强氧化自由基杀灭压载水微生物的模拟试验研究

在强电离电场作用下,H2O、O2分子发生电离、分解电离和电荷交换反应,在分子层次上加工成高浓度羟基溶液。试验是在每小时处理2t压载水的试验系统进行的。把羟基溶液加入压载水输送管道内,仅距加入点4m长度地方取样检测,当压载水的羟基比值浓度达到0 63mg/L时,原生动物、单胞藻、细菌浓度分别从4 4×104/mL、6 0×104/mL、1 9×105/mL均减少到低于检测方法的最低限;剩余羟基药剂分解成H2O、O2等。从试验数据表明,羟基溶液是治理压载水有效、廉价、无残留物的创新方法。     

新型绿色化学反应介质的研究进展

综述了绿色化学在反应介质方面的研究进展。新型的有机合成反应介质主要包括离子液体、超临界流体、水溶剂及微波无溶剂技术。这些新型反应介质不仅可以取代传统的挥发性有毒有害有机溶剂,同时还可提高反应的活性和选择性,加速反应的进行,且有利于催化剂的回收利用及产品的分离。新型绿色化学反应介质是实现有机合成绿色化的重要途径。     

一株硝基苯高效降解菌的筛选及其降解特性

自南京化工厂下水道底泥和废水处理系统曝气池活性污泥中驯化分离得到一株能快速降解硝基苯的菌株,初步鉴定其为不动杆菌属菌株。该菌株降解硝基苯的最适宜环境条件为温度25℃～35℃,pH7～8,振荡速率大于120r/m。在适宜环境条件下,该菌株能够在24h内全部降解初始浓度不超过400mg/L的硝基苯,该浓度范围内硝基苯的降解过程符合零级动力学特征;当硝基苯的初始浓度超过400mg/L时,降解菌的生长受到毒害作用,该浓度范围内硝基苯的降解在开始有一个明显的停滞期,降解过程不再符合零级或一级动力学特征。     

低床层烟炱吸附法脱硫试验及机理探讨

研究了以锅炉烟气沉降物为吸附剂的烟炱吸附法脱除SO2的工艺条件，结果表明该法较适宜的工艺条件为SO2浓度小于2400mg/L,烟气流速小于36m/h，烟气温度低于100℃，此时脱硫效率可达30％以上。初步探讨了烟炱吸附法脱硫的作用机理。     

硝酸甲胺反应过程的安全性研究

用反应量热仪(RC1e)对硝酸溶液与一甲胺溶液在反应过程中的热安定性进行初步研究,分别测试不同反应温度、加料速度和初始硝酸浓度下反应的放热情况。实验结果表明:该中和过程反应迅速,在室温就能进行;与反应温度、加料速度相比,起始硝酸浓度对反应安全性影响最大,且硝酸浓度越高,反应的速度和反应的完全程度也越高。实验还表明:RC1e是研究反应过程中热安定性情况的有效工具,能通过反应过程的热量变化体现反应速率,所得结果对硝酸甲胺的工业化生产具有重要的参考价值。     

Evaluation of thermal reaction for two azo compounds by using 20-L apparatus and calorimetry

Azo compounds are widely involved in the industrial processes of dyes, pigments, initiators, and blowing agents. Unfortunately, these compounds have a bivalent unstable –NN– composition, which can be readily broken when the ambient temperature is elevated. Self-accelerating decomposition might cause a runaway reaction and lead to a fire, explosion, or leakage when the cooling system fails or other events occur. This study investigated the explosion properties, thermal stability parameters, and thermal hazard and mechanism of 2,2′–azobisisobutyronitrile (AIBN) and 2,2′–azobis–2–methylbutyronitrile (AMBN). We used a 20-L apparatus, vent sizing package 2, synchronous thermal analysis, and differential scanning calorimetry under explosive, adiabatic, and dynamic conditions to acquire the explosive curves, thermal curves, and thermodynamic parameters of the substances. Moreover, the differential isoconversional method (Friedman method) and ASTM E698 equation were employed to obtain the apparent activation energy E_a. All the experimental results revealed that AIBN is more dangerous than AMBN. The E_a of AIBN was lower than that of AMBN. The results can be used to construct an azo compound thermal hazard database for use for searches and reference examples by industry and related research areas.     

308 nm光作用下α-Fe2O3表面HNO3的光解

采用紫外可见光谱(UV-Vis)、傅立叶变换红外光谱(FTIR)及离子色谱(IC)技术对HNO3在α-Fe2O3表面暗反应和308nm下光解反应进行了研究.考察了时间、HNO3浓度、相对湿度(RH)等条件对反应的影响.结果表明,随着HNO3浓度、光照时间的增加,HNO3在气相与α-Fe2O3表面光解产物浓度均呈指数增加;HNO3在α-Fe2O3表面光解产生的NO2、NO分别为气相产生的3.27及3.87倍,而无论气相还是表面光解的NO2浓度均约为NO的2倍.随着RH的增加,HNO3光解产生的HONO的浓度随之呈指数增大,其产率从RH 20%时的0.023增加到90%时的0.087.α-Fe2O3的表面效应在HNO3的表面光解反应中起主导作用.     

Quantum chemical investigation on photodegradation mechanisms of sulfamethoxypyridazine with dissolved inorganic matter and hydroxyl radical

Sulfamethoxypyridazine(SMP) is one of the commonly used sulfonamide antibiotics(SAs).SAs are mainly studied to undergo triplet-sensitized photodegradation in water under natural sunlight with other coexisting aquatic environmental organic pollutants.In this work,SMP was selected as a representative of SAs.We studied the mechanisms of triplet-sensitized photodegradation of SMP and the influence of selected dissolved inorganic matter,i.e.,anions(Br~-,Cl~-,and NO~-_3) and cations ions(Ca~(2+),Mg~(2+),and Zn~(2+)) on SMP photodegradation mechanism by quantum chemical methods.In addition,the degradation mechanisms of SMP by hydroxyl radical(OH·) were also investigated.The creation of SO_2 extrusion product was accessed with two different energy pathways(pathway-1 and pathway-2) by following two steps(step-I and step-II) in the tripletsensitized photodegradation of SMP.Due to low activation energy,the pathway-1 was considered as the main pathway to obtain SO_2 extrusion product.Step-II of pathway-1 was measured to be the rate-limiting step(RLS) of SMP photodegradation mechanism and the effect of the selected anions and cations was estimated for this step.All selected anions and cations promoted photodegradation of SMP by dropping the activation energy of pathway-1.The estimated low activation energies of different degradation pathways of SMP with OH·radical indicate that OH·radical is a very powerful oxidizing agent for SMP degradation via attack through benzene derivative and pyridazine derivative ring.     

固体云爆剂热分解性能研究

目的研究固体云爆剂的热分解特性。方法利用差示扫描量热(DSC)和热重分析(TG)测定该固体云爆剂的热分解过程。分别得到固体云爆剂在不同温度下的DSC和TG曲线,以及同一温度下云爆剂不同组分的DSC和TG曲线。结合线性回归分析的方法,利用Ozawa法、Starink法以及Kissinger法计算了反应活化能。结果其表观活化能为208 k J/mol左右。结论该固体云爆剂的热分解是一个连续的过程,具有良好的安定性。