Fenton法和类Fenton法降解土壤中的二苯砷酸

本文对Fenton法与类Fenton法降解土壤中的二苯砷酸(diphenylarsinic acid,DPAA)进行了研究.考察了H2O2投加量和催化剂种类(Fe2+/Fe3+)对红壤及黑土中DPAA降解效果的影响,并采用高效液相色谱-质谱联用法(HPLC-MS/MS)对降解中间产物进行了初步鉴定.结果显示,针对红壤与黑土分别采用类Fenton法与Fenton法,在H2O2投加浓度为1 mol·L-1,含铁催化剂浓度为0.25 mol·L-1,土水比为1∶3,反应时间为1h的条件下,红壤及黑土中DPAA的降解率均可达到65%以上.HPLC-MS/MS的分析结果表明,DPAA可脱苯环形成降解产物苯砷酸(phenylarsinic acid,PAA),而PAA进一步氧化生成无机砷,这可能是Fenton/类Fenton法降解DPAA的途径之一.     

卡鲁塞尔氧化沟水力学特性的大涡模拟

本文基于大涡模拟中的Smagorinsky-Lilly模型,对Carrousel氧化沟模型进行了水力学特性模拟,并研究了沟内流速和涡量分布规律.速度与压力耦合求解使用了压力隐式算子分裂PISO(Pressure-Implicit with Splitting of Operators)算法,采用VOF(Volume of fluid)方法追踪自由液面.模拟结果表明,回流现象主要出现在上中层混合液中,逆流现象主要出现于上层混合液中;转轮与转刷的推流作用是造成水面变化剧烈的原因;距转轮与转刷较近的区域、转速较快的转轮与转刷区域及直道段转刷下游水面较高一侧中上层区域的涡量较大.根据实验验证,本次模拟结果和实验值吻合度较好,Smagorinsky-Lilly模型可以准确模拟氧化沟水力学特性.     

Kinetics characteristics of coal low-temperature oxidation in oxygen-depleted air

The longwall gob (mined-out) area is one of the main places that are prone to coal spontaneous combustion and most of the residual coal in it is in oxygen-depleted air as it is a semi-enclosed space. A DSC (Differential scanning calorimetry) test system was designed to accurately test the heat generation of coal oxidation in different oxygen concentration atmosphere, based on which the kinetics parameters (activation energy and pre-exponential factor) of coal low-temperature oxidation in oxygen-depleted air were solved out. The results show that the kinetics parameters present obvious stage features and the lower the oxygen concentration is, the smaller is the difference of the kinetics parameters that in different oxidation stages. When the oxygen concentration is lower than 5% and 3% for jet coal and meagre coal respectively, the kinetics parameters of slow oxidation start to be greater than that of rapid oxidation. Both in the slow oxidation and rapid oxidation stage, with the decrease of oxygen concentration, kinetics parameters present significant decline on the whole while in different oxygen concentration range, the decline rate is different. It's concluded that when assessing the residual coal's self-heating risk, we need to use the corresponding kinetics parameters of coal oxidation in the oxygen concentration of the location where the residual coal is and the safety factor will be greater to only use the kinetics parameters of coal oxidation in slow oxidation stage. This study is of great significance for the assessment and control of the self-heating risk of coal that in different oxygen concentration atmospheres of the longwall gob areas.     

电解铝生产含氟工业烟气湿法吸收治理中试装置设计实现

本文通过对国内外近几年有关电解铝含氟化氢工业尾气净化处理大量的参考文献的分析研究及国内外电解铝生产企业在尾气治理方面的技术应用和尾气净化装置运行状况的调研,结合自己的专业特长和工程经验,建立一套有关电解铝含氟化氢尾气在处理、净化氟化氢方面的技术方案,设计制作一套湿法氟化氢吸收中试装置,从工艺方案优化设计、安全运行、设备设计及选材、自动控制、建立相关的副产物检测方法和后续产物的综合利用等方面进行了研究和探讨。     

化学沉淀组合电催化氧化处理脱硫废液技术研究

真空碳酸钾脱硫工艺碱洗段废液因含有高浓度硫化物、COD等有毒成分而影响焦化废水后续生物处理。以焦化企业实际碱洗段废液为研究对象,选用化学沉淀和电催化氧化的组合方式对其进行预处理。结果表明,室温下当氧化铜的投加量为65 g/L、反应时间60 min时废液中S2-去除率可达93%,且经过高温灼烧可实现Cu O沉淀剂的再生使用。沉淀后出水经电催化氧化处理,在电流10 A、电压4.9 V、电解时间120 min的条件下,出水COD可降至2 400 mg/L,满足常规生化系统进水的要求。     

大气氮磷沉降量分析——以杭州北里湖为例

为更好地了解大气氮磷沉降量的影响因素及其对水环境的影响,采用自制采样器,对杭州北里湖2011年4月-2012年2月大气氮、磷的总、湿沉降进行采集,并通过对干、湿沉降量的计算,探讨了大气干、湿沉降中TN、TP、NH4+-N和NO3--N的变化趋势.结果表明,因秋季利于沉降而不利于扩散,夏季降水多,各物质的干沉降量表现出秋季高、夏季低的特点,湿沉降量则夏季较高.TN干沉降以NH4+-N为主,其干沉降量与气温、气压及降水量有关,而NO3--N干沉降量与风速有关;大气湿沉降量除NO3--N外,TN、TP和NH4+-N与降水量均呈现出较强的相关性,相关系数分别为0.882、0.700和0.827.在研究期间,TN、NH4+-N和NO3--N以湿沉降为主,TP以干沉降为主;北里湖大气总沉降的入湖TN量为4 503.74kg/km2,TP为100.14 kg./km2,入湖的TN/TP比值高达45,远超出正常水平,这对北里湖水体的富营养化产生了严重影响.     

Oxidation of Cr(III) on birnessite surfaces: The effect of goethite and kaolinite

Oxidation of Cr(III) by manganese oxides may pose a potential threat to environments due to the formation of toxic Cr(VI) species. At present, it was still unclear whether the extent of Cr(III) oxidation and fate of Cr(VI) would be changed when manganese oxides co-exist with other minerals, the case commonly occurring in soils. This study investigated the influence of goethite and kaolinite on Cr(III) oxidation by birnessite under acidic pH condition (pH 3.5) and background electrolyte of 0.01 mol/L NaCl. Goethite was found not to affect Cr(III) oxidation, which was interpreted as the result of overwhelming adsorption of cationic Cr(III) onto the negatively-charged birnessite (point of zero charge (PZC) < 3.0) rather than the positively-charged goethite (PZC = 8.8). However, more Cr(VI) would be retained by the surface with the increase in addition of goethite because of its strong ability on adsorption of Cr(VI) at low pH. Moreover, either Cr(III) oxidation or distribution of the generated Cr(VI) between the solid and solution phases was not affected by kaolinite (PZC < 3.0), indicating its low affinity for Cr species. Reactions occurring in the present mixed systems were suggested, which could be partly representative of those in the soils and further indicates that the mobility and risk of Cr(VI) would be decreased if goethite was present.     

Enhanced catalytic complete oxidation of 1,2-dichloroethane over mesoporous transition metal-doped γ-Al2O3

High-surface-area mesoprous powders of γ-Al₂O₃ doped with Cu^2 +, Cr^3 +, and V^3 + ions were prepared via a modified sol–gel method and were investigated as catalysts for the oxidation of chlorinated organic compounds. The composites retained high surface areas and pore volumes comparable with those of undoped γ-Al₂O₃ and the presence of the transition metal ions enhanced their surface acidic properties. The catalytic activity of the prepared catalysts in the oxidation of 1,2-dichloroethane (DCE) was studied in the temperature range of 250–400°C. The catalytic activity and product selectivity were strongly dependent on the presence and the type of dopant ion. While Cu^2 +- and Cr^3 +-containing catalysts showed 100% conversion at 300°C and 350°C, V^3 +-containing catalyst showed considerably lower conversion. Furthermore, while the major products of the reactions over γ-alumina were vinyl chloride (C₂H₃Cl) and hydrogen chloride (HCl) at all temperatures, Cu- and Cr-doped catalysts showed significantly stronger capability for deep oxidation to CO₂.     

Remarkable promotion effect of trace sulfation on OMS-2 nanorod catalysts for the catalytic combustion of ethanol

OMS-2 nanorod catalysts were synthesized by a hydrothermal redox reaction method using MnSO₄ (OMS-2-SO₄) and Mn(CH₃COO)₂ (OMS-2-AC) as precursors. SO₄^2 −-doped OMS-2-AC catalysts with different SO₄^2 − concentrations were prepared next by adding (NH₄)₂SO₄ solution into OMS-2-AC samples to investigate the effect of the anion SO₄^2 − on the OMS-2-AC catalyst. All catalysts were then tested for the catalytic oxidation of ethanol. The OMS-2-SO₄ catalyst synthesized demonstrated much better activity than OMS-2-AC. The SO₄^2 − doping greatly influenced the activity of the OMS-2-AC catalyst, with a dramatic promotion of activity for suitable concentration of SO₄^2 − (SO₄/catalyst = 0.5% W/W). The samples were characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), inductively coupled plasma optical emission spectroscopy (ICP-OES), NH₃-TPD and H₂-TPR techniques. The results showed that the presence of a suitable amount of SO₄^2 − species in the OMS-2-AC catalyst could decrease the Mn–O bond strength and also enhance the lattice oxygen and acid site concentrations, which then effectively promoted the catalytic activity of OMS-2-AC toward ethanol oxidation. Thus it was confirmed that the better catalytic performance of OMS-2-SO₄ compared to OMS-2-AC is due to the presence of some residual SO₄^2 − species in OMS-2-SO₄ samples.     

Promoting effect of vanadium on catalytic activity of Pt/Ce–Zr–O diesel oxidation catalysts

A series of Pt–V/Ce–Zr–O diesel oxidation catalysts was prepared using the impregnation method. The catalytic activity and sulfur resistance of Pt–V/Ce–Zr–O were investigated in the presence of simulated diesel exhaust. The effect of vanadium on the structure and redox properties of the catalysts was also investigated using the Brunauer–Emmett–Teller method,X-ray diffraction, H2temperature-programmed reduction, CO temperature-programmed desorption, X-ray photoelectron spectroscopy, and Energy Dispersive Spectroscopy. Results showed that the Pt particles were well dispersed on the Ce–Zr–O carrier through the vanadium isolation effect, which significantly improved the oxidation activity toward CO and hydrocarbons. An electron-withdrawing phenomenon occurred from V to Pt, resulting in an increase in the metallic nature of platinum, which was beneficial to hydrocarbon molecular activation.