Green synthesis of tert-butyl hydroperoxide via oxidation of tert-butanol in various reactors

IF 2.8 4区生物学 Q3 BIOTECHNOLOGY & APPLIED MICROBIOLOGY

Journal of chemical technology and biotechnology Pub Date : 2025-02-07 DOI:10.1002/jctb.7821

Angus Shiue, Jyh-Cheng Jeng, Kai-Yen Chin, Jie-An Chen, Ming-Hao Lin, Shu-Mei Chang, Graham Leggett

{"title":"Green synthesis of tert-butyl hydroperoxide via oxidation of tert-butanol in various reactors","authors":"Angus Shiue, Jyh-Cheng Jeng, Kai-Yen Chin, Jie-An Chen, Ming-Hao Lin, Shu-Mei Chang, Graham Leggett","doi":"10.1002/jctb.7821","DOIUrl":null,"url":null,"abstract":"<div>\n \n \n <section>\n \n <h3> BACKGROUND</h3>\n \n <p>In this study, tert-butyl hydroperoxide (TBHP) was prepared by the oxidation of TBA via the catalysis of sulfuric acid by the green and environmentally-friendly hydrogen peroxide oxidant sustainable method using micro-channel reactor - Corning Advanced-Flow Reactors (AFR), AFR connected pipe, tubular reactor, and batch reactor. The effects of process parameters such as temperature, molar ratio of catalyst, molar ratio of oxidant, and residence time to TBHP on the reaction performance were systematically investigated to explore the conversion and the ratio of main and by-products. The reliability of this method at a certain temperature was verified with a kinetic study.</p>\n </section>\n \n <section>\n \n <h3> RESULTS</h3>\n \n <p>The reaction temperature was 70 °C, the optimum molar ratio of TBA to H<sub>2</sub>SO<sub>4</sub> was determined to be 1:1, and the optimum molar ratio of H<sub>2</sub>O<sub>2</sub> to TBA was determined to be 0.8. AFR and AFR connected pipe process significantly improved the efficiency and safety of the reaction and greatly increased TBA conversion and TBHP yield compared with the tubular and batch reactor. In the range of 60 to 70 °C, a second order kinetic expression characterizes the tert-butyl alcohol conversion well (R<sup>2</sup> = 0.9499).</p>\n </section>\n \n <section>\n \n <h3> CONCLUSIONS</h3>\n \n <p>Our findings revealed that the observed correlation is a practical tool to figure the TBA conversion and TBHP and di-tert-butyl peroxide (DTBP) production. The activation energies of the corresponding reactions AFR and AFR external pipeline were 45.26 and 86.98 kJ mol<sup>−1</sup>, respectively. The overall heat transfer coefficient achieved in the Corning AFR was validated as scalable. © 2025 Society of Chemical Industry (SCI).</p>\n </section>\n </div>","PeriodicalId":15335,"journal":{"name":"Journal of chemical technology and biotechnology","volume":"100 4","pages":"841-857"},"PeriodicalIF":2.8000,"publicationDate":"2025-02-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of chemical technology and biotechnology","FirstCategoryId":"5","ListUrlMain":"https://onlinelibrary.wiley.com/doi/10.1002/jctb.7821","RegionNum":4,"RegionCategory":"生物学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q3","JCRName":"BIOTECHNOLOGY & APPLIED MICROBIOLOGY","Score":null,"Total":0}

引用次数: 0

Abstract

BACKGROUND

In this study, tert-butyl hydroperoxide (TBHP) was prepared by the oxidation of TBA via the catalysis of sulfuric acid by the green and environmentally-friendly hydrogen peroxide oxidant sustainable method using micro-channel reactor - Corning Advanced-Flow Reactors (AFR), AFR connected pipe, tubular reactor, and batch reactor. The effects of process parameters such as temperature, molar ratio of catalyst, molar ratio of oxidant, and residence time to TBHP on the reaction performance were systematically investigated to explore the conversion and the ratio of main and by-products. The reliability of this method at a certain temperature was verified with a kinetic study.

RESULTS

The reaction temperature was 70 °C, the optimum molar ratio of TBA to H₂SO₄ was determined to be 1:1, and the optimum molar ratio of H₂O₂ to TBA was determined to be 0.8. AFR and AFR connected pipe process significantly improved the efficiency and safety of the reaction and greatly increased TBA conversion and TBHP yield compared with the tubular and batch reactor. In the range of 60 to 70 °C, a second order kinetic expression characterizes the tert-butyl alcohol conversion well (R² = 0.9499).

CONCLUSIONS

Our findings revealed that the observed correlation is a practical tool to figure the TBA conversion and TBHP and di-tert-butyl peroxide (DTBP) production. The activation energies of the corresponding reactions AFR and AFR external pipeline were 45.26 and 86.98 kJ mol⁻¹, respectively. The overall heat transfer coefficient achieved in the Corning AFR was validated as scalable. © 2025 Society of Chemical Industry (SCI).

查看原文本刊更多论文

在不同反应器中通过氧化叔丁醇绿色合成过氧化叔丁基

本研究采用绿色环保的双氧水氧化剂可持续法，采用微通道反应器-康宁先进流动反应器（AFR）、AFR连接管式反应器、管式反应器和间歇式反应器，在硫酸催化下将TBA氧化制备了叔丁基过氧化氢（TBHP）。系统考察了反应温度、催化剂的摩尔比、氧化剂的摩尔比、停留时间等工艺参数对反应性能的影响，探讨了反应的转化率和主副产物的比例。通过动力学研究验证了该方法在一定温度下的可靠性。结果反应温度为70℃，TBA与H2SO4的最佳摩尔比为1:1，H2O2与TBA的最佳摩尔比为0.8。与管式和批式反应器相比，AFR和AFR连接管工艺显著提高了反应效率和安全性，TBA转化率和TBHP产率也大大提高。在60 ~ 70℃范围内，叔丁醇转化的二阶动力学表达式具有较好的表征（R2 = 0.9499）。结论：观察到的相关性是计算TBA转化率与TBHP和过氧化二叔丁基（DTBP）产量的实用工具。AFR和AFR外管道反应的活化能分别为45.26和86.98 kJ mol−1。在康宁AFR中实现的整体传热系数被验证为可扩展的。©2025化学工业学会（SCI）。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

求助全文

约1分钟内获得全文求助全文

来源期刊

Journal of chemical technology and biotechnology 工程技术-工程：化工

CiteScore

7.00

自引率

5.90%

发文量

268

审稿时长

1.7 months

期刊介绍： Journal of Chemical Technology and Biotechnology(JCTB) is an international, inter-disciplinary peer-reviewed journal concerned with the application of scientific discoveries and advancements in chemical and biological technology that aim towards economically and environmentally sustainable industrial processes.