Calorimetry studies of ammonium nitrate – Effect of inhibitors,confinement, and heating rate

Ammonium nitrate (AN) has been widely used as a fertilizer for almost a century because it is an excellent nitrogen source. However, AN related explosions continue to occur time and again, despite the fact that AN has been extensively investigated. There have been more than 70 AN-related incidents during the last century, which reemphasize the dire need for further research on AN reactive hazards. This research focuses on the alternatives to make AN safer as a fertilizer by reducing its explosivity, by studying the effect of inhibitors, confinement, and heating rate on AN thermal decomposition using the Reactive Systems Screening Tool (RSST). First, the thermal decomposition of AN in the presence of different types of additives, including sodium bicarbonate, potassium carbonate, and ammonium sulfate, was studied under two concentrations, i.e., 2.8 wt.% and 12.5 wt.%. The results show that they are good inhibitors for AN. Second, the effect of confinement was tested by observing AN decomposition under five different initial pressures, varying from ambient pressure to 187 psig. It is concluded that confinement is dangerous to AN, which should be avoid in AN storage and transportation. Lastly, the effect of heating rate was studied by heating up AN under two heating rates of 0.25 °C min⁻¹ and 2 °C min⁻¹. The lower the heating rate, the lower the “onset” temperature detected.     

Effect of urea on detonation characteristics and thermal stability of ammonium nitrate

A study has examined the effect of urea on the thermal stability and detonation characteristics of ammonium nitrate (AN). The thermal decomposition temperature and surface morphology of samples were investigated by differential scanning calorimetry (DSC) and scanning electron microscopy (SEM). For further research on the thermal sensitivity and shock sensitivity of the samples, the Koenen test and UN gap test were conducted. The results indicate that urea can substantially increase the thermal stability of AN (the greatest exothermic peak is increased by more than 100 °C) and reduce the thermal sensitivity of AN. However, AN-50wt. % urea mixtures can still produce a steady detonation in the UN gap test. Urea cannot reduce the ability to propagate a detonation. Possible explanations for these results are discussed.     

敞开气氛中硝酸铵热分解过程危险特性的实验研究

利用差热分析仪分析和研究了敞开气氛中硝酸铵的热分解过程,通过在硝酸铵样品中加入酸性物质、KCl、有机物等各种杂质,研究硝酸铵热分解过程的影响因素。结果表明,在敞开气氛中,酸性物质和KCl对硝酸铵热分解过程具有催化作用,有机物会降低硝酸铵的热稳定性,研究结论可以为解决硝酸铵的生产、储存和运输过程中的安全问题提供重要参考。     

硝酸异辛酯热安定性的实验研究

使用加速量热仪(ARC)研究硝酸异辛酯(EHN)的热分解,得到热分解温度随时间的变化曲线,自放热速率、分解压力随温度的变化曲线以及分解压力随升温速率的变化曲线。分析在绝热条件下硝酸异辛酯的热分解反应动力学和热分解过程,计算表观活化能、指前因子和反应热等参数。根据绝热热分解的起始温度和反应热数据,给出硝酸异辛酯在反应危险度等级中的分类,并计算在75℃时的反应风险指数。     

硝酸及氯离子对高温硝酸铵水溶液热危险性的影响研究

国内外学者对硝酸铵的危险性进行了大量的研究,而对其水溶液的危险性至今开展不多。笔者采用差示扫描量热仪(DSC)及全自动反应量热仪(RC1e)对高温状态下的硝酸铵水溶液的热分解危险性、杂质离子对其稳定性的影响进行了研究。纯硝酸铵和90%硝酸铵水溶液的DSC实验表明,90%硝酸铵溶液和分析纯硝酸铵具有相似的热爆炸危险;90%硝酸铵水溶液在140~180℃之间的RC1e试验表明:硝酸或氯离子单独存在时,对硝酸铵分解都有不同程度的抑制作用,而同时存在时则大大降低体系的热稳定性。该结果对保障硝酸铵在生产、使用过程中的安全具有重要的参考价值。     

无机酸对硝酸铵热稳定性影响的研究

为了研究硫酸、盐酸两种无机酸对含能材料硝酸铵热稳定性的影响,使用绝热加速量热仪ARC和微量量热仪C80,对纯硝酸铵及硝酸铵和硫酸、盐酸的混合物进行了热分析实验并研究各种样品在恒温以及升温条件下的吸、放热特性。根据化学反应动力学和热力学理论,确定了硝酸铵及其与无机酸的混合物发生放热分解反应的反应动力学参数和热力学参数。基于Semenov热爆炸模型,计算并比较了各样品标准包装的自加速分解反应温度。     

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.     

Investigation of ammonium nitrate based emulsion ignition characteristic

This paper presents an analysis of the observed ignition behaviors of ammonium nitrate (AN) and emulsion explosives (EE). Pure AN and EE locally ignited by a heat source do not undergo sustained combustion when the pressure is lower than some threshold value usually called the Minimum Burning Pressure (MBP). A reason for pure AN's and EE's incapable of burning was suggested, and the roles of sample water, inorganic salts, oil phase, and sensitizer were discussed. Accelerating rate calorimeter (ARC) was used to study the thermal stability of EE and AN. The results also showed that MBP is of vital importance and useful for the manufacture and application of AN and EE in terms of accident prevention.     

Green thermal analysis for predicting thermal hazard of storage and transportation safety for tert-butyl peroxybenzoate

Liquid organic peroxides, such as tert-butyl peroxybenzoate (TBPB), have been widely employed in the petrifaction industry as a polymerization formation agent. This study investigated the thermokinetic parameters of TBPB by isothermal kinetic algorithms and non-isothermal kinetic equations, using thermal activity monitor III (TAM III) and differential scanning calorimetry (DSC), respectively. Simulations of 0.5 L, 25 kg, 55 gallon, and 400 kg reactors in liquid thermal explosion models were performed and compared to the results in the literature. A green thermal analysis was developed for a reactor containing TBPB to prevent pollution and reduce the energy consumption by thermal decomposition. It is based on the thermal hazard properties, such as the heat of decomposition (ΔH_d), activation energy (E_a), self-accelerating decomposition temperature (SADT), control temperature (CT), emergency temperature (ET), and critical temperature (TCR). From the experimental results, the optimal conditions to avoid violent runaway reactions during the storage and transportation of TBPB were determined.     

硝铵炸药生产中的事故防范

通过分析硝铵炸药生产中发生的火灾和爆炸事故，认为硝铵混合物在高温条件下的热分解是引发这类事故的主要原因；还给出硝酸铵热分解的要点，并提出预防恶性事故的措施。【关键词】     

Detonation characteristics of ammonium nitrate and activated carbon mixtures

To better understand the detonation characteristics of ammonium nitrate (AN) and activated carbon (AC) mixtures, steel tube tests were carried out for AN/AC mixtures of various compositions and different forms of AN (powdered, prilled, phase stabilized and granular), and the detonation velocity was measured. The powdered AN/AC mixtures gave higher detonation velocities than the other AN forms. For all the AN/AC mixtures, the experimentally observed detonation velocities at each loading density were far below the theoretically predicted values calculated by the CHEETAH code based on thermohydrodynamics, exhibiting so-called non-ideal detonation. The lowest detonation velocity of powdered AN/AC mixtures was obtained as D=1.25 km/s for an AC content of 0.1 wt%. This was considered to be close to the critical condition for stable detonation.     

Modeling thermal analysis for predicting thermal hazards relevant to transportation safety and runaway reaction for 2,2′-azobis(isobutyronitrile)

The pure decomposition behavior of 2,2′-azobis (isobutyronitrile) (AIBN) and its physical phase transformation were examined and discussed. The thermal decomposition of this self-reactive azo compound was explored using differential scanning calorimetry (DSC) to elucidate the stages in the progress of this chemical reaction. DSC was used to predict the kinetic and process safety parameters, such as self-accelerating decomposition temperature (SADT), time to maximum reaction rate under adiabatic conditions (TMR_ad), and apparent activation energy (E_a), under isothermal and adiabatic conditions with thermal analysis models. Moreover, vent sizing package 2 (VSP2) was applied to examine the runaway reaction combined with simulation and experiments for thermal hazard assessment of AIBN. A thorough understanding of this reaction process can identify AIBN as a hazardous and vulnerable chemical during upset situations. The sublimation and melting of AIBN near its apparent onset decomposition temperature contributed to the initial steps of the reaction and explained the exothermic attributes of the peaks observed in the calorimetric investigation.     

氯化钠和二氧化硅对过硫酸铵热稳定性的影响

采用绝热加速量热仪（ARC）对分析纯过硫酸铵、含10%氯化钠杂质的过硫酸铵以及含10%二氧化硅杂质的过硫酸铵进行热分析实验,得到了实验过程中温度、温升速率和压力等数据,计算了3组样品的反应动力学参数,引入热惰性因子对实验数据进行修正,得到了3组样品在严格绝热条件下的热危险性参数,分析了3组样品的反应过程和热危险性。通过Semenov理论计算了3组样品的自加速分解温度（SADT）。结果表明,过硫酸铵加入氯化钠或二氧化硅杂质后,热危险性增大,自加速分解温度降低,更容易发生反应且反应更剧烈。     

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.     

Thermal risk analysis of cumene hydroperoxide in the presence of alkaline catalysts

Many studies have been performed to clarify the basic thermal runaway hazards and kinetics of cumene hydroperoxide (CHP) decomposition. However, materials that are incompatible with CHP have not been clearly identified. Alkaline solutions have been used as a catalyst to form dimethylphenyl carbinol (DMPC) and dicumyl peroxide (DCPO); however, these solutions also affect the reaction and storage temperature of CHP. In this study, thermal calorimeters, differential scanning calorimetry (DSC) and vent sizing package 2 (VSP2), were used to compare the effects of various bases on the decomposition of CHP in cumene. Specifically, the exothermic onset temperature, change in pressure over time, self-heating rate and heat of decomposition were evaluated. Moreover, to appraise the degree of hazard associated with the use of CHP, the compatibility of CHP with various substances was analyzed, and a risk matrix for thermal runaway reactions was obtained. The results of the present study could be used to design safety procedures for the production of CHP and its derivatives.     

液体石蜡乳化液的制备及对甲苯废气的吸收性能研究

以液体石蜡和水制备乳化液,以制备的乳化液吸收甲苯废气。考察了制备乳化液时油水质量比、乳化剂的质量分数、HLB值(亲水亲油平衡值)、乳化时间、乳化温度的选择及Tween 80、正辛醇、NaCl、Na2SO4对甲苯吸收效果的影响。结果表明,室温下油水质量比为7∶3,乳化剂质量分数为7%,HLB值为10,乳化时间为0.5 h时制备的乳化液稳定性最好。试验条件下乳化液对甲苯的初始吸收率可达96.53%,增加Tween 80的量和添加正辛醇能提高乳化液的吸收效果,添加NaCl和Na2SO4则降低乳化液对甲苯的吸收能力。     

硝酸铵水溶液热稳定性研究

采用加速度量热法(ARC)对高温状态下的硝酸铵水溶液的热分解危险性、杂质对其稳定性的影响进行了研究.实验结果表明,硝酸促进硝酸铵的分解,而氯离子对其有抑制作用;当两者同时存在时大大降低系统的稳定性,且硝酸对硝酸铵的影响远大于氯离子.     

Thermal hazard and decomposition kinetics of 1-butyl-2,3-dimethylimidazolium nitrate via TGA/DSC and FTIR

1-Butyl-2,3-dimethylimidazolium nitrate ([Bmmim][NO₃]), a kind of versatile and novel ionic liquids, is widely applied in the modern petrochemical industry. Nevertheless, its thermal hazard safety data at high temperature or thermal disturbance conditions are currently unavailable. Therefore, this study aimed to characterize the thermal risk of [Bmmim][NO₃] through auto-ignition temperature measurements, flash point analysis, thermal gravimetric analysis/differential scanning calorimetry (TGA/DSC), TGA-Fourier transform infrared spectroscopy (TGA-FTIR) and thermal decomposition kinetics analysis. Additionally, [Bmmim][NO₃] was examined using isothermal thermogravimetric analysis at different temperatures (220, 230, 240, 250, 260 and 270 °C). The experimental results show that the flash point of [Bmmim][NO₃] is 305.70 ± 9.30 °C and the auto-ignition temperature is 341.00 ± 21.60 °C with an ignition delay time of 8.6 s. In addition, using the nitrogen atmosphere TGA data to calculate the activation energy according to the Friedman, Kissinger and Flynn-Wall-Ozawa methods, roughly the same results were obtained. Finally, TGA-FTIR results show that [Bmmim][NO₃] produced acetylene, butane, butanol and carbon dioxide during the thermal decomposition process. This study could provide data support and some guidance for the thermal hazard assessment and safety control of [Bmmim][NO₃] during its use and storage.     

Reaction hazard and mechanism study of H2O2 oxidation of 2-butanol to methyl ethyl ketone using DSC,Phi-TEC II and GC-MS

Methyl ethyl ketone (MEK) oxidation via H₂O₂ with tungsten-based polyoxometalate catalysts has gained much attention with an ever-growing body of knowledge focusing on the development of environmentally benign processes in chemical industry. In this study, two calorimetry techniques, differential scanning calorimetry (DSC) and Phi-TEC II adiabatic calorimetry, were employed to analyze the thermal hazards associated with the 2-butanol oxidation reaction system. Hydrogen peroxide was the oxidant and a tungsten-based polyoxometalate as the catalyst. Gas chromatography-mass spectrometry was used for identification of the organic products. Important thermal kinetic data were obtained including “onset” temperature, heat of reaction, adiabatic temperature rise and self-heat rate. From DSC results, three exothermic peaks were detected with a total heat generation of approximately 1.26 kJ/g sufficiently to induce a thermal runaway. Possible reaction pathway for three stages were proposed based on both DSC and GC-MS results. One exotherm was detected by Phi-TEC II calorimeter and the pressure versus temperature profile together with the DSC and GC-MS data demonstrate the complexity of 2-butanol reaction system under both thermal screening and adiabatic conditions.     

Study of flotation conditions for cadmium(II) removal from aqueous solutions

Flotation conditions for cadmium(II) removal from aqueous solutions were investigated. Precipitate flotation techniques “of the first kind” (PFFK) and “of the second kind” (PFSK) were tested, using potassium ethyl xanthate (KEtX) as a precipitating agent for cadmium(II). The surfactants sodium dodecyl sulfate (SDS) and hexadecyltrimethylammonium bromide (HDTMA) were used as collectors for PFFK. The effects of KEtX and collector concentrations, induction time, bubbling time, solution pH and some foreign ions on cadmium(II) removal were studied. Under optimum conditions, cadmium(II) could be removed by PFFK by ∼93% and >99% using SDS and HDTMA, respectively. By PFSK, removal of about 64% for cadmium(II) was obtained. The two developed precipitate flotation methods were also tested for simultaneous removal of cadmium(II), nickel(II) and cobalt(II) from distilled water and tap water. The effectiveness of PFFK suggests its employment for metal-polluted wastewaters.