Insights into the coke deposited on HZSM-5, Hβ and HY zeolites during the cracking of polyethylene
TL;DR: In this article, the effect of the zeolite structure (HZSM-5, Hβ and HY) on coke deposition during the cracking of high-density polyethylene has been studied by combining the results of multiple spectroscopic and analytical techniques: FTIR, Raman, UV-vis, 13 C NMR and coke extraction.
Abstract: The effect of the zeolite structure (HZSM-5, Hβ and HY) on coke deposition during the cracking of high-density polyethylene has been studied by combining the results of multiple spectroscopic and analytical techniques: FTIR, Raman, UV–vis, 13 C NMR and coke extraction, followed by GC-MS and 1 H NMR analysis. In addition, by combining FTIR and temperature programmed oxidation (TPO) analysis we obtained information on the coke: properties, burn-off, and changes in composition during catalyst regeneration. Samples of the spent catalysts were obtained in a state-of-the-art pilot plant (conical spouted bed reactor) after the continuous treatment of 900 g (1 g min −1 , 15 h) of high-density polyethylene at 500 °C, using 30 g of catalyst. The results show that as the pore diameter of the zeolite is increased, bimolecular reactions (hydrogen transfer and oligomerizations), condensations and cyclizations are enhanced, yielding more aromatic coke. Furthermore, the pore topology of the HZSM-5 zeolite improves the flow of coke precursors (also favored by the high flow rate of N 2 ) to the outside of the catalyst; viz. HZSM-5 catalyst preserves its activity for longer.
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TL;DR: In this paper, the main thermochemical routes for the valorization of waste polyolefins to produce chemicals and fuels are analyzed for the purpose of producing more sustainable waste management policies.
Abstract: The continuous increase in the generation of waste plastics together with the need for developing more sustainable waste management policies have promoted a great research effort dealing with their valorization routes. In this review, the main thermochemical routes are analyzed for the valorization of waste polyolefins to produce chemicals and fuels. Amongst the different strategies, pyrolysis has received greater attention, but most studies are of preliminary character. Likewise, the studies pursuing the incorporation of waste plastics into refinery units (mainly fluid catalytic cracking and hydrocracking) have been carried out in batch laboratory-scale units. Other promising alternative to which great attention is being paid is the process based on two steps: pyrolysis and in-line intensification for olefin production by means of catalytic cracking or thermal cracking at high temperatures.
498 citations
TL;DR: In this paper, the current scenario of the plastic recycling technology is reviewed in order to provide the reader with an in-depth analysis with respect to the pyrolysis of plastic waste as obtained in the current recycling technology.
Abstract: Due to the depleting fossil fuel sources such as crude oil, natural gas, and coal, the present rate of economic growth is unsustainable. Therefore, many sources of renewable energy have been exploited, but the potentials of some other sources such as plastics waste are yet to be fully developed as full scale economic activity. Development and modernization have brought about a huge increase in the production of all kinds of plastic commodities, which directly or indirectly generate waste due to their wide range of applications coupled with their versatility of types and relatively low cost. The current scenario of the plastic recycling technology is reviewed in this paper. The aim is to provide the reader with an in-depth analysis with respect to the pyrolysis of plastic waste as obtained in the current recycling technology. As the calorific value of the plastics is comparable to that of hydrocarbon fuel, production of fuel from plastic waste would provide a good opportunity to utilize the waste as a better alternative to dumpsites. Different techniques of converting plastics waste into fuel including thermal and catalytic pyrolysis, microwave-assisted pyrolysis and fluid catalytic cracking are discussed in detail. The co-pyrolysis of plastics waste with biomass is also highlighted. Thus, an attempt was made to address the problem of plastic waste disposal as a partial replacement of the depleting fossil fuel with the hope of promoting a sustainable environment.
439 citations
TL;DR: In this article, a review of catalytic cracking of polyolefins over solid acids is presented, focusing on the role played by the catalysts toward the synthesis of fuels and chemicals as well as on the reaction systems currently used.
Abstract: The present review is aimed at exploring the field of the catalytic cracking of polyolefins over solid acids, focusing on the role played by the catalysts toward the synthesis of fuels and chemicals as well as on the reaction systems currently used. Initially, conventional solid acids, such as micrometer sized crystal zeolites and silica–alumina, were used to establish the relationship among their activity, selectivity, and deactivation in the polyolefin cracking and the inherent properties of the catalysts (acidity, pore structure); however, the occurrence of steric and diffusional hindrances for entering the zeolite micropores posed by the bulky nature of the polyolefins highlighted the importance of having easily accessible acid sites, either through mesopores or by a high external surface area. This fact led toward the investigation of mesoporous materials (Al-MCM-41, Al-SBA-15) and nanozeolites, which allowed increasing the catalytic activities, especially for the case of polypropylene. Further advan...
293 citations
TL;DR: In this article, a review deals with the currently existing alternatives at the catalyst and reactor level to cope with catalyst deactivation and increase process stability, and then delves with the fundamental phenomena occurring during this catalysts deactivation.
Abstract: Undoubtedly, hydrogen (H2) is a clean feedstock and energy carrier whose sustainable production should be anticipated. The pyrolysis of biomass or waste plastics and the subsequent reforming over base (transition) or noble metals supported catalysts allows reaching elevated H2 yields. However, the catalyst used in the reforming step undergoes a rapid and severe deactivation by means of a series of physicochemical phenomena, including metal sintering, metallic phase oxidation, thermal degradation of the support and, more notoriously, coke deposition. This review deals with the currently existing alternatives at the catalyst and reactor level to cope with catalyst deactivation and increase process stability, and then delves with the fundamental phenomena occurring during this catalyst deactivation. An emphasis is placed on coke deposition and its influence on deactivation, which depends on its location, chemical nature, morphology, precursors or formation mechanism, among others. We also discuss the challenges for increasing the value of the carbon materials formed and therefore, enhance process viability.
248 citations
TL;DR: In this article, the authors summarized the current techniques of brominated flame retardant (BFR)plastics recycling with a view to solving energy crisis and the environmental degradation of BFR-plastics.
Abstract: Electronic waste plastics (e-waste plastics) have been one of the emerging and fastest-growing waste streams due to the increasing number of generation in waste electrical and electronic equipment (WEEE). Given that brominated flame retardant (BFR) materials in e-waste plastics have been the major impediment for recycling treatment, chemical recycling has been proposed as an environmentally friendly method of recycling e-waste plastics for clean fuels production or chemical feedstocks. This paper summarized the current techniques of BFR-plastics recycling with a view to solving energy crisis and the environmental degradation of BFR-plastics. Emphasis was paid on the recent chemical treatment of BFR-plastics, including pyrolysis, co-pyrolysis and catalytic cracking, which are yet to be completely feasible in conversion of BFR-plastics for clean fuels production. Hydrothermal treatment is regarded as a novel high-efficiency technology to recycle BFR-plastics, which can be a potential process for the in situ debromination of oil products. An advanced chemical recycling technique, pyrolysis-catalytic upgrading process, is highlighted. The recycling route of pyrolyzing BFR-plastics prior to catalytic upgrading was intended to obtain high quantity oils, and then the upgrading process of pyrolysis oils was conducted by means of catalytic hydrodebromination with the aim of obtaining bromine-free oils for commercial applications. In short, the integration of pyrolysis with catalytic upgrading process can provide significant economic and environmental options in conversion of e-waste plastics into useful and high-value materials. Further investigations are required to develop the pyrolysis-catalytic upgrading process to become sustainable and commercially viable for clean fuels production.
190 citations
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TL;DR: In this paper, a model and theoretical understanding of the Raman spectra in disordered and amorphous carbon is given, and the nature of the G and D vibration modes in graphite is analyzed in terms of the resonant excitation of \ensuremath{\pi} states and the long-range polarizability of the long range bonding.
Abstract: The model and theoretical understanding of the Raman spectra in disordered and amorphous carbon are given. The nature of the G and D vibration modes in graphite is analyzed in terms of the resonant excitation of \ensuremath{\pi} states and the long-range polarizability of \ensuremath{\pi} bonding. Visible Raman data on disordered, amorphous, and diamondlike carbon are classified in a three-stage model to show the factors that control the position, intensity, and widths of the G and D peaks. It is shown that the visible Raman spectra depend formally on the configuration of the ${\mathrm{sp}}^{2}$ sites in ${\mathrm{sp}}^{2}$-bonded clusters. In cases where the ${\mathrm{sp}}^{2}$ clustering is controlled by the ${\mathrm{sp}}^{3}$ fraction, such as in as-deposited tetrahedral amorphous carbon (ta-C) or hydrogenated amorphous carbon (a-C:H) films, the visible Raman parameters can be used to derive the ${\mathrm{sp}}^{3}$ fraction.
12,593 citations
TL;DR: Raman spectra are reported from single crystals of graphite and other graphite materials as mentioned in this paper, and the Raman intensity of this band is inversely proportional to the crystallite size and is caused by a breakdown of the k-selection rule.
Abstract: Raman spectra are reported from single crystals of graphite and other graphite materials. Single crystals of graphite show one single line at 1575 cm−1. For the other materials like stress‐annealed pyrolitic graphite, commercial graphites, activated charcoal, lampblack, and vitreous carbon another line is detected at 1355 cm−1. The Raman intensity of this band is inversely proportional to the crystallite size and is caused by a breakdown of the k‐selection rule. The intensity of this band allows an estimate of the crystallite size in the surface layer of any carbon sample. Two in‐plane force constants are calculated from the frequencies.
9,373 citations
TL;DR: Although primary and secondary recycling schemes are well established and widely applied, it is concluded that many of the PSW tertiary and quaternary treatment schemes appear to be robust and worthy of additional investigation.
1,672 citations
TL;DR: The origin and interpretation of the Raman features of amorphous (hydrogenated) carbonfilmsdeposited at room temperature in the region of 1000-1700 cm−1 is discussed in this paper.
Abstract: The origin and interpretation of the Raman features of amorphous (hydrogenated) carbonfilmsdeposited at room temperature in the region of 1000–1700 cm−1 is discussed in this paper. Possible interpretations of the linewidths, positions of the ‘‘G’’ graphite peak and ‘‘D’’ disordered peak, and their intensity ratios are examined using results obtained from magnetron sputtered and magnetic field enhanced plasmadepositedfilms. It is shown that even small ‘‘clusters’’ of condensed benzene rings (cluster size below 20 A) in carbonfilms can explain the observed Raman scattering. Besides the care that should be taken in the correct interpretation of Raman results, the utility of Raman scattering in obtaining an estimate of cluster sizes in amorphous (hydrogenated) carbonfilms is discussed. Carbonfilms prepared by magnetron sputtering show two additional Raman features at 1180 and 1490 cm−1 in addition to the G and D peaks. It is shown that a correlation exists between the 1180 cm−1 peak and the sp 3 content in the films.
1,229 citations
TL;DR: In this paper, an interband effective electron mass was defined for carbon systems, where the mass density was derived from the valence electron density via the plasmon energy, which is measured by electron energy-loss spectroscopy (EELS).
Abstract: Grazing-angle x-ray reflectivity (XRR) is described as an efficient, nondestructive, parameter-free means to measure the mass density of various types of amorphous carbon films down to the nanometer thickness range. It is shown how XRR can also detect layering if it is present in the films, in which case the reflectivity profile must be modeled to derive the density. The mass density can also be derived from the valence electron density via the plasmon energy, which is measured by electron energy-loss spectroscopy (EELS). We formally define an interband effective electron mass ${m}^{*},$ which accounts for the finite band gap. Comparison of XRR and EELS densities allows us to fit an average ${m}^{*}=0.87m$ for carbon systems, m being the free-electron mass. We show that, within the Drude-Lorentz model of the optical spectrum, ${m}^{*}=[1\ensuremath{-}{n(0)}^{\ensuremath{-}2}]m,$ where $n(0)$ is the refractive index at zero optical frequency. The fraction of ${\mathrm{sp}}^{2}$ bonding is derived from the carbon K-edge EELS spectrum, and it is shown how a choice of ``magic'' incidence and collection angles in the scanning transmission electron microscope can give ${\mathrm{sp}}^{2}$ fraction values that are independent of sample orientation or anisotropy. We thus give a general relationship between mass density and ${\mathrm{sp}}^{3}$ content for carbon films.
511 citations