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.     

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。     

Flash point of biodiesel/glycerol/alcohol mixtures for safe processing and storage

Mixtures of biodiesel, glycerol, and ethanol/methanol are commonly processed and stored in biodiesel production. In this work, non-ideal models are used to calculate the Flash Points (FPs) of binary and ternary mixtures, using data available from different feedstocks. Despite the fact that biodiesel is considered safer than common diesel fuels, results show a synergistic effect of biodiesel/methanol and biodiesel/ethanol mixtures, resulting in a reduction of the flash point of mixtures to values lower than the ones of pure compounds. Most soluble ternary mixtures were found flammable, the only exception being mixtures with a relatively lower alcohol content (45% mol. ethanol or 42% methanol) at temperature lower than 303 K. Accidental increase in temperature can cause domino effect, due to the higher solubility and the formation of new flammable ternary mixtures.     

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。     

A prediction model for the flash point of binary liquid mixtures

A prediction model based on the partial least squares of the multivariate statistical analysis methods was developed for the flash point (FP) of binary liquid mixtures. Estimation of the FP of flammable substances is important for safety measures in industrial processes. Since experimental FP data of liquid mixtures are scarce in the literature, there have been many researches to estimate the FP of liquid mixtures using physicochemical laws. In this study, the partial least squares (PLS) method using experimental data was used as a prediction model of the FP of binary liquid mixtures. The FPs predicted from the PLS method were also compared to results from the existing calculating methods using physicochemical laws such as Raoult's law and the Van Laar equation.     

基于多元线性回归的煤矿驾驶员情绪预测模型*

为研究煤矿人车驾驶员情绪状态不良引发的煤矿驾驶事故问题,设计眼动实验并建立基于多元线性回归的驾驶员情绪状况预测模型对驾驶员情绪状况进行预测;通过眼动仪采集煤矿驾驶员良好情绪与不良情绪状态下的各项眼动指标,记录其主观情绪状态;使用多元线性回归方程对数据进行分析与建模,采用平均相对误差对预测模型进行评估。结果表明:每秒注视点个数、平均扫视速度、反应时间、危险源辨识个数在情绪变化前后存在显著差异,且与情绪状态呈较强相关;基于多元线性回归的驾驶员情绪状况预测模型预测精度较高,平均相对误差为8.16%。模型适用于煤矿人车驾驶员的情绪监测,可为煤矿驾驶员安全行驶提供保障。     

QSPR在混合物典型燃爆特性预测中的研究进展

为全面了解定量结构-性质关系（QSPR）方法在混合物燃爆特性预测中的研究现状,展望其发展趋势,综述其在混合物闪点、爆炸极限与自燃温度预测中的国内外研究进展,分析预测目标参数的选择、数据收集、描述符计算和筛选以及模型建立和验证等方面的不足与研究方向。结果表明:QSPR在混合物燃爆特性预测中尚处于起步阶段,当前研究的首要限制是混合物燃爆特性参数实验数据样本不足,关键点及难点是混合物结构的准确表征,未来研究应关注的重点是大量数据源统一的数据样本的获取方法、非加和性混合物分子描述符的计算方法以及机器学习等非线性建模方法。     

Flash point prediction for the binary mixture of phosphatic solvents and n-dodecane from UNIFAC group contribution model

The flash point temperature of Tri-n-butyl phosphate(TBP) and Tri-iso-amyl phosphate(TiAP) in n-dodecane binary mixture has been measured for the entire concentration range using the continuously closed cup flash point apparatus based on the ASTM D6450 method. The flash point was predicted using the UNIFAC group contribution model. The measured flash point was also compared with the prediction from the NRTL, UNIQUAC and Ideal solution models. The UNIFAC model is able to predict the flash point fairly well for the TBP–dodecane mixture and for TiAP–dodecane mixture no improvements is obtained over the ideal solution assumption. The flash point shows positive deviation from ideal solution behavior for both the binary mixture.     

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.     

基于BP神经网络的二元混合液体自燃温度预测

为了给工业界提供一种快速预测二元混合液体自燃温度的有效途径,将试验所测不同组分及配比的168个二元混合液体的自燃温度作为期望输出,将基于电性拓扑状态指数(ETSI)理论、引入混合ETSI概念而计算出的9种原子类型所对应的混合ETSI作为输入,采用三层BP神经网络技术建立了根据原子类型混合ETSI来预测混合液体自燃温度的BP神经网络模型,并应用改进的Garson算法进行多参数敏感性分析。经模型评价验证及稳定性分析,得到训练集的决定系数R2为0.965,平均绝对误差MAE为11.892 K,测试集的交叉验证系数Q2ext为0.923,平均绝对误差MAE为15.530 K,发现该模型的预测性能优于已有的多元非线性回归(MNR)模型,表明BP神经网络模型具有较好的拟合能力和预测能力,对烷、醇类混合体系自燃温度的预测精度最佳。     

混合液体火灾爆炸危险性——闪点预测与实验研究

支持向量机应用核函数技术,已经成为当前国际上一个研究的热点,由于支持向量机具有良好的理论基础和泛化性能,可将其引入到混合液体闪点预测的研究之中,以期建立准确、高效的预测模型。本文建立了一个基于支持向量机的理论模型,用于预测二元互溶混合液体的闪点。根据所研究混合液体的物理性质,选择了纯物质的粘度、表面张力、配比、燃烧下限等物理参数来表征闪点,以这些参数作为输入参数,二元混合液体的闪点作为输出值,应用支持向量机方法对两者之间的内在定量关系进行模拟。结果表明,闪点预测值与实验值符合良好。本方法的提出为工程上提出了一种预测二元互溶液体闪点的有效方法,可应用于评估混合溶液的火灾爆炸危害性及本质较安全设计。     

基于随机搜索优化XGBoost的瓦斯涌出量预测模型*

为防治瓦斯灾害,解决井下瓦斯涌出量在预测过程中因影响因素繁多带来的精度较低问题,提出1种基于套索(Lasso)回归与随机搜索优化极限梯度提升(XGBoost)的模型进行瓦斯涌出量预测。以沈阳某煤矿综采面瓦斯涌出量历史数据为例,综合考虑影响瓦斯涌出量的影响因素。首先利用Lasso回归提取对瓦斯涌出量有重要影响的特征数据,作为预测输入;采用随机搜索算法对XGBoost模型4种主要参数进行寻优,选取最优参建立预测模型获得预测指标并分析比较其他模型。研究结果表明:Lasso回归筛选出的影响因素结合随机搜索获得的最优参数组合优化XGBoost比其他模型预测精度更高,平均相对误差为1.53%,均方根误差为0.140 3 m3/min,希尔不等系数为0.013 2,研究结果可为现场瓦斯管理提供参考依据。     

基于循环神经网络的缓坡场地液化侧移预测*

为预测缓坡场地地震液化侧向位移,基于改进自适应算法（Rectified Adam）和循环神经网络模型（RNN）,提出液化侧移预测模型RA-RNN,通过对侧移数据进行样本学习,并利用改进自适应算法优化循环神经网络结构,验证RA-RNN模型可靠性,并与多元线性回归法（MLR）计算结果进行对比。结果表明:RA-RNN模型计算得到侧移一般为实测位移的0.7~1.3倍,训练结果R2,RMSE,MAE分别为0.977,0.375,0.141;土耳其科喀艾里RA-RNN模型预测结果RMSE和MAE为MLR模型的1/26,1/830;中国台湾集集镇RA-RNN模型预测结果RMSE和MAE为MLR模型的1/18,1/350,RA-RNN模型预测结果较优,预测精度及泛化能力得到很大提升。     

基于人工神经网络的二元液体闪点预测

建立了一个基于人工神经网络的理论模型,用于预测二元混合液体的闪点.根据所研究混合液体的物理性质,选择了相关黏度、表面张力等物理参数来表征闪点,以这些参数作为输入参数,二元混合液体的闪点作为输出值,应用反向传播(BP)人工神经网络方法对两者之间的内在定量关系进行模拟.结果表明,闪点预测值与实验值符合良好,优于传统的计算方...     

有机过氧化物反应热的危险性预测研究

为了采用非实验的方法对安全物质学的研究内容及研究方法进行初探,基于定量结构-性质关系法,选择13种与有机过氧化物热危险性的影响因子密切相关的描述符,分别对起始分解温度T0和分解热△H的实验数据进行多元线性回归、偏最小二乘和支持向量机回归分析,从而获得3种相应的预测模型。对比T0与△H的实验值和预测值,结果发现:SVM预测模型的精度高于PLS预测模型,MLR预测模型的精度最低;同种预测模型对分解热的预测结果均优于起始分解温度。此外,分析各预测模型的稳定性数据发现:MLR模型的预测过程发生了过拟合现象,不具备预测能力;PLS模型的交互验证系数均大于0.5,具备较稳定的预测能力;SVM模型的交互验证系数均大于0.9,具备非常稳定的预测能力。     

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.     

基于新型拓扑指数的咪唑类离子液体捕集CO2性能预测

大量温室气体CO_2的存在严重影响环境,而咪唑型离子液体具有独特的气体溶解性,在CO_2捕集方面的应用较为广泛。基于定量结构-性质相关性(QSPR)原理提出了一种新的描述符——拓扑指数(Topological Index,TI)描述符,研究了咪唑类离子液体捕集CO_2的性能与其拓扑指数描述符之间的内在定量关系。应用遗传算法获得与捕集量最为密切相关的一组拓扑指数描述符,将其与温度和压力一起作为输入参数,分别采用多元非线性回归算法及支持向量机算法建立了咪唑类离子液体捕集CO_2性能与其拓扑指数描述符之间的非线性模型。通过多元非线性回归算法得出训练集和测试集的决定系数分别为0.771和0.754,由支持向量机算法得出训练集和测试集的决定系数分别为0.990和0.981。对预测模型进行了评价验证及稳定性分析,结果表明,两种模型均具有良好的稳定性能和预测能力。根据拓扑指数描述符所建立的预测模型为工程应用提供了一种预测咪唑类离子液体捕集CO_2性能的有效方法。     

Correlation between flash points and vapor pressures of organic compounds

Correlations between flash points and vapor pressures at 25 °C for pure organic compounds were investigated. It was found that classification of organic compounds according to their chemical-structural characteristics (e.g., functional groups) was necessary for the correlation study. Under this classification, linearity seems to be the most appropriate correlation to explain the relationship between the inverse of flash points (°K) and the logarithm of vapor pressures (mm Hg) at 25°C for pure organic compounds. A test study to evaluate the validity of a regression line as an estimation of an unknown flash point from a known vapor pressure was carried out with a data set containing 31 alkanes and aromatics; 55% of the flash points were predicted within ±5°Cand89% were within ±10°C. Within limits of ± 5 to 10°C the procedure is useful but should be improved.