Gas-phase thermal explosions in catalytic direct oxidation of alkenes

The metal-based catalytic oxidation of alkenes to the corresponding epoxides is playing a significant role in the modern chemical industry. Nevertheless, these key processes are still lacking proper understanding with respect to the gas-phase runaway behaviour (thermal explosion) and to the hot spot formation on the catalytic surface, under the typical process conditions.This work aims to enlighten these aspects by considering either the catalytic or the gas-phase chemistry for the development of reactor operative diagrams, in order to define the best-operating conditions with respect to the selectivity, the productivity, and the process safety aspects.The proposed methodology has been applied to the oxidation of ethylene and propylene for the direct oxidation process by pure oxygen, considering a detailed kinetic model accounting for the homogeneous reactions, coupled with the heterogeneous catalytic mechanisms.Sensitivity and reaction path analyses were performed to individuate the ruling species and reactions determining the transition to runaway conditions.     

A generalized differential method to calculate lumped kinetic triplet of the nth order model for the global one-step heterogeneous reaction using TG data

Computing kinetic triplet is of importance for the process safety of combustion/gasification industries to establish the chemical reaction scheme and to assess the hazardous risk. Few approaches have been capable of calculating lumped kinetic triplet at one time efficiently, which might be attributed to the fact that the analytical solution for the nonlinear ordinary differential equation (NNODE) for the n^th order reaction model has not been found yet. This paper presents an analytical solution of NNODE to compute kinetic triplet. Results showed that the proposed method (mass fraction curve-fitting error ϕ = 1.49%–2.07%) is more efficient to compute kinetic triplet of the n^th order reaction model, comparing to genetic algorithm (GA) optimization (ϕ = 1.43%–1.81%), Coats-Redfern (ϕ = 2.36%–3.16%), peak-shape, and isoconversional methods. A compensation effect between lnA and E_a is observed due to heating rates. Effects of exported data quality and smooth processing on computation of kinetic triplet are discussed. It is the first time that an analytical solution of NNODE (n^th order model) for global one-step heterogeneous reaction is derived for computing kinetic triplet. This work may help to search for analytical solutions of power-law and Avrami-Erofeev models in the future to efficiently calculate kinetic triplet for accelerating and sigmoidal reaction systems.     

新显色剂NPBPDT的合成及在环境监测中的应用研究

研究了1(4硝基苯基)3(5溴吡啶)三氮烯(NPBPDT)的合成及其与汞的显色反应。在TX100存在下,pH值为11.5的Na2B4O7NaOH缓冲溶液中,该试剂能与汞发生显色反应,汞与NPBPDT形成摩尔比为1∶2型的黄色配合物,在440nm处有一最大正吸收峰,在535nm处有一最大负吸收。以440nm为参比波长,535nm为测量波长进行双波长测定,表观摩尔吸光系数为2.80×105Lmol·cm,汞的浓度在0～12μg25mL范围内符合比尔定律。用拟定方法测定废水中的微量汞,有较高的准确度和精密度。     

内电解还原-高效厌氧反应工艺处理化工生产废水

化工生产废水中有机物浓度高,成分复杂,采用常规的处理工艺难以达标。本工艺采用分级处理的方法,先通过催化氧化、内电解铁屑还原反应装置,降低生产浓废水中的有机物含量,改善污水的可生化性;再采用高效厌氧反应器进一步处理废水,有机物去除率高,出水水质稳定,实现了达标排放。     

2-n-丙基酚在模拟海水中的耗氧特性及降解动力学

以2-n-丙基酚为研究对象,分3个质量浓度系列研究其在人工模拟海水中的耗氧特性及降解过程.试验结果表明,在该模拟海水体系中,ρ(DO)呈现先下降后上升的趋势,ρ(DO)变化过程与2-n-丙基酚的生物降解过程密切相关,ρ(DO)最低值出现在2-n-丙基酚降解率达85%～90%的阶段.2-n-丙基酚在该体系中的生物降解反应符合一级反应动力学规律,其生物降解速率与2-n-丙基酚初始质量浓度有关.2-n-丙基酚初始质量浓度增加,生物降解速率下降,滞后期和半衰期也相应延长.      

厌氧氨氧化菌的培养与推流式反应器氨厌氧工艺

采用推流式固定化絮体生物反应器培养出高活性的厌氧氨氧化(ANAMMOX)红色颗粒污泥.在稳定运行后,反应器的NH₄⁺-N和NO₂^--N去除率皆大于98%,TN平均去除率为86%,NO₃^--N的生成率约为14%,TN去除负荷达2.56kg/(m³·d).同时考察了进水基质比例对反应器性能的影响,并用扫描电镜观察了颗粒结构.     

石灰在填埋场防渗层中的改性研究

渗滤液是城市固体废物填埋场污染环境的主要来源之一。防渗层可以减少其对环境的污染。鉴于天然防渗层中存在防渗性能差等问题,提出将石灰作为配比填料加入到填埋场底部防渗层中。实验表明,在天然防渗层中分别加入配比为0%、5%和10%的石灰后,配比为10%的防渗层防渗性能良好,对COD和锌离子去除能力较强,效果最佳。     

雌二醇在铁(Ⅲ)-草酸盐配合物体系中的光降解

以125W高压汞灯为光源,研究了水中雌二醇(E2)在铁(Ⅲ)-草酸盐体系中的光降解;考查了初始pH值、铁(Ⅲ)/草酸盐配比、E2初始浓度对E2光降解的影响.结果表明,铁(Ⅲ)/草酸盐体系能引发E2光降解.在pH=3·50,Fe(Ⅲ)/草酸盐配比为10·0/120·0μmol·l-1时,2mg·l-1E2光照160min可降解48·0%.在pH3·0—6·0范围内,pH值为3·0—4·0时E2降解率较高;在2·0—10·0mg·l-1范围内,光降解效率随水溶液中E2初始浓度的增加而降低.     

水体中苯与亚硝酸的紫外光解交叉反应机理研究

利用激光闪光光解技术对不同条件下苯与亚硝酸水溶液的交叉反应机理进行研究,考察了瞬态物种的生长与衰减等行为;得到了C6H6-OH加合物,C6H6-NO^ π络合物等中间产物,并结合其光解产物的GC／MS分析,对其可能的反应机理进行了探讨,得出了一些微观反应速率常数．     

非均相Fenton反应技术研究进展

Fenton氧化法是较为常用的一种高级氧化技术。非均相Fenton反应适用的pH值范围较宽,能避免均相Fen ton反应产生铁泥沉淀的缺点,成为近年来Fenton反应的重要研究方向。本文对非均相Fenton氧化技术的研究现状及发展动态进行较为详尽的评述。