The formation mechanism and thermal decomposition kinetics of 2,4,6-trinitroresorcinol in the dinitrobenzene production

Weng, Shichun; Wu, Wei; Guo, Zichao; Meng, Fuqing; Chen, Ying; Chen, Wanghua

doi:10.1016/j.psep.2021.11.014

Cited by 10 publications

(3 citation statements)

References 10 publications

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“…During the nitration reactions, the formation of self‐reactive nitrophenols is difficult to avoid [19] . 2,4,6‐trinitroresorcinol, a major by‐product in the dinitrobenzene production process, is self‐reactive substance and has led to tragic explosion incidents in China [20] . Notably, the amount of nitrophenol is very small and must be concentrated 50 times before it can be detected.…”

Section: Resultsmentioning

confidence: 99%

Safe, Green, and Efficient Synthesis of m‐Dinitrobenzene via Two‐Step Nitration in a Continuous‐Flow Microreactor

Zhao¹,

Zhang²,

Wei³

et al. 2023

ChemistrySelect

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In industry, m-dinitrobenzene is mainly obtained by two-step nitration of benzene, but still faces the problem of being heterogeneous and highly exothermic. In this work, a two-step continuous-flow nitration was developed in a microreactor, combining benzene nitration and mononitrobenzene nitration in series. The waste acid after the mononitrobenzene nitration stage was utilized in the benzene mononitration stage, and the waste acid in the benzene mononitration stage was treated and concentrated for reuse. The whole process consumes almost no sulfuric acid. Under optimal conditions, the yield of dinitrobenzene was more than 99.0 % and the selectivity of mdinitrobenzene was more than 91 % with a residence time of 4 min at 70 °C. In addition, the space-time yield of the continuous microreactor was 800 times higher than the batch reactor. It provides a safe and efficient method for the industrial production of m-dinitrobenzene.

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Section: Resultsmentioning

confidence: 99%

Safe, Green, and Efficient Synthesis of m‐Dinitrobenzene via Two‐Step Nitration in a Continuous‐Flow Microreactor

Zhao¹,

Zhang²,

Wei³

et al. 2023

ChemistrySelect

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“…Zhao et al used a nonisothermal differential scanning calorimeter (DSC) to study the thermal decomposition kinetic of sodium 2,4-dinitrophenolate . Recently, our group investigated the formation mechanism and decomposition kinetic of trinitroresorcinol, which was the main hazardous waste during production of dinitrobenzene . In addition, the difference in thermal stability (mainly including the decomposition onset temperature, exothermic rates, and so on) of nitrophenols and its sodium nitrophenols was an important factor to cause the high thermal risk in the post process during production of MNB.…”

Section: Introductionmentioning

confidence: 99%

Thermal Behavior and Decomposition Pathway for Nitrophenols and Sodium Nitrophenolates

Weng

Feng

et al. 2023

Org. Process Res. Dev.

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Nitrophenols and corresponding sodium nitrophenolates are the main side products in the production of mononitrobenzene (MNB). These side products are hazardous due to their thermal instability nature. In this article, the thermal decomposition behaviors of nitrophenols and sodium nitrophenolates were first characterized by differential scanning calorimeter and accelerating rate calorimetry techniques. Then, the influence of phenol and sodium phenolate on the thermal decomposition of MNB was studied to clarify the effect of phenolic hydroxyl groups on the thermal stability of nitrophenols. It was found that compared to nitrophenols, the exothermic peaks of sodium nitrophenolates were more intense and presented strongly autocatalytic features. Sodium phenolate could significantly decrease the decomposition temperature of MNB. Aniline was detected as the unique product in the decomposition processes of pure MNB and MNB/sodium phenolate mixtures, and the nitrosobenzene was verified as the intermediate product. It was experimentally proven that sodium phenolate could catalyze the decomposition of nitrosobenzene (the decomposition intermediate of MNB). The violent decomposition of sodium nitrophenols was caused by the intermolecular catalysis effect of phenoxy groups.

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“…Understanding the thermal stability of materials is crucial to ensure the safe operation of chemical manufacturing processes, with the study of species containing nitro functional groups remaining an active field of research in recent years. − Such materials are widely used and produced throughout the chemical industry due to the useful nature of the nitro functional group; , however, the high heat of decomposition (with reported values of around −300 kJ/mol for each nitro group present), gaseous decomposition products, and the autocatalytic nature of the decomposition of nitro-containing species mean that particular care and knowledge are required for safe handling and usage of such materials. Unfortunately, industrial incidents involving the decomposition of nitro-containing species still occur in modern times, − suggesting that those employing or producing nitro-containing materials do not always fully understand the hazards they pose, particularly the concept, implications, and what can affect the levels of autocatalysis.…”

Section: Introductionmentioning

confidence: 99%

Reduction in the Thermal Stability of Nitro-Containing Compounds due to Cross-Catalyzed Autocatalytic Decomposition Caused by Nitro-Containing Impurities

Gaywood

Cushing

Allison

2022

Org. Process Res. Dev.

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Testing performed by ramped and isothermal differential scanning calorimetry has demonstrated a previously unreported effect wherein the thermal stability of nitro-containing compounds can be significantly reduced by the presence of low levels of a secondary nitro-containing compound, where the impurity is of lower thermal stability than the bulk material. This effect is believed to be due to the autocatalytic decomposition of nitro-containing species being catalyzed by a common catalyst, such that the catalyst generated from an impurity can cross-catalyze the decomposition of the bulk material. Accordingly, this effect does not occur when the impurity is of similar or greater thermal stability than the bulk. This effect reiterates the importance of performing thermal stability testing on samples whose impurity profile is representative of that to be utilized or produced.

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The formation mechanism and thermal decomposition kinetics of 2,4,6-trinitroresorcinol in the dinitrobenzene production

Cited by 10 publications

References 10 publications

Safe, Green, and Efficient Synthesis of m‐Dinitrobenzene via Two‐Step Nitration in a Continuous‐Flow Microreactor

Safe, Green, and Efficient Synthesis of m‐Dinitrobenzene via Two‐Step Nitration in a Continuous‐Flow Microreactor

Thermal Behavior and Decomposition Pathway for Nitrophenols and Sodium Nitrophenolates

Reduction in the Thermal Stability of Nitro-Containing Compounds due to Cross-Catalyzed Autocatalytic Decomposition Caused by Nitro-Containing Impurities

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