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Conventional thermochemical syntheses by continuous heating under near-equilibrium conditions face critical challenges in improving the synthesis rate, selectivity, catalyst stability and energy efficiency, owing to the lack of temporal control over the reaction temperature and time, and thus the reaction pathways1-3. As an alternative, we present a non-equilibrium, continuous synthesis technique that uses pulsed heating and quenching (for example, 0.02 s on, 1.08 s off) using a programmable electric current to rapidly switch the reaction between high (for example, up to 2,400 K) and low temperatures. The rapid quenching ensures high selectivity and good catalyst stability, as well as lowers the average temperature to reduce the energy cost. Using CH4 pyrolysis as a model reaction, our programmable heating and quenching technique leads to high selectivity to value-added C2 products (>75% versus <35% by the conventional non-catalytic method and versus <60% by most conventional methods using optimized catalysts). Our technique can be extended to a range of thermochemical reactions, such as NH3 synthesis, for which we achieve a stable and high synthesis rate of about 6,000 µmol gFe-1 h-1 at ambient pressure for >100 h using a non-optimized catalyst. This study establishes a new model towards highly efficient non-equilibrium thermochemical synthesis.
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Polyolefins can be converted into C2-C5 hydrocarbons and benzene-toluene-xylene (BTX) aromatics as high-demand petrochemical feedstocks via catalytic pyrolysis on acidic zeolites. BroÌ·nsted and Lewis acid sites are responsible for cracking polyolefins into olefins and subsequent aromatic formation. In this study, we have subjected the parent HZSM-5 zeolite to postsynthetic partial metal exchange with Fe, Co, Ni, Cu, and Ce cations to perturb BroÌ·nsted/Lewis acidity. We have investigated these metal-modified HZSM-5 on the catalytic pyrolysis of polypropylene (PP) in a micropyrolyzer connected to a two-dimensional gas chromatograph coupled to a time-of-flight mass spectrometer and flame ionization detector (Tandem Pyrolyzer-GC × GC-TOF-MS/FID setup). Whereas Fe-, Co-, Cu-, and Ce-exchanged zeolites (with 2.5, 2.3, 1.9, and 0.8 wt % metal, respectively) had comparable product yields with the parent zeolite, Ni-exchanged zeolites with Ni content of 0.5 to 2 wt % were associated with enhanced BTX formation (28-38 wt %) compared to that of the parent zeolite (22 wt %). Pyridine-FTIR indicated that the BroÌ·nsted/Lewis acid ratio of the parent zeolite decreased upon metal ion exchange. According to Pyridine-TPD, the parent zeolite's medium-strength acid sites were redistributed into weak and strong acid sites in Ni-exchanged zeolites. The higher amount of carbon deposits on Ni-exchanged zeolites compared to the parent and other metal ion exchanged zeolites was attributed to the enhanced aromatization activity by the simultaneous decrease in the BroÌ·nsted/Lewis acid ratio and emergence of strong acid sites.
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Plastics incorporate diverse additives, including primary antioxidants with a typical amount between 0.05 to 3 wt.%, to enhance plastics functionality and durability, preventing their oxidation and maintaining their mechanical properties. While these antioxidants offer substantial benefits, their degradation can significantly impact plastic pyrolysis by changing the pyrolysis oil product distribution. Understanding the intricate distribution of decomposition products resulting from pyrolysis is essential yet often overlooked. This study delved into the analysis of the decomposition of common primary antioxidants, namely, Irganox 1010, Irganox 1076, and butylated hydroxytoluene (BHT), utilizing both one-dimensional gas chromatography coupled with a quadruple mass spectrometer (GC-MS) and two-dimensional gas chromatography equipped with flame ionization detector and time-of-flight mass spectrometer (GC×GC-FID/TOF-MS). This study showed that GC×GC-FID/TOF-MS provided a more detailed characterization of the pyrolysis product distribution of primary antioxidants used in plastics in comparison to GC-MS. For each of the antioxidants, using the GC×GC-FID/TOF-MS analytical approach enhanced the identification of degradation products at least fivefold. Furthermore, GC×GC-FID/TOF-MS identified products of more chemical classes than GC-MS. For instance, compounds from 14 chemical classes were identified from GC×GC-FID/TOF-MS in the pyrolysis of Irganox 1010, whereas only 9 chemical classes were identified in GC-MS. Olefins were the major chemical class for both Irganox 1010 and Irganox 1076 in the decomposition process, accounting for 23.25 wt.% and 20.76 wt.%, respectively. Ketones were the major chemical class in the case of BHT, having a 6.68 wt.% yield. This research enhanced the understanding of the decomposition of primary antioxidant and their product distribution during pyrolysis and shed light on the potential necessity for using two-dimensional gas chromatography.
Assuntos
Antioxidantes , Hidroxitolueno Butilado , Cromatografia Gasosa-Espectrometria de Massas , Pirólise , Hidroxitolueno Butilado/análise , Hidroxitolueno Butilado/química , Hidroxitolueno Butilado/análogos & derivados , Antioxidantes/análise , Antioxidantes/química , Cromatografia Gasosa-Espectrometria de Massas/métodos , Plásticos/química , Cromatografia Gasosa/métodosRESUMO
Plastic production has experienced a significant increase in the last sixty years due to its cost-efficiency and adaptable characteristics, leading to the extensive use of additives to improve its performance and longevity. Due to the high demand for plastic, plastic waste production has increased, contaminating the environment and living beings by leaching additives, among other substances. Pyrolysis stands out among recycling techniques because it can handle mixed polymer waste feedstock. However, understanding the pyrolyzates distribution of additives is fundamental to assessing pyrolysis process of plastic waste. This study investigated the pyrolysis product distributions of two commonly used antioxidants, namely, Irgafos 168 and zinc stearate (ZnSt), using one-dimensional gas chromatography equipped with a quadruple mass spectrometer (GC-MS) and two-dimensional gas chromatography coupled to flame ionization detector and time-of-flight mass spectrometer (GC×GC-FID/TOF-MS). While GC separation technique provided limited information on product distribution, GC×GC offered enhanced resolution and identification of the decomposition products. In the pyrolysis of Irgafos 168 at 550 °C, GC identified 18 products, while GC×GC identified 198 products, representing an increase of approximately 11-fold. Similarly, for ZnSt, GC identified 67 products, while GC×GC identified 434 products, representing a 6-fold increase. GC×GC identified decomposition products from 15 different chemical classes for Irgafos 168 and 16 chemical classes for ZnSt, compared to 4 and 11 chemical classes identified by GC, respectively. Phenols and their derivatives were the major chemical class in the decomposition products of Irgafos 168 with a yield of 9.51 wt.%. In contrast, olefinic products were the dominant ones for ZnSt, with a yield of 9.73 wt.%. The major decomposition product of Irgafos 168 and ZnSt was 2tertbutylmethylphenol (C11H16O) and C6 olefin (C6H12) with yields of 3.88 wt.%, and 1.13 wt.%, respectively. Utilizing the GC×GC separation method improved the ability to identify decomposition products, which can ultimately lead to a better understanding of antioxidant degradation that occurs during the pyrolysis process. GC×GC also provided thorough characterization of minor and co-eluted products along with major antioxidant degradation products. Additionally, the decomposition product distribution of Irgafos 168 and ZnSt was also compared with the primary antioxidants, Irganox 1010, Irganox 1076, and BHT, studied in part 1. The analysis indicated that the olefinic chemical class was the predominant one in Irganox 1010, Irganox 1076, and ZnSt, while ketones were the major chemical class in the decomposition of BHT and phenolics had the highest yield in Irgafos 168.
Assuntos
Antioxidantes , Cromatografia Gasosa-Espectrometria de Massas , Pirólise , Ácidos Esteáricos , Cromatografia Gasosa-Espectrometria de Massas/métodos , Antioxidantes/análise , Antioxidantes/química , Ácidos Esteáricos/análise , Ácidos Esteáricos/química , Cromatografia Gasosa/métodos , Plásticos/químicaRESUMO
Genetic engineering is a powerful tool to steer bio-oil composition towards the production of speciality chemicals such as guaiacols, syringols, phenols, and vanillin through well-defined biomass feedstocks. Our previous work demonstrated the effects of lignin biosynthesis gene modification on the pyrolysis vapour compositions obtained from wood derived from greenhouse-grown poplars. In this study, field-grown poplars downregulated in the genes encoding CINNAMYL ALCOHOL DEHYDROGENASE (CAD), CAFFEIC ACID O-METHYLTRANSFERASE (COMT) and CAFFEOYL-CoA O-METHYLTRANSFERASE (CCoAOMT), and their corresponding wild type were pyrolysed in a Py-GC/MS. This work aims at capturing the effects of downregulation of the three enzymes on bio-oil composition using principal component analysis (PCA). 3,5-methoxytoluene, vanillin, coniferyl alcohol, 4-vinyl guaiacol, syringol, syringaldehyde, and guaiacol are the determining factors in the PCA analysis that are the substantially affected by COMT, CAD and CCoAOMT enzyme downregulation. COMT and CAD downregulated transgenic lines proved to be statistically different from the wild type because of a substantial difference in S and G lignin units. The sCAD line lead to a significant drop (nearly 51%) in S-lignin derived compounds, while CCoAOMT downregulation affected the least (7-11%). Further, removal of extractives via pretreatment enhanced the statistical differences among the CAD transgenic lines and its wild type. On the other hand, COMT downregulation caused 2-fold reduction in S-derived compounds compared to G-derived compounds. This study manifests the applicability of PCA analysis in tracking the biological changes in biomass (poplar in this case) and their effects on pyrolysis-oil compositions.
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Cotton stalks were subjected to alkaline pretreatment for the co-production of glucose and hemicellulose based films with a multi-product approach. Three pretreatment temperatures (25, 60 and 90 °C) were evaluated for their effects both on the glucose yield and on the properties of hemicellulose based films. Compared to untreated cotton stalks, the glucose yields were enhanced 3.9, 4.1 and 4.2 times for pretreatments conducted at 25, 60 and 90 °C, respectively. The pretreatment temperature of 90 °C was detrimental in terms of film formation. Tensile energy to break values of the films obtained after pretreatments conducted at 25, 60 and 90 °C were 1.1, 0.8, and 0.4 MJ/m3, respectively. The hemicellulosic part of the process, which considers the production of hemicellulose based films, should govern the pretreatment temperature since it was more responsive to the changes in the pretreatment temperature compared to the cellulosic part that accounts for glucose production.