过氧化脲微波辅助煤炭脱硫的机理

IF 6.9 2区环境科学与生态学 Q1 ENGINEERING, CHEMICAL

Process Safety and Environmental Protection Pub Date : 2024-10-26 DOI:10.1016/j.psep.2024.10.086

Hai Yang , Jin Liu , Bo Zhang , Tao Cheng , Debing Zou , Xing Lv

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引用次数: 0

摘要

为有效去除煤炭中的有机硫，提高资源利用效率，设计了一种创新的微波辅助过氧化脲脱硫系统。为了证明微波与过氧化脲协同作用的脱硫效果，实验组设置了不同微波频率的实验组和常规热解对照组。实验结果表明，在 1000 W 微波辐照和过氧化脲的促进下，脱硫效率可达 67.29 %，比常规热解提高了 38.32 %，而常规热解仅为 28.97 %。根据傅立叶变换红外（FTIR）分析，微波与过氧化脲配位的脱硫效果从宏观角度得到了解释。量子化学计算选择了亚苄基硫醇、二苄基硫醚和二苄基二硫醚作为模型化合物。模拟结果表明，脱硫路径能垒的变化与实验材料的转化一致，证实了模拟的准确性。硫醇的含硫键会被破坏形成硫化氢，未被破坏的键会留在有机物中。被氧化后，含硫键会断裂，形成水溶性磺酸自由基。硫醚中未氧化的硫键会被破坏，生成不稳定的苯基自由基和游离硫自由基。为了达到稳定性，苯基自由基可以配对形成二苯基乙烷或与其他自由基（如-H）结合。相反，硫自由基只能与氢自由基反应生成硫化氢。然而，系统中氢自由基的有限性限制了脱硫效率。过氧化脲氧化后，硫醚会形成砜。含硫键断裂后会直接生成苯基和二氧化硫，从而减少了对氢自由基的依赖。模拟了微波协同过氧化脲实验的三维脱硫路径，并将其转换为分析键的断裂和形成机理。该研究证明，微波与过氧化脲协同作用可强化脱硫过程。它为煤的清洁绿色利用提供了一种高效方法，有利于支持环境可持续发展。

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Mechanism of microwave-assisted coal desulfurization with urea peroxide

To effectively remove organic sulfur from coal for higher resource efficiency, an innovative microwave-assisted urea peroxide for desulfurization system was designed. The experimental group with different microwave frequencies and the conventional pyrolysis control group were set up to prove the desulfurization effect of microwave in coordination with urea peroxide. The experimental results showed that under 1000 W microwave irradiation and the promotion of urea peroxide, the desulfurization efficiency can reach 67.29 %, with an increase of 38.32 % while the conventional pyrolysis is only 28.97 %. According to the Fourier transform infrared (FTIR) analysis, the effectiveness of microwave coordination with urea peroxide for desulfurization is explained from macroscopic point of view. Benzylidene thiol, dibenzyl sulfide, and dibenzyl disulfide were selected as model compounds for the quantum chemical calculation. The simulation results demonstrated that the changes in the pathway energy barriers for desulfurization align with the experimental material transformations, confirming the accuracy of the simulation. The sulfur-containing bonds of mercaptans will be destroyed to form hydrogen sulfide, and the undestroyed bonds will remain in the organic matter. After being oxidized, the sulfur-containing bond will break to form a water-soluble sulfonic acid free radical. The unoxidized sulfur bonds of thioethers will be destroyed to generate unstable phenyl free radicals and free sulfur radicals. To achieve stability, phenyl free radicals can pair to form diphenylethane or combine with other radicals (such as •H). In contrast, sulfur free radicals can only react with hydrogen radicals to form hydrogen sulfide. However, the limited availability of hydrogen radicals in the system restricts the desulfurization efficiency. After oxidation by urea peroxide, the thioethers will form sulfones. The sulfur-containing bonds will be fractured and directly generate phenyl and sulfur dioxide, which reduces the dependence on hydrogen free radicals. The three-dimensional desulfurization path of microwave collaboration with urea peroxide experiment was simulated and converted to the analytical bond breaking and formation mechanism. This study proved that microwave synergizes with urea peroxide can intensify the desulfurization process. It provides a high-efficiency method for the clean and green utilization of coal, which is conducive to supporting environmentally sustainable development.

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来源期刊

Process Safety and Environmental Protection 环境科学-工程：化工

CiteScore

11.40

自引率

15.40%

发文量

929

审稿时长

8.0 months

期刊介绍： The Process Safety and Environmental Protection (PSEP) journal is a leading international publication that focuses on the publication of high-quality, original research papers in the field of engineering, specifically those related to the safety of industrial processes and environmental protection. The journal encourages submissions that present new developments in safety and environmental aspects, particularly those that show how research findings can be applied in process engineering design and practice. PSEP is particularly interested in research that brings fresh perspectives to established engineering principles, identifies unsolved problems, or suggests directions for future research. The journal also values contributions that push the boundaries of traditional engineering and welcomes multidisciplinary papers. PSEP's articles are abstracted and indexed by a range of databases and services, which helps to ensure that the journal's research is accessible and recognized in the academic and professional communities. These databases include ANTE, Chemical Abstracts, Chemical Hazards in Industry, Current Contents, Elsevier Engineering Information database, Pascal Francis, Web of Science, Scopus, Engineering Information Database EnCompass LIT (Elsevier), and INSPEC. This wide coverage facilitates the dissemination of the journal's content to a global audience interested in process safety and environmental engineering.