Chemical valorization of forest and agricultural by-products. Obtention, chemical characteristics, and mechanical behavior of a novel family of hydrophobic films

Esterification of hemicelluloses of the xylan family was performed in order to produce hydrophobic films. Acylation reactions were carried out with lauroyl chloride in the N,N-dimethylacetamide/lithium chloride homogeneous system using 4-dimethylaminopyridine as activator and were induced by microwave irradiation. In the experimental conditions used, 108 and 172% mass ratios were obtained for the dodecyl-grafted xylan and heteroxylan, respectively. The degrees of substitution (DS) were 1.3 (maximum 2) for xylan and 1.2 (maximum 2.1) for heteroxylan. These products were further characterized by FT-IR spectroscopy. The mechanical and thermomechanical behavior of this new family of hydrophobic films were analyzed and compared to those obtained from cellulose with a similar DS by the means of tensile tests. Our results indicate that the dodecyl-grafted xylan film presents the best rigidity-resistance to traction ratio.     

Anaerobic formation and degradation of toxic aromatic compounds in agricultural and communal sewage deposits

Relatively high concentrations of phenol, p-cresol, phenylacetic acid and other aromatic compounds were found in agricultural and communal sewage deposits. These toxic aromatic compounds are products of the bacterial degradation of aromatic amino acids under anaerobic conditions. In laboratory experiments at 26 degrees C and under N2-atmosphere, the same aromatics were formed from the amino acid tyrosine and from gelatine in assays inoculated with sewage sludge. After exhaustion of tyrosine and gelatine, respectively, concentrations of the accumulated phenol and other aromatics remained stable for months, i.e., phenol, p-cresol, phenylacetic acid etc. are dead-end products of the bacterial metabolism under these conditions. After addition of sodium nitrate the aromatic compounds are metabolically decomposed by denitrification within weeks.     

Removal of famoxadone, fluquinconazole and trifloxystrobin residues in red wines: effects of clarification and filtration processes

The effects of six clarification agents [egg albumin, blood albumin, bentonite + gelatine, charcoal, polyvinylpolypyrrolidine (PVPP) and silica gel] on the removal of residues of three fungicides (famoxadone, fluquinconazole and trifloxystrobin) applied directly to a racked red wine, elaborated from Monastrell variety grapes from the D.O. Region of Jumilla (Murcia, Spain) were studied. The clarified wines were filtered with 0.45 microm nylon filters to determine the influence of this winemaking process in the disappearance of fungicide residues. Analytical determination of fluquinconazole and trifloxystrobin was performed by gas chromatography with electron captor detector (ECD), while that of famoxadone using an HPLC equipped with a diode array detector (DAD). Generally, trifloxystrobin is the fungicide that is the lowest persistent one in wines, except in the egg albumin study whereas, the most persistent one is fluquinconazole. The elimination depends on the nature of the active ingredient, though the water stability in the presence of light within it has more influence than the solubility and polarity of the product itself. The most effective clarifying agents were the charcoal and PVPP. The silica gel and bentonite plus gelatine were not enough to reduce considerably the residual contents in the wine clarified with them. In general terms, filtration is not an effective step in the elimination of wine residues. The greatest removal after filtration is obtained in wines clarified with egg albumine and bentonite plus gelatine, and the lowest in those clarified with PVPP.     

Removal of famoxadone,fluquinconazole and trifloxystrobin residues in red wines: Effects of clarification and filtration processes

The effects of six clarification agents [egg albumin, blood albumin, bentonite + gelatine, charcoal, polyvinylpolypyrrolidine (PVPP) and silica gel] on the removal of residues of three fungicides (famoxadone, fluquinconazole and trifloxystrobin) applied directly to a racked red wine, elaborated from Monastrell variety grapes from the D.O. Region of Jumilla (Murcia, Spain) were studied. The clarified wines were filtered with 0.45 μ m nylon filters to determine the influence of this winemaking process in the disappearance of fungicide residues. Analytical determination of fluquinconazole and trifloxystrobin was performed by gas chromatography with electron captor detector (ECD), while that of famoxadone using an HPLC equipped with a diode array detector (DAD). Generally, trifloxystrobin is the fungicide that is the lowest persistent one in wines, except in the egg albumin study whereas, the most persistent one is fluquinconazole. The elimination depends on the nature of the active ingredient, though the water stability in the presence of light within it has more influence than the solubility and polarity of the product itself. The most effective clarifying agents were the charcoal and PVPP. The silica gel and bentonite plus gelatine were not enough to reduce considerably the residual contents in the wine clarified with them. In general terms, filtration is not an effective step in the elimination of wine residues. The greatest removal after filtration is obtained in wines clarified with egg albumine and bentonite plus gelatine, and the lowest in those clarified with PVPP.     

Chemical Valorization of Forest and Agricultural By-Products. Obtention,Chemical Characteristics,and Mechanical Behavior of a Novel Family of Hydrophobic Films

Abstract

Esterification of hemicelluloses of the xylan family was performed in order to produce hydrophobic films. Acylation reactions were carried out with lauroyl chloride in the N,N-dimethylacetamide/lithium chloride homogeneous system using 4-dimethylaminopyridine as activator and were induced by microwave irradiation. In the experimental conditions used, 108 and 172% mass ratios were obtained for the dodecyl-grafted xylan and heteroxylan, respectively. The degrees of substitution (DS) were 1.3 (maximum 2) for xylan and 1.2 (maximum 2.1) for heteroxylan. These products were further characterized by FT-IR spectroscopy. The mechanical and thermomechanical behavior of this new family of hydrophobic films were analyzed and compared to those obtained from cellulose with a similar DS by the means of tensile tests. Our results indicate that the dodecyl-grafted xylan film presents the best rigidity—resistance to traction ratio.     

Use of diffuse reflectance spectrometry in spot test reactions for quantitative determination of cations in water

Diffuse reflectance spectroscopy can be successfully used for the quantitative determination of small amounts of pollutants like metals. The remission function was found to be linearly proportional to the concentration, when we applied the Kubelka–Munk equation. The color reactions of Cu(II), Co(II), and Ni(II) with dithiooxamide, were realised on filter paper. Reaction between Fe(III) and ammonium thiocyanate was realized on filter paper and gelatine matrix. All measurements were accomplished with a laboratory-constructed reflectometer. We have obtained a calibration curve by plotting the optical density of reflectance A_R vs log of the mol l⁻¹ concentration. Limits of detection at the 10⁻⁴ M level were estimated for all the compounds. Linear dynamic range extend over one order of magnitude and shows the potential of device for the quantitative analysis of environmental pollutants.     

纳米TiO2薄膜在不同陶瓷表面的负载及其光催化性能研究

利用2种不同表面处理的陶瓷作为载体,用溶胶凝胶法在其表面进行了纳米TiO2光催化薄膜的负载.采用X射线衍射法(XRD)、X射线光电子能谱仪(XPS)和扫描电镜(SEM)对薄膜的粒径、横断面及表面组成进行了表征和分析,结果表明,TiO2的平均粒径约为15 nm,釉面陶瓷TiO2薄膜分布均匀,膜厚约为300 nm;无釉陶瓷TiO2薄膜分布不均,膜层不明显;2种载体中的一些基质离子在TiO2薄膜有渗透.苯酚的降解实验表明,以2种不同表面处理的陶瓷为载体的TiO2薄膜对苯酚的降解均符合一级反应动力学,就催化活性而言,TiO2/釉面陶瓷＞TiO2/无釉陶瓷,分析认为基质渗透的Ca2 有降低TiO2光催化活性的作用;该薄膜对实际生产多菌灵废水具有催化降解作用.重复降解实验20次,TiO2/釉面陶瓷和TiO2/无釉陶瓷对苯酚的去除率仅分别降低9%和6%.     

Photocatalytic activity of TiO2 films grown on different substrates

Titanium dioxide films were prepared on glass, indium-tin oxide (ITO) glass and p-type monocrystalline silicon and studied for the photocatalytic degradation of rhodamine B in an aqueous medium. Raman, AFM, and XPS spectroscopic investigations of these films indicated that microstructure of titanium oxide films were greatly affected by the substrate materials. Rutile was confirmed to be easily formed on the surface of ITO glass, and TiO2 tended to grow as closely packed particles that were elongated strips with an average size of 20 nm, and had lovely contrast with the perfectly round particles grown on p-type monocrystalline silicon. Charge transfer between the film and silicon substrate was verified by surface photovoltage spectra. This may be the real reason why the films grown on ITO glass and silicon substrates exhibit higher photocatalytic reactivity than the film on glass substrate. Moreover, the different surface properties also seem to be responsible for the different activity.     

明胶废水治理工程设计

采用沉淀-加酸中和-循环性活性污泥法(CASS)生物氧化工艺处理明胶废水。工程实践运行表明，该工艺处理效果好、运行稳定、投资省。     

Dust build-up on surfaces in the indoor environment

The concentration and the composition of dust in the indoor environment has been associated with reported symptoms of the sick building syndrome. Levels of airborne concentrations of dust particles are well known. However, the relation to dust on surfaces for office environments are not well described. In this study, 662 measurements were performed of surface dust concentrations on hard surfaces in 19 buildings within Harvard University based on a sticking gelatine foil method. The measure is the dust covered area of the surface as a percentage. In three offices, the build-up of dust on surfaces was measured for a period of five days. Close to these surfaces the airborne PM_2.5 and PM₁₀ particle mass concentrations were measured simultanously. A significant correlation between the dust build-up and the difference between the PM₁₀ and the PM_2.5 was established. The particle size distribution was measured by means of an Aerodynamic Particle Sizer. The mean dust build-up normalized with the measured PM₁₀ was approximately four times higher than the equivalent calculated by a deposition model. This may in part be due to the effect of preferred orientation when particles settle to a surface. Different data for dust on surfaces and airborne particles in offices were compared. The levels of airborne particles in offices in Europe seem to be higher than the levels in the US.     

氮掺杂氧化钛的简易制备及可见光催化活性的研究

为开发对可见光响应的催化剂,以尿素为氮掺杂剂,采用简易溶胶-凝胶法制备氮掺杂氧化钛,并以2,4-DCP的降解检验其光催化活性。XRD、BET、XPS和UV-Vis漫反射光谱分析表明,随着氮/钛原子比（N/Ti)的增大,各催化剂晶粒尺寸减小,比表面积增大,锐钛矿相向金红石相的转变得到抑制,除0#样品出现金红石相外,其他催化剂均只出现锐钛矿相;掺入催化剂的N位于晶格O位点和晶格间隙,替代N和间隙N掺杂使催化剂的光吸收发生明显的红移。荧光光谱分析表明,当N/Ti在0～6范围内增加时,反应体系中·OH自由基的产生速率增加,当N/Ti增大至8时,速率则下降。相似的规律也表现在氮掺杂量对光催化活性的影响。适量氮掺杂能增强氧化钛的可见光催化活性,该改性催化剂可用于有机污染物的太阳光激催化降解。     

Technique for aerosol generation with controllable micrometer size distribution

The purpose of this study is to develop an aerosol generating system that can produce particles of micrometer size in a convenient and efficient way. This system is comprised of an ultrasonic atomizer, potassium sodium tartrate tetrahydrate (PST) as solute and a program-controlled solute feeding unit with different PST concentrations. Both the aerosol concentration and size distribution pattern can be easily controlled and reproduced in the developed system. While the initial size of droplets generated from atomizer may remain unchanged, the size of residual dry aerosols was controlled by the solute concentration adjusted by the mixing ratio of solute and water. In addition, PST concentration could be alternatively adjusted in any cyclic way to provide particles with relatively mono-disperse, bimodal, varying size as well as skew distribution to meet requirements for various applications. The main advantage of the generating system is to generate particles of specific size distribution in order to simulate aerosols in ambient air or working places.     

光纤ZnO薄膜的制备及光催化性能研究

实验利用射频磁控溅射镀膜工艺,分别在光纤和石英玻璃上成功制备了ZnO薄膜。采用X射线衍射仪、原子力显微镜和荧光分光光度计对薄膜进行了测试分析,并对其光催化降解苯酚的性能进行了对比测试。结果表明,该薄膜具有良好的C轴取向性,光致发光峰分别位于362nm、421nm和486nm附近,且随着薄膜样品晶粒的减小而出现蓝移,光纤上ZnO薄膜的光催化能力是以石英玻璃为基底的ZnO薄膜的193倍,光催化效果显著。     

工艺条件对磷回收过程中鸟粪石沉淀颗粒粒径的影响

在鸟粪石沉淀法回收废水中磷的过程中,鸟粪石颗粒的大小将直接影响其沉淀的速率,进而影响鸟粪石的沉淀效果和磷的回收率。本文采用激光粒度分析仪测定鸟粪石的平均粒径,详细考察在小型连续搅拌反应-沉淀磷回收装置中不同的工艺条件下鸟粪石颗粒粒径的变化规律,并结合Stokes公式计算鸟粪石颗粒在废水出口处的沉降速率,为沉淀池的设计提供参考依据。结果表明:鸟粪石的平均粒径在12～25μm之间,沉降速率在5.46×10-5～2.37×10-4m/s之间。随着反应室水力停留时间的延长,鸟粪石颗粒的粒径逐渐增大,当停留时间超过18 min时,颗粒的粒径基本不变;随着沉淀室水力停留时间的延长,鸟粪石颗粒的平均粒径缓慢增大,当停留时间超过70 min后颗粒粒径的变化不大;鸟粪石颗粒的平均粒径在一定程度上受废水中磷初始浓度变化的影响,在磷初始浓度为62～128 mg/L时颗粒的粒径变化不大,当磷浓度为496 mg/L时粒径有较大增加,此时鸟粪石颗粒的沉降速率也大幅度增加;鸟粪石颗粒的平均粒径受pH值的影响不大;随氮磷摩尔比的增大,鸟粪石颗粒的平均粒径略有增加;随镁磷摩尔比的增大,鸟粪石颗粒的平均粒径逐渐减小,沉降速率则有明显的下降。     

耐盐性毒死蜱降解混合菌的构建及其降解特性

为明确蜡状芽孢杆菌(Bacillus cereus)混合菌株对毒死蜱的降解效果,采用正交实验的方法构建混合菌。以混合菌对毒死蜱的降解率和菌株的生长量为依据,利用单一因素实验考察了不同因素对混合菌降解毒死蜱的影响。结果表明:构建的混合菌中三菌株的体积比为1∶1∶3。在含80 mg/L毒死蜱的反应体系中,最适接菌量为8%(V/V),最适pH为7。在实验浓度下,混合菌对毒死蜱的降解符合一级动力学方程。混合菌对盐分有较高的耐受度,当反应液中氯化钠浓度在20～100 g/L之间时,混合菌对80 mg/L毒死蜱的降解率最高达61%。     

铁炭微电解工艺处理采油废水的研究

随着采油废水产生量的逐渐增大以及排放标准的日益严格,寻找一种经济、高效的处理方法显得十分必要。采用铁炭微电解技术对冀东油田采油废水进行了处理。考察了铁屑粒径、pH值、Fe/C质量比和反应时间对COD去除率的影响并设计了正交实验,结果表明,影响微电解工艺的因素主次关系为:pH>Fe/C质量比>反应时间,在最佳条件pH=5,Fe/C质量比为7∶1,反应时间50 min下,原水COD由170 mg/L降至95.6 mg/L,去除率达43.85%,出水满足国家二级排放标准。     

垂直潜流人工湿地有机物积累及去向初步分析

为防治湿地堵塞、改善湿地处理效果,初步探讨了湿地中有机物的积累规律,并估算湿地中有机物不同去除途径的贡献率。结果表明,垂直潜流人工湿地中基质间积累的有机物主要是不可溶有机物,且粒径主要集中在5.00μm以上,分析是不同粒径有机物凝聚积累的缘故;垂向沿程基质间有机物的积累量受进水水力负荷影响明显;进入垂直潜流人工湿地中的有机物绝大部分都被生物(植物和微生物)吸收和利用而得以去除,该途径贡献率可达99.9%以上。     

气液两相旋流喷嘴雾化特性

为提高烟尘净化用喷嘴的雾化性能,提出一种气液两相旋流喷嘴,用CFX软件对该喷嘴内部流场模拟的结果表明,强烈的气旋作用使液流呈环状,使气液混合流在达到喷嘴末端时易于破碎成雾。在实验室条件下,利用Winner313型喷雾激光粒度分析仪对喷嘴进行了雾化粒度测定,分析发现雾滴中位径与气液比的关系呈幂函数衰减,这一规律将有助于在工程应用时确定喷嘴工况。     

Effect of SO4 2-/Al3+ ratio and OH-/Al3+ value on the characterization of coagulant poly-aluminum-chloride-sulfate (PACS) and its coagulation performance in water treatment

A poly-aluminum-chloride-sulfate (PACS) was prepared at various experimental conditions. It was found that the coagulation performance of PACS in water treatment was affected by the PACS particle size distribution and zeta potential value. The experimental results indicated that the PACS particle size distribution and zeta potential value were highly influenced by SO(4)(2-)/Al(3+) molar ratio and bacicities (gamma,gamma=[OH]/[Al]) value. At a fixed gamma value of 2.0, the average PACS particle size increased from 25 to 80nm with the increase of SO(4)(2-)/Al(3+) ratio from 0 to 0.1. Further increase of the SO(4)(2-)/Al(3+) ratio resulted in acute increment particle size of PACS extremely, which can be attributed to its aggregation. At a fixed SO(4)(2-)/Al(3+) ratio of 0.0664, the largest average size of PACS occurred at gamma=2.0. It was also found that the zeta potential value of PACS was strongly influenced by the SO(4)(2-)/Al(3+) ratio, gamma value and pH of the aquatic solution. The zeta potential value of PACS increased with increasing of SO(4)(2-)/Al(3+) ratio. At a fixed SO(4)(2-)/Al(3+) ratio of 0.0664, PACS achieved greatest zeta potential value at gamma value of around 2.0. The maximum positive zeta potential value of PACS was found at pH5.3. At a fixed gamma value of 2.0 and SO(4)(2-)/Al(3+) ratio of 0.0664, the PACS achieved an optimum natural organic matter and turbidity removal efficiency.     

Wastes of multilayer containers as substrate in composting processes

An evaluation of the influence and degradation of ground multilayer containers, such as Tetra Brik Aseptic (TBA), in the composting process of municipal solid wastes (MSW) is presented. Two composting piles were formed by mixing, in different proportions, an organic fraction of MSW and TBA material ground as flakes or stripes. Piles were periodically aerated by mechanical mixing. Evolution of the composting was followed by frequent measurements of suitable parameters such as temperature, moisture, ashes, total organic carbon (TOC), nitrogen, C/N ratio, pH, conductivity, nutrients, and heavy metals. As expected, aluminum and polyethylene films from TBA were not degraded during the processes, but the cardboard fraction of TBA showed a partial decomposition that was more intense in the material ground as flakes. After two months of curing, the composts were refined and analyzed to determine their nutrient and heavy-metals contents. Despite their poor aesthetic properties, mainly resulting from the presence of little pieces of plastic and aluminum films, the composts contained the required amounts of nutrients; furthermore, their heavy-metals content was below the limits proposed by some official European organizations.