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A comprehensive kinetic model for phenol oxidation in seven advanced oxidation processes and considering the effects of halides and carbonate.

ABSTRACT: As one of the most powerful approaches to mechanistically understanding complex chemical reactions and performing simulations or predictions, kinetic modeling has been widely used to investigate advanced oxidation processes (AOPs). However, most of the available models are built based on limited systems or reaction mechanisms so they cannot be readily extended to other systems or reaction conditions. To overcome such limitations, this study developed a comprehensive model on phenol oxidation using over 540 reactions, covering the most common reaction mechanisms in nine AOPs-four peroxymonosulfate (PMS), four peroxydisulfate (PDS), and one H₂O₂ systems-and considering product formation and the effects of co-existing anions (chloride, bromide, and carbonate). Existing models in the literature were first gathered and then revised by correcting inaccurately used reactions and adding other necessary reactions. Extensive model tuning and validation were next conducted by fitting the model against experimental data from both this study and the literature. The effects of anions were found to follow PDS/CuO > H₂O₂/UV > other PDS or PMS systems. Halogenated organic byproducts were mainly observed in the PMS systems in the presence of halides. Most of the 543 reactions were found to be important based on the sensitivity analysis, with some anions-involved reactions being among the most important, which explained why these anions substantially altered some of the reaction systems. With this comprehensive model, a deep understanding and reliable prediction can be made for the oxidation of phenol (and likely other phenolic compounds) in systems containing one or more of the above AOPs.

SUBMITTER: Huang K

PROVIDER: S-EPMC8766555 | biostudies-literature |

REPOSITORIES: biostudies-literature

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Project description:The pyrolytic and oxidative behaviour of the biofuel 2,5-dimethylfuran (25DMF) has been studied in a range of experimental facilities in order to investigate the relatively unexplored combustion chemistry of the title species and to provide combustor relevant experimental data. The pyrolysis of 25DMF has been re-investigated in a shock tube using the single-pulse method for mixtures of 3% 25DMF in argon, at temperatures from 1200-1350 K, pressures from 2-2.5 atm and residence times of approximately 2 ms. Ignition delay times for mixtures of 0.75% 25DMF in argon have been measured at atmospheric pressure, temperatures of 1350-1800 K at equivalence ratios (ϕ) of 0.5, 1.0 and 2.0 along with auto-ignition measurements for stoichiometric fuel in air mixtures of 25DMF at 20 and 80 bar, from 820-1210 K. This is supplemented with an oxidative speciation study of 25DMF in a jet-stirred reactor (JSR) from 770-1220 K, at 10.0 atm, residence times of 0.7 s and at ϕ = 0.5, 1.0 and 2.0. Laminar burning velocities for 25DMF-air mixtures have been measured using the heat-flux method at unburnt gas temperatures of 298 and 358 K, at atmospheric pressure from ϕ = 0.6-1.6. These laminar burning velocity measurements highlight inconsistencies in the current literature data and provide a validation target for kinetic mechanisms. A detailed chemical kinetic mechanism containing 2768 reactions and 545 species has been simultaneously developed to describe the combustion of 25DMF under the experimental conditions described above. Numerical modelling results based on the mechanism can accurately reproduce the majority of experimental data. At high temperatures, a hydrogen atom transfer reaction is found to be the dominant unimolecular decomposition pathway of 25DMF. The reactions of hydrogen atom with the fuel are also found to be important in predicting pyrolysis and ignition delay time experiments. Numerous proposals are made on the mechanism and kinetics of the previously unexplored intermediate temperature combustion pathways of 25DMF. Hydroxyl radical addition to the furan ring is highlighted as an important fuel consuming reaction, leading to the formation of methyl vinyl ketone and acetyl radical. The chemically activated recombination of HȮ2 or CH3Ȯ2 with the 5-methyl-2-furanylmethyl radical, forming a 5-methyl-2-furylmethanoxy radical and ȮH or CH3Ȯ radical is also found to exhibit significant control over ignition delay times, as well as being important reactions in the prediction of species profiles in a JSR. Kinetics for the abstraction of a hydrogen atom from the alkyl side-chain of the fuel by molecular oxygen and HȮ2 radical are found to be sensitive in the estimation of ignition delay times for fuel-air mixtures from temperatures of 820-1200 K. At intermediate temperatures, the resonantly stabilised 5-methyl-2-furanylmethyl radical is found to predominantly undergo bimolecular reactions, and as a result sub-mechanisms for 5-methyl-2-formylfuran and 5-methyl-2-ethylfuran, and their derivatives, have also been developed with consumption pathways proposed. This study is the first to attempt to simulate the combustion of these species in any detail, although future refinements are likely necessary. The current study illustrates both quantitatively and qualitatively the complex chemical behavior of what is a high potential biofuel. Whilst the current work is the most comprehensive study on the oxidation of 25DMF in the literature to date, the mechanism cannot accurately reproduce laminar burning velocity measurements over a suitable range of unburnt gas temperatures, pressures and equivalence ratios, although discrepancies in the experimental literature data are highlighted. Resolving this issue should remain a focus of future work.

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A comprehensive kinetic model for phenol oxidation in seven advanced oxidation processes and considering the effects of halides and carbonate.

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