氮掺杂二氧化钛负载钒磷氧催化氧化NO的实验研究

以VPO为活性组分,N掺杂TiO 2为载体,采用浸渍法制备了VPO/TiN催化剂,基于单因素实验研究了其对NO的选择性催化氧化(SCO)性能以及抗硫抗水性能。研究表明:当P/V为1/5、N/Ti为1、活性组分负载量为10%、焙烧温度为350℃时,催化剂的SCO活性最好,NO氧化率达到61%;光致发光光谱(PL)表征显示N掺杂TiO 2在催化剂表面形成的氧空位可增强催化剂对O 2的吸附;VPO/TiN催化剂抗硫抗水性能较强,反应后的催化剂表面未发现硫酸根的特征峰,水蒸气主要通过与NO竞争吸附占据活性位点来抑制催化剂的SCO活性。     

Preparation of rare-earth metal complex oxide catalysts for catalytic wet air oxidation

Catalytic wet air oxidation (CWAO) is one of the most promising technologies for pollution abatement. Developing catalysts with high activity and stability is crucial for the application of the CWAO process. The Mn/Ce complex oxide catalysts for CWAO of high concentration phenol-containing wastewater were prepared by coprecipitation. The catalyst preparation conditions were optimized by using an orthogonal layout method and single-factor experimental analysis. The Mn/Ce serial catalysts were characterized by Brunauer-Emmett-Teller (BET) analysis and the metal cation leaching was measured by inductively coupled plasma torch-atomic emission spectrometry (ICP-AES). The results show that the catalysts have high catalytic activities even at a low temperature (80°C) and low oxygen partial pressure (0.5 MPa) in a batch reactor. The metallic ion leaching is comparatively low (Mn<6.577 mg/L and Ce<0.6910 mg/L, respectively) in the CWAO process. The phenol, COD_Cr, and TOC removal efficiencies in the solution exceed 98.5% using the optimal catalyst (named CSP). The new catalyst would have a promising application in CWAO treatment of high concentration organic wastewater. Translated from Techniques and Equipment for Environmental Pollution Control, 2005, 6(2): 40–44 [译自: 环境污染治理技术与设备]     

铁法煤业集团三台子污水处理厂的工艺改造

介绍了将铁法煤业（集团）有限责任公司三台子矿区污水处理工程工艺由以卡鲁塞尔氧化沟为主体的二级生化处理工艺改造为更适宜在北方气候条件下运行的A-O法工艺；同时对系统的启动进行了介绍。     

复合氧化物汽车尾气净化催化剂抗SO2中毒机理研究

复合氧化物催化剂(ASC)具有较高的活性和良好的抗SO_2中毒性能.用IR、XPS、TPD等技术研究了该催化剂抗SO_2中毒机理,结果表明,与易失活催化剂相比,ASC经500h反应(反应气含SO_2约20ppm),其活性组分价态无显著变化,仅表面发生SO_2的化学吸附,经与约500ppm的SO_2作用20h后,发现仅有少量SO_4~(2-)形成.这是由于在ASC催化剂中添加了特殊助剂,而使催化剂活性组分得到保护的缘故.     

Promotional effect of cobalt doping on catalytic performance of cryptomelane-type manganese oxide in toluene oxidation

The cryptomelane-type manganese oxide (OMS-2)-supported Co (xCo/OMS-2; x = 5, 10, and 15 wt.%) catalysts were prepared via a pre-incorporation route. The as-prepared materials were used as catalysts for catalytic oxidation of toluene (2000 ppmV). Physical and chemical properties of the catalysts were measured using the X-ray diffraction (XRD), Fourier transform infrared spectroscopic (FT-IR), scanning electron microscopic (SEM), X-ray photoelectron spectroscopy (XPS), and hydrogen temperature-programmed reduction (H₂-TPR) techniques. Among all of the catalysts, 10Co/OMS-2 performed the best, with the T_90%, specific reaction rate at 245°C, and turnover frequency at 245°C (TOF_Co) being 245°C, 1.23 × 10⁻³ mol_toluene/(g_cat·sec), and 11.58 × 10⁻³ sec⁻¹ for toluene oxidation at a space velocity of 60,000 mL/(g·hr), respectively. The excellent catalytic performance of 10Co/OMS-2 were due to more oxygen vacancies, enhanced redox ability and oxygen mobility, and strong synergistic effect between Co species and OMS-2 support. Moreover, in the presence of poisoning gases CO₂, SO₂ or NH₃, the activity of 10Co/OMS-2 decreased for the carbonate, sulfate and ammonia species covered the active sites and oxygen vacancies, respectively. After the activation treatment, the catalytic activity was partly recovered. The good low-temperature reducibility of 10Co/OMS-2 could also facilitate the redox process accompanied by the consecutive electron transfer between the adsorbed O₂ and the cobalt or manganese ions. In the oxidation process of toluene, the benzoic and aldehydic intermediates were first generated, which were further oxidized to the benzoate intermediate that were eventually converted into H₂O and CO₂.     

Greenhouse impacts of anthropogenic CH4 and N2O emissions in Finland

The Finnish anthropogenic CH₄ emissions in 1990 are estimated to be about 250 Gg, with an uncertainty range extending from 160 to 440 Gg. The most important sources are landfills and animal husbandry. The N₂O emissions, which come mainly from agriculture and the nitric acid industry are about 20 Gg in 1990 (uncertainty range 10–30 Gg). The development of the emissions to the year 2010 is reviewed in two scenarios: the base and the reduction scenarios.According to the base scenario, the Finnish CH₄ emissions will decrease in the near future. Emissions from landfills, energy production, and transportation will decrease because of already decided and partly realized volume and technical changes in these sectors. The average reduction potential of 50%, as assumed in the reduction scenario, is considered achievable.N₂O emissions, on the other hand, are expected to increase as emissions from energy production and transportation will grow due to an increasing use of fluidized bed boilers and catalytic converters in cars. The average reduction potential of 50%, as assumed in the reduction scenario, is optimistic.Anthropogenic CH₄ and N₂O emissions presently cause about 30% of the direct radiative forcing due to Finnish anthropogenic greenhouse gas emissions. This share would be even larger if the indirect impacts of CH₄ were included. The contribution of CH₄ can be controlled due to its relatively short atmospheric lifetime and due to the existing emission reduction potential. Nitrous oxide has a long atmospheric lifetime and its emission control possiblities are limited consequently, the greenhouse impact of N₂O seems to be increasing even if the emissions were limited somehow.     

不同温湿度条件下微米硼的氧化过程研究

目的 探究不同温湿度条件下微米硼的氧化层结构特征。方法 利用高温水浴浸泡处理去除原料微米硼的表面氧化层,然后在恒温恒湿条件下对微米硼进行加速氧化,利用扫描电子显微镜、透射电子显微镜和X射线光电子能谱对加速氧化后硼颗粒的氧化层厚度及组成进行分析,总结表面氧化层结构及成分组成变化规律,揭示温湿度条件下微米硼的氧化机制。结果 微米硼经高温水浴浸泡处理后,表面氧化层去除率达到50%。随着加速氧化时间的延长,硼颗粒氧化层的厚度逐渐增大,由内向外硼颗粒表面可以用B-BxOy-B2O3三层结构来表示,BxOy总是伴随着B2O3同时出现的,且随着氧化反应的进行,颗粒表面BxOy的含量将超过B的含量。结论 不同温湿度条件下微米硼的氧化机制为O2向B颗粒内部单向扩散的反应机制,B先与O2反应,形成低氧化物BxOy,BxOy进而与O2反应生成B2O3。随着氧化层厚度的增加,O2向B颗粒内部扩散的阻力增大,氧化反应速率随之降低。相比湿度的影响,温度的升高可显著加快硼表面氧化层的形成;温度一定时,湿度的增加可促进硼氧化层的形成。     

石墨烯氧化物气凝胶修饰金属阳极促进微生物燃料电池的产电性能

微生物燃料电池（microbial fuel cell,MFC）阳极的比表面积、生物相容性以及导电性被认为是影响微生物燃料电池产电性能的关键因素。三维金属阳极因其导电性强、比表面积较二维电极材料大等优点可用来取代碳基电极。为了提高微生物燃料电池的产电性能,本研究选用2种具有三维结构的不锈钢刷（SSB）和泡沫镍（Ni-foam）为金属阳极基材,并将石墨烯氧化物（GO）通过一步冷冻干燥法合成石墨烯氧化物气凝胶复合金属电极（GOA-SSB/Ni-foam）,将其作为阳极进行MFC的产电性能研究。结果显示：在MFC运行中,GOA-SSB和GOA-Ni-foam作为阳极,最大功率密度分别达到490和119 mW·m-2,比未修饰SSB和Ni-foam提高8.1和5.5倍。扫描电镜（SEM）表征显示三维复合金属阳极表面附着的微生物量远高于未修饰电极,且未修饰的SSB和Ni-foam电极表面较GOA-SSB和GOA-Ni-foam电极表面腐蚀更严重,说明GOA不仅可提升阳极比表面积、生物相容性还可减缓阳极基材的腐蚀。电化学阻抗（EIS）结果表明GOA-SSB和GOA-Ni-foam阳极相比于未修饰阳极能够极大的降低传荷电阻,证实GOA修饰阳极加快了电子传递速率。另外,拉曼（Raman）表征显示Shewanella oneidensis MR-1菌可原位还原GOA,佐证了GOA修饰阳极运行后欧姆内阻降低的原因。     

Cu (Ⅱ)和Cd (Ⅱ)在氧化石墨烯/聚酰胺-胺复合材料上的竞争吸附

以“grafting to”法制备的氧化石墨烯/聚酰胺-胺（GO/PAMAMs）作为吸附剂,研究了Cu（Ⅱ）和Cd（Ⅱ）在GO/PAMAMs上的竞争吸附行为,考察了溶液pH值、吸附时间、初始离子浓度及吸附剂用量等因素对吸附过程的影响,探讨了Cu（Ⅱ）和Cd（Ⅱ）在GO/PAMAMs上的竞争吸附机理。研究表明：GO/PAMAMs对Cu（Ⅱ）的吸附最佳pH值是5.0,Cd（Ⅱ）的最佳pH值为5.5;Cu（Ⅱ）和Cd（Ⅱ）在GO/PAMAMs上的竞争吸附过程符合Lagergren准二级动力学模型,等温吸附过程遵循Langmuir模型;热力学研究表明Cu（Ⅱ）和Cd（Ⅱ）在GO/PAMAMs上的吸附是自发进行的吸热过程,且属于物理吸附。     

氧化铁改性砂联合生物预处理对氨氮的吸附特性

对含氨氮(NH3-N)的微污染原水,采用自制氧化铁改性石英砂(iron oxide coated sand,IOCS)滤料强化过滤与生物预处理技术联合,进行强化处理与吸附效果研究.结果表明,采用强化挂膜法,生物预处理反应器的生物膜成熟期约为7 d,其对氨氮的去除率为60%~70%,但反应器中存在亚硝酸盐氮积累的现象.IOCS与生物预处理技术联合,对NH3-N的平均去除率为84.67%,出水NH3-N浓度均低于0.5 mg/L,NO2--N含量趋于0;而普通石英砂(RQS)在同等条件下,对氨氮的去除效果不稳定,平均去除率为74.31%,出水NH3-N平均浓度未达标,对NO2--N平均去除率仅有33.29%.在4 m/h滤速工况下,与生物预处理技术联合,IOCS和RQS对NH3-N最高去除率分别为94.3%和82.72%.IOCS与RQS的表面形态结构存在明显差异:前者的表面结构更加复杂多孔,比表面积大,有利于生物牢固附着;后者表面较光滑,比表面积小,挂膜后生物易脱落.