Thermal safety assessment for solid organic peroxides

The thermal hazards of dicumyl peroxide (DCP) and benzoyl peroxide (BPO), self-reactive chemicals are identified and characterized using high-pressuredifferential scanning calorimeter, and simultaneous thermogravimetric analyzer, a C80 micro-calorimeter is used. The apparent exothermic onset temperature of DCP is found to be between the range of 112–122 °C for different heating rates in DSC tests. There are two coupled peaks of BPO around 105 °C at both the heating rates of 4.0 and 8.0 °C/min while no endothermic peak showed at lower heating rates. Furthermore, another endothermic peak appears immediately after the exothermic peak at about 211 °C of DCP under high-pressure conditions. For BPO, the endothermic peak before the exothermic peak disappears as the pressure increases to 1.0 and 1.5 MPa. The average values of apparent activation energy calculated by Flynn-Wall-Ozawa and Kissinger-Akahira-Sunose methods during the conversion rate between 15 and 75% of DCP are 80.69 and 74.05 kJ/mol, and that of BPO are 119.96 and 112.93 kJ/mol, respectively. According to the isothermal tests, the thermal decomposition of DCP behaviors is an n-th order reaction while BPO conforms to the laws of autocatalytic reaction.     

基于Winkler模型的沿空留巷底板变形力学分析

沿空留巷顶板岩层垮落到底板时,会影响底板的受力和变形,进而导致底臌,底臌的产生将直接影响采煤工作开展。为了对巷道底板的变形机理进行研究,根据空留巷底板受力特点,将巷道底板视为弹性地基梁,建立顶板岩层垮落在巷道底板上的不均匀荷载作用下的Winkler弹性地基梁力学模型,通过对高阶微分方程求解,分析巷道底板任一处的挠度、转角、弯矩及剪力的分布规律,并结合内力分布规律对底板破坏机理进行分析。结合工程实践,提出了防止底板变形的措施,为类似工程的设计及施工提供参考。     

差速器壳体疲劳寿命仿真分析方法

目的 研究差速器壳体疲劳寿命分析方法,调查差速器壳体断裂的根本原因.方法 以具体试验工况为输入,以减速器壳体支撑刚度为边界条件,以齿轮啮合力为输入载荷,建立弹性支撑条件下的差速器壳体有限元模型,并进行强度计算.以强度分析结果为输入,在疲劳寿命计算软件FEMFAT中进行疲劳寿命校核.考虑到差速器壳体分析工况较多、载荷复杂,采用Neuber公式,结合材料的循环应力-应变曲线方程和应力-应变迟滞回线方程,进行线弹性应力修正的方法进行校核.同时,为了更好地模拟差速器的运行极限工况,分析载荷采用了三正一负交替变化的载荷.最后,基于线性疲劳累积损伤理论的Miner法则对结果进行判断.结果 基于线性疲劳累积损伤理论的Miner法则,初始设计方案的计算结果表明,疲劳破坏发生在壳体过渡圆角处,其可承受的载荷循环次数为270次,不满足大于350次的设计目标,结果与疲劳台架试验相符,且失效区域对应性较好.通过增大差速器壳体过渡圆角半径及增加壳体厚度的方法对差速器壳体进行优化,优化后的疲劳分析结果显示,疲劳寿命增加至417次,满足350次设计目标,并顺利通过耐久台架试验.结论 通过优化前后台架试验结果与仿真结果的对比证实,该仿真分析方法能准确预测差速器壳体的疲劳水平,且该分析方法在计算精度方面是完全可信的,可以在实际项目开发中应用,可提前识别并规避风险,减少后期台架验证成本.     

响应面法优化Fenton预处理精细化工废水

甘肃省某精细化工企业实际生产废水成分复杂、有机物含量高、可生化性差,为满足后续生化工艺需求,急需开展适宜的预处理技术研究.采用Fenton氧化工艺对该企业废水进行预处理,在单因素试验基础上,以初始pH、H₂O₂投加量、n（H₂O₂）:n（Fe2+）、反应时间为考察因素,COD_Cr去除效果为响应值,构建响应曲面模型,分析4个独立因素及各因素之间的交互作用对COD_Cr去除效果的影响;同时,对反应过程进行表观反应动力学分析,采用紫外光谱及傅立叶变换红外光谱分析废水有机物结构变化,探究该反应过程机理.结果表明:①废水预处理的最佳工艺条件为初始pH 4、H₂O₂投加量8 mL/L、n（H₂O₂）:n（Fe2+）12、反应时间88 min,废水COD_Cr去除率达30.15%;模型的实际运行结果与预测值接近,模型可靠.②Fenton氧化降解该精细化工废水中有机物途径复杂,难以通过单一的底物模型进行拟合.③Fenton氧化能有效降解废水中不饱和有机物,但出水中仍含有酰胺类、不饱和醛类和芳香类化合物.研究显示,Fenton预处理能有效降解废水中难降解有机物,但出水仍未达到后续生化处理要求,还需进一步优化或与其他预处理工艺组合.      

Simultaneous voltammetric determination of four triazine herbicides in water samples with the aid of chemometrics

A novel differential pulse voltammetry (DPV) method was developed for the simultaneous analysis of herbicides in water. A mixture of four herbicides, atrazine, simazine, propazine and terbuthylazine was analyzed simultaneously and the complex, overlapping DPV voltammograms were resolved by several chemometrics methods such as partial least squares (PLS), principal component regression (PCR) and principal component–artificial networks (PC–ANN). The complex profiles of the voltammograms collected from a synthetic set of samples were best resolved with the use of the PC–ANN method, and the best predictions of the concentrations of the analytes were obtained with the PC-ANN model (%RPE_T = 6.1 and average %Recovery = 99.0). The new method was also used for analysis of real samples, and the obtained results were compared well with those from the GC-MS technique. Such conclusions suggest that the novel method is a viable alternative to the other commonly used methods such as GC, HPLC and GC-MS.     

含油污泥离心脱水中离心机参数的选择

通过对含油污泥离心脱水的批量处理和连续处理的研究,取得了含油污泥水固两相离心分离的满意效果.实验表明,适宜的操作参数可提高离心脱水效果.对LWD-430卧式螺旋离心机,当离心速度在1200～1400r/min之间,处理量在1～3 m3/h之间,差转速(转鼓与螺旋推料器的转速差)为20r/min时,离心液体积和COD均达到最佳状况.离心速度过高,会使絮体中的油离解出来,从而使离心液COD增加.差转速增加能明显改善"三泥"的离心脱水效果.     

基于差异进化算法的爆破震速参数识别与优化

爆破震动衰减特性研究通常采用经典的萨道夫斯基公式实现。如何根据不同爆破条件合理选择公式中的场地系数K和衰减指数α是确定爆破控制参数的关键。实际工程分析中,通常采用可监测参数反演识别方法获取K和α值。以大连地铁2号线201标段接收井横通道爆破作业为背景,基于差异进化(DE)算法中缩放因子F和交叉概率Cr贡献值的合理选择,研究萨道夫斯基公式K和α的反演问题。首先,通过对算法中F和Cr不同取值对萨道夫斯基公式计算结果的影响分析,得到各向震速条件下收敛最小的F和Cr值;然后,根据F和Cr取值反演K和α参数。工程实践表明,基于DE算法反演识别得到的K和α值代入萨道夫斯基公式,计算得到的垂向、纬向、经向速度及合速度与实测速度变化趋势一致,并处在合理误差范围之内。     

原料和热解温度对生物炭中可溶性有机质的影响

以水稻秸秆和杉木凋落物为原料,选择不同热解温度（350、500和650℃）制备生物炭,研究原料与热解温度对生物炭中可溶性有机质（dissolved organic matter,DOM）含量和光谱特征的影响.结果表明,随着热解温度的升高,两类生物炭pH值分别从8.10和6.56上升至10.53和8.23;热解温度对生物炭全碳（TC）含量的影响并不明显,但原料及其与温度交互作用的影响显著（P<0.05）.两类生物炭中可溶性有机碳（dissolved organic carbon,DOC）含量呈先降低后升高的趋势,相同热解温度下水稻生物炭的显著高于杉木生物炭的（P<0.05）.原料对DOM芳香化指数（SUVA₂₅₄值）无显著影响,但温度及其与原料交互作用的影响显著（P<0.05）,在500℃时该值最大,芳香化程度最高.三维荧光光谱表明,DOM组分以类富里酸和类腐殖酸为主,但这两种物质对热解温度的响应不同.傅里叶红外光谱分析发现,两类生物炭DOM在5个区域的相似位置存在吸收峰,其中,脂肪族C-H的伸缩振动随着热解温度的升高逐渐减弱.因此,高温（500℃和650℃）与低温（350℃）制备的生物炭相比,DOC含量降低,但其芳香化和腐殖化程度升高,稳定性增强.     

Characterization of Environmentally Friendly Polymers by Inverse Gas Chromatography: I Amylopectin

Amylopectin, as a potato starch based polymer, with a molecular weight of six million gram/mol was characterized using the Inverse Gas Chromatography Method (IGC). DSC method was also used to measure the glass and melting temperatures. Both DSC and IGC agreed well on a T_g of 105°C and T_m of 160–166°C. Nineteen solutes (solvents) were injected onto a chromatographic column containing amylopectin. These solutes revealed the interaction of alkanes with AP, and the wettability and water intake of AP. Alkanes showed exothermic values of interaction parameters which were increased as the temperature increased and as the number of carbons in the alkane series decreased. Retention diagrams of these solutes in a temperature range of 80–200°C revealed two zones, crystalline and amorphous. T_g and T_m were measured using these zones which complimented the DSC values. The two zones were used to calculate the degree of crystallinity below the melting temperature which ranged from 85% at 104°C to 0% at 161°C. The dispersive component of the surface energy of amylopectin was measured using alkanes which ranged from 25.35 mJ/m² at 80°C to 8.47 mJ/m² at 200°C. This is attributed to the weak crystalline surface of AP at 80°C and when the surface melted at 160°C the surface energy decreased due to the thermal expansion of the surface.     

塔里木盆地北缘盐渍地遥感调查及成因分析——以渭干河-库车河三角洲绿洲为例

土壤盐渍化严重威胁着干旱区绿洲的稳定与可持续发展，因此监测盐渍地的分布范围和程度以及分析其成因有着重要的意义。以塔里木盆地北缘盐渍地普遍发育区域渭干河-库车河三角洲绿洲为例，利用TM遥感影像，在野外调查的基础上，采用监督分类中的波谱角度分类法进行了盐渍地调查研究。该方法对盐渍地的提取精度可达到92％左右，是干旱区盐渍地监测的一种有效方法。在此基础上分析了渭干河-库车河三角洲绿洲盐渍地的分布范围与程度，并结合气候、地貌、水文、人类活动等因素，对盐渍化成因进行了讨论。结果表明：干旱荒漠气候是形成盐渍地的前提条件，母岩和母质含盐是形成盐渍地的物质基础，地表水和地下水的补给是形成盐渍地的动力，人为因素是形成灌区次生盐渍地的重要条件。