A reappraisal of the flash point of formic acid

The currently accepted closed-cup flash points of four common organic compounds—formic acid, glycerol, ethylamine and dimethylamine—are examined for consistency with the principles of stoichiometry, vapour pressures and flammability limits. For all four, the examination suggests that the flash points are in significant error on the hazardous side.     

Decomposing deflagration properties of acetylene under low temperatures

In this study, the decomposing deflagration properties of acetylene under temperatures down to −60 °C and pressures up to 0.2 MPa in a 1-L cylindrical closed vessel were experimentally investigated. The gases were ignited by an electric spark at the center of the vessel. The lower-limit pressures of decomposing deflagration by electric spark ignition were determined. The lower-limit pressure at 10 °C was 0.15 MPa, and it gradually increased with decreasing temperature. The lower-limit pressure at −60^oC was 0.18 MPa. The flame propagation properties, such as the pressure, were measured with pressure transducers mounted along the vessel. The maximum decomposing deflagration pressures and pressure rising rates also increased with decreasing temperature.     

Flash points measurements and prediction for binary miscible mixtures

Flash point is one of the most important parameters used to characterize the potential fire and explosion hazards for flammable liquids. In this study, flash points of twenty eight binary miscible mixtures comprised eighteen flammable pure components with different compositions were measured by using the closed cup apparatus. The obtained experimental data are further employed to develop simple and accurate models for predicting the flash points of binary miscible mixtures. Based on the vapor–liquid equilibrium theory, the normal boiling point, the standard enthalpy of vaporization, the average number of carbon atoms, and the stoichiometric concentration of the gas phase were selected as the dominant physicochemical parameters that were relevant to the overall flash point property of liquids. With these parameters for pure components as well as the compositions of mixtures, the new form of characteristic physicochemical parameters for mixtures were developed and used as the input parameters for the flash point prediction of mixtures. Both the modeling methods of multiple linear regression (MLR) and multiple nonlinear regression (MNR) were employed to model the possible quantitative relationships between the parameters for mixtures and the flash points of binary miscible mixtures. The resulted models showed satisfactory prediction ability, with the average absolute error for the external test set being 2.506 K for the MLR model and 2.537 K for the MNR model, respectively, both of which were within the range of the experimental error of FP measurements. Model validation was also performed to check the stability and predictivity of the presented models, and the results showed that both models were valid and predictive. The models were further compared to other previously published models. The results indicated the superiority of the presented models and revealed which can be effectively used to predict the FP of binary miscible mixtures, requiring only some common physicochemical parameters for the pure components other than any experimental flash point or flammability limit data as well as the use of the Le Chatelier law. This study can provide a simple, yet accurate way for engineering to predict the flash points of binary miscible mixtures as applied in the assessment of fire and explosion hazards and the development of inherently safer designs for chemical processes.     

MNLR and ANN structural group contribution methods for predicting the flash point temperature of pure compounds in the transportation fuels range

A QSPR method is presented for predicting the flash point temperature (FPT) of pure compounds in the transportation fuels range. A structural group contribution method is used to determine the flash point temperature using two techniques: multivariable nonlinear regression and artificial neural networks. The method was used to probe the structural groups that have significant contribution to the overall FPT of pure compounds and arrive at the set of 37 atom-type structural groups that can best represent the flash point for about 375 substances. The input parameters to the model are the number of occurrence of each of the 37 structural groups in each molecule. The neural network method was the better of the two techniques and can predict the flash point of pure compounds merely from the knowledge of the molecular structure with an overall correlation coefficient of 0.996 and overall average and maximum errors of 1.12% and 6.62%, respectively. The results are compared to the more traditional approach of the SGC method along with other methods in the literature.     

Investigation of a drum explosion of 30% aqueous KOCN

A 30% aqueous solution of KOCN placed in a 55 gallon HDPE drum at 50 °C began venting gas almost immediately. Although a vent was kept open the drum exploded within 1–2 h of being filled. This report reviews the steps taken after the accident to find its cause and to recommend safe operating conditions. The DIERS vent sizing package (VSP), used as a closed system adiabatic reactor, was able to simulate the incident under controlled laboratory conditions. Data were thereby collected for the first time on the runaway kinetics of the KOCN hydrolysis. Isothermal data were obtained in a highly sensitive microwatt heat flow calorimeter in an open system. It was demonstrated that even under isothermal conditions, the hydrolysis rates accelerated once underway, reaching maxima in 30 h at 25 °C and 6.7 h at 40 °C. There is satisfactory agreement of these results with other work on 0.5% KOCN solutions reported in earlier studies.     

A new method for the prediction of flash points for ternary miscible mixtures

The flash point is one of the most important physicochemical parameters used to characterize the fire and explosion hazard for flammable liquids. The flash points of ternary miscible mixtures with different components and compositions were measured in this study. Four model input parameters, being normal boiling point, the standard enthalpy of vaporization, the average number of carbon atoms and the stoichiometric concentration of the gas phase for mixtures, were employed and calculated based on the theory of vapor–liquid equilibrium. Both multiple linear regression (MLR) and multiple nonlinear regression (MNR) methods were applied to develop prediction models for the flash points of ternary miscible mixtures. The developed predictive models were validated using data measured experimentally as well as taking data on flash points of ternairy mixtures from the literature. Results showed that the obtained average absolute error of both the MLR and the MNR model for all the datasets were within the range of experimental error of flash point measurements. It is shown that the presented models can be effectively used to predict the flash points of ternary mixtures with only some common physicochemical parameters.     

二元混合液体闪点的计算

以混合溶液纯组分易燃液体闪点的饱和蒸气压为基础,应用乌拉尔定律、双液系的气-液相平衡理论,运用Le Chatelier方程和安托因方程导出二元混合液的闪点计算方法。并例举易燃液体与易燃液体组成的理想混合液、易燃液体与易燃液体组成的非理想混合液、易燃液体与不燃液体组成的非理想混合液的计算过程。乙醇溶液闪点的计算结果与现有的文献资料比较,误差在允许范围内。计算数据用Excel处理,快捷准确,用于确定二元混合液体的火灾危险性。     

Sizing pressure relief valves in flashing and two-phase service: an alternative procedure

In view of the greater accuracy of the ω HEM correlation and the resulting conservative PR valve sizing (relative to the traditional PR valve sizing methods), the ω HEM-based flow calculations are recommended for all situations where flashing or two-phase flow occurs within the PR valve. However, as with any correlation, the accuracy of the ω HEM correlation results drops as the system to which it is applied diverges from the data used to develop it. Analysis of 15 different systems representative of actual refinery streams indicate that for fluids with a wide boiling range and for very non-ideal systems such as those containing hydrogen, the HEM correlation underpredicts the mass flux significantly (i.e. overpredicts the PR valve size). Since the large deviations are on the conservative side, the procedure will result in excessively large PR valves that may cause problems because of chattering of the PR valves, but would not present potential for vessel failure. The majority of the deviations are a result of the fact that the simplifying assumptions built into the correlation for single component do not truly characterize the actual flashing behaviour of many multicomponent fluids. The alternative approach presented, in which the correlation parameter ω is based on the actual flashing behaviour, eliminates nearly all the deviations and significantly improves the results of the correlation regardless of the system analysed. For trouble systems (those containing more than 0.1 wt% hydrogen and for some multicomponent fluids with a nominal boiling range greater than 80°C (150°F), the alternative approach should be used to define the correlation parameter ω. Use of this alternative approach is valid for any system (and will improve the accuracy of the correlation) but does require an additional flash calculation. However, for other systems the original formulation of ω is adequate and can be used.     

Prediction of methanol loss in vapor phase during gas hydrate inhibition using Arrhenius-type functions

Gas hydrate formation in natural gas and NGL systems can block pipelines, equipment, and instruments, restricting or interrupting flow leading to safety hazards to production/transportation systems and to substantial economic risks. The amount of hydrate inhibitor to be injected not only must be sufficient to prevent freezing of the inhibitor water phase, but also must be sufficient to provide for the equilibrium vapor phase content of the inhibitor. The vapor pressure of methanol must be high enough so that significant quantities will vaporize. Therefore to estimate methanol vaporization losses, it is necessary to develop a new predictive tool. In this work, a simple correlation, which is a mathematically compact and reasonably accurate equation containing few tuned coefficients, is presented here for the prediction of methanol vaporization loss and vapor pressures of aqueous methanol solutions as a function of temperature and methanol mass fraction in aqueous solutions using a novel and theoretically meaningful Arrhenius-type asymptotic exponential function and Vandermonde matrix. The proposed correlation predicts the vapor pressures of aqueous methanol solutions for temperatures up to 100 °C and methanol vaporization loss for temperature between ?16 and 16 °C. Estimations are found to be in excellent agreement with the reliable data in the literature where the average absolute deviation from data is less than 1.5%. The tool developed in this study can be of immense practical value for the engineers and scientists to have a quick check on the methanol vaporization loss and vapor pressures of aqueous methanol solutions at various conditions without opting for any experimental measurements. In particular, chemical and process engineers would find the approach to be user-friendly with transparent calculations involving no complex expressions.     

The effect of vent ducts on the reduced explosion pressures of vented dust explosions

An investigation into the effects of vent ducts on reduced explosion pressures is described. Experiments were made using an 18.5m³ explosion vessel and a modified 20 1 sphere, with dusts having K_st values ranging from 144 bar ms⁻¹ to 630 bar ms⁻¹. The vent area/vessel volume ratio bursting pressure of the vent cover, and the length to diameter ratio of the vent duct have been varied. Straight vent ducts, and ducts containing sharp 45° and 90° bends have been used.A simple model to describe the effect of vent ducts on the reduced explosion pressure has been derived and compared with the experimental results. Agreement is shown to be satisfactory in nearly all cases. A comparison between the experimental results and guidance on the effect of vent ducts already available in the literature is discussed.     

Reliable method for prediction of the flash point of various classes of amines on the basis of some molecular moieties for safety measures in industrial processes

This work presents a novel, reliable and simple method of estimating the flash point of various types of flammable amines, which are important for safety measures in industrial processes. Different amines include aliphatic amines such as primary, secondary, tertiary and cyclic amines as well as aromatic amines and hetero arenes containing nitrogen heteroatom. The proposed correlation is based on the contribution of some specific molecular moieties and functional groups, which can easily be used for any types of amines. Intermolecular forces are important in the new method, which are counted by two increasing and decreasing parameters. The root mean square (rms) deviation is 18 K for different classes of amines including 133 diverse compounds. The estimated flash points have been compared with one of the best available predictive methods, which gives much lower value of the rms deviation.     

基于QSPR方法的脂肪醇化合物闪点预测

为提高脂肪醇化合物闪点预测精度,提出基于定量结构-性质关系(QSPR)原理的脂肪醇化合物闪点预测方法。应用Dragon软件计算出91种脂肪醇的分子描述符,利用遗传函数算法(GFA)从1 481个描述符中筛选出3个与脂肪醇闪点关系最密切的分子描述符。分别用多元线性回归(MLR)方法和支持向量机(SVM)方法进行建模,并采用内部验证和外部检验的方式对模型的拟合度、预测性等性能进行验证。结果表明:预测集的MLR方法和SVM方法的平均绝对误差(AAE)分别为2.870 K和2.706 K;均方根误差(RMSE)为3.451 K和3.371 K。SVM模型在精度上略优于MLR模型,而MLR模型更为简单和方便。     

烃类及其衍生物闪点、沸点的定量构效关系

基于定量结构一性质相关性（QSPR）原理,研究了烃类及其衍生物闪点、沸点与其分子结构间的内在定量关系。应用CODESSA软件计算384种烃类及其衍生物的分子结构描述符,建立了闪点和沸点的QSPR模型。用最佳多元线性回归（B．MLR）方法筛选得到的分子描述符建立了线性回归模型。用B-MLR方法所选择的5个描述符作为支持向量机（SVM）的输入建立了非线性模型。所有的化合物被分为训练集和测试集,对每个模型的训练集和测试集的复相关系数、交互验证系数、均方根误差等进行了计算,并用测试集对模型的预测能力进行检验,预测结果表明：预测值与实验值均符合良好,所建立的闪点模型稳健,泛化能力强,预测误差小,预测的效果令人满意,但沸点的模型预测效果有待加强。相比烃类物质的模型,加了衍生物的模型性能均有所下降。     

Thermal hazard in a batch process involving hydrogen peroxide

Hydrogen peroxide is a versatile and interesting reagent for many industrial processes; nevertheless, it is very sensitive to impurities that can catalyze its decomposition, so that the desired reaction could be accompanied by undesired parallel and consecutive reactions. As an example, the butadiene free radical polymerization with hydrogen peroxide in the presence of an organic solvent was studied. Batch polymerization occurs in the liquid phase at about 120 °C. Because of the involved reactive compounds and the relatively high temperature, this is an intrinsically dangerous reaction. Therefore calorimetric data can give important information about safety and process optimization during the scale-up. The aim of this research project was to study the influence of impurities on the overall heat of reaction. The experiments were made in a high-pressure reaction calorimeter. The study has revealed that impurities do indeed affect the reaction course. Most importantly, the presence of carboxylic acids and/or ionic iron must be avoided and the recycle of unreacted reagents must be carefully controlled to minimize the build-up of these impurities.     

Sensitivity analysis and optimization for gasoline vapor condensation recovery

Volatile organic compounds (VOCs) are easily evaporated and discharged from everywhere into the atmosphere, especially in various operations of gasoline. The emission of VOCs is always a significant environmental problem, and the control of VOCs pollution has been a hot topic in the field of air purification. In this paper, the condensation separation method for gasoline vapor recovery was investigated and four gasoline vapors of S1–S4 were selected for the sensitivity analysis and optimization of the condensation process, using the Model Analysis Tools from Aspen Plus. Generally, to control VOCs pollution efficiently, both the vapor recovery efficiency and the outlet vapor concentration of the condensation recovery system should be simultaneously considered. Then an optimized three-stage condensation process was proposed, whose condensation temperatures were optimized and designed at 1 °C, −40 °C and −110 °C, respectively. Further, based on the comprehensive consideration of both meeting the more strict VOCs emission standard and ensuring the condensation recovery system work stably and economically, it was recommended that the maximum total vapor recovery efficiencies for S1–S4 should be 99.73%, 99.79%, 99.82% and 99.19%, and the minimum outlet vapor concentrations be 2.87 g/m³, 2.75 g/m³, 3.04 g/m³ and 16.98 g/m³, respectively. Accordingly, the condensation temperature of the copious cooling stage should be set at −130 °C. Moreover, the total cooling duties for the single-stage and three-stage condensation processes were investigated and compared when the condensation temperature of the recovery system ranged from 20 °C to −110 °C. The total cooling duties of the three-stage condensation process for S1–S4 would be saved by 12.23%, 15.68%, 13.96% and 15.65%, respectively. Finally, a three-stage condensation system was developed for the industrial gasoline vapor recovery, which has performed well since its installation.     

Industrial system for mitigation of vapor cloud explosions

The oil industry operates installations and processes with important quantities of flammable substances within a wide range of pressures and temperatures. A particular hazard for this type of installations is an accidental release of a large quantity of flammable material resulting in a devastating vapor cloud explosion.Extensive research was conducted to assess the efficiency of chemicals for inhibition of flames. Especially alkali metal compounds (especially carbonates and bicarbonates of sodium and potassium) have shown to be one of the more efficient flame inhibitor species.In this paper, the principles of flame inhibition by alkali metal compounds are briefly explained. Based on these principles, a practical implementation of an industrial system for chemical inhibition of vapor cloud explosions is discussed. This implementation is based on the use of dry powders of carbonates and bicarbonates of sodium and potassium as flame inhibitor species.The efficiency of the final design of the inhibition system was tested and confirmed on a very large scale in Vapor Cloud Explosion tests in California (US) in September 2016. Several projects in TOTAL were identified in which the VCE inhibition technology is implemented (new cracker units in Daesan (South-Korea) and in Port Arthur (United States)).     

Ignitability characteristics of aluminium and magnesium dusts that are generated during the shredding of post-consumer wastes

The authors investigated the ignitability of aluminium and magnesium dusts that are generated during the shredding of post-consumer waste. The relations between particle size and the minimum explosive concentration, the minimum ignition energy, the ignition temperature of the dust clouds, etc. the relation between of oxygen concentration and dust explosion, the effect of inert substances on dust explosion, etc. were studied experimentally.

The minimum explosive concentration increased exponentially with particle size. The minimum explosive concentrations of the sample dusts were about 170 g/m³ (aluminium: 0–8 μm) and 90 g/m³ (magnesium: 0–20 μm). The minimum ignition energy tended to increase with particle size. It was about 6 mJ for the aluminium samples and 4 mJ for the magnesium samples. The ignition temperature of dust clouds was about 750 °C for aluminium and about 520 °C for magnesium. The lowest concentrations of oxygen to produce a dust explosion were about 10% for aluminium and about 8% for magnesium. A large mixing ratio (more than about 50%) of calcium oxide or calcium carbonate was necessary to decrease the explosibility of magnesium dust. The experimental data obtained in the present investigation will be useful for evaluating the explosibility of aluminium and magnesium dusts generated in metal recycling operations and thus for enhancing the safety of recycling plants.     

医药行业蒸馏系统蒸气云爆炸模型的研究

医药行业对药品生产的纯度控制相当重要,蒸馏操作是医药行业普遍运用的工艺手段之一.但由于蒸馏工序所涉及的物料常伴随具有较强燃爆性的危险化学品,且闪点以上操作加剧了物料的燃爆危险,因此医药行业蒸馏系统便成了事故多发的工艺单元之一.通过对某公司蒸馏系统的危险性分析,找出了蒸馏系统存在燃爆危险的主要因素,再进一步采用蒸汽云爆炸事故模拟评价方法,结合拉乌尔定律和道尔顿分压定律对该公司蒸馏系统进行安全评价,确定蒸馏系统二元混合物蒸气云爆炸冲击波损害半径.     

Flammability hazard analysis of imidazolium-based ionic liquid binary mixtures under high temperatures

Ionic liquid (IL) mixtures are promising because they can optimize the involved properties according to industrial needs. It has already been demonstrated that IL flammability is due mainly to IL decomposition generating flammable substances. Four different ILs, 1-Butylimidazolium tetrafluoroborate ([BIM][BF₄]), 1-butylimidazolium nitrate ([BIM][NO₃]), 1-butyl-3-methylimidazolium tetrafluoroborate([BMIM][BF₄]), and 1-butyl-3-methylimidazolium nitrate ([BMIM][NO₃]), were selected as the parent salts to form the different imidazolium-based IL binary mixtures. These mixtures were tested via isothermal thermogravimetric analyzer (TGA) at different temperatures (120, 150, 180, 210, and 240 °C), then tested by the flash point analyzer after isothermal heating pretreatment at the above temperatures. Results show that the mixtures' flash point values decrease with the heating temperature increase. Vaporization of the IL mixtures’ decomposition products results in a higher concentration of flammable gases and a flash point decrease, which lead to the flammability hazard increasing. Moreover, results show that the flash points of the studied binary imidazolium IL mixtures are more similar to those of the more unstable IL in their parent ILs. Also, the flammability hazard of IL binary mixtures may obviously increase under the high temperature environment for a long time.