Evaluation on thermal hazard of methyl ethyl ketone peroxide by using adiabatic method

Ketone peroxides are capable of spontaneous decomposition, and violent decomposition occurs if they contact with strong mineral acids. In this paper, an adiabatic method is used to investigate the thermal hazard of Methyl Ethyl Ketone Peroxide (MEKPO) and mixture of MEKPO with sulfuric acid in order to understand the effect of the contamination of sulfuric acid on the thermal stability of MEKPO. On the basis of experimental results, kinetic parameters of exothermic reaction of MEKPO and mixture of MEKPO with 1% sulfuric acid are estimated, and thermal hazard parameters, such as the initial exothermic temperature and the adiabatic temperature rise are obtained under real adiabatic condition. It can be seen from the results that the thermal hazard of MEKPO with sulfuric acid is more remarkable than that of MEKPO itself.     

过氧化甲乙酮的热危险性研究

为研究过氧化甲乙酮(MEKPO)在运输与储存中的热危险性,利用差示扫描量热仪(DSC)对质量分数为52%的MEKPO溶液(以2,2,4-三甲基-1,3-戊二醇二异丁酸酯为溶剂)进行测试,得到其起始分解温度T0约为40℃,比放热量ΔH约为1.24 kJ/g。运用加速量热仪(ARC)对3种MEKPO溶液(40%,45%和52%)及MEKPO纯品(化学纯)在绝热条件下进行了热分解测试,并在此基础上,借助Semenov热爆炸模型,计算得到上述样品在50 kg包件下的自加速分解温度(TSADT)分别为65.64,63.72,55.88和51.17℃。研究结果表明,加入稀释稳定剂是降低MEKPO热危险性的有效途径,且MEKPO混合物中其质量分数越大,其危险性越高。     

Use of isoperibolic calorimetry for the study of the effect of water concentration,temperature and reactor venting on the rate of hydroxylamine thermal decomposition

Hydroxylamine, NH₂OH, thermal decomposition has been responsible for two serious accidents. However, its reactive behavior and the synergy of factors affecting the rate of its decomposition are not understood. In this work, isoperibolic calorimetric measurements were performed in a metal reactor, in the temperature range 130–150 °C, employing 30–80 ml solutions containing 1.4–20 g of pure hydroxylamine (2.8–40 g of the supplied reagent). The calorimetric measurements were performed in order to assess the effects that NH₂OH concentration, temperature and reactor venting has on NH₂OH rate of decomposition. The measurements showed that increased concentration or temperature, results in faster reactions and probably higher pressure generation per mass of reactant, with concentration having a more pronounced effect. However, when both factors work synergistically the result is dramatically worse in terms of reaction rate. The pressure generation is also different, thus indicating that different reaction pathways predominate each time. Venting the produced gases in stages resulted in the highest mass loss of the solution.     

The thermal hazard evaluation of 1,1-di (tert-butylperoxy) cyclohexane by DSC using non-isothermal and isothermal-kinetic simulations

1,1-Di (tert-butylperoxy) cyclohexane (DTBPH) has been widely employed in the chemical industry. Unfortunately, organic peroxides have been involved in many serious fires and explosions in manufacturing processes, storage, and transportation. This study investigated the thermokinetic parameters by isothermal kinetic and non-isothermal-kinetic simulation, using differential scanning calorimetry (DSC) tests. DSC was applied to assess the kinetic parameters, such as kinetic model, frequency factor (ln k₀), activation energy (E_a), reaction order, and heat of reaction (ΔH_d). Comparisons of non-isothermal and isothermal-kinetic model simulation led to a beneficial kinetic model of thermal decomposition to predict the thermal hazard of DTBPH. Simulations of a 0.5 L Dewar vessel and 25 kg barrel commercial package in liquid thermal explosion models were performed and compared to the results in the literature. From the results, the optimal conditions for use of DTBPH to avoid violent runaway reactions during the storage and transportation were determined. This study established the features of thermal decomposition that could be executed as a reduction of energy potential and storage conditions in view of loss prevention.     

Thermal hazard evaluation for γ-valerolactone production by using formic acid as hydrogen donor

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.     

Thermal kinetics analysis of polymerization reaction of styrene-ethylbenzene system

To explore the reaction thermodynamics of a styrene-ethylbenzene mixed system, a differential scanning calorimetry (DSC) analysis was performed on the mixed system with styrene: ethylbenzene mass ratios of 1:0, 4:1, 3:2, and 2:3 at heating rates of 2.5, 5, 7.5, and 10 K/min. The activation energy of the mixed reaction system was calculated using the model-free Kissinger kinetic method, to determine a mixed system of relative stability mixing proportion. The thermodynamic parameters of the styrene-ethylbenzene mixture system at the optimal ratio were obtained using an adiabatic accelerating calorimeter. Further, dynamic thermal parameters such as the activation energy of the hybrid system, pre-exponential factor and order of reaction, TMR, TMRad, and T_D24 were calculated.     

Biosorption of zinc(II) on rapeseed waste: Equilibrium studies and thermogravimetric investigations

The removal of heavy metals from aqueous effluents so as to avoid their toxic, bioaccumulation and biomagnification effects to humans and environment is usually realized by means of physical, chemical treatment, and biological processes. The aim of this study is to evaluate the potential of rapeseed waste from biodiesel production as a biosorbent for Zn(II) ions.The ability of the rapeseed waste for Zn(II) biosorption exhibited a maximum at pH 4.5–5. The removal efficiency of Zn(II) from solution with an initial concentration of 72 mg L⁻¹ varied from 39% to 89% for an increase of the rapeseed waste dose from 2 to 30 g L⁻¹. The amount of Zn(II) retained on the tested rapeseed increased with increasing metal ion concentration, but the Zn(II) sorption percentage decreased. The equilibrium data are fitted to the Langmuir isotherm better than to the Freundlich isotherm. The kinetics of Zn(II) biosorption process follows a pseudo-second order model. The thermal stability of the rapeseed before and after Zn(II) biosorption was studied by thermogravimetric analysis. It was found that the zinc loaded rapeseed exhibits a better initial thermal stability than the original rapeseed, presumably due to the cross linking generated by the intermolecular complexation of Zn(II) ions. In both cases, the thermal decomposition takes place according to some reassembling kinetic models, in two phases with order n reactions. The results of this study strongly suggest the possibility to use rapeseed as an effective biosorbent for Zn(II) ions removal from aqueous effluents (municipal/industrial wastewaters).     

Detailed thermal and kinetic modeling of cumene hydroperoxide decomposition in cumene

The characterization of thermal decomposition of cumene hydroperoxide (CHP) in cumene from kinetic point of view is of great interest for industrial applications. However, the efforts done so far by the researchers lead only to the availability of single kinetic laws (first order, autocatalytic, etc.) whose usefulness is strongly limited by the presence in the starting solutions of some impurities. A detailed model aiming at simulating both, thermal and kinetic behavior of the system, is now presented. In other words, the proposed model tries to simulate CHP thermal decomposition process at varying reaction conditions (different initial temperature, in the range 120–160 °C, different initial CHP concentrations, addition of α-methylstyrene to CHP solutions in cumene) and during isothermal, scanning and adiabatic runs. A good capability of the model is observed to simulate the system behavior by using data collected under isothermal and adiabatic conditions and during scanning calorimetric runs. It is important to stress that the use of the model proposed in the present investigation does not require the adoption of adjustable parameters.     

聚碳酸酯/ABS/蒙脱土纳米复合材料的热重动力学分析

利用直接熔融插层技术制备聚碳酸酯/ABS聚合物合金/蒙脱土纳米复合材料.用热重分析法(TGA)研究了聚合物合金和纳米复合材料的热氧化降解行为.分别采用了无模式函数法(model-freemethod)和多元非线性回归法(multivariate nonlinearregression method)进行动力学评价.由此确定了整个降解过程的表观动力学参数.研究结果表明聚碳酸酯/ABS/蒙脱土纳米复合材料具有较高的热稳定性和阻燃性.两种材料的热氧化降解模型是一个两步分解过程.     

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.     

Optimization of biodiesel production by alkali-catalyzed transesterification of used frying oil

Biodiesel as an alternative fuel for fossil diesel has many benefits such as reducing regulated air pollutants emissions, reducing greenhouse gases emissions, being renewable, biodegradable and non-toxic. In this study, used frying oil was applied as a low cost feedstock for biodiesel production by alkali-catalyzed transesterification. The design of experiments was performed using a double 5-level-4-factor central composite design coupled with response surface methodology in order to study the effect of factors on the yield of biodiesel and optimizing the reaction conditions. The factors studied were: reaction temperature, molar ratio of methanol to oil, catalyst concentration, reaction time and catalyst type (NaOH and KOH). A quadratic model was suggested for the prediction of the ester yield. The p-value for the model fell below 0.01 (F-value of 27.55). Also, the R² value of the model was 0.8831 which indicates the acceptable accuracy of the model. The optimum conditions were obtained as follows: reaction temperature of 65 °C, methanol to oil molar ratio of 9, NaOH concentration of 0.72% w/w, reaction time of 45 min and NaOH as the more effective catalyst. In these conditions the predicted and observed ester yields were 93.56% and 92.05%, respectively, which experimentally verified the accuracy of the model. The fuel properties of the biodiesel produced under optimum conditions, including density, kinetic viscosity, flash point, cloud and pour points were measured according to ASTM standard methods and found to be within specifications of EN 14214 and ASTM 6751 biodiesel standards.     

Study on decomposition of hydroxylamine/water solution

The risk evaluation of decomposition of hydroxylamine(HA)/water solution was studied experimentally. The thermal property of HA/water solution was studied from the calorimetric data obtained using the differential thermal analysis (DTA). The intensity of decomposition was studied on the basis of the results of the mini closed pressure vessel test (MCPVT) and the pressure vessel test (PVT) in addition to the steel tube test.The thermal property of HA/water solution was evaluated on the basis of results of the DTA. The heat-release onset temperatures using the no-treated stainless steel cells were more than 70 K below those measured using the GSC. This result implies that the heat-release onset temperature depends on the materials of sample cell. On the other hand, the heat of reaction did not depend on the materials of sample cell.The intensity of the thermal decomposition was investigated on the basis of results of the MCPVT, the PVT and the steel tube test. The intensity of the thermal decomposition increased as the HA concentration increased in the MCPVT. The intensity of the thermal decomposition increased greatly when the HA concentration was beyond 80wt.% in the MCPVT. It was elucidated that the thermal decomposition of HA 70wt.%/water solutions was very violent in the PVT. In addition, HA/water solutions of more than 80wt.% concentration could detonate in the steel tube test. HA 80 wt.% water/solution was easily detonated by a detonator without RDX in the steel tube test.In addition, the decomposition hazard of HA/water solution by the metal ion and the iron powder was studied in this paper. The thermal stability of HA85%/water solution with the iron ion or the iron powder was discussed on the basis of the heat-release onset temperature by the DTA. The heat-release onset temperatures decreased when the concentration of the iron ion or the iron powder increased in the DTA measurements. The reactiveness of HA/water solution with the metal ion of iron, manganese, nickel, chromium and copper was examined by measuring the mass loss of HA/water solution after the metal ion was added to HA/water solution at room temperature. The reactiveness of HA/water solution with the iron powder was also studied in this paper. The ferrous ion, the ferric ion and the iron powder reacted with HA/water solution. Ignition automatically began when the 0.2wt.% ferric ion solution was added to HA85wt.%/water solution. The mass loss rate depended on the HA concentration greater than the iron ion concentration. The mass loss rate increased when an amount of the iron powder increased. On the other hand, the decomposition reaction of HA85wt.%/water solution with Cu²⁺ was calm compared to that of the iron ion. HA/water solution did not react with Mn²⁺, Ni²⁺ and Cr³⁺ at room temperature.     

A generalized differential method to calculate lumped kinetic triplet of the nth order model for the global one-step heterogeneous reaction using TG data

Computing kinetic triplet is of importance for the process safety of combustion/gasification industries to establish the chemical reaction scheme and to assess the hazardous risk. Few approaches have been capable of calculating lumped kinetic triplet at one time efficiently, which might be attributed to the fact that the analytical solution for the nonlinear ordinary differential equation (NNODE) for the n^th order reaction model has not been found yet. This paper presents an analytical solution of NNODE to compute kinetic triplet. Results showed that the proposed method (mass fraction curve-fitting error ϕ = 1.49%–2.07%) is more efficient to compute kinetic triplet of the n^th order reaction model, comparing to genetic algorithm (GA) optimization (ϕ = 1.43%–1.81%), Coats-Redfern (ϕ = 2.36%–3.16%), peak-shape, and isoconversional methods. A compensation effect between lnA and E_a is observed due to heating rates. Effects of exported data quality and smooth processing on computation of kinetic triplet are discussed. It is the first time that an analytical solution of NNODE (n^th order model) for global one-step heterogeneous reaction is derived for computing kinetic triplet. This work may help to search for analytical solutions of power-law and Avrami-Erofeev models in the future to efficiently calculate kinetic triplet for accelerating and sigmoidal reaction systems.     

Kinetic mechanism and effects of molecular structure on thermal hazards of azo compounds

In this paper, the kinetic mechanism of AIBN, AMBN, and ABVN was proposed, and the effect of molecular structure on their thermal hazards based on the kinetic mechanism was investigated. Calculated by non-isothermal DSC datum, the kinetic mechanism of AIBN, AMBN, and ABVN is revealed by the linear relationship between the integrated form of mechanical function and reaction time. The results indicate that the thermal decomposition process is controlled by the Johnson-Mehl-Avrami equation. Based on the determination of kinetic mechanism function, the reaction rate constants at various heating rates are directly calculated, and the intercept of the best fitting straight line of reaction rate constants with heating rate is approximately equal to the reaction rate constant under isothermal conditions. Besides, theoretical values obtained by multiplying kinetic mechanism function by reaction rate are well consistent with the experimental values, suggesting that the kinetic mechanism obtained is credible. Bond Dissociation Energies (BDE) calculated by quantum chemical equations are employed to evaluate the thermodynamics stability of AIBN, AMBN, and ABVN. Depending on similar molecular structures, the influence of differentiated group structure on the thermodynamic stability represented by BDE and heat release and the kinetic stability characterized by reaction rate constant were revealed. Finally, the results demonstrate that the thermal hazard increases as the volume of substituent group and molecular weight.     

Preparation of n-Octadecane@MF resin microPCMs and its application in temperature control of esterification reactions

Reaction thermal runaway accidents occur frequently and occupy a high proportion in chemical accidents. Reducing accidents by controlling reaction temperature is of great implication to enhance the safety level of chemical processes. Phase change materials (PCMs) have a good energy storage potential, which can rapidly convert the reaction exotherm in the reaction process into its own phase change latent heat, urgently control the reaction temperature, and enhance the process thermal safety level. In this study, using n-octadecane as the core and melamine-formaldehyde (MF) resin as the shell, microencapsulated phase change materials (microPCMs) was made, which has a smooth spherical shape, good thermal stability, and a phase change enthalpy up to 162.87 J/g. The homogeneous esterification reaction of 2-butanol (2 B) and propionic anhydride (PA) was selected as the target reaction, and then the reaction was scaled up equivalently to investigate the effect of amplification to the reaction system. The results indicated that the temperature control of the esterification reaction system by microPCMs is the synergy between physical inhibition and chemical inhibition. The reaction temperature could be controlled by adding microPCMs, and the temperature control effect improved with the increase of microPCMs addition. In large scale reactors, microPCMs still has certain temperature control ability after being added.     

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.     

MIE determination and thermal degradation study of PA12 polymer powder used for laser sintering

Pulverized materials such as metallic or polymer powders play a considerable role in many industrial processes. Their use requires the introduction of preventive safeguards to control the plant's safety.PA12 polymer powder processing by laser sintering is characteristic of this tendency. The present work concerns PA12 powder (bimodal particle size distribution: 10 μm and 55 μm) and relates to explosion sensitivity and the thermal degradation of this powder, which can occur during laser sintering. Minimum Ignition Energy is determined using a modified Hartmann tube combined with the Langlie method developed in the PRISME Laboratory. This study shows the influence of parameters such as distance between the electrodes, powder concentration and arc power on MIE values. Theses parameters vary in the range of 3–6 A for the current intensity of the spark and the electrode gap in the range of 2.5–4 mm. The MIE is obtained for a spark gap of 3 mm and current intensity of the 4 A spark in our device. It shows that the MIE is less than 40 mJ for concentrations approaching 1000 g/m³. At lower concentrations (under 150 g/m³) the MIE increases but discrepancies in measurements appear, probably because of the static electricity that creates strong irregularities in dust dispersion. The second part of this study concerns the thermal degradation of the PA12 which is performed by thermogravimetric experiments coupled with mass spectrometric (MS) analysis for gas investigation. The mass loss measurement combined with the gas analysis allows the principal stages of degradation to be determined so as to calculate the kinetics parameter PA12. Experiments have been performed for different heating rates between 1 and 30 K min^?1 and the reproducibility of experiments has been verified. The activation energy is determined using two methods: Freidman and KAS. For a reaction rate of between 0.2 and 0.6, the activation energy is nearly constant. The KAS method gives a value of E_a = 250 kJ mol^?1 and the Friedman method gives E_a = 300 kJ mol^?1. The gas analysis by MS shows that oxidation begins at over 350 °C and finishes at under 650 °C with the formation of CO₂ and H₂O. Other major peaks with an m/z ratio of 29, 28 and 30 are noticed in this range of temperature. They show the presence of intermediate species such as C₂H₆, NO or CH₂O. The presence of HCN is also detected (m/z ratio of 27).     

Dilute Acid Hydrolysis of Cellulose and Cellulosic Bio-Waste Using a Microwave Reactor System

The dilute acid hydrolysis of grass and cellulose with phosphoric acid was undertaken in a microwave reactor system. The experimental data and reaction kinetic analysis indicate that this is a potential process for cellulose and hemi-cellulose hydrolysis, due to a rapid hydrolysis reaction at moderate temperatures. The optimum conditions for grass hydrolysis were found to be 2.5% phosphoric acid at a temperature of 175°C. It was found that sugar degradation occurred at acid concentrations greater than 2.5% (v/v) and temperatures greater than 175°C. In a further series of experiments, the kinetics of dilute acid hydrolysis of cellulose was investigated varying phosphoric acid concentration and reaction temperatures. The experimental data indicate that the use of microwave technology can successfully facilitate dilute acid hydrolysis of cellulose allowing high yields of glucose in short reaction times. The optimum conditions gave a yield of 90% glucose. A pseudo-homogeneous consecutive first order reaction was assumed and the reaction rate constants were calculated as: k₁ = 0.0813 s⁻¹; k₂ = 0.0075 s⁻¹, which compare favourably with reaction rate constants found in conventional non-microwave reaction systems. The kinetic analysis would indicate that the primary advantages of employing microwave heating were to: achieve a high rate constant at moderate temperatures: and to prevent ‘hot spot’ formation within the reactor, which would have cause localised degradation of glucose.     

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.