JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
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2024
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IF 5.9
Ruixiang Zhou,Weilong Li,Jiayi Li,Jiwen Hu,Xuefeng Gui,Yonglu Dong,Hongcai Yang,Xiaohua Huang,Shudong Lin
Polyurethane materials are widely used, yet their thermal hazards remain underexplored. This study investigates the solvent-free polyaddition of hexamethylene diisocyanate (HDI) and hydroxyethyl acrylate (HEA) under trace moisture conditions. Titration results showed that moisture significantly reduces the reaction rate, while Karl Fischer titration confirmed effective moisture removal using molecular sieves. NMR and FTIR revealed that dehydration enhances isocyanate electrophilicity and hydroxyl nucleophilicity, accelerating the reaction. DSC indicated that moisture induces additional exothermic peaks due to side reactions, and ARC testing showed elevated initial temperatures and reduced adiabatic temperature rise. A kinetic model revealed a consistent reaction order of 0.8, regardless of moisture. T D8 and T D24 were predicted, and a risk matrix assessed the thermal hazards. This study provides essential guidance for the safe and efficient development of novel eco-friendly polyurethane formulations and offers valuable insights for large-scale industrial safety.
研究领域:
材料科学
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化学工程
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安全工程
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产品关联
DOI
高影响因子
International Journal of Chemical Engineering
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2022
·
IF 2.729
Wei Wang,Jiancun Gao,Chenguang Shi,Shengnan Wang,Yujing Li,Xiong Dai,Tianmeng Jiang
Thermal safety during the synthesis of a Grignard reagent under different dosing rates was evaluated in this work. A reaction calorimeter (SIMULAR) was used to investigate the heat release under isothermal experiment in the range of 0.5–2.0 g⋅min−1 dosing rates. The thermal decomposition of the Grignard reagent was analyzed using accelerating rate calorimetry (ARC). Furthermore, the risk assessment of thermal runaway was analyzed using a risk matrix and a Stoessel criticality diagram. The results indicate that decreasing the dosing rate can decrease the risk level of synthesizing the Grignard reagent from class 3 to class 1. However, the risk level was class 3 at different dosing rates when the induction period was considered. In the case of cooling failure, the most hazardous moment was the induction period, followed by the dosing period. These findings provide further evidence that the dose rate of 0.5 g⋅min−1 was safer to produce Grignard reagents.
研究领域:
化学工程
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安全科学
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物理化学
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产品关联
DOI
高影响因子
THERMOCHIMICA ACTA
·
2021
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IF 3.115
Jihe Zhao,Xuefeng Gui,Wenhai Zhang,Shudong Lin,Yuanyuan Tu,Jiwen Hu,Daguang He,Xiaohua Huang
Thermal runaway primarily occurs during the course of copolymerization due to the release of large amounts of heat. In this paper, the thermal risk associated with styrene-methyl methacrylate bulk copolymerization was firstly investigated by differential scanning calorimetry (DSC) and accelerating rate calorimetry (ARC). The result found that the exothermic behavior was greatly affected by the initiator concentration, in contrast the exothermic enthalpy was not. This exothermic behavior was firstly illustrated via polymerization mechanism. The temperature and pressure have changed dramatically during the adiabatic runaway copolymerization, which demonstrated a great potential risk of thermal runaway. Kinetic parameters, such as T NR , T SADT was calculated accordingly, which provided guidance for the safety of storage and transportation. This study will provide a helpful safety assessment for the styrene-methyl methacrylate bulk copolymerization, which is widely used in industry.
研究领域:
化学工程
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材料科学
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安全科学
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产品关联
DOI
高影响因子
JOURNAL OF LOSS PREVENTION IN THE PROCESS INDUSTRIES
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2022
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IF 3.916
Yong Pan,Chaoqin Ren,Gan Wang,Yanjun Wang,Xin Zhang,Juncheng Jiang,Chi-Min Shu
Aiming at the green and sustainable energy substitution and supply, biomass valorization has become a potential strategy to face the energy crisis and increasing demand all over the world from long-term perspectives. Among the bio-based chemicals, γ-valerolactone (GVL) production from hydrogenation of levulinic acid (LA) and its esters has attracted great interests due to its wide applications, such as fuel, solvent, and additives. However, the safety evaluation for this hydrogenation reaction has received few attentions. To fill this gap, thermal hazard evaluation for GVL production from LA hydrogenation by using formic acid (FA) as hydrogen donor was first performed. The process conditions were optimized by using orthogonal experimental method for further calorimetry study. Thermal stability of chemicals and thermal risk of reaction process under adiabatic conditions were investigated by applying differential scanning calorimetry and accelerating rate calorimeter Phi-Tec II, respectively. The results revealed that the chemicals were stable in temperature range from 30 to 250 °C except FA due to its evaporation and decomposition with endothermic behaviors. The reaction process under isothermal and adiabatic conditions demonstrates that the decomposition of FA was rapid and followed by the hydrogenation of LA to GVL. Based on kinetic model under adiabatic conditions and risk matrix , the thermal runaway risk was found to be medium, indicating that certain safety measures should be properly designed and taken for loss prevention. This work could benefit the safety design and thermal risk prevention for GVL production by using FA as hydrogen donor.
研究领域:
化学工程
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能源科学
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安全工程
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产品关联
DOI
高影响因子
PROCESS SAFETY AND ENVIRONMENTAL PROTECTION
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2022
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IF 7.926
Qingwei Song,Lei Ni,Juncheng Jiang,Zhiquan Chen,Gang Fu,Hang Yao,Zhen Cheng
In this study, diphenyl sulfoxide was prepared by oxidizing diphenyl sulfide with hydrogen peroxide using phosphotungstic acid as catalyst in semi-batch mode. In order to optimize the synthesis process, a four-factor three-level Box-Behnken design was adopted. The result showed that under the optimal condition, namely catalyst concentration 0.19 mmol/mol, oxygen-sulfur ratio 1.08, reaction temperature 30 ºC, and dosing time 15 min, the yield of diphenyl sulfoxide could reach up to 79.05%. In addition, the thermal behavior of synthesis process was systematically investigated using a reaction calorimeter (EasyMax 102) equipped with a situ FTIR monitoring. The receivable mechanism is that H 2 O 2 is activated by the catalyst and subsequently reacts with diphenyl sulfide to produce oxidized product. H 2 O 2 was relatively stable when PTA was used as catalyst. Thermal risk index was used to assess the thermal hazard of H 2 O 2 & PTA. Furthermore, risk matrix method as well as Stoessel criticality diagram was used to assess the thermal risk of the process and an unacceptable risk was obtained. One of the main hidden dangers was the potential chemical splatter caused by decomposition of H 2 O 2 . It should be equipped with a pre-set quench or sufficient emergency discharge to avoid further loss. The results of this work proposed a solid foundation for the safe operation of this process and can be further used for scale-up.
研究领域:
化学工程
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安全科学
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DOI
高影响因子
JOURNAL OF THERMAL ANALYSIS AND CALORIMETRY
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2024
·Vol. 149
·期 10
·4827-4838
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IF 3
Li Weilong,Zhang Fengyan,Li Xiaoquan,Hu Jiwen,Gui Xuefeng,Lin Shudong
Epoxy acrylate is produced by esterifying epoxy resin and acrylic acid through a ring-opening reaction. This process is highly exothermic and can be challenging to control gel formation. The thermal hazards of epoxy acrylate preparation were evaluated in this study by investigating the ring-opening esterification reaction between acrylic acid (AA) and bisphenol A epoxy resin (E-51) catalyzed by triethylamine (TEA). The heat release during the reaction process was analyzed using a reaction calorimeter (RC1 mx ) to simulate industrial conditions. Increasing the TEA catalyst content from 0.3 to 1.0 mass% resulted in a significant rise in reaction conversion from 75.35 ± 0.10% to 98.44 ± 0.10%. Differential scanning calorimetry (DSC) and accelerating rate calorimeter (ARC) were used to examine the thermal runaway process during epoxy acrylate synthesis. Increasing the TEA content from 0.3 to 1.0 mass% decreased the initial reaction temperature from 60.16 ± 0.62 to 45.33 ± 0.40 °C and the critical temperature of side reactions from 153.71 ± 1.51 to 117.85 ± 1.19 °C. The severity of the runaway was classified as medium at process temperatures of 80–110 °C. This study highlights the importance of considering reaction conditions to prevent uncontrolled reactions during epoxy acrylate synthesis, providing valuable insights for industrial epoxy acrylate preparation.
研究领域:
化学工程
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安全科学
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产品关联
DOI
高影响因子
JOURNAL OF LOSS PREVENTION IN THE PROCESS INDUSTRIES
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2025
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IF 4.2
Gang Fu,Kai Ma,Juncheng Jiang,Lei Ni
In this study, pendimethalin synthesis was carried out in a microreactor to reduce its thermal risk. First, the nitration reaction was conducted in a semi-batch mode in the micro calorimeter. It was found the process was highly exothermic with a high adiabatic temperature rise (>133 °C). Then the reaction was transformed to a continuous flow mode in a microreactor. Effects of molar ratio, residence time and reaction temperature on the thermal behavior of the nitration process as well as the yield of pendimethalin were investigated and analyzed. Response surface methodology was used to optimize the reaction condition. The results showed that under the optimum condition in the microreactor, the yield reached 54.32%. The space-time yield in the microreactor was 1.38 g⋅L −1 ∙s −1 , which was two orders of magnitude higher than that in the batch reactor. Further, a risk assessment using a recently developed method (m-ITHI) was carried out to compare the thermal hazards of the nitration process in the microreactor and the batch reactor. The index for the continuous flow mode was 3.77, corresponding to a risk level of Class I, which was safer than the batch mode with a risk level of Class II. Overall, this paper showcased an inherently safer design with the microreactor and provided a theoretical basis for the one-step synthesis of pendimethalin.
研究领域:
化学工程
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安全工程
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产品关联
DOI
高影响因子
PROCESS SAFETY PROGRESS
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2022
·Vol. 41
·期 4
·783-792
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IF 1.294
Xue Zhou,Yue Pan,Lifan Zhang,JiaJia Jiang
Epoxidized soybean oil was widely used in industrial production. However, the epoxidized soybean oil production process releases a lot of heat, which could cause a runaway reaction, resulting in fires and explosions. Therefore, the thermal risk of the soybean oil epoxidation reaction process has been studied. Differential scanning calorimetry was used to investigate the thermal stability of reaction materials. The parameters such as initial exothermic temperature and reaction heat were obtained based on heat flow diagrams. EasyMax was used to analyze the soybean oil epoxidation reaction under different reaction temperatures and dosing rate conditions. The maximum temperature of the synthesis reactions, time to maximum rate under adiabatic condition ( TMR ad ), and adiabatic temperature rise ( ∆ T ad ) were obtained by analyzing the epoxidation reaction. An adiabatic accelerating calorimeter was used to study the adiabatic decomposition of reaction products to obtain safety criteria such as adiabatic temperature rise and maximum reaction rate. The results obtained by the risk matrix evaluation method show that the risk level of the soybean oil epoxidation process was unacceptable. According to the results of the runaway scenario analysis method, the risk level of soybean oil epoxidation reaction was level 5. Therefore, the reaction process needs to be improved to ensure safe production.
研究领域:
化学工程
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安全科学
✓ 已验证
DOI
高影响因子
JOURNAL OF LOSS PREVENTION IN THE PROCESS INDUSTRIES
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2025
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IF 4.2
Yong Pan,Chaoqin Ren,Jingshu Jin,Yanjun Wang,Sébastien Leveneur,Juncheng Jiang
Sustainable and renewable energy plays a key role in coping with the global energy crisis and increasing demand for development. Biomass valorization is regarded as a potential way to substitute the fossil raw materials in various fields such as electricity, fuel, chemicals, pharmaceuticals, etc. Among the numerous chemicals derived from biomass, γ-valerolactone (GVL) is identified to be an important platform chemical with wide applications. Hydrogenation of levulinic acid (LA) with formic acid (FA) as hydrogen donor for GVL production attracts great attention from the principle of green chemistry. Compared to the enormous efforts on catalyst design, few studies focus on the safety issues of this hydrogenation process, such as thermal runaway risk. Aiming to fill this gap, hydrogenation of LA with FA catalyzed by synthesized homogeneous catalyst Ru-TsDPEN was chosen as a typical efficient process for the production of GVL. In particular, solvent effect and acid-base synergetic effect by adjusting acid-base loading were investigated for process optimization and further calorimetry study. Apparent pH was measured to indicate the strength of acidity and alkalinity of the reaction mixture. Thermal stability of chemicals and thermal risk assessment were performed by differential scanning calorimetry and accelerated rate calorimeter Phi-Tec II, respectively. The results showed significant acid-base synergetic effect on the desired catalytic system and thermal risk was medium under the optimized condition, which needs specific safety measures for loss prevention. Suggestions for inherently safer chemical process for GVL production with FA as hydrogen donor were proposed.
研究领域:
化学工程
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可再生能源
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绿色化学
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产品关联
DOI
高影响因子
JOURNAL OF LOSS PREVENTION IN THE PROCESS INDUSTRIES
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2022
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IF 3.916
Yuying Zhang,Lei Ni,Hang Yao,Qiang Chen,Juncheng Jiang,Chi-Min Shu,Zhiquan Chen,Chenghao Li,Wen Zhu
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 (Ac 2 O) and TBHP under the catalysis of sulphuric acid (H 2 SO 4 ) 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 Ac 2 O 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.
研究领域:
化学工程
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安全科学
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物理化学
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产品关联
DOI
高影响因子
Reaction Chemistry & Engineering
·
2023
·Vol. 8
·期 8
·1993-2000
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IF 3.9
Shichun Weng,Wei Feng,Wenqian Wu,Zichao Guo,Junjie Li,Huanhuan Chen,Liping Chen,Wanghua Chen
3-Amino-4-amidoximinofurazan (AAOF) is an important precursor for the synthesis of high energy furazan energetic materials. The traditional batchwise synthesis approach has the shortcomings of low productivity and high possibility of thermal runaway. This article aims to develop a continuous-flow and safe synthesis approach for AAOF. To achieve this goal, the precipitation problems appearing in the oximation and cyclization reaction stages have been first tackled by diluting the hydroxylamine hydrochloride and sodium hydroxide solution with water, which also reduced the thermal risk of AAOF synthesis. The continuous-flow platform for AAOF synthesis has been established, and the continuous-flow operation parameters have been optimized. The optimal temperatures for the nitrosation–rearrangement coupling reaction, neutralization reaction, oximation and cyclization were 15 °C, 15 °C, 25 °C and 115 °C, respectively. The optimal set retention times for these four stages were 15 min, 5 min, 60 min and 10 min, respectively. The continuous-flow synthesis approach offered an optimal yield of AAOF (95%), which is comparable to the result of batch operation. The total flow rate of the whole process is 10.34 mL min−1, and the final productivity is calculated to be about 0.546 mol h−1 of AAOF. The main merits for the continuous-flow synthesis of AAOF include the following: (1) the reaction time is only one-third of that for batch operation and (2) continuous-flow operation is inherently safe due to the lower liquid holdup and stronger temperature control ability. This work is supposed to be beneficial to the continuous and safe synthesis of AAOF.
研究领域:
化学工程
·
能源材料科学
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产品关联
DOI
高影响因子
PROCESS SAFETY AND ENVIRONMENTAL PROTECTION
·
2023
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IF 7.8
Hang Yao,Gang Fu,Yuqing Ni,Lei Ni,Juncheng Jiang,Han Zhang,Zhen Cheng,Zhiquan Chen
Nitro-m-xylenes (NMX) was synthesized in semi-batch mode via m-xylene nitration using nitric acid-acetic anhydride (HNO 3 -Ac 2 O) as nitrating reagent in this work. The nitration process was optimized by response surface methodology . The yield of NMX could reach 92.40% under the optimal conditions of jacket temperature of 20 °C, 0.15 mol of HNO 3 and 0.19 mol of Ac 2 O. Corresponding large reaction enthalpy (Δ H =240.9 kJ/mol) and adiabatic temperature rise (Δ T ad,r =398.1 K) indicated the serious hazards of nitration in a thermal runaway scenario. Pyrolysis of nitration products occurred at about 320–400 °C by differential scanning calorimetry tests. The reaction order of the pyrolysis was determined to be 1.2 by adiabatic kinetic analysis . Thermal risk of the nitration process was assessed to be acceptable and level 1 via the risk matrix and Stoessel criticality diagram analyses, respectively. Furthermore, detailed nitration mechanisms for NO 2 + generation and aromatic substitution were presented. The activation free enthalpy and free energy parameters for each step were calculated by density functional theory (DFT). These findings can help understand the exothermic sources of m-xylene nitration and guide the intrinsically safer design and scale-up of the process.
研究领域:
化学工程
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安全科学
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理论化学
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产品关联
DOI
高影响因子
危险品化学品经营许可证（带存储）