Reaction mechanism and process safety assessment of acid-catalyzed synthesis of tert-butyl peracetate |
| |
| Affiliation: | 1. Jiangsu Key Laboratory of Hazardous Chemicals Safety and Control, College of Safety Science and Engineering, Nanjing Tech University, Nanjing, 210009, China;2. School of Environment and Safety Engineering, Changzhou University, Changzhou, 213164, Jiangsu, China;3. School of Materials Engineering, Changshu Institute of Technology, Changshu, 215500, China;4. Department of Safety, Health, and Environmental Engineering, National Yunlin University of Science and Technology, 123, University Rd., Sec. 3, Douliou, Yunlin, 64002, Taiwan, ROC;5. BASF Corporation, 1609 Biddle Avenue, Wyandotte, MI, 48192, USA;1. College of Safety and Environmental Engineering, Shandong University of Science and Technology, Qingdao, 266590, China;2. Mine Disaster Prevention and Control-Ministry of State Key Laboratory Breeding Base, Shandong University of Science and Technology, Qingdao, 266590, PR China;3. Qingdao Intelligent Control Engineering Center for Production Safety Fire Accident, Qingdao, 266590, PR China;1. Physikalisch-Technische Bundesanstalt (PTB), Braunschweig, Germany;2. thuba AG, Basel, Switzerland;3. Otto-von-Guericke-Universität Magdeburg, Magdeburg, Germany;1. College of Safety Science and Engineering, Nanjing Tech University, Nanjing, 211816, China;2. Department of Process Engineering & Applied Science, Dalhousie University, Halifax, B3H 4R2, Canada;3. Fire & Explosion Protection Laboratory, Northeastern University, Shenyang, 110819, China;1. College of Safety Science and Engineering, Nanjing Tech University, Nanjing, 210009, China;2. Shenzhen Urban Public Safety and Technology Institute, Shenzhen, 518019, China;3. Shenzhen Key Laboratory of Disaster City Digital Twin, Shenzhen, 518019, China;1. Anhui Engineering Laboratory of Explosive Materials and Technology of Anhui University of Science and Technology, Huainan, 232001, China;2. Postdoctoral Mobile Station of Safety Science and Engineering, Anhui University of Science and Technology, Huainan 232001, China;3. School of Chemical Engineering, Anhui University of Science and Technology, Huainan, 232001, China;4. Postdoctoral Mobile station of Mineral Engineering, Anhui University of Science and Technology, Huainan, 232001, China;5. Department of Chemical and Materials Engineering, National Yunlin University Science and Technology (YunTech), 123, University Rd. Sec. 3, Douliou, 64002, Yunlin, Taiwan, ROC |
| |
| Abstract: | Esterification during the synthesis of tert-butyl peracetate (TBPA) is highly exothermic. Since peroxides (tert-butyl hydroperoxide TBHP and TBPA) are intrinsically thermosensitive, this synthesis process is potentially dangerous. In this work, the exothermic process and mechanism of TBPA synthesis using acetic anhydride (Ac2O) and TBHP under the catalysis of sulphuric acid (H2SO4) were clarified by calorimetry, infrared spectroscopy, and high-performance liquid chromatography. To substantially alleviate the thermal risk of the reaction, and to feasibly select appropriate synthesis conditions for ensuring the process safety of the synthesized products, several sets of isothermal and isoperibol experiments were performed using calorimetry. The intermediates formed and concentration changes during the reaction were monitored using in-situ Fourier-transform infrared spectroscopy. Differential scanning calorimetry and adiabatic calorimetry were used to assess the thermal hazard of the materials during the synthesis process. The reaction mechanism was verified using density functional theory calculations. The results revealed that a controlled increase in exothermicity could be achieved by adding aqueous TBHP to Ac2O in semi-batch experiments in isothermal mode, and accordingly, the highest yield was 95.71%. Experiments combined with theoretical calculations revealed that the primary exothermic event was the TBPA formation reaction, and the removal of a large amount of water from TBHP prior to this is favourable for the reaction. The criticality classes of this reaction were of Grade 2. |
| |
| Keywords: | Esterification Acetic anhydride Process safety Reaction mechanism Semi-batch experiment |
| 本文献已被 ScienceDirect 等数据库收录！ |
|
