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Free radicals formation on thermally decomposed biomass

机译：热分解生物质上自由基的形成

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Pyrolysis provides an attractive alternative for the upgrading of agro-wastes to energy and chemicals. However, consistent quality of the final products is still a goal to be achieved at industrial level. The present study aims at complementing existing results recently published by the authors and investigating the physico-chemical evolution and oxidative reactivity of solid products of pyrolysis of citrus waste. Chars derived from slow pyrolysis (50 degrees C min(-1), 200-650 degrees C peak temperature) of orange and lemon pulp (OP and LP) in a horizontal batch reactor were characterized by means of Thermo-Gravimetric Analysis (TGA), Differential Scanning Calorimetry (DSC), Electron Paramagnetic Resonance (EPR) and Raman spectroscopy. Results show how the onset of breaking of covalent bonds in matrix is triggered by reaching pyrolysis temperatures of 330-350 degrees C. Around those temperatures, the population of free-radicals significantly increases on solids and chars become more reactive, thereby favoring retrogressive, recombination and secondary solid-vapor reactions. Results also show that the higher content of lignin on LP may facilitate the formation of aromatic networks via lignin fragmentation and condensation above 500 degrees C. This trend is also confirmed by DSC patterns in which, above 500 degrees C, significantly more endothermic reactions occur in LP as a comparison to OP. This conclusion is further corroborated by more pronounced G-band Raman shifts shown for LP as a comparison to OP. The present results shed new light on the thermochemical breakdown of solid agro-wastes and provide insights for development of slow pyrolysis technology toward the production of valuable renewable carbonaceous materials.
机译：热解为将农业废料升级为能源和化学物质提供了一种有吸引力的替代方法。但是，最终产品的稳定质量仍然是工业水平上要实现的目标。本研究旨在补充作者最近发表的现有结果，并研究柑橘废物热解固体产物的理化演变和氧化反应性。通过热重分析（TGA）表征了卧式分批反应器中橙和柠檬浆（OP和LP）的缓慢热解（50°C min（-1），峰值温度200-650°C）衍生的炭，差示扫描量热法（DSC），电子顺磁共振（EPR）和拉曼光谱。结果表明，如何通过达到330-350摄氏度的热解温度来触发基质中共价键断裂的开始。在这些温度附近，自由基的总数在固体上显着增加，并且炭变得更具反应性，从而有利于回归，重组和二次固体蒸气反应。结果还表明，LP上木质素含量较高，可能在500摄氏度以上通过木质素破碎和缩合促进芳香网络的形成。DSC模式也证实了这一趋势，在500摄氏度以上，DSC发生的吸热反应明显更多。 LP与OP的比较。与OP相比，LP显示的更明显的G波段拉曼位移进一步证实了这一结论。本研究结果为固体农业废料的热化学分解提供了新的思路，并为开发缓慢的热解技术以生产有价值的可再生含碳材料提供了见识。

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