Reaction hazard and mechanism study of H2O2 oxidation of 2-butanol to methyl ethyl ketone using DSC, Phi-TEC II and GC-MS

Sun, Yue; Ni, Lei; Papadaki, Maria; Jiao, Zeren; Zhu, Wen; Jiang, Juncheng; Mashuga, Chad V.; Mannan, M. Sam; Wilhite, Benjamin

doi:10.1016/j.jlp.2020.104177

Cited by 16 publications

(3 citation statements)

References 59 publications

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“…The high ozone utilization generally observed in our work suggests that peroxide could not exist in high concentrations. Further, peroxides cannot possibly activate butanols − and butanes without a catalyst at ambient temperature. Therefore, trioxides are more likely involved, although, at ambient temperature, they are probably too unstable , to observe by 1 H NMR spectroscopy …”

Section: Resultsmentioning

confidence: 99%

Facile Ozonation of Light Alkanes to Oxygenates with High Atom Economy in Tunable Condensed Phase at Ambient Temperature

Zhu

Jackson

Subramaniam

2023

JACS Au

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We have demonstrated the oxidation of mixed alkanes (propane, nbutane, and isobutane) by ozone in a condensed phase at ambient temperature and mild pressures (up to 1.3 MPa). Oxygenated products such as alcohols and ketones are formed with a combined molar selectivity of >90%. The ozone and dioxygen partial pressures are controlled such that the gas phase is always outside the flammability envelope. Because the alkane−ozone reaction predominantly occurs in the condensed phase, we are able to harness the unique tunability of ozone concentrations in hydrocarbon-rich liquid phases for facile activation of the light alkanes while also avoiding over-oxidation of the products. Further, adding isobutane and water to the mixed alkane feed significantly enhances ozone utilization and the oxygenate yields. The ability to tune the composition of the condensed media by incorporating liquid additives to direct selectivity is a key to achieving high carbon atom economy, which cannot be achieved in gas-phase ozonations. Even in the liquid phase, without added isobutane and water, combustion products dominate during neat propane ozonation, with CO 2 selectivity being >60%. In contrast, ozonation of a propane+isobutane+water mixture suppresses CO 2 formation to 15% and nearly doubles the yield of isopropanol. A kinetic model based on the formation of a hydrotrioxide intermediate can adequately explain the yields of the observed isobutane ozonation products. Estimated rate constants for the formation of oxygenates suggest that the demonstrated concept has promise for facile and atom-economic conversion of natural gas liquids to valuable oxygenates and broader applications associated with C−H functionalization.

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Section: Resultsmentioning

confidence: 99%

Facile Ozonation of Light Alkanes to Oxygenates with High Atom Economy in Tunable Condensed Phase at Ambient Temperature

Zhu

Jackson

Subramaniam

2023

JACS Au

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“…The adiabatic temperature rise (Δ T ad ) is an important parameter for risk assessment. , The reactive system cannot effectively exchange heat with its surroundings after cooling failure, and the energy released by the reaction continues to increase the system temperature. As the heat released by a chemical reaction is directly related to the severity of the runaway reaction, Δ T ad is a convenient way to evaluate the severity of a runaway reaction. ,, The value of Δ T ad is calculated using eq : where Q r is the heat of reaction, M r is the mass of the reaction, and c p is the specific heat capacity of the reaction.…”

Section: Materials and Methodsmentioning

confidence: 99%

“…As the heat released by a chemical reaction is directly related to the severity of the runaway reaction, ΔT ad is a convenient way to evaluate the severity of a runaway reaction. 29,33,34 The value of ΔT ad is calculated using eq 1:…”

Section: Introductionmentioning

confidence: 99%

Research on the Risk of Thermal Runaway in the Industrial Process of Styrene Solution Polymerization

Zhao

Zhang²,

et al. 2021

Org. Process Res. Dev.

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Polymerization reactions are exothermic processes that are often accompanied by viscosity changes, and they can pose hazards due to thermal runaway. This paper describes an investigation of the potential for thermal runaway in the industrial process of styrene solution polymerization, in which particular focus was devoted to the effects of the monomer concentration and the solvent. As the monomer concentration increased from 20.0 to 50.0 wt %, the heat of reaction Q r and the adiabatic temperature rise ΔT ad increased in a linear manner from 19.0 ± 0.2 to 58.1 ± 0.6 kJ and 21.7 ± 0.1 to 64.8 ± 0.6 K, respectively, and the maximum temperature attained by the synthesis reaction (MTSR) was also increased from 86.1 ± 0.2 to 101.5 ± 0.2 °C. In addition, the molecular weight distribution of polystyrene was around 1.9, and the distribution was broad. The risk of a potential runaway reaction was evaluated using the Stoessel assessment criteria and Zurich Hazard Analysis. The criticality of runaway polymerization remained constant with increasing concentration, and class 1 risk was observed. However, the severity of a potential runaway reaction was increased from negligible to medium class. It was found that the solvent had an important effect on the risk of thermal runaway during polymerization. The criticality of the high-boiling solvents toluene and cyclohexanone used in this work was class 1, while that of the low-boiling solvent ethyl acetate was class 3. This work provides valuable insight that can help to control thermal risk in the chemical industry.

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Reuse of waste welding powder in Fenton-like process for RO16 dye removal and Cr(VI) reduction

Bulut,

Eskikaya,

Belibagli

et al. 2023

Environ Dev Sustain

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Reaction hazard and mechanism study of H2O2 oxidation of 2-butanol to methyl ethyl ketone using DSC, Phi-TEC II and GC-MS

Cited by 16 publications

References 59 publications

Facile Ozonation of Light Alkanes to Oxygenates with High Atom Economy in Tunable Condensed Phase at Ambient Temperature

Facile Ozonation of Light Alkanes to Oxygenates with High Atom Economy in Tunable Condensed Phase at Ambient Temperature

Research on the Risk of Thermal Runaway in the Industrial Process of Styrene Solution Polymerization

Reuse of waste welding powder in Fenton-like process for RO16 dye removal and Cr(VI) reduction

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