic liquid fuel: a source of renewable energy in Makkah. (2018) used NZ from Lampung, Indonesia for the catalytic pyrolysis of municipal solid waste. doi: 10.1016/j.jaap.2004.01.005, Chandrasekaran, S. R., Kunwar, B., Moser, B. R., Rajagopalan, N., and Sharma, B. K. (2015). Plastic waste production and consumption is increasing at an alarming rate, with the increase of the human population, rapid economic growth, continuous urbanization, and changes in life style. (2000). These results agree with several other studies (Lee, 2012; Xue et al., 2017). Technol. Lin et al. liquefaction pyrolysis In the pyrolysis and catalytic degradation of polymer at temperature 300-450C the melted reactant is degraded into a smaller molecule and also upgraded to oil product with a high quality. Thermal degradation studies of terephthalate polyesters: 1. (2017) also reported the dealkylation of styrene, due to the delay in evaporation inside the reactor, which may lead to an enhanced reforming process and result in the production of a styrene derivate. Sarker, M., and Rashid, M. M. (2013). Pyrolysisgasification of plastics, mixed plastics and real-world plastic waste with and without NiMgAl catalyst. Pyrolysis based biorefineries have great potential to convert waste such as plastic and biomass waste into energy and other valuable products, to achieve maximum economic and environmental benefits. 2, 19241941. 1, 7484. However, microporous and less acidic catalysts favor the production of long chain hydrocarbons as the cracking process occurred only on the outer surface of the catalysts. doi: 10.1016/j.polymdegradstab.2013.02.013, Dziecio, M., and Trzeszczynski, J. Catal. The feeding system is continuously controlled with a constant reactant amount and classified as heated or nonheated case of the extruder. 98, 972979. 2016:2857162. doi: 10.1155/2016/2857162. The integrated approach helps to achieve maximum economic and environmental benefits with minimal waste production. doi: 10.1021/ie970605c, Uemichi, Y., Nakamura, J., Itoh, T., Sugioka, M., Garforth, A. In this section we discuss the process flow diagram for the pyrolysis of waste plastics.

The initial degradation of PET was perhaps due to the presence of some volatile impurities such as diethylene glycol (Dimitrov et al., 2013). The degradation of PP enhances the carbocation process due to the presence of tertiary carbon in its carbon chain (Jung et al., 2010). doi: 10.1016/j.polymdegradstab.2005.01.056, Mukherjee, M. K., and Thamotharan, P. C. (2014). Similarly, more focus is needed to conduct further research and development work on enriching the biorefinery concept and to tap into its true potential. Plastics are made of petrochemical hydrocarbons with additives such as flame-retardants, stabilizer, and oxidants that make it difficult to bio-degrade (Ma et al., 2017). Bernando, M. (2011). Stab. Furthermore, in the presence of acid catalysts, PS degradation followed a carbenium mechanism, which further underwent hydrogenation (inter/intramolecular hydrogen transfer) and -scission (Serrano et al., 2000). ASA and IMII supported the project financially and technically. 1. J. Chem. (1997) reported the production of aromatics and aliphatic compounds from the catalytic pyrolysis of PE with HZSM-5, while the use of mesoporous MCM-41 decreased the aromatic compounds produced due to its low acid catalytic activity. Afterward, the sample was washed with deionized water until a normal pH was obtained. The liquid oil produced from catalytic pyrolysis of PS with TA-NZ and AA-NZ, contains different kinds of compounds. J. Anal.

Overall, the liquid oil obtained from catalytic pyrolysis of different plastic waste using the AA-NZ catalyst, showed more peaks than the samples from the TA-NZ catalysts. All types of plastic waste show similar degradation behavior with the rapid loss of weight of hydrocarbons within the narrow range of temperature (150250C) (Figure 2). doi: 10.1016/S0926-3373(99)00130-7, Serrano, D. P., Aguado, J., and Escola, J. M. (2012). Fuel production from LDPE plastic waste over natural zeolite supported Ni, Ni-Mo, Co and Co-Mo metals. (2016) also reported the maximum production of gas from catalytic pyrolysis of PE, with highly acidic ZSM-5 catalyst. (2016b) reported that feedstock composition also affects the quality and chemical composition of the oil. Pyrolysis of mixed plastics for the recovery of useful products. The use, distribution or reproduction in other forums is permitted, provided the original author(s) and the copyright owner(s) are credited and that the original publication in this journal is cited, in accordance with accepted academic practice. Degrad. Catalytic degradation of polypropylene over alumina loaded mesoporous catalysts.

In addition, maximum char production was also reported when PET catalytic pyrolysis was carried out with other plastics (Bhaskar et al., 2004). Thermal degradation of polyethylene and polystyrene from the packaging industry over different catalysts into fuel-like feed stocks. doi: 10.1016/j.jaap.2008.11.002, Ma, C., Yu, J., Wang, B., Song, Z., Xiang, J., Hu, S., et al. Moreover, the produced aromatic compounds can be used as raw material for polymerization in various chemical industries (Sarker and Rashid, 2013; Shah and Jan, 2015). (2016) carried out the thermal and catalytic pyrolysis of PE and reported that produced liquid oil contained alkanes and alkenes as a major functional group. However, there are many technical, operational, and socio-economic challenges, as discussed above, that need to be overcome in order to achieve the maximum economic and environmental benefits of biorefineries. 2, 4451. were the major compounds found in the liquid oil (Figures 4A, 5A). Degrad. Kim et al. Dev. Energy 111, 884892. Wu, C., and Williams, P. T. (2010). Catalytic pyrolysis of c-irradiated polypropylene (PP) over HY-zeolite for enhancing the reactivity and the product selectivity. Waste Manag.

The used column and detectors were limited only with hydrocarbons. Cooking up fuel. According to Kim et al. The produced liquid oil composition is affected by different types of feedstock and catalysts used in the pyrolysis process (Miandad et al., 2016a,b,c). doi: 10.1016/j.wasman.2011.05.021, Lopez, G., Olazar, M., Artetxe, M., Amutio, M., Elordi, G., and Bilbao, J. The catalytic reaction during the pyrolysis of plastic waste on solid acid catalysts may include cracking, oligomerization, cyclization, aromatization and isomerization reactions (Serrano et al., 2012). Polym.

The global plastic production was estimated at around 300 million tons per year and is continuously increasing every year (Miandad et al., 2016a; Ratnasari et al., 2017). doi: 10.1016/j.compchemeng.2012.10.013, Heras, F., Jimenez-Cordero, D., Gilarranz, M. A., Alonso-Morales, N., and Rodriguez, J. J. The FT-IR analysis was conducted using a minimum of 32 scans with an average of 4 cm1 IR signals within the frequency range of 5004,000 cm1. However, the highest amounts of gases (50.8 and 47.0%) were produced from PE, using AA-NZ and TA-NZ respectively, compared to all other types of plastic studied. 27, 857869. doi: 10.1038/nclimate1466, Jung, S. H., Cho, M. H., Kang, B. S., and Kim, J. S. (2010). Int. HK, JD, JG, and AH have carried out the detailed characterization of the process products. Gaca et al. In addition, the presence of the oxygen atom also favors the high production of char from catalytic pyrolysis of PET (Xue et al., 2017). doi: 10.1016/j.biortech.2017.05.097, Nizami, A. S., Shahzad, K., Rehan, M., Ouda, O. K. M., Khan, M. Z., Ismail, I. M. I., et al. doi: 10.1021/ie980341+, Ukei, H., Hirose, T., Horikawa, S., Takai, Y., Taka, M., Azuma, N., et al. Effects of the types of zeolites on catalytic upgrading of pyrolysis wax oil. In the unheated case, a hard reactant of several millimeter size is adequately controlled by a continuous feeding system. (2015) reported that 20:80% blend ratio of pyrolytic liquid oil and conventional diesel, respectively, gave similar engine performance results than conventional diesel. However, some of the aromatic hydrocarbons are known carcinogens and can cause serious human health and environmental damage. After being sufficiently heated in the sludge system, the product obtained is used as a valuable oil, but the solid char/coke retained is landfilled or incinerated.

Energy Ins. The effect of thermal and acid activation of NZ on the product yield of the pyrolysis process was examined (Figure 3). Today 62, 6775. Gaca, P., Drzewiecka, M., Kaleta, W., Kozubek, H., and Nowinska, K. (2008). Xue et al. Fuel 133, 276282. (2014).

doi: 10.1016/j.wasman.2016.09.023. The catalytic pyrolysis of PP/PE (50/50% ratio) did not show any significant difference in the overall product yields when using both AA-NZ and TA-NZ. Catalytic degradation of waste polypropylene by pyrolysis.

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plastic pyrolysis process diagram