精细化工固定源废气采样时机的选择探讨

以某医药企业某产品生产过程为实例,综合各工段生产步骤、时间、废气产生情况及估算的污染物浓度等因素,绘制各污染因子排放规律图,从而确定各污染因子排放浓度(排放量)最大的1 h为最佳采样时机。     

化工装置停工放空过程中VOCs排放及估算方法

通过分析化工企业典型开、停车过程的排污节点，表明停车过程中大气挥发性有机污染物主要来自装置退料结束后挂壁、底部滞留和内部空间蒸气等滞留在设备内部的残余物料。在总结化工装置停工放空过程中大气挥发性有机物来源的基础上，讨论并提出大气污染排放量估算方法。     

基于GM-SVR的小样本条件下化工设备可靠性预测

为了准确预测化工设备可靠性趋势，针对化工设备失效寿命数据为小样本的情形，基于灰色估计法与支持向量回归机在小样本数据处理中的优势，建立了失效寿命时间服从三参数威布尔分布的化工设备可靠性模型；结合GM（1，1）和SVR对模型进行参数估计，在压缩机可靠性分析中进行了实例应用，对比分析了最小二乘法、灰色估计法和GM-SVR的估计效果。研究结果表明:GM-SVR对威布尔分布参数的估计精度明显优于最小二乘法和灰色估计法，可以有效地应用于化工设备失效数据为小样本时的可靠性预测。     

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。     

TiO2气溶胶快速去除空气中的芥子气模拟剂

在自制反应器内,通过喷射法将纳米TiO_2分散成气溶胶形式,用以降解空气中的芥子气模拟剂二乙基硫醚(DES)。利用自行设计的一套气溶胶沉降行为评价装置,对TiO_2气溶胶的释放条件进行了优化。系统研究了相对湿度、反应温度、光强、催化剂加入量、反应物浓度等因素对DES降解速率和彻底矿化速率的影响。结果表明:TiO_2气溶胶对2.80 mg/L(近似芥子气快速致死浓度)DES降解的半衰期由涂覆型TiO_2的34.5 min缩短至8.5 min;TiO_2气溶胶光催化降解DES的最佳相对湿度为35%,此时CO_2最快生成速率可达34.64μg/(L·min),150 min内彻底矿化比例达66.1%;对于1.5 L反应器,催化剂加入量为30 mg时降解DES的量效比达到最佳状态;TiO_2气溶胶光催化适用于含低浓度DES空气的快速净化。     

铁路沿线可燃重气储罐最小隔离区域划分探讨*

为保护铁路线，以某化工厂距离高铁路线最近的丙烯球罐为例，提出丙烯球罐泄漏最小隔离区域划分方法以及2种保护高铁线路方案，利用重气扩散模型和定量风险评价（QRA）软件分别进行丙烯扩散模拟、爆炸模拟，并进行危险与可操作性分析（HAZOP）和保护层分析（LOPA）。结果表明:球罐发生泄漏及火灾爆炸等事故，会给附近铁路线带来严重破坏；丙烯泄漏或球罐因周围其他设备设施或可燃物质着火而温度升高时，保护措施不足；隧道的安全可靠性要高于仅设1道防爆墙，隧道长度需覆盖最小隔离区域的可及范围，在扩散区域内也需设立普通挡墙，在极度危险情况下，需要实施高铁停开等保护措施。     

肥煤自燃全过程热动力学特征参数研究

实验测定了林西矿肥煤样品30~900℃煤自燃全过程热动力学特征参数,得出:TG/DTG曲线显示煤样DTG初始临界温度45℃,干裂温度122℃,活性温度195℃,增速温度265℃,质量极大值温度342℃,着火温度465℃,最大热失重速率温度515℃和燃尽温度690℃;DSC曲线显示,煤样初始放热温度60℃、最大热释放速率温度511℃。结合TG-DTG-DSC曲线综合分析可知,煤温达到510℃左右时煤样反应最剧烈。由煤自燃标志气体测定实验系统得出:煤温130℃后CO,CO 2释放量迅速增加,210℃增加速度下降;CH 4,C 2 H 6含量变化具有规律性且两者变化相近;C 2 H 4出现温度为130℃;C 2 H 4/C 2 H 6比值在190~350℃有较强的规律性,呈上升趋势且上升速度较快;350℃之后,CH 4,C 2 H 6,C 2 H 4体积分数均开始急剧增大;C 2 H 4/CO与C 2 H 4/CO 2变化趋势大致相同,在130~350℃时缓慢增长,达到350℃后比值呈指数形式上升。经拟合曲线,得到活化能的3个突变点温度:70,180,220℃,其中180℃与交叉点温度相吻合。通过以上研究,得到了肥煤自燃全过程的热力学特征参数,为实际生产中防治煤自燃提供了理论依据。     

Effect of pyrolysis and oxidation characteristics on lauric acid and stearic acid dust explosion hazards

The effect of pyrolysis and oxidation characteristics on the explosion sensitivity and severity parameters, including the minimum ignition energy MIE, minimum ignition temperature MIT, minimum explosion concentration MEC, maximum explosion pressure P_max, maximum rate of pressure rise (dP/dt)_max and deflagration index K_st, of lauric acid and stearic acid dust clouds was experimentally investigated. A synchronous thermal analyser was used to test the particle thermal characteristics. The functional test apparatuses including the 1.2 L Hartmann-tube apparatus, modified Godbert-Greenwald furnace, and 20 L explosion apparatus were used to test the explosion parameters. The results indicated that the rapid and slow weight loss processes of lauric acid dust followed a one-dimensional diffusion model (D1 model) and a 1.5 order chemical reaction model (F1.5 model), respectively. In addition, the rapid and slow weight loss processes of stearic acid followed a 1.5 order chemical reaction model (F1.5 model) and a three-dimensional diffusion model (D3 model), respectively, and the corresponding average apparent activation energy E and pre-exponential factor A were larger than those of lauric acid. The stearic acid dust explosion had higher values of MIE and MIT, which were mainly dependent on the higher pyrolysis and oxidation temperatures and the larger apparent activation energy E determining the slower rate of chemical bond breakage during pyrolysis and oxidation. In contrast, the lauric acid dust explosion had a higher MEC related to a smaller pre-exponential factor A with a lower amount of released reaction heat and a lower heat release rate during pyrolysis and oxidation. Additionally, due to the competition regime of the higher oxidation reaction heat release and greater consumption of oxygen during explosion, the explosion pressure P_m of the stearic acid dust was larger in low concentration ranges and decayed to an even smaller pressure than with lauric acid when the concentration exceeded 500 g/m³. The rate of explosion pressure rise (dP/dt)_m of the stearic acid dust was always larger in the experimental concentration range. The stearic acid dust explosion possessed a higher P_max, (dP/dt)_max and K_st mainly because of a larger pre-exponential factor A related to more active sites participating in the pyrolysis and oxidation reaction. Consequently, the active chemical reaction occurred more violently, and the temperature and overpressure rose faster, indicating a higher explosion hazard class for stearic acid dust.     

基于ALOHA软件的某化工厂选址合理性评估

为了研究化工厂选址的合理性,以山东省某化工厂为例,采用ALOHA(有害大气空中定位软件)模拟软件定量确定厂区内环氧乙烷毒气扩散事故的影响区域和敏感点毒气浓度,结合GoogleEarth地图对影响范围进行实地拟合。结果表明化工厂的环氧乙烷储罐泄漏后,毒气扩散到厂区范围之外,毒气浓度在50~500ppm之间的重伤区(ERPG-2)扩散距离可达1.7km,对周围居民的人身安全构成严重威胁;厂区应根据拟合结果重新规划工厂中环氧乙烷储罐的位置;ALOHA软件对化工厂选址评价提供了新的手段。     

Fatty acids composition of Caenorhabditis elegans using accurate mass GCMS-QTOF

The free living nematode Caenorhabditis elegans is a proven model organism for lipid metabolism research. Total lipids of C. elegans were extracted using chloroform and methanol in 2:1 ratio (v/v). Fatty acids composition of the extracted total lipids was converted to their corresponding fatty acids methyl esters (FAMEs) and analyzed by gas chromatography/accurate mass quadrupole time of flight mass spectrometry using both electron ionization and chemical ionization techniques. Twenty-eight fatty acids consisting of 12 to 22 carbon atoms were identified, 65% of them were unsaturated. Fatty acids containing 12 to17 carbons were mostly saturated with stearic acid (18:0) as the major constituent. Several branched-chain fatty acids were identified. Methyl-14-methylhexadecanoate (iso- 17:0) was the major identified branched fatty acid. This is the first report to detect the intact molecular parent ions of the identified fatty acids in C. elegans using chemical ionization compared to electron ionization which produced fragmentations of the FAMEs.