简单放热化学反应体系热安全性研究判据

许多危险化学物质在发生热化学反应的同时通常会放出热量,如果能量不能有效释放就可能引起火灾和爆炸事故,考虑到化学物质对热的响应方式非常复杂,从分析绝热条件下化学物质的热化学反应动力学入手,利用化学物质的物理化学特性参数计算化学反应体系在绝热条件下发生热化学反应的温升速率dT/dt,进而获得有关的动力学因子A,E等。结果表明,尽管在近似绝热条件下化学反应体系的热化学反应与其本身的特性和反应容器有关,但温升速率dT/dt只与物质的物理化学特性参数有关。含氯酸钾的几种简单放热反应体系的ARC实验结果进一步验证了这一结论。因此,同一种化学物质与不同物质构成的多元混合反应体系在相同近似绝热条件下的热化学反应特征参数,可以作为判据用来比较并评价体系的相对安全性,该判据对表征热化学反应的难易程度以及物质的相对安全性起到一定的指导意义。     

三氯乙醛的光降解反应研究

研究了太阳光照下,水溶液中FeC l3-三氯乙醛的光化学反应速率,采用紫外分光光度计定时对含有不同浓度Fe（Ⅲ）的溶液进行实验测定,并根据三氯乙醛标准溶液曲线进行分析。实验结果表明,在波长为480nm的紫外光照射下：室内自然光下含有Fe（Ⅲ）和室外太阳光下不含Fe（Ⅲ）的三氯乙醛溶液中,三氯乙醛的浓度基本保持不变;但在室外太阳光下含有Fe（Ⅲ）的三氯乙醛溶液中,三氯乙醛的浓度随着Fe（Ⅲ）浓度的增加而减小。由此表明,Fe（Ⅲ）是三氯乙醛光化学反应的催化剂,FeC l3-三氯乙醛的光化学反应随着Fe（Ⅲ）浓度的增加而加快。     

2-氨基-2,3-二甲基丁酰胺氧化合成热危险性研究

为研究2-氨基-23,-二甲基丁酰胺氧化合成的热危险性,采用差示扫描量热仪(DSC)测试2-氨基-2,3-二甲基丁腈和2-氨基-2,3-二甲基丁酰胺的热分解情况,采用反应量热仪(RC1)研究反应温度、双氧水滴加速度和氢氧化钠用量对反应的影响。研究结果显示,2-氨基-2,3-二甲基丁腈吸热热分解温度为149.5℃2,-氨基-2,3-二甲基丁酰胺表现为吸热和放热2段分解过程,吸热和放热分解温度分别为234.4℃和456℃。反应放热速率主要为加料控制,但是,存在一定的热累积。热失控体系最高温度(MTSR)低于2-氨基-23,-二甲基丁腈和2-氨基-23,-二甲基丁酰胺的分解温度,高于体系沸腾温度,在热失控的条件下,反应体系容易导致冲料危险;在优惠的工艺条件范围内,提高反应温度,延长滴加时间,可降低反应的MTSR,提高热转化率和反应安全性。     

公路滑坡灾害链式反应阶段性识别方法研究

为了对公路滑坡的发育阶段做出准确判别,研究了公路滑坡灾害发育的链式反应机理,将滑坡的发育阶段划分为3个阶段。采用广泛调研和专家咨询的技术手段,从发育阶段的表现特征中选定了滑坡识别的相关因素集和评分,在此基础上采用模糊数学的方法对公路滑坡灾害的发育阶段进行了识别,并在陕南公路滑坡调查中初步应用。     

Fe（0）/H_2O_2协同降解亚甲基蓝的研究

进行了Fe（0）和H2O2协同催化降解亚甲基蓝的研究,分析了Fe（0）投加量、H2O2投加量、溶液初始pH值和染料初始质量浓度等因素的影响。研究表明：Fe（0）和H2O2协同可有效催化降解亚甲基蓝;在pH为4.5,Fe（0）用量为2.0 g.L-1,H2O2用量为3.0 mmol.L-1时对10 mg.L-1亚甲基蓝的去除率在60 min内达到90%以上。MB的降解去除率随着Fe（0）投加量与H2O2用量的增加而增加,但随着其初始质量浓度的增大而降低。研究结果还表明,Fe（0）和H2O2可在接近中性条件下有效协同催化降解亚甲基蓝。UV-Vis光谱在反应过程的变化说明亚甲基蓝降解生成了一些小分子物质。     

Observer reactions to interpersonal injustice: The roles of perpetrator intent and victim perception

The present research contributes to a growing literature on observer reactions to injustice experienced by others. In particular, we separated two variables that have previously been confounded in prior research, namely perpetrator intent to cause harm and victim perception of harm. We expected that injustice intent and injustice perceptions would have both unique and joint effects on observer reactions. The results of three experiments in which we manipulated perpetrator injustice intent and victim injustice perceptions supported our predictions. First, we found that observers had more negative reactions toward superiors who intended to inflict high versus low levels of interpersonal injustice toward a subordinate. Second, the injustice intent of the superior influenced observers' reactions more than did victim perceptions of injustice. Third, most novel, we found that the mere intent to cause injustice generated negative reactions in observers, even in the absence of a “true” victim—that is, when the subordinate perceptions of injustice were low. Together, our results emphasize the importance of examining observers' reactions to injustice and incorporating perpetrator intentions into the study of organizational justice. Copyright © 2012 John Wiley & Sons, Ltd.     

One-step formation of oligopeptide-like molecules from Glu and Asp in hydrothermal environments

Biopolymer accumulation in the absence of enzymes is an essential step for the chemical evolution of primitive life-like systems, and successful simulation experiments of prebiotic biopolymer formation have suggested that oligopeptides could have formed near submarine hydrothermal vent environments on primitive earth. However, the yield and length of oligopeptides -- typically limited to 6-mers -- seems to be inadequate. One reason is the rapid formation of diketopiperazines (DKPs) from dipeptides. In this study, using a hydrothermal microflow reactor, we show that the one-step synthesis of oligopeptide-like molecules of length up to 20-mers proceeds from Glu and Asp. Yields of up to 0.17-0.57% were obtained in an acidic solution within 183 s at 250-310 degrees C, as evaluated by matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS) analysis and different types of high-performance liquid chromatography (HPLC) analyses. The present study indicates that Glu and Asp may have played important roles in the chemical evolution of oligopeptide-like molecules in hydrothermal vent environments on primitive earth.     

室温Fenton反应过程H2O2有效利用率的影响因素研究

Fenton反应是H2O2在Fe^2＋催化作用下产生氧自由基并氧化污染物的高效方法。但影响Fenton反应过程H2O2分解及其有效利用率的因素是很多的,其中[Fe^2＋]要求控制在3mmol／L以上。酚类体系H2O2的有效利用率不受H2O2浓度变化的影响,但受初始COD的影响,一般表现为随COD的增加,H2O2有效利用率迅速增加。当初始COD一定时,H2O2浓度在600mg／L和1800mg／L时,一元酚与二元酚体系的H2O2有效利用率均出现了两个峰值,前者的峰值分别为11．83gCOD／gH2O2和12．99gCOD／gH2O2,后者的峰值分别为9．01和11．95gCOD／gH2O2。而醇类体系H2O2的有效利用率受H2O2浓度的影响较大,但与初始COD的关系不明显。当H2O2浓度低于300mg／L时,乙醇比对照体系H2O2的分解率高1-3％,而有效利用率仅为0．6gCOD／gH2O2;随H2O2用量的继续增加,其有效利用率趋于0gCOD／gH2O2。而二元醇体系H2O2有效利用率与其浓度间呈“倒U”型规律,H2O2低于300mg／L时,其有效利用率仅为1．25gCOD／gH2O2;H2O2浓度在300mg／L～900mg／L之间时,其有效利用率可达8．96gCOD／gH2O2;其后随着H2O2的增加,有效利用率迅速下降到与乙醇体系相当。在混合体系中,醇羟基和酚羟基所占比例对H2O2有效利用率也有显著的影响,当乙醇比例小于60％时,H2O2有效利用率稳定在13．0gCOD／gH2O2;随乙醇比例的增加,其对H2O2的分解抑制效应表现出剂量依赖关系,H2O2有效利用率也逐渐下降到近于0gCOD／gH2O2,说明这部分H2O2并没有得以有效地分解用于氧化废水中的COD,这在工程实践中应引起高度的重视。     

Biodegradation of trace pharmaceutical substances in wastewater by a membrane bioreactor

The biodegradation of selected pharmaceutical micropollutants, including two pharmaceuticals with argued biodegradation, was studied by a lab-scale membrane bioreactor. The reaction kinetics and affecting factors were also investigated in this paper. Clofibric acid (CA) with contradictive biodegradation reported was degraded almost completely at different hydraulic retention times (HRTs) after adaptation to microorganisms. The biodegradation of CA was disturbed at low pH operation, while the activity of microorganisms recovered again after pH adjustment to neutral condition. Ibuprofen (IBP) degraded under neutral and acidic conditions. Removals of IBP and CA were zero-order and first-order reactions under high and low initial concentrations, respectively. Carbamazepine and diclofenac were not degraded regardless of HRTs and pH.     

水涤脱附条件下活性炭脱硫中有效吸附位的研究

以不同活性炭材料吸附性能测试实验的结果为依据,研究了在水涤脱附条件下活性炭脱硫的机理,指出水在吸附位部分失效过程中起到的几种作用,并从有效吸附位的角度进一步分析了吸附材料特性与吸附性能之间的关系,提出产生有效吸附位的前提是具有一定的反应空间,使之能满足反应分子间距和空间构型的条件.研究表明:吸附材料的孔径分布和外表面积是影响吸附性能的两个关键因素;平均孔径40～50A、颗粒直径为3 mm左右的中孔型颗粒活性炭,是一种理想的吸附材料.