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过氧化物是一类具有高度反应性的化学物质，广泛应用于化工、制药、塑料合成等多个工业领域，但其高氧化性和复杂反应热力学特性导致显著安全隐患。研究表明，过氧化物分解反应焓值达-400～-200 kJ/mol,苯甲酰过氧化物在70℃时分解速率可达150mg/min,且对温度、压力及环境成分变化极为敏感。通过ReaxFF分子动力学模拟和事故案例分析发现，微量金属离子可使H_2O2分解速率增加2～5倍。针对这些分解机制与特性，研究探讨了微通道反应器和新型耐腐蚀材料等本质安全解决方案，结合自动化监控系统有望使生产过程事故率有效降低。此外，该研究还系统揭示了过氧化物在不同工况下的危险性特征，提出的安全管理措施和技术创新方案为过氧化物产业的安全管理与技术革新提供了重要的理论支持和实践指导。
Abstract：Peroxides are a class of highly reactive chemical substances widely used in various industrial sectors, including chemical engineering, pharmaceuticals, and plastic synthesis. However, their high oxidizing properties and complex thermodynamic characteristics pose significant safety hazards. Research indicated that the enthalpy values of peroxide decomposition reactions range from-400 to-200 kJ/mol, with benzoyl peroxide reaching a decomposition rate of 150 mg/min at 70 ℃, demonstrating extreme sensitivity to variations in temperature, pressure, and environmental composition. Through ReaxFF molecular dynamics simulations and accident case studies, it was found that trace metal ions may accelerate H_2O2 decomposition by 2 to 5 times. To address these decomposition mechanisms and characteristics, this study explored intrinsic safety solutions such as microchannel reactors and novel corrosion-resistant materials. Combined with automated monitoring systems, these approaches hold promise for effectively reducing accident rates in production processes. Furthermore, the research systematically revealed the hazardous characteristics of peroxides under different operating conditions. The proposed safety management measures and technological innovations provided important theoretical support and practical guidance for the safety management and technological advancement of the peroxide industry.
[1] POURSAITIDIS E T,GKIZIS P L,TRIANDAFILLIDI I,et al.Organocatalytic activation of hydrogen peroxide:Towards green and sustainable oxidations[J].Chemical Science,2024,15(4):1177-1203.
[2] LIU Y K,WEI B,YANG L,et al.Recent research progress in hydrogen peroxide synthesized by electrocatalytic process with two-electron transfer:A brief review[J].Journal of Environmental Chemical Engineering,2024,12(3):112972.
[3] MURPHY E C,FRIEDMAN A J.Hydrogen peroxide and cutaneous biology:translational applications,benefits,and risks[J].Journal of the American Academy of Dermatology,2019,81(6):1379-1386.
[4] BITYUKOV O V,SERDYUCHENKO P Y,KIRILLOV A S,et al.Advances in radical peroxidation with hydroperoxides[J].Beilstein Journal of Organic Chemistry,2024,20(1):2959-3006.
[5] TIAN Q B,JIANG Y,DUAN X G,et al.Low-peroxide-consumption fenton-like systems:The future of advanced oxidation processes[J].Water Research,2025,268:122621.
[6] QAISER M A,KHAN S,QURESHI W A,et al.Eco-friendly sacrificial agents-free photocatalytic synthesis of hydrogen peroxide:Recent innovations and future prospects[J].International Journal of Hydrogen Energy,2024,95(2):935-956.
[7] ZHU S X,YAN J X,ZHOU Y,et al.Pyridinium-catalyzed decarboxylative borylation of benzoyl peroxides[J].Green Synthesis and Catalysis,2021,2(3):299-302.
[8] LUO K,YANG W-C,WEI K,et al.Di-tert-butyl peroxide-mediated radical c(sp2/sp3)-s bond cleavage and group-transfer cyclization[J].Organic Letters,2019,21(19):7851-7856.
[9] TANG X,LI J,LI J,et al.Peroxidation of methyl ethyl ketone catalyzed by UiO-66 and the thermal stability analysis[J].Inorganic Chemistry Communications,2024,170:113474.
[10] YU A D,ZHOU N C,LIANG X M,et al.Process hazard and decomposition mechanism of benzoyl peroxide in the presence of incompatible substances[J].Journal of Molecular Liquids,2023,372:121146.
[11] SONG Q W,NI L,JIANG J C,et al.Process optimization and thermal hazard analysis of the preparation of diphenyl sulfoxide using hydrogen peroxide as oxidant[J].Process Safety and Environmental Protection,2022,168(4):698-711.
[12] FU T Y,GENT P,KUMAR V.Efficacy,efficiency and safety aspects of hydrogen peroxide vapour and aerosolized hydrogen peroxide roomdisinfection systems[J].Journal of Hospital Infection,2012,82(4):199-205.
[13] GÓMEZ GARCÍA M Á,DOBROSZ-GÓMEZ I,OJEDA TORO J C.Thermal safety assessment for catalytic decomposition of hydrogen peroxide by dynamic analysis[J].Process Safety and Environmental Protection,2017,109(1):46-54.
[14] YUAN S,YANG M,RENIERS G.Integrated process safety and process security risk assessment of industrial cyber-physical systems in chemical plants[J].Computers in Industry,2024,155:104056.
[15] AB RAHIM MS,RENIERS G,YANG M,et al.Risk assessment methods for process safety,process security and resilience in the chemical process industry:A thorough literature review[J].Journal of Loss Prevention in the Process Industries,2024,88:105274.
[16] MOHAMMADI H,JAFARI M J,POUYAKIA2.3N M,et al.Development of a new index for assessing the inherent safety level of chemical processes using a multi-criteria fuzzy decision-making approach[J].Journal of Loss Prevention in the Process Industries,2024,87:105238.
[17] BAI M,QI M,SHU C M,et al.Why do major chemical accidents still happen in China:Analysis from a process safety management perspective[J].Process Safety and Environmental Protection,2023,176(3):411-420.
[18] WU Y,YE H,DONG H G.An inherently safer design approach based on process safety time for batch chemical reaction processes[J].Process Safety and Environmental Protection,2023,171(2):353-364.
[19] PU W,ABDUL RAMAN A A,HAMID M D,et al.Process & occupational safety integrated inherently safer chemical plant design:Framework development and validation[J].Journal of Loss Prevention in the Process Industries,2024,87:105204.
[20] SOLTANZADEH A,ZAREI E,MAHDINIA M,et al.An integrated approach to assess safety and security risks in chemical process industries[J].Journal of Loss Prevention in the Process Industries,2024,90:105344.
[21] GUNTHER M R.Probing the free radicals formed in the metmyoglobin-hydrogen peroxide reaction[J].Free Radical Biology and Medicine,2004,36(11):1345-1354.
[22] MILAEVA E R.The role of radical reactions in organomercurials impact on lipid peroxidation[J].Journal of Inorganic Biochemistry,2006,100(3):905-915.
[23] DAVIES A G.Organosilicon peroxides:radicals andrearrangements[J].Tetrahedron,2007,63(42):10385-10405.
[24] SHI X,PAN Y,GONG Z,et al.Pyrolysis behaviors of di-tert-butyl peroxide in gas and liquid phases:A ReaxFF molecular dynamics simulation[J].Fuel,2023,351(6):86-99.
[25] GALLIGAN J J,BAEUMNER A J,DUERKOP A.Recent advances and trends in optical devices and sensors for hydrogen peroxide detection[J].TrAC Trends in Analytical Chemistry,2024,180:117948.
[26] WEHRSTEDT K D,KNORR A,SCHUURMAN P.The “Mini Closed Pressure Vessel Test (MCPVT)” as a screening or classification test for explosive properties of organic peroxides[J].Journal of Loss Prevention in the Process Industries,2003,16(6):523-531.
[27] UMRÃO S,JANG M-H,OH J-H,et al.Microwave bottom-up route for size-tunable andswitchable photoluminescent graphene quantum dots using acetylacetone:New platform for enzyme-free detection of hydrogen peroxide[J].Carbon,2015,81(9):514-524.
[28] RODRIGUES A P,DA FONSECA L M,DE FARIA OLIVEIRA O M,et al.Oxidation of acetylacetone catalyzed by horseradish peroxidase in the absence of hydrogen peroxide[J].Biochimica et Biophysica Acta (BBA)-General Subjects,2006,1760(12):1755-1761.
[29] RAZMARA Z,RAZMARA F,SHAHRAKI S.Selective peroxidative conversion of ethylbenzene catalyzed by Mn(II) complex under solvent-free conditions[J].Inorganic Chemistry Communications,2024,161:112078.
[30] ZHANG W,LI M,LIN L,et al.Peroxyacetic acid activation by cobalt-doped peanut shell biochar for efficient CBZ degradation:Role of organic radicals,singlet oxygen,and high-valent cobalt species[J].Separation and Purification Technology,2024,330:125592.
[31] ZANG N,QIAN X M,SHU C M,et al.Parametric sensitivity analysis for thermal runaway in semi-batch reactors:Application to cyclohexanone peroxide reactions[J].Journal of Loss Prevention in the Process Industries,2021,70:104436.
[32] SHABALIN I I,SIMANOV V A.Thermal decomposition kinetics of technical isopropylbenzene hydroperoxide (IPBHP)[J].Petroleum Chemistry USSR,1966,5(1):73-78.
[33] YAN H M,YIN N,LUO J P,et al.Runaway reaction investigation of di-tert-butyl peroxide using adiabatic calorimetry[J].Thermochimica Acta,2023,726:179555.
[34] 马纪，黄国霞，李军生，等.基于铜离子(Ⅱ)类过氧化物酶性质可视化比色法检测过氧化氢[J].光谱学与光谱分析，2022,42(9):2795-2799.
[35] YANG Y,YE Y H,ZHU P,et al.Reaction rate and thermal effects of hydrogen peroxide decomposition in microfluidic chips containing channel-type silver catalysts[J].Catalysis Science & Technology,2024,14(11):3113-3124.
[36] CHEN Z,WANG Y,JI W,et al.Thermal decomposition kinetics of benzoyl peroxide based on thermogravimetric analysis and DFT simulations[J].Organic Process Research & Development,2024,28(9):3674-3684.
[37] MAHMOUD H R,SAIF M,NAGHMASH M A.Synthesis of M/BS@Ag core-shell nanoparticles (M:Cu,Ni,Co,Fe or Mn ions and BS:Bi12SiO20) as novel catalysts for the catalytic decomposition of hydrogen peroxide[J].Journal of Physics and Chemistry of Solids,2022,161:110389.
[38] YANG Y,LIU M,YOU X,et al.A novel bimetallic Fe-Cu-CNT catalyst for effective catalytic wet peroxide oxidation:reaction optimization and mechanism investigation[J].Chemical Engineering Journal,2024,479(6):54-65.
[39] ARORA N,BICKNELL L M.Assessment of increased public interest in the safety of benzoyl peroxide[J].International Journal of Dermatology,2024,63(8):192-193.
[40] VARALA R,KAMSALI M M A,SEELLA R,et al.Di-tert-butyl peroxide (DTBP)-promoted heterocyclic ring construction[J].Current Organic Chemistry,2024,29(4):274-300.
[41] DAI S,LIANG M,CHENG H,et al.Thermal decomposition characteristics of BHT and its peroxide (BHTOOH)[J].BMC Chemistry,2024,18(1):21-32.
[42] LIANG W X,YE Z X,HU D F,et al.Performance evaluation approach for accelerating rate calorimeters by means of Joule heat[J].Thermochimica Acta,2024,735(9):52-58.
[43] LI X C,HUANG Y Y,WU Z,et al.High conversion hydrogen peroxide microchannel reactors:Design and two-phase flow instability investigation[J].Chemical Engineering Journal,2021,422(4):47-55.
[44] ATCHISON B.Automated well control:A step change in safety[J].Digital Chemical Engineering,2022,3:100022.
[45] SADEGHI H,ZHANG X Q.Towards safer tower crane operations:An innovative knowledge-based decision support system for automated safety risk assessment[J].Journal of Safety Research,2024,90(8):272-294.
[46] LEE C,SCHÄTZLE S,LANG S A,et al.Design considerations of a perception system infunctional safety operated and highly automated mobile machines[J].Smart Agricultural Technology,2023,6:100346.
[47] 张小龙，张毅城，李庆朝，等.SBA-15分子筛负载对甲苯磺酸催化合成过氧化二异丙苯的性能和反应过程模拟[J].高等学校化学学报，2024,45(6):84-92.
[48] 宋军，邓秀琼，纪红兵.有机过氧化物在生产、储运过程中的危险与可操作性分析[J].中国安全生产科学技术，2015,11(1):156-160.
[49] LIN C P,TSENG J M,CHANG Y M,et al.Green thermal analysis for predicting thermal hazard of storage and transportation safety for tert-butyl peroxybenzoate[J].Journal of Loss Prevention in the Process Industries,2012,25(1):1-7.
[50] 江美丽，郑俊鹤，王犇.过氧化二异丙苯的热稳定性及安全性研究[J].安全与环境学报，2014,14(1):117-121.
[51] BECKER L C,CHERIAN P A,BERGELD W F,et al.Safety assessment of hydrogen peroxide as used in cosmetics[J].International Journal of Toxicology,2024,43(3):5-63.
[52] CHI J H,WU S H,CHARPENTIER J C,et al.Thermal hazard accident investigation of hydrogen peroxide mixing with propanone employing calorimetric approaches[J].Journal of Loss Prevention in the Process Industries,2012,25(1):142-147.
[53] WU S H,CHI J H,HUANG C C,et al.Thermal hazard analyses and incompatible reaction evaluation of hydrogen peroxide by DSC[J].Journal of Thermal Analysis and Calorimetry,2010,102(2):563-568.
[54] LIN M L,CHEN K Y,WU S H,et al.Thermal explosion simulation of hydrogen peroxide in three types of vessels by explosion models[J].Research Journal of Chemistry and Environment,2010,14(2):88-92.
[55] HONG S H,TANG Y L,WANG S F.Investigation on critical heat flux of flow boiling in parallel microchannels with large aspect ratio:Experimental and theoretical analysis[J].International Journal of Heat and Mass Transfer,2018,127(12):55-66.
[56] CHU X Y,CHEN W,TANG X J,et al.Research on the hydrogen production performance of methanol reforming microchannels with multi-scale structures[J].International Journal of Hydrogen Energy,2022,47(90):38155-38169.
[57] 朱红伟，朱云峰，冯俊杰，等.微通道内火焰淬熄安全尺寸研究[J].高校化学工程学报，2022,36(6):807-814.
[58] 周伟，李新颖，钟雨晨，等.甲醇重整制氢微反应器的研究进展[J].厦门大学学报(自然科学版),2021,60(3):598-613.
[59] 庞焦.PO/SM法和CHPPO法生产环氧丙烷的技术对比[J].云南化工，2024,51(5):123-126.
[60] 朱永明，屠振密，李宁，等.钛及钛合金表面绿色化学处理新进展[J].电镀与涂饰，2010,29(2):37-39.
[61] XIONG R,LI Y,REN Z.Research on on-line detection method and system for nitrate in groundwater[J].Applied Sciences-Basel,2023,13(17):12-21.
[62] ASUA J M.On-line control of emulsion polymerization reactors:A perspective[J].Canadian Journal of Chemical Engineering,2023,101(9):4907-4913.
[63] WANG J,AI C,GUO F,et al.Research of on-line monitoring technology based on laser triangulation for surface morphology of extreme high-speed laser cladding coating[J].Coatings,2023,13(3):64-79.
[64] CHEN Y H,PARVEZ A M,SCHMID M,et al.20 kW pilot scale steam-oxygen gasification of solid recovered fuel with a focus on newly developed off-line and on-line tar measurement methods[J].Fuel Processing Technology,2022,227:107096.
[65] 周梦鑫，吴军，樊志彬，等.大气腐蚀在线监测技术研究现状与展望[J].中国腐蚀与防护学报，2023,43(1):38-46.
基本信息:
中图分类号:TQ086
引用信息:
[1]孟凡志.过氧化物的工业危险特性及安全对策研究[J].安全、健康和环境,2026,26(02):12-23.
基金信息:
中国石化科技部项目(224243),25万吨/年流化床蒽醌法制双氧水工艺包开发及工程放大研究
2025-03-10
2025
2026-02-10
2026
2
2026-02-15
2026-02-15