Thermal safety assessment for solid organic peroxides

The thermal hazards of dicumyl peroxide (DCP) and benzoyl peroxide (BPO), self-reactive chemicals are identified and characterized using high-pressuredifferential scanning calorimeter, and simultaneous thermogravimetric analyzer, a C80 micro-calorimeter is used. The apparent exothermic onset temperature of DCP is found to be between the range of 112–122 °C for different heating rates in DSC tests. There are two coupled peaks of BPO around 105 °C at both the heating rates of 4.0 and 8.0 °C/min while no endothermic peak showed at lower heating rates. Furthermore, another endothermic peak appears immediately after the exothermic peak at about 211 °C of DCP under high-pressure conditions. For BPO, the endothermic peak before the exothermic peak disappears as the pressure increases to 1.0 and 1.5 MPa. The average values of apparent activation energy calculated by Flynn-Wall-Ozawa and Kissinger-Akahira-Sunose methods during the conversion rate between 15 and 75% of DCP are 80.69 and 74.05 kJ/mol, and that of BPO are 119.96 and 112.93 kJ/mol, respectively. According to the isothermal tests, the thermal decomposition of DCP behaviors is an n-th order reaction while BPO conforms to the laws of autocatalytic reaction.     

Inherently safer reactors: Improved efficiency of 3-picoline N-oxidation in the temperature range 110–125 °C

Alkylpyridine N-oxides are important intermediates in the pharmaceutical and agrochemicals industries. The N-oxides are produced via the homogeneously catalyzed oxidation of the respective alkylpyridines using a 50% excess of hydrogen peroxide. The competitive hydrogen peroxide decomposition produces oxygen in the flammable environment of alkylpyridines and thus forms a key hazard for this reaction. In this work, the N-oxidation was performed under pressure in the temperature range of 110–125 °C with different catalyst concentrations. It was shown that temperature had an undisputable positive effect on the N-oxidation efficiency. The accurate measurement of the pressure rise due to decomposition was difficult. However, only 5% of the added H₂O₂ decomposed when stoichiometric quantities were employed, even in the temperature of 110 °C. The N-oxidation was very efficient, even when the lowest concentration of catalyst employed in this study was used.     

过氧化苯甲酰合成工艺热危险性分析

采用RC1e反应量热仪对过氧化苯甲酰(BPO)合成工艺危险性进行研究,测试不同Na OH溶液初始浓度(1.96 mol/L、3.93 mol/L、7.14 mol/L)下反应的放热历程,获得BPO合成反应过程中的热危险性参数,并采用PHI-TECⅡ绝热加速量热仪对产物进行热稳定性分析,最后评估该反应热风险。结果表明,Na OH浓度为7.14 mol/L时,反应初期放热速率慢,热累积度大,后期反应剧烈,绝热温升(ΔTad)及热失控时工艺反应达到的最高温度(MTSR)最大。热稳定性试验表明,合成的粗产物BPO初始分解温度、活化能、指前因子、最大放热速率到达时间为24 h时的对应温度(TD24)均低于纯BPO。利用合成粗产物BPO的TD24对反应进行危险度评估,该工艺热危险性等级均为5级,工艺危险性大。     

Environmentally friendly hide unhairing: Enzymatic-oxidative unhairing as an alternative to use of lime and sodium sulfide

Various studies have been conducted to develop technologies that minimize the environmental concerns associated with the leather industry. The use of enzymes and oxidizing products during the unhairing step reduces pollution by tanneries as well as process time. In this study, were used an enzymatic extract produced by a strain of Bacillus subtilis – BLBc 11 – and hydrogen peroxide to conduct enzymatic-oxidative unhairing as an alternative to the conventional process (lime and sodium sulfide). Tests for enzymatic-oxidative unhairing were performed by applying crude enzymatic extract at concentrations of 100 U g⁻¹ and 300 U g⁻¹ of hide and hydrogen peroxide at concentrations of 4% and 8%. Tests were conducted comparing the proposed unhairing method, the conventional unhairing and purely enzymatic unhairing, performed with crud enzymatic extract produced by strain BLBc 11. The results showed that the proposed enzymatic-oxidative unhairing method can be used as an alternative to lime and sodium sulfide.     

Wet bench reactive hazards of cleaning stages in semiconductor manufacturing processes

According to the research from FM Global (Factory Mutual Insurance Company), most of the incidents that have occurred in semiconductor plants in the past two decades were reported as “Fire Cases”. They claim that the fires in wet chemical cleaning processes were mainly caused by heater failure. However, depending on the process conditions, electrical heaters are designed to turn off automatically when the temperature reaches a set point. Therefore, a thorough study of the situations related to possible fires in wet chemical cleaning processes is necessary.

This study focused on the incompatible behaviors of cleaning materials used in the wet bench stage. These results can be applied to determine the causes of fires in the wet bench stage from using reactive chemicals for cleaning purposes.

Another purpose of this study was to investigate the potential hazards of widely used chemicals (hydrogen peroxide, concentrated sulfuric acid, hydrochloric acid and isopropyl alcohol) within similar processes in semiconductor plants. Experimental data were also verified in order to establish a concentration triangular diagram, which could be used to identify a combustion, deflagration or even detonation zone. Finally, this study can provide basic design data for an inherently safer process to avoid potential hazards caused by dangerous mixtures, which may result in large property loss in semiconductor plants.     

2-Methylpyridine-N-oxidation runaway studies

Calorimetry has been used in order to identify the runaway behavior of 2-methylpyridine-N-oxidation (2-picoline-N-oxidation). Experiments were performed in an Automatic Pressure Tracking Adiabatic Calorimeter (APTAC), employing 2-methylpyridine-N-oxide (2-picoline-N-oxide) with or without catalyst, 2-methylpyridine-N-oxide, hydrogen peroxide, 2-methylpyridine (2-picoline) and catalyst, and 2-methylpyridine, hydrogen peroxide and catalyst. Approximately 16.5 g of aqueous solutions were used in 100 ml closed glass cells in all but one measurement. Measurements were performed isothermally or employing the Heat-Wait-Search (HWS) technique. During reaction runaway, any excess of hydrogen peroxide and the produced 2-methylpyridine-N-oxide decompose releasing non-condensable gases and raising the pressure. It was found that the reaction runaway is condition-sensitive. Catalyst, the presence of 2-picoline and/or its N-oxide, affect hydrogen peroxide and/or 2-picoline-N-oxide decomposition rates. Further research accompanied by analytical measurements of the gas and liquid phase would provide indications in regard to the decomposition mechanisms followed in those cases.     

Thermal hazard analysis of triacetone triperoxide (TATP) by DSC and GC/MS

Thermal degradation of triacetone triperoxide (TATP) was studied using differential scanning calorimetry (DSC) and gas chromatography/mass spectrometry (GC/MS). TATP, a potential explosive material, is powerful organic peroxide (OP) that can be synthesized by available chemicals, such as acetone and hydrogen peroxide in the laboratory or industries. The thermokinetic parameters, such as exothermic onset temperature (T₀) and heat of decomposition (ΔH_d), were determined by DSC tests. The gas products from thermal degradation of TATP were identified using GC/MS technique.In this study, H₂O₂ was mixed with propanone (acetone) and H₂SO₄ catalysis that produced TATP. The T₀ of TATP was determined to be 40 °C and E_a was calculated to be 65 kJ/mol. A thermal decomposition peak of H₂O₂ was analyzed by DSC and two thermal decomposition peaks of H₂O₂/propanone were determined. Therefore, H₂O₂/propanone mixture was applied to mix acid that was discovered a thermal decomposition peak (as TATP) in this study. According to risk assessment and analysis methodologies, risk assessment of TATP for the environmental and human safety issue was evaluated as 2-level of hazard probability rating (P) and 6-level of severity of consequences ratings (S). Therefore, the result of risk assessment is 12-point and was evaluated as “Undesirable” that should be enforced the effect of control method to reduce the risk.     

Canadian wildlife-vehicle collisions: An examination of knowledge and behavior for collision prevention

Objectives: This study examines drivers' responses to wildlife on Canadian roads. The objective of this paper is to demonstrate that knowledge of what to do when encountering wildlife on the road does not always translate into the appropriate behavior to avoid a collision. Methods: Data from the Traffic Injury Research Foundation's (TIRF) 2016 Road Safety Monitor (RSM) and data from TIRF's National Fatality Database from 2000 to 2014 were analyzed to test hypotheses based on the theory of planned behavior. Logistic regression and piecewise linear regression were used. Results: Analyses of the data showed that the prevalence of fatal WVCs has remained relatively consistent, and that the majority of persons killed in WVCs died in crashes that involved large mammals. The majority of fatalities occurred in the summer (182 or 38.4%) and fall (163 or 34.4%). The RSM data revealed that 60.9% [50.5, 70.4] of respondents who previously hit an animal indicated that drivers should slow down and steer straight when confronted with wildlife, while 47.3% [37.1, 57.6] of respondents indicated this was the action they took when they hit wildlife. Comparatively, 59.5% [56.6, 62.4] of respondent who have not hit an animal indicated this was an appropriate response. Additionally, 33.2% [24, 44] of respondents who previously hit an animal indicated that drivers should swerve to avoid a collision with wildlife, while 37.5% [28.2, 47.8] of respondents indicated this was the action they took when they hit wildlife. Conclusions: Many drivers are unaware of what the safest method of WVC prevention is. Further, while a subgroup of drivers may have the knowledge and intention to slow down and steer straight even if the animal is directly in the path, i.e., the safest possible behavior, they are not necessarily adopting this behavior. Practical applications: Recommendations are formulated to address this discrepancy, as well as practical applications.     

A hybrid approach to faults detection and diagnosis in batch and semi-batch reactors by using EKF and neural network classifier

This work deals with a new hybrid approach for the detection and diagnosis of faults in different parts of fed-batch and batch reactors. In this paper, the fault detection method is based on the using of Extended Kalman Filter (EKF) and statistical test. The EKF is used to estimate on-line in added to the state of reactor the overall heat transfer coefficient (U). The diagnosis method is based on a probabilistic neural network classifier. The Inputs of the probabilistic classifier are the input–output measurements of reactor and the parameter U estimated by EKF, while the outputs of the classifier are fault types in reactor. This new approach is illustrated for simulated as well as experimental data sets using two cases of reactions: the first is the oxidation of sodium thiosulfate by hydrogen peroxide and the second is alkaline hydrolyse of ethyl benzoate in homogeneous hydro-alcoholic. Finally, the combination of the estimated parameter U using EKF and probabilistic neural network classifier provided the best results. These results show the performance of the proposed approach to monitoring the semi-batch and batch reactors.     

Thermal risk in batch reactors: Case of peracetic acid synthesis

The present paper deals with accidents risk in batch reactors. It identifies the conditions for the occurrence of a thermal runaway and develops a probabilistic approach to assess the relevant risk. It investigates also the conditions for optimal synthesis of peracetic acid (PAA) with hydrogen peroxide (HP) and acetic acid (AA). The kinetic model of reversible reaction and side reaction of PAA synthesis is used to predict reactor temperature and molar ratio of PAA by ASPEN PLUS software. A sensitivity analysis is performed under different conditions such as constant temperature or adiabatic process with different concentrations of sulfuric acid. Assuming a prior cooling system failure, the conditions for reaction runaway triggering a thermal accident are identified in the case of PAA synthesis. Monte Carlo simulations are used in order to calculate the conditional probability of accident and optimize the synthesis of PAA.     

Essential hazard and process safety assessment of para-toluene sulfonic acid through calorimetry and advanced thermokinetics

Para-toluene sulfonic acid is a typical intermediary for the synthesis of pharmaceuticals, pesticides, and dyes and is a catalyst for organic synthesis. The consumption of para-toluene sulfonic acid used in organic synthesis has increased substantially. The toluene sulfonation process is the central path for synthesizing para-toluene sulfonic acid in China. However, the process has risks and has resulted in numerous disasters. This study utilized a reaction calorimeter 1 to reproduce the commercial toluene sulfonation process in a laboratory. The para-toluene sulfonic acid product was examined with an accelerating rate calorimeter and through differential scanning calorimetry. Both differential and integral isoconversional methods were used to determine the thermal stability of and appropriate thermokinetic models for para-toluene sulfonic acid. The safety parameters of para-toluene sulfonic acid were estimated. The research findings can be used for optimization of the toluene sulfonation process and for safe handling of para-toluene sulfonic acid.     

Two-way left turn lane or raised median? A truck safety based study

Introduction: Due to their size and weight, trucks require more space and time to make left turns when exiting or entering a roadway. Therefore, appropriate median treatments are critical for roadways with substantial truck traffic. The two-way left-turn lane (TWLTL) and raised median (RM) are the two types of median most commonly used to improve roadway mobility and manage roadway accessibility. However, previous studies on these median treatments have focused primarily on the general traffic conditions and geometric roadway features without considering the truck traffic impact. Method: To fill this gap, this study investigates the truck impacts on TWLTL and RM by considering two major influencing factors – truck percentage and roadway access point density. First, a negative binomial regression is developed to analyze the relationship between crash frequency and various influencing factors. Next, the crash rate difference analysis between the TWLTL and RM is conducted to identify critical points for these two factors. Results: The findings indicate that, compared with RM, TWLTL has significantly higher crash frequency, especially for roadways with a higher percentage of trucks. This suggests that the percentage of trucks should be taken into consideration when selecting an appropriate type of roadway median.     

Thermal hazard evaluation for iso-octanol nitration with mixed acid

2-Ethylhexyl nitrate (2-EHN), an important additive to diesel fuel, is produced from the nitration of iso-octanol with HNO₃–H₂SO₄ mixed acid. In this study, the differential scanning calorimeter (DSC), accelerating rate calorimeter (ARC) and reaction calorimeter were used to analyze the thermal stability of 2-EHN and the thermal hazard of iso-octanol nitration. Four samples with different ratios of 2-EHN to mixed acid were tested using DSC. The results indicated that more mixed acid could catalyze the decomposition of 2-EHN. Three samples were tested using ARC and the results showed that sample 4 contained the lowest onset temperatures, T_D8 and T_D24. This shows that there is a higher probability of triggering the decomposition of the product 2-EHN from the iso-octanol nitration process. This conclusion was verified using RC1e tests at different temperatures. The RC1e experiments also indicated that the overall heat generation of these reactions was considerably large despite the high yields of the nitration process at 45 °C and 55 °C. This heat generation makes these semi-batch processes difficult to control, especially on a pilot or plant scale. Based on the maximum temperature of the synthesis reaction (MTSR) corrected by the yield, the only acceptable semi-batch process is the nitration reaction at 10 °C.     

Toward an inherently safer design and operation of batch and semi-batch processes: The N-oxidation of alkylpyridines

This work shows an application of inherent safety principles to a reaction widely used in the pharmaceutical industry. More specifically, it incorporates the teachings of Trevor Kletz into the design of an inherently safer process for the N-oxidation of alkylpyridines. This reaction is of interest because of the hazards resulting from the undesired, gas-generating decomposition of hydrogen peroxide, the oxidizing agent. The generation of oxygen, combined with the flammability of the alkylpyridines, represents a serious fire and explosion hazard for this process. The purpose of this paper is to demonstrate how an inherently safer process can be potentially achieved by designing improved reactors and by assessing conditions that reduce or eliminate the hazards. Furthermore, it is shown that such improvement in safety increases the efficiency of the process and results in a cost reduction.     

Evaluation of thermal reaction for two azo compounds by using 20-L apparatus and calorimetry

Azo compounds are widely involved in the industrial processes of dyes, pigments, initiators, and blowing agents. Unfortunately, these compounds have a bivalent unstable –NN– composition, which can be readily broken when the ambient temperature is elevated. Self-accelerating decomposition might cause a runaway reaction and lead to a fire, explosion, or leakage when the cooling system fails or other events occur. This study investigated the explosion properties, thermal stability parameters, and thermal hazard and mechanism of 2,2′–azobisisobutyronitrile (AIBN) and 2,2′–azobis–2–methylbutyronitrile (AMBN). We used a 20-L apparatus, vent sizing package 2, synchronous thermal analysis, and differential scanning calorimetry under explosive, adiabatic, and dynamic conditions to acquire the explosive curves, thermal curves, and thermodynamic parameters of the substances. Moreover, the differential isoconversional method (Friedman method) and ASTM E698 equation were employed to obtain the apparent activation energy E_a. All the experimental results revealed that AIBN is more dangerous than AMBN. The E_a of AIBN was lower than that of AMBN. The results can be used to construct an azo compound thermal hazard database for use for searches and reference examples by industry and related research areas.     

The effect of contextual information on professional judgment: Reliability and biasability of expert workplace safety inspectors

Introduction: A critical aspect of occupational safety is workplace inspections by experts, in which hazards are identified. Scientific research demonstrates that expectation generated by context (i.e., prior knowledge and experience) can bias the judgments of professionals and that individuals are largely unaware when their judgments are affected by bias. Method: The current research tested the reliability and biasability of expert safety inspectors’ judgments. We used a two-study design (Study 1, N = 83; Study 2, N = 70) to explore the potential of contextual, task-irrelevant, information to bias professionals’ judgments. We examined three main issues: (1) the effect that biasing background information (safe and unsafe company history) had on professional regulatory safety inspectors’ judgments of a worksite; (2) the reliability of those judgments amongst safety inspectors and (3) inspectors’ awareness of bias in their judgments and confidence in their performance. Results: Our findings establish that: (i) inspectors’ judgments were biased by historical contextual information, (ii) they were not only biased, but the impact was implicit: they reported being unaware that it affected their judgments, and (iii) independent of our manipulations, inspectors were inconsistent with one another and the variations were not a product of experience. Conclusion: Our results are a replication of findings from a host of other professional domains, where honest, hardworking professionals underappreciate the biasing effect of context on their decision making. The current paper situates these findings within the relevant research on safety inspection, cognitive bias and decision making, as well as provides suggestions for bias mitigation in workplace safety inspection. Practical Application: Our results have implications for occupational health and safety given that inspection is an integral aspect of an effective safety system. In addition to our findings, this study contributes to the literature by providing recommendations regarding how to mitigate the effect of bias in inspection.     

Effect of pyrolysis and oxidation characteristics on lauric acid and stearic acid dust explosion hazards

The effect of pyrolysis and oxidation characteristics on the explosion sensitivity and severity parameters, including the minimum ignition energy MIE, minimum ignition temperature MIT, minimum explosion concentration MEC, maximum explosion pressure P_max, maximum rate of pressure rise (dP/dt)_max and deflagration index K_st, of lauric acid and stearic acid dust clouds was experimentally investigated. A synchronous thermal analyser was used to test the particle thermal characteristics. The functional test apparatuses including the 1.2 L Hartmann-tube apparatus, modified Godbert-Greenwald furnace, and 20 L explosion apparatus were used to test the explosion parameters. The results indicated that the rapid and slow weight loss processes of lauric acid dust followed a one-dimensional diffusion model (D1 model) and a 1.5 order chemical reaction model (F1.5 model), respectively. In addition, the rapid and slow weight loss processes of stearic acid followed a 1.5 order chemical reaction model (F1.5 model) and a three-dimensional diffusion model (D3 model), respectively, and the corresponding average apparent activation energy E and pre-exponential factor A were larger than those of lauric acid. The stearic acid dust explosion had higher values of MIE and MIT, which were mainly dependent on the higher pyrolysis and oxidation temperatures and the larger apparent activation energy E determining the slower rate of chemical bond breakage during pyrolysis and oxidation. In contrast, the lauric acid dust explosion had a higher MEC related to a smaller pre-exponential factor A with a lower amount of released reaction heat and a lower heat release rate during pyrolysis and oxidation. Additionally, due to the competition regime of the higher oxidation reaction heat release and greater consumption of oxygen during explosion, the explosion pressure P_m of the stearic acid dust was larger in low concentration ranges and decayed to an even smaller pressure than with lauric acid when the concentration exceeded 500 g/m³. The rate of explosion pressure rise (dP/dt)_m of the stearic acid dust was always larger in the experimental concentration range. The stearic acid dust explosion possessed a higher P_max, (dP/dt)_max and K_st mainly because of a larger pre-exponential factor A related to more active sites participating in the pyrolysis and oxidation reaction. Consequently, the active chemical reaction occurred more violently, and the temperature and overpressure rose faster, indicating a higher explosion hazard class for stearic acid dust.     

The influence of ClO− and acidity in the reaction between H2O2 and CuCl2

The potentially explosive reaction of hydrogen peroxide (H₂O₂) and copper chloride (CuCl₂) was investigated. Pressure tests revealed that the reaction was strongly temperature - dependent and can easily undergo runaway reaction. Nevertheless, there was only a slight pressure increase at the low temperatures studied or when using low concentrations of CuCl₂. Under the conditions generating the slight pressure increase, hypochlorite anions (ClO⁻) are generated and the acidity increases. As the reaction reaches completion, ClO⁻ disappears, and the acidity decreases. Interestingly, the addition of phosphate buffer to maintain the weakly acid conditions led to a runaway reaction, and the use of basic ClO⁻ promoted the exothermic reaction. Based on the results, acidity has a strong impact on the reaction behaviour.     

Effects of metal ions on thermal hazard of tert-butyl peroxy-3,5,5-trimethylhexanoate

As a commonly used initiator for polyethylene, tert-butyl peroxide 3,5,5-trimethylhexanoate (TBPTMH), with the molecular formula of C₁₃H₂₆O₃, is more likely to decompose and cause fires and explosions. Understanding the thermal risks of TBPTMH mixed with common metal ions, potentially in containers and pipes, is important. In this work, by using differential scanning calorimetry (DSC) and Phi-Tec adiabatic calorimetry, the effects of CuCl₂, FeCl₃, CuBr_2, and FeBr₃ on the thermal decomposition of TBPTMH were investigated. Adiabatic kinetic analysis was performed and the apparent activation energy (E_a) was calculated by thermodynamic analysis. Time to maximum rise under adiabatic conditions (TMR_ad) and the self-accelerating decomposition temperature (SADT) under different packing qualities were reckoned. It was found that the thermal risk of TBPTMH was increased while mixing these metal ions, especially CuBr₂. To ensure the safety of the substance in process industry, the temperature of TBPTMH in the presence of metal should be governed below 39.48 °C. This work was expected to provide some guidance for improving the process safety of TBPTMH.     

A thermal hazard risk evaluation of emulsion polymerisation and vinyl acetate monomers in the latex manufacturing process

Latex is extensively used in industrial products. However, completing some processes at scale leads to unacceptable levels of risk that need to be quantified and mitigated. Systemic risks must be eliminated wherever possible, and safety takes priority over efficiency and quality. To assess the process risks accurately, four raw materials were examined in this study: polyvinyl acetate (PVA), latex process-initiator-ammonium persulfate (APS) and hydrogen peroxide (H₂O₂), and vinyl acetate monomer (VAM). The physicochemical composition of the PVA latex process was determined via calorimeters, including differential scanning calorimetry (DSC) and vent sizing package 2 (VSP2). The calorimetry results showed that the protective colloid was a critical component in the polymerisation reaction. In addition, when adding initiators to the system, it is vital to observe the normal ratio of materials and keep the stirring system operating. The scenario system also simulated the effects of shutting down various inhibitory programs, including the build-up of free radicals that could result in a runaway reaction when the initiator was added in excess. On the other hand, the result of the risk matrix displayed as a medium level, indicating that although the probability of an accident is low, the resulting severity is at disaster level. As a result, this study provides process safety engineers with a reliable frame of reference for assessing the potential dangers in the PVA latex manufacturing process.