纤维素热裂解的二次反应研究

在热重红外联用分析仪上开展了纤维素的热裂解失重研究,通过对纤维素热裂解的TG和DTG曲线以及热解产物的红外析出图谱的分析研究,探讨了纤维素热裂解的二次反应过程及机理,并在经典Broido—Shafizdeh模型的基础上．提出了改进的纤维素热裂解模型。     

Removal of a type of endocrine disruptors-di-n-butyl phthalate from water by ozonation

Ozonation of synthetic water containing a type of endocrine disruptor-di-n-butyl phthalate （DBP） was examined. Key impact factors such as pH, temperature, ionic strength, ozone dosage and initial DBP concentration were investigated. In addition, the activities of radicals on uncatalysed and catalysed ozonation were studied. The degradation intermediate products were followed and the kinetic of the ozonation were assessed as well. Results revealed that ozonation of DBP followed two mechanisms. Firstly, the reaction rate of direct ozonation was slower at lower pH, temperature, and ionic strength. Secondly, when these factors were increased for indirect radical reaction, higher percentage of DBP was removed with the increase of the initial ozone dosage and the decrease of the initial DBP concentration. In addition, tea-butanol, humic substances and Fe（Ⅱ） affected DBP ozonation through the radical pathway. It was determined that ozonation was restrained by adding tea-butanol for its radical inhibition effect. Furthermore, humic substances enhanced the reaction to some extent, but a slight negative effect would be encountered if the optimum dosage was exceeded. As a matter of fact, Mn（Ⅱ） affected the ozonation by ＂active sites＂ mechanism. In the experiment, three different kinds of intermediate products were produced during ozonation, but the amount of products for each one of them decreased as pH, temperature, ionic strength and initial ozone dosage increased. A kinetic equation of the reaction between ozone and DBP was obtained.     

燃料NO生成的总包反应速率

基于全面化学反应体系,对燃料ＮＯ的反应特性进行了详细的数值计算和理论分析,指出了目前应用较多的ＤｅＳｏｅｔｅＮＯ总反应模型的不足,同时,通过引入燃料氮氧化过程中关联组分Ｏ与ＯＨ离子的浓度和,用多元回归的方法得到了燃料ＮＯ生成的总包反应速率表达式。     

加压条件下石灰石的脱硫反应研究

对石灰石在加压条件下的脱硫反应进行了实验研究。实验采用加压热重分析（PTGA）法,得出了加压时石灰石脱硫反应转化率数据。当压力为1.15MPa时,转化率在30.5％～45％之间。测定了加压条件下反应温度、SO₂浓度和石灰石品种对CaCO₃转化率的影响并建立了反应数学模型并由模型计算了脱硫反应动力学参数。最后对反应机理进行了分析。     

近地层氮氧化物和臭氧的区域分布研究

介绍了近地层氮氧化物和臭氧的区域分布研究方法,使用简化的区域尺度大气污染物传输模型和光化学反应模型,模拟计算了1990年中国主要城市排放氮氧化物的情景下,夏季(7月)主要城市的氮氧化物和相应的臭氧在近地层的浓度分布。      

燃煤流化床中N2O生成与分解的均相反应机理

介绍由燃料氮生成Ｎ２Ｏ的主要途径是：ＮＣＯ→ＮＯ→Ｎ２Ｏ＋ＣＯ,ＮＨ＋ＮＯ→Ｎ２Ｏ＋Ｈ;分解Ｎ２Ｏ的主要反应是：Ｎ２Ｏ＋Ｈ→Ｎ２十ＯＨ。分析了挥发分中的燃料氮成分、煤种、炉内温度、过量空气系数、分级与单级燃烧方式等因素对Ｎ２Ｏ排放的影响。     

甲苯法生产己内酰胺污水治理研究

通过对己内酰胺生产污水治理的研究 ,总结出以ENSBR法处理高含氮、高浓度有机物污水的一些规律 ,以及CODCr负荷、氨化作用、碱度 (pH值 )等对硝化反应的影响。     

大气臭氧损耗中双自由基反应机理的量子化学研究

用量子化学ＲＨＦ理论方法研究了单重态双自由基ＮＨ,ＣＨ２、ＣＣＬ２与大气臭氧Ｏ３的反应机理。在３－２１Ｇ水平上用梯度解析技术优化了上述瓜在的反应物、中间体和产物构型,６－３１Ｇ或６－２１Ｇ计算能量,得到了各构型的有关结构数据。计算表明：上述反应分２步进行,双自由基先与Ｏ３反应生成稳定的中间体,然后在光照条件下中间体分解为ＮＨＯ、Ｈ２Ｃ烽ＣＬ２ＣＯ等稳定分子。从动力学看,２步反应分别为「π４ｓ＋Ｗ２     

α-Fe2O3/AC催化剂的制备及光Fenton反应降解双酚A

采用温和的无模板溶液反应合成了α-Fe₂O₃/AC复合催化剂,作为光Fenton降解双酚A反应的催化剂。通过XRD、SEM、FTIR、DRS、BET、XPS等方法对催化剂的形貌和理化特性进行了分析。结果表明：该催化剂晶型良好,为介孔材料,能够有效吸收和利用紫外光和可见光;该催化剂具有较高的催化活性,稳定性良好;在初始双酚A质量浓度为30 mg/L、溶液pH为4、H₂O₂加入量为320 mg/L、反应温度为40 ℃、催化剂加入量为1.33 g/L的条件下,双酚A降解率可达91.4%。     

Dual-reaction-center catalytic process continues Fenton’s story

• Dual-reaction-center (DRC) system breaks through bottleneck of Fenton reaction. • Utilization of intrinsic electrons of pollutants is realized in DRC system. • DRC catalytic process well continues Fenton’s story. Triggered by global water quality safety issues, the research on wastewater treatment and water purification technology has been greatly developed in recent years. The Fenton technology is particularly powerful due to the rapid attack on pollutants by the generated hydroxyl radicals (•OH). However, both heterogeneous and homogeneous Fenton/Fenton-like technologies follow the classical reaction mechanism, which depends on the oxidation and reduction of the transition metal ions at single sites. So even after a century of development, this reaction still suffers from its inherent bottlenecks in practical application. In recent years, our group has been focusing on studying a novel heterogeneous Fenton catalytic process, and we developed the dual-reaction-center (DRC) system for the first time. In the DRC system, H₂O₂ and O₂ can be efficiently reduced to reactive oxygen species (ROS) in electron-rich centers, while pollutants are captured and oxidized by the electron-deficient centers. The obtained electrons from pollutants are diverted to the electron-rich centers through bonding bridges. This process breaks through the classic Fenton mechanism, and improves the performance and efficiency of pollutant removal in a wide pH range. Here, we provide a brief overview of Fenton’s story and focus on combing the discovery and development of the DRC technology and mechanism in recent years. The construction of the DRC and its performance in the pollutant degradation and interfacial reaction process are described in detail. We look forward to bringing a new perspective to continue Fenton’s story through research and development of DRC technology.