Experimental investigation on oxidation of sulfurized rust in oil tank

Oxidation of sulfurized rust in oil tank is complicated, and it is influenced by numerous factors such as water content, air humidity, operating temperature etc. The paper focuses on the oxidation process of sulfurized rust in the wild. Firstly, samples collected from a petrochemical company were put into the sulfurization & oxidation experimental apparatus to gain wet and dry sulfurized rusts. Their chemical compositions and phase were analyzed by Energy Dispersive X-ray Spectrometer (EDS) -scanning electron microscope (SEM) technique. The results showed that both wet and dry sulfurized rusts had S, Fe₂O₃, Fe₃S₄ and FeS₂, whereas FeS only existed in wet sulfurized rust. The two kinds of rusts gave a short length of side, diamond appearance and a large pore size in structure. Then oxidation of wet sulfurized rust was investigated, which included electrochemical reaction stage, electrochemical & chemical reaction coexisting stage and chemical reaction stage. The final oxidation product of wet sulfurized was determined to be Fe₂O₃. On the basis of this study, an indicator for monitoring and early-warning was proposed to prevent plants in vicinity of the accidental vessel or tank from fire and explosion.     

Evaluation of the spontaneous combustion tendency of corrosion products in oil tanks based on TOPSIS methodologies

Spontaneous ignition of the corrosion products of an oil tank may lead to an explosion. To evaluate the spontaneous combustion tendency of corrosion products in oil tanks, the thermodynamic characteristic parameters of the corrosion products of oil tanks were obtained by thermogravimetry as evaluation indexes. Then, the objective weights of these indexes were calculated via the CRITIC method, and TOPSIS theory was used to comprehensively evaluate the spontaneous combustion tendency of corrosion product samples from oil tanks. The results show that the weight of the mass loss rate at the ignition point is the highest, and the apparent activation energy of the corrosion products is not the decisive factor affecting their spontaneous combustion tendency. As such, the spontaneous combustion tendency of the corrosion products of oil tanks cannot be based on only the apparent activation energy. The spontaneous combustion tendency of the corrosion products of a gasoline tank is lower than that of a diesel tank. The higher the heating rate is, the stronger the tendency of spontaneous combustion will be.     

植物油布的自燃火灾特性和抑制效果研究

为探究植物油布的自燃危险性,利用TG-DSC热重分析技术讨论其自燃火灾特性及防老剂对其的抑制效果.结果表明:油布混合样品的特征温度分别为171.7℃,380.7℃,466.7℃和555.0℃,根据特征温度将油布氧化过程划分为5个阶段:低温氧化阶段、前期燃烧阶段、混合燃烧阶段、后期燃烧阶段和燃尽阶段;植物油活化能大小顺序...     

SVM application in hazard assessment: Self-heating for sulfurized rust

In order to assess the oxidation self-heating hazard of sulfurized rust, for particular ambient conditions in crude oil tanks, the support vector machine (SVM) technique is applied to predict the maximum temperature (T_max) of oxidation self-heating process. Five governing parameters are selected, i.e. the water content, mass of sulfurized rust, operating temperature, air flow rate and oxygen concentration in the respiratory/safety valve. The efficiency and validity of the SVM predictions are investigated in the case of two sets of data: more than 85 experiments performed in academic lab (China) and almost 17 additional results collected from existing literature. Two main steps are also discussed: the training process (on selected subsets of data) and prediction process (for the remaining subsets of data). It can be concluded that for both datasets the maximum temperature (T_max) values calculated by SVM technique were in good accordance with the experimental results, with relative errors smaller than 15% except for a few cases.The SVM technique seems therefore to be relevant and very helpful for complex implicit processes such as chemical reactions, as it is the case of the oxidation of sulfurized rust in oil tanks. Furthermore, such predictive methods can be continuously be improved through additional experiments feedback (larger databases) and can then be of crucial help for monitoring and early warning of hazardous reactions.     

煤自燃预测气体及活化能变化研究

为了研究煤在低温阶段的自燃活化能及气体产生规律,基于耗氧量与煤温间的计算模型,利用煤氧化动力学测试系统,分析了3种不同自燃性煤的低温氧化表征。结果表明:1)随着煤自燃倾向性增强,煤的耗氧量和耗氧速率逐渐增大,且其耗氧速率急剧增大的拐点温度逐渐升高;2)不同自燃性煤活化能变化规律存在显著差异,利用阶段耗氧量拐点计算出铜川和大同煤样温度分别为203℃、228℃时,活化能快速减小,开始进入自发氧化阶段;晋城煤样活化能经历先减小后增大的过程,其中过渡温度段91~135℃时,活化能最小;同时拟合出活化能(E)与指前因子(A)关系式满足动力补偿效应,验证了机理函数的合理性;3)依据复合气体CO_2/CO、CH_4/C_2H_6、C_2H_4/C_2H_6、C_3H_8/C_2H_6随温度的变化趋势,结合煤低温氧化特性,可预测煤样的氧化进程和煤体温度。     

硫铁化物氧化自燃的动力学分析

为研究含硫油品储油罐中硫铁化物的自燃倾向性，采用STA8000同步热分析仪对10，15，20℃/min等不同升温速率和15，20，25 mL/min等不同空气流量下的硫铁化物进行试验，并通过获得的TG-DSC曲线研究试样的自燃特性；在此基础上，根据Coat模型，利用不同反应机理函数对热重数据进行分析。结果表明:该试验条件下，硫铁化物的氧化进程符合三级反应动力学机制；得出了硫铁化物在不同升温速率和空气流量下的表观活化能；在560～746℃温度区间内，随着升温速率的增加，空气流量的加大，活化能数值明显减小，自燃倾向性增大。研究结果可为预防和控制因硫铁化物自燃引发的火灾、爆炸事故提供理论参考。     

单轴应力对煤自燃特性参数和导热系数的影响研究

为探究单轴应力作用下煤氧化和传热特性，利用自制荷载加压煤自燃特性参数测定装置对炉体内长焰煤煤样进行程序升温。结合程序升温过程中煤临界温度Tc和Tg，对其进行阶段划分:阶段1为30℃~Tc；阶段2为Tc~Tg。计算了不同单轴应力下2个阶段煤表观活化能和平均耗氧速率。根据能量守恒得出程序升温过程煤导热系数随温度的变化，进一步分析煤导热系数与单轴应力的关系。结果表明:阶段1单轴应力为4 MPa时为临界轴压，煤表观活化能最大，平均耗氧速率最小；阶段2煤表观活化能和平均耗氧速率随单轴应力增大均呈抛物线变化，单轴应力为2.7 MPa时为临界轴压，煤表观活化能最大，平均耗氧速率最小；阶段1和2煤导热系数随温度升高均先减小后增大，并且煤导热系数随单轴应力增大呈三次函数变化。     

FeS引发储油罐着火温度动态变化曲线的研究

储油罐着火事故被推测是由硫腐蚀产生的FeS氧化引起的。笔者阐述了储罐中FeS形成的原因 ,并采用自然发火绝热测试系统对FeS自然氧化进行 1 9h的跟踪实验 ,观察FeS绝热氧化过程中温度动态变化特性。实验发现 ,FeS氧化由诱导氧化期、中速氧化期和加速氧化期 3个阶段组成。诱导氧化期是积蓄能量 ,激发FeS活性的过程 ,试样温度基本未发生变化 ;中速氧化期是FeS试样表面的分子活性被激发 ,与FeS试样表面吸附的氧气发生氧化反应的过程 ,温度增加较慢 ;加速氧化期是FeS分子内部的活性被激活并进行氧化反应的过程 ,温度迅速升高。结果证明 :随着反应的进行 ,温度随反应时间变化的幅度越来越大 ,氧化反应的反应热不能及时散开而急剧地积累 ,温度急剧地升高 ,将引起油品自燃。此外 ,通过X衍射图和氧化升温曲线证明 ,水是影响FeS氧化的重要因素。     

煤炭自燃指标性气体确定的实验研究

矿井火灾是矿井五大灾害之一,煤炭自燃则是矿井火灾最主要的起因。为了了解煤炭氧化、自燃规律,本文采用TG-DSC技术研究了不同煤种在水分蒸发、吸氧增重、受热分解及燃烧等不同氧化阶段的氧化特征值;并采用TG-DSC-GC联用技术研究了不同煤种在整个氧化阶段的气体产物生成规律及其特征。在煤的低温氧化阶段,找出了CO等可作为判别煤自燃的指标性气体及C2H4等辅助指标性气体;并得出了各煤种氧化阶段的耗氧规律。     

Kinetics characteristics of coal low-temperature oxidation in oxygen-depleted air

The longwall gob (mined-out) area is one of the main places that are prone to coal spontaneous combustion and most of the residual coal in it is in oxygen-depleted air as it is a semi-enclosed space. A DSC (Differential scanning calorimetry) test system was designed to accurately test the heat generation of coal oxidation in different oxygen concentration atmosphere, based on which the kinetics parameters (activation energy and pre-exponential factor) of coal low-temperature oxidation in oxygen-depleted air were solved out. The results show that the kinetics parameters present obvious stage features and the lower the oxygen concentration is, the smaller is the difference of the kinetics parameters that in different oxidation stages. When the oxygen concentration is lower than 5% and 3% for jet coal and meagre coal respectively, the kinetics parameters of slow oxidation start to be greater than that of rapid oxidation. Both in the slow oxidation and rapid oxidation stage, with the decrease of oxygen concentration, kinetics parameters present significant decline on the whole while in different oxygen concentration range, the decline rate is different. It's concluded that when assessing the residual coal's self-heating risk, we need to use the corresponding kinetics parameters of coal oxidation in the oxygen concentration of the location where the residual coal is and the safety factor will be greater to only use the kinetics parameters of coal oxidation in slow oxidation stage. This study is of great significance for the assessment and control of the self-heating risk of coal that in different oxygen concentration atmospheres of the longwall gob areas.     

碱性水对煤自燃特性影响实验研究

为了研究碱性水对煤自燃特性的影响，选取葫芦素煤矿102工作面煤样作为实验煤样，利用STA-449C型同步热分析仪进行热重实验，研究加入PH=8 NaOH的煤样与原煤以及加入蒸馏水煤样在空气氛围中燃烧失重、放热量、特征温度点等变化规律，并根据Coats-Redfern积分模型计算了3种煤样燃烧反应动力学参数（活化能、指前因子）。研究结果表明:加入碱性水的2号煤样失重量较1，3号少，燃烧失重速率更低；2号煤氧化燃烧温度区间缩短，着火温度点升高，放热量少，比1，3号煤分别少485.0，480.4 J/g；3种煤样反应机理基本遵循一级化学反应函数，2号煤各段活化能高于1，3号煤，但2号煤失水活化能小于3号，表明碱性水具有抑制煤自燃效应。     

煤氧化-热解进程的增失重阶段与动力学三因子分析

为分析煤氧化-热解进程的增失重阶段与动力学三因子,根据同一氧体积分数、5种不同升温速率下煤氧化-热解的TG-DTG曲线,探讨了煤氧化-热解进程经历的增失重阶段,基于Popescu法计算了不同阶段的动力学三因子。结果表明实验煤样的氧化-热解进程可分为失水失重、氧化增重、燃烧失重和燃尽恒重4个阶段。失水失重、氧化增重和燃烧失重阶段的反应机理分别为Mample单行法则、三维扩散模型和相边界反应的收缩球体模型;活化能分别为54.128 kJ·mol-1、152.252 kJ·mol-1和134.458 kJ·mol-1;指前因子的自然对数分别为16.832 s-1、32.597 s-1和18.365 s-1。     

含硫油品储罐中硫化铁自燃引发事故原因分析

通过分析含硫油品储罐中活性硫的主要组成及对油品储罐的腐蚀方式,总结了含硫油品储罐中硫化铁的生成方式、自燃性及其主要影响因素。分析认为,尽管活性硫对设备的腐蚀形式多样,但低温湿H2S腐蚀是活性硫对油品储罐的主要腐蚀方式,腐蚀产物极易自燃而引发油品储罐发生火灾和爆炸事故。建立了含硫油品储罐硫化铁自燃事故的故障树(FTA)图并对其最小割集的分析认为:储罐防腐涂层脱落、水的存在和原油含硫是引起顶事件发生的最重要基本事件。通过故障树分析,探讨了硫化铁自燃事故的主要原因并提出相应的预防措施。     

煤自燃特性及自然发火预测预报指标体系研究

以梁宝寺矿3号煤层为背景,采用色谱吸氧法和氧化动力法对其自燃倾向性进行了对比分析。同时,通过煤氧化升温热解实验对其升温过程中各气体随温度的变化规律进行了分析,以实验所得和灰色关联分析所得定性和定量相结合的方式,优选出了不同温度阶段煤自然发火预测预报所对应的第一、第二和第三预测指标,建立了煤自然发火预测预报体系,为有效抑制该矿及同类矿井火灾的发生具有重要意义。     

Assessment of the thermal hazards and oxidization mechanism of coloured corn starch dust by TG–FTIR

Starch is widely used in industrial production and in every life, and an increasing number of accidents of starch dust burning and explosions are occurring and have caused serious casualties and economic losses. Previous studies on the oxidative properties and microscopic characterization of coloured corn starch dust have been less systematic than the present study. To prevent coloured corn starch dust explosion accidents more effectively, thermogravimetry and Fourier transform infrared spectroscopy were applied to study the oxidation characteristics of coloured corn starch dust. Seven characteristic temperatures were determined from the thermogravimetric curves and derivative thermogravimetric curves of coloured corn starch dust. The entire oxidation process of coloured corn starch dust was divided into five stages, and a 60% mass loss occurred in the rapid oxidation stage. Three iso-conversion methods were used to calculate the apparent activation energy (E_a) and pre-exponential factor (A) at different oxidation stages. The value of E_a was found to be related to the difficulty of the reaction, and it had a positive correlation with lnA. Six kinds of gases were detected during the oxidation process. The oxidation mechanism was further analysed by the macro and micro characterization of the oxidation process. The findings provide a theoretical basis for preventing and controlling explosion accidents that involve coloured corn starch dust.     

煤低温氧化热解的热分析实验研究

在热分析动力学的基础上,对阳泉煤样运用同步热分析仪进行150℃下的氧化以及热解实验,得出该煤样相应的TG-DSC曲线。通过两者的TG-DSC曲线,对比分析煤样的热量释放情况,并结合曲线设定多项式形式的机理函数以分析其动力学特性。实验研究得出:该煤的低温氧化过程较之热解过程是个明显的氧化放热过程;该煤低温氧化和热解过程的最佳机理函数都为多项式,并且相应过程中的TG曲线和DSC曲线适用于同一个机理函数,这与一般所定义的机理函数不同;热解过程较之氧化过程所需的表观活化能较大,相同条件下较易发生煤的氧化自燃。     

以活化能的观点研究煤炭自燃机理

笔者对煤体的性质和结构进行了分析 ,简要地介绍了关于煤炭自燃机理的各种学说。目前有许多学者用不同的方法来研究煤炭的自燃机理 ,笔者从煤活化能的角度来研究煤炭的自燃。由氧化反应方程提出了活化能 ,根据活化分子运动理论解释了活化能的基本概念 ;并建立了相应的煤氧化反应的活化能方程 ,该方程直线部分的斜率 (E/R)可求出氧化反应的活化能。在煤炭自燃进程中 ,随着煤体温度的升高 ,活化能降低 ,氧化反应加速 ,大量的热量产生 ,如此循环 ,最终导致了煤的燃烧。     

油品储罐H_2S对铁锈腐蚀产物自燃性研究

为了分析有氧条件下H2S对铁锈腐蚀产物的自燃性,模拟含硫油品储罐中铁锈(Fe2O3:75%;Fe(OH)3:7%;Fe3O4:18%)在有氧条件下与H2S气体的反应试验。将铁锈与H2S气体、O2按不同比例混合形成的混合物进行反应,再进行所得产物的氧化反应。采用X射线衍射分析法鉴定混合气体与铁锈的反应产物,并研究不同初始O2体积分数下的混合气体与铁锈的反应及其产物的再氧化反应,通过温度变化评价铁锈与H2S气体反应产物的自燃性。结果表明,在有氧条件下,H2S对铁锈腐蚀产物主要是FeS;随着初始O2体积分数的增加,铁锈与H2S的反应伴随其产物的氧化反应,HS对铁锈腐蚀产物的量减小,这种产物再氧化自燃性降低。     

The effect of N2/CO2 blend ratios on the pyrolysis and combustion behaviors of coal particles: Kinetic and thermodynamic analyses

The aim of this work is to investigate the impact of various CO₂/N₂ ratios on coal pyrolysis and combustion properties and to provide theoretical guidance for better preventing and controlling coal spontaneous combustion in the goaf. The dynamic pyrolysis and combustion characteristics of DX coal were analyzed by using a thermal gravimetric analyzer (TGA) in a constant oxygen atmosphere with different CO₂/N₂ blend ratios. The Málek method combining Coats-Redfern and Achar methods was used to determine the most probable mechanism functions. CO₂ containing atmospheres increased characteristic temperatures, burnout rate, maximum mass loss rate and comprehensive combustion performance index compared to O₂/N₂ atmospheres. In stages I-III, a lower apparent activation energy was observed in O₂/CO₂ atmospheres. Apparent activation energy and enthalpy changes showed upward trends in the reaction stage (I→III→IV), whereas Gibbs free energy change and entropy change decreased. The dynamic pyrolysis and combustion of DX coal necessitated increased energy in environment with a CO₂/N₂ ratio of 4:6, revealing the optimal inhibitory effect on DX coal with this particular ratio.     

典型装饰织物在不同氧浓度下热分析研究

人民生活水平的提高使人民对室内环境的舒适程度提出了更高要求 ,室内装饰织物的用量迅速增加 ,室内装饰织物在燃烧时会释放出大量有毒物质和热量 ,对人及环境构成了巨大危害。因此 ,研究装饰织物的燃烧特性非常重要。笔者利用热重 -差热 (TG -DTA)分析仪对纯棉、棉麻和腈纶这几种典型的装饰织物在不同的氧气浓度 (10 % ,15 % ,2 1% )和升温速率 (10K/min ,30K/min)条件下进行了热重分析 (TG)和差热分析 (DTA)实验 ,研究了它们的燃烧特性 ,并着重进行了不同氧浓度下的对比研究 ,发现试样的燃烧分为两个阶段。建立了以一级反应模型为主的动力学方程 ,并得出了各阶段的动力学参数、表观活化能和频率因子。