Magnetic resonance imaging of nonaqueous phase liquid during soil vapor extraction in heterogeneous porous media

Soil vapor extraction (SVE) is commonly used to remediate nonaqueous phase liquids (NAPLs) from the vadose zone. This paper aims to determine the effect of grain size heterogeneity on the removal of NAPL in porous media during SVE. Magnetic resonance imaging (MRI) was used to observe and quantify the amount and location of NAPL in flow-through columns filled with silica gel grains. MRI is unique because it is nondestructive, allowing three-dimensional images to be taken of the phases as a function of space and time. Columns were packed with silica gel in three ways: coarse grains (250-550 microm) only, fine grains (32-63 microm) only, and a core of fine grains surrounded by a shell of coarse grains. Columns saturated with water were drained under a constant suction head, contaminated with decane, and then drained to different decane saturations. Each column was then continuously purged with water-saturated nitrogen gas and images were taken intermittently. Results showed that at residual saturation, a sharp volatilization front moved through the columns filled with either coarse-grain or fine-grain silica gel. In the heterogeneous columns, the volatilization front in the core lagged just behind the shell because gas flow was greater through the shell and decane in the core diffused outward to the shell. When decane saturation in the core was above residual saturation, decane volatilization occurred near the inlet, the relative decane saturation throughout the core dropped uniformly, and decane in the core flowed in the liquid phase to the shell to replenish volatilized decane. These results indicate that NAPL trapped in low-permeability zones can flow to replenish areas where NAPL is lost due to SVE. However, when residual NAPL saturation is reached, NAPL flow no longer occurs and diffusion limits removal from low-permeability zones.     

微波诱导NiO催化降解水中邻苯二甲酸二甲酯

采用超声辐射沉淀-氧化法制备了纳米催化剂NiO,用XRD、XPS、BET和SEM等方法对其进行了表征.构建了微波-NiO催化反应体系,考察了该体系对DMP的去除效率及影响因素,并利用GC/MS、LC/MS鉴定降解产物,提出了可能的降解机理.结果表明：微波诱导NiO催化氧化技术是降解DMP的有效方法,在微波（750W）诱导NiO（0.4mg/L）催化降解体系中,15min内10mg/L DMP的去除率达70%以上.降解效率受到反应体系中不同条件的影响：微波功率的增加可以提高降解效率;催化剂NiO浓度越高,降解速率越快;溶液初始pH值对DMP的降解效率影响非常大,随着pH值的增大,降解效率明显提高.通过GC/MS、LC/MS分析,反应过程中DMP的降解产物主要包括双链水解产物邻苯二甲酸以及异构化产物对苯二甲酸、单链水解产物邻甲酯苯甲酸、苯环三取代产物甲酯基-邻苯二甲酸、侧链缩合形成的双环产物和少量小分子有机酸,由此推断DMP在微波诱导NiO催化体系中的降解主要包括6个途径：水解、异构化、甲酯基反应、侧链缩合成环、羟基化和开环等.     

Using X-ray computed tomography and micro-Raman spectrometry to measure individual particle surface area, volume, and morphology towards investigating atmospheric heterogeneous reactions

Heterogeneous reactions on the aerosol particle surface in the atmosphere play important roles in air pollution, climate change, and global biogeochemical cycles. However, the reported uptake coefficients of heterogeneous reactions usually have large variations and may not be relevant to real atmospheric conditions. One of the major reasons for this is the use of bulk samples in laboratory experiments, while particles in the atmosphere are suspended individually. A number of technologies have been developed recently to study heterogeneous reactions on the surfaces of individual particles. Precise measurements on the reactive surface area, volume, and morphology of individual particles are necessary for calculating the uptake coefficient, quantifying reactants and products, and understanding the reaction mechanism better. In this study, for the first time we used synchrotron radiation X-ray computed tomography(XCT) and micro-Raman spectrometry to measure individual CaCO_3 particle morphology, with sizes ranging from 3.5–6.5 μm. Particle surface area and volume were calculated using a reconstruction method based on software threedimensional(3-D) rendering. The XCT was first validated with high-resolution fieldemission scanning electron microscopy(FE-SEM) to acquire accurate CaCO_3 particle surface area and volume estimates. Our results showed an average difference of only 6.1% in surface area and 3.2% in volume measured either by micro-Raman spectrometry or X-ray tomography. X-ray tomography and FE-SEM can provide more morphological details of individual Ca CO3 particles than micro-Raman spectrometry. This study demonstrated that X-ray computed tomography and micro-Raman spectrometry can precisely measure the surface area, volume, and morphology of an individual particle.     

Photodegradation of Orange Ⅱ using waste paper sludge-derived heterogeneous catalyst in the presence of oxalate under ultraviolet light emitting diode irradiation

A waste paper sludge-derived heterogeneous catalyst(WPS-Fe-350) was synthesized via a facile method and successfully applied for the degradation of Orange Ⅱ in the presence of oxalic acid under the illumination of ultraviolet light emitting diode(UV-LED) Powder X-ray diffraction,Fourier-transform infrared spectroscopy,scanning electronic microscopy and N2 sorption isotherm analysis indicated the formation of α-Fe2O3 in the mesoporous nanocomposite.The degradation test showed that WPS-Fe-350 exhibited rapid Orange Ⅱ(OⅡ) degradation and mineralization in the presence of oxalic acid under the illumination of UV-LED.The effects of p H,oxalic acid concentration and dosage of the catalyst on the degradation of OⅡ were evaluated,respectively.Under the optimal conditions(1 g/L catalyst dosage,2 mmol/L oxalic acid and p H 3.0),the degradation percentage for a solution containing 30 mg/L OⅡ reached 83.4% under illumination by UV-LED for 80 min.Moreover,five cyclic tests for OⅡ degradation suggested that WPS-Fe-350 exhibited excellent stability of catalytic activity.Hence,this study provides an alternative environmentally friendly way to reuse waste paper sludge and an effective and economically viable method for degradation of azo dyes and other refractory organic pollutants in water.     

微波诱导技术用于氧烛制氧的理论研究

传统的氧烛是将氯酸盐或高氯酸盐与金属燃料、催化剂混合后压缩所制得。其产氧原理是利用燃料燃烧所释放的热量来促成氯酸盐或高氯酸盐分解,释放出氧气。氧烛不仅因燃料燃烧而消耗所产生的氧气,而且在产氧过程中往往会产生少量的氯气等有害副产品。为解决上述两个缺陷,笔者提出一种新的微波诱导催化技术来代替传统的燃料加热方法。即在氧烛配方中舍弃燃料,而使用外加的微波作为氯酸盐分解的热源。具体方法是先对氯酸钠氧烛的热过程进行数值模拟,通过反应温度的差异解释氯气作为副产品产生的机理;为验证利用微波诱导加热代替燃料加热的可行性,对TE10基模微波场中氯酸钠的热过程进行数值模拟。计算结果表明,氯酸钠在微波场中升温均匀。因此,微波诱导是抑制产氧过程中有害副产品产生的一种有效途径。     

Ex-ante environmental assessments of novel technologies - Improved caprolactam catalysis and hydrogen storage

Utrecht University has conducted a pilot sustainability assessment for the executive board of the chemistry program ACTS (Advanced Chemical Technologies for Sustainability) of the Netherlands’ Organization for Scientific Research (NWO). These assessments represent prospective, i.e. ’ex-ante’ studies on the production of caprolactam by an improved catalyst and on different hydrogen storage options (i.e. compressed and liquefied hydrogen, storage in metal hydrides and storage in a metal organic framework). The pilot sustainability assessments followed the principles of environmental life cycle assessment (LCA), thereby focusing on non-renewable energy use (NREU) and climate change (GWP100). It was found that caprolactam with the novel catalyst has lower impacts than petrochemical caprolactam production from benzene but higher impacts than bio-based caprolactam produced via fermentation. Regarding hydrogen storage, it was found that compressed and liquid hydrogen have the highest impacts. The impacts of the metal hydrides and the metal organic frameworks show by far the lowest environmental impacts. The main reason is that these materials can be reused up to 1500 times (refilling of tank), while for compressing and liquefaction of hydrogen energy is needed each time a tank needs to be refilled. The study demonstrates the successful application of ex-ante technology assessment.     

有机废水的电催化法降解研究现状

阐释了有机废水电催化法降解机理;综述了传统二维电极、新型三维电极电催化降解有机废水的原理及其应用现状,PbO2电极在三维电极处理有机废水中的应用现状、反应机理以及改性PbO2电极的研究进展;最后对未来发展方向进行了展望。     

纳米二氧化钛制备与表征

通过水热反应法合成出了两种纳米二氧化钛粉体材料,通过差热分析、X衍射分析、扫描电镜分析,粉体的平均直径小于100nm,通过光催化试验分析,纳米二氧化钛的光催化性能可以达到47%.     

吸附-电催化氧化降解非水溶性有机废气

在水溶液电解质中,以活性炭纤维(ACF)为电极,采用微孔曝气方式,吸附-电催化氧化两步联动降解非水溶性气态VOCs。以苯为研究对象,正交实验和单因素分析实验结合,正交实验确立最佳实验条件为:鼓气速率80L/h、苯/乙醇(体积)=30/150、电压10V、电解质浓度2g/L;最佳实验条件下,气相中苯的去除率为93.3%。单因素分析实验考虑了鼓气速率、苯浓度、电解电压、电解质浓度等因素的变化对去除率的影响。     

烧结金属催化材料净化印刷工艺中VOCs废气的试验研究

采用以烧结金属粉末微孔过滤材料为吸附材料和催化剂基体、CuMn／γ-Al2O3为催化剂的烧结金属催化净化装置,可实现对VOCs废气的有效去除。实验室试验表明：苯、甲苯和二甲苯的催化转化率均随温度的升高而增加。在250℃以上,甲苯和二甲苯的催化转化率高于99％;在280℃以上,苯的催化转化率高于99％。空速为2．0s^-1时催化荆的催化转化率要较空速为3．0s^-1时高。现场试验表明：在300℃左右,VOCs气体经过由烧结金属催化材料刺成的金属过滤器后,苯、甲苯、二甲苯的去除率均高于99％。经金属过滤器处理后,苯、甲苯、二甲苯的排放浓度可低于北京市《大气污染物综合排放标准》DB11／501—2007中的排放限值排放。