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Combining multivariate curve resolution and lumped kinetic modelling for the analysis of lignin degradation by copper-catalyzed Fenton-like systems
Reaction Chemistry & Engineering ( IF 3.4 ) Pub Date : 2022-05-19 , DOI: 10.1039/d2re00056c Andrea M. Berkovic 1, 2 , Mariana R. Costante 1 , Fernando S. García Einschlag 1
Reaction Chemistry & Engineering ( IF 3.4 ) Pub Date : 2022-05-19 , DOI: 10.1039/d2re00056c Andrea M. Berkovic 1, 2 , Mariana R. Costante 1 , Fernando S. García Einschlag 1
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Lignin degradation by Cu(II)-catalyzed Fenton-like systems was studied around neutral pH. Kinetic runs were carried out under dark conditions, at 60 °C and using Cu(II) concentrations below 0.1 mM. The surface response methodology was used to evaluate the effect of reaction conditions on the system behavior. The time required to achieve an absorbance reduction of 80% at 280 nm (t80%) was used as a response variable. To further characterize the process, time-resolved UV-vis absorption spectra, TOC decrease, and H2O2 consumption were measured. Key spectral contributions and the main kinetic trends under different reaction conditions derived from multivariate curve resolution by alternating least squares (MCR-ALS) in combination with the corresponding TOC and H2O2 profiles were used to develop a pseudo-mechanism for lignin degradation. The numerical resolution of the kinetic model was used to fit, by nonlinear regression, the rate constants that better explain MCR-ALS data as well as both TOC and H2O2 profiles. Results show an efficient lignin mineralization at reasonable timescales, with the minimum t80% being 60 min under the most effective conditions. In addition, the lumped kinetic mechanism based on MCR-ALS decomposition of UV-vis spectra properly reproduced the experimental trends and allowed a comprehensive analysis of the organic carbon evolution associated with both the residual lignin and potentially toxic aromatic intermediates. Moreover, the proposed modeling strategy is valuable for technical purposes since it predicts not only the overall treatment rates but also those conditions required to minimize the contribution of secondary reactions that lead to the inefficient consumption of H2O2.
中文翻译：
结合多元曲线分辨率和集中动力学建模分析铜催化类芬顿系统对木质素的降解
在中性pH 附近研究了Cu( II ) 催化的类芬顿系统对木质素的降解。动力学运行在黑暗条件下进行，温度为 60 °C，Cu( II ) 浓度低于 0.1 mM。表面响应方法用于评估反应条件对系统行为的影响。在 280 nm ( t 80% )处达到 80% 的吸光度降低所需的时间用作响应变量。为了进一步表征该过程，时间分辨 UV-vis 吸收光谱、TOC 降低和 H 2 O 2消耗量进行了测量。通过交替最小二乘法 (MCR-ALS) 与相应的 TOC 和 H 2 O 2曲线相结合的多变量曲线分辨率得出的不同反应条件下的关键光谱贡献和主要动力学趋势用于开发木质素降解的伪机制。动力学模型的数值分辨率用于通过非线性回归拟合更好地解释 MCR-ALS 数据以及 TOC 和 H 2 O 2曲线的速率常数。结果显示在合理的时间尺度上有效的木质素矿化，最小t 80%在最有效的条件下为 60 分钟。此外，基于紫外-可见光谱的 MCR-ALS 分解的集中动力学机制正确地再现了实验趋势，并允许对与残留木质素和潜在有毒芳香族中间体相关的有机碳演化进行全面分析。此外，所提出的建模策略对于技术目的是有价值的，因为它不仅可以预测总体处理速率，还可以预测最小化导致 H 2 O 2低效消耗的二次反应的贡献所需的那些条件。
更新日期：2022-05-19
中文翻译：
结合多元曲线分辨率和集中动力学建模分析铜催化类芬顿系统对木质素的降解
在中性pH 附近研究了Cu( II ) 催化的类芬顿系统对木质素的降解。动力学运行在黑暗条件下进行，温度为 60 °C，Cu( II ) 浓度低于 0.1 mM。表面响应方法用于评估反应条件对系统行为的影响。在 280 nm ( t 80% )处达到 80% 的吸光度降低所需的时间用作响应变量。为了进一步表征该过程，时间分辨 UV-vis 吸收光谱、TOC 降低和 H 2 O 2消耗量进行了测量。通过交替最小二乘法 (MCR-ALS) 与相应的 TOC 和 H 2 O 2曲线相结合的多变量曲线分辨率得出的不同反应条件下的关键光谱贡献和主要动力学趋势用于开发木质素降解的伪机制。动力学模型的数值分辨率用于通过非线性回归拟合更好地解释 MCR-ALS 数据以及 TOC 和 H 2 O 2曲线的速率常数。结果显示在合理的时间尺度上有效的木质素矿化，最小t 80%在最有效的条件下为 60 分钟。此外，基于紫外-可见光谱的 MCR-ALS 分解的集中动力学机制正确地再现了实验趋势，并允许对与残留木质素和潜在有毒芳香族中间体相关的有机碳演化进行全面分析。此外，所提出的建模策略对于技术目的是有价值的，因为它不仅可以预测总体处理速率，还可以预测最小化导致 H 2 O 2低效消耗的二次反应的贡献所需的那些条件。
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