天然沸石负载La2O3-ZnO-TiO2光催化降解活性艳红K-2BP

利用80目天然斜发沸石作载体制备La₂O₃(0.5%)-ZnO(20%)-TiO₂/沸石复合光催化剂，以20 W紫外灯为光源，在自制的光催化反应器中降解活性艳红K-2BP，考察了光照时间、空气通入量、催化剂用量、溶液初始浓度、H₂O₂与Fe³⁺投加量等对活性艳红K-2BP光催化降解率的影响。结果表明，当溶液初始浓度为60 mg/L，催化剂投加量为12 g/L，通气量为1 200 mL/min，光照2.5 h，活性艳红K-2BP的降解率可达99.2%；H₂O₂和Fe³⁺投加量为4 mL/L和3 g/L时，光照1 h活性艳红K-2BP降解率分别为100%和97.2%。紫外可见吸收光谱显示，LZTZ光催化剂可有效降解印染废水。     

Au/SnO2催化氧化CO性能的研究

以SnO₂为载体，Au为活性组分，采用真空浸渍法、共沉淀法、沉积沉淀法制备CO氧化的催化剂，同时还制备双金属体系催化剂Au-Pd/SnO₂和Au-Pt/SnO₂。用气相色谱对所制备的催化剂进行活性评价，运用DSC、SEM、XRD、BET等对催化剂进行表征。在本实验条件下，载体二氧化锡焙烧温度为500 ℃，催化剂成型温度为350 ℃，金负载量为3%(wt.)时，用沉积-沉淀法制备的Au/SnO₂活性最好，在18 ℃，空速为24 000 h-1条件下就能将CO（浓度为4%）完全氧化为CO₂；添加铂和钯可提高Au/SnO₂对CO的催化活性。     

Co3O4/介孔分子筛催化剂对苯催化完全氧化的研究

分别以介孔分子筛MCM-41、MCM-48、SBA-15为载体，采用等体积浸渍法制备了氧化钴/介孔分子筛催化剂，利用N₂吸附、X射线衍射、程序升温还原等技术对催化剂进行了表征，考察了Co₃O₄的负载量及载体的孔结构对催化剂完全催化氧化苯的性能的影响。结果表明，Co₃O₄的负载量为20%时，催化剂的催化活性最好；载体的孔径和催化剂的可还原性能是影响催化活性的主要因素，催化剂活性顺序为Co₃O₄ /SBA-15> Co₃O₄ /MCM41> Co₃O₄ /MCM-48。     

银钛共负载型光催化材料降解甲基橙废水简

以膨胀珍珠岩为载体，采用溶胶凝胶法对其进行负载，制备出不同类型的光催化材料（TiO₂-EP、Ag⁺-TiO₂-EP），并在模拟日光条件下，研究其对甲基橙溶液的降解效果。结果表明，浸渍3次且担载0.04% Ag⁺的负载型TiO₂光催化活性最高，在光催化剂用量为0.3 g，20 mL初始浓度为10 mg/L甲基橙溶液光照4 h后降解率可达81.6%，且甲基橙的光催化降解服从一级动力学方程。回收3次后仍有较强的活性，其2 h降解率为24.8%。     

微乳法制备Fe-TiO2纳米晶复合体及光催化性能

采用微乳法制备铁掺杂TiO₂纳米晶(Fe-TiO₂)复合体, 通过热重-差热(TG-DTA)、X射线衍射(XRD)、扫描电镜（SEM）和紫外漫反射光谱(DRS)等对其结构和形态进行表征; 以亚甲基蓝溶液(MB)为标准模拟降解物, 对Fe-TiO₂, 纯TiO₂和P25光催化降解性能进行评价。结果表明，Fe-TiO₂的光催化活性明显＞P25，原因是Fe掺杂不仅能抑制TiO₂晶粒     

TiO2纳米管催化降解4，4’-二溴联苯的影响因素和动力学研究

利用TiO₂纳米管催化降解水中的4，4’-二溴联苯，对催化降解过程和影响因素进行研究。结果表明，TiO₂纳米管对其有较高的催化降解效率且降解过程符合Langmuir-Hinshelwood动力学模式。不同光源、4，4’-二溴联苯的初始浓度、纳米管添加量和pH值对催化降解过程都有较大影响，其中pH值的影响最为明显。反应液在中性状态下的降解率明显低于pH=1或11的情况。在pH=1时，4，4’-二溴联苯的降解率达86%。     

光助Ce-Fe/Al2O3催化H2O2降解阳离子红GTL模拟废水

利用Ce-Fe/Al₂O₃为催化剂的非均相光Fenton体系降解阳离子红GTL模拟废水，考察了H₂O₂浓度、催化剂用量、初始pH值及不同工艺过程对降解效果的影响，通过紫外-可见漫反射光谱、红外光谱、XPS手段研究铁在反应中的价态变化。结果表明，在11 W低压汞灯照射下，非均相光Fenton体系能够有效地降解结构稳定的阳离子红GTL，在pH 6，反应温度20℃，时间90 min，Ce-Fe/Al₂O₃ 2 g/L，H₂O₂浓度340 mg/L，含50 mg/L阳离子红GTL模拟废水TOC去除率为92.40%；光Fenton反应中Fe(Ⅲ)转化为Fe(Ⅱ)。     

La2O3/ZnO/TiO2光催化降解活性艳红K-2BP的研究

采用溶胶-凝胶法制备了La₂O₃/ZnO/TiO₂复合光催化剂,以紫外灯为光源,活性艳红K-2BP为模型降解物,研究了La₂O₃/ZnO/TiO₂的光催化性能。结果表明：当锌和镧的掺杂量w(ZnO)=20%, w(La₂O₃)=0.5%, 煅烧温度为500℃时,La₂O₃/ZnO/TiO₂复合光催化剂的光催化活性最高；当催化剂投加量4 g/L,通气量800 mL/min,初始pH值3.12时,La₂O₃/ZnO/TiO₂对活性艳红K-2BP的降解效果最好。实验证明,La₂O₃/ZnO/TiO₂对活性艳红K-2BP的降解遵从Langmuir-Hinshelwood动力学模型,测得其反应速率常数k＝11.5 mg/(L·min)；吸附常数K＝2.88×10^-2 L/mg。     

负载型Mn-Ce/TiO2催化剂的制备及其低温脱硝活性简

以成型TiO₂作为载体，通过浸渍法制备了Mn-Ce/TiO₂低温SCR催化剂，并系统研究了制备方法、煅烧条件、活性组分担载量、Mn含量等参数对催化剂催化还原NO性能的影响。结果表明，煅烧温度的升高会促使活性组分结晶度的提高，从而引起催化活性的降低，在500℃和600℃下所得Mn-Ce/TiO₂催化剂活性组分为无定型态，表现出较高的脱硝活性。活性组分担载量的增加有利于催化活性的提高。Mn含量对Mn-Ce/TiO₂催化剂的活性有较大影响，当Mn/（Mn+Ce）摩尔比为40%和85%时，催化剂活性最高。     

几种印染助剂对壳聚糖稳定纳米铁去除酸性品红的影响

以氯化铁为铁源，硼氢化钠为还原剂，壳聚糖为稳定剂，采用液相还原法制备壳聚糖稳定纳米铁（CS-nZⅥ）；研究了印染废水中常见助剂NaNO₃、Na₂SO₄、NaH₂PO₄、K₂Cr₂O₇、EDTA二钠盐存在下，超声波辅助CS-nZⅥ对酸性品红（AF）降解的影响。结果表明，反应15 min，0.01 g CS-nZⅥ对25 mL、100 mg/L AF的去除率高达99.9%；各种助剂的存在使得纳米铁表面不同程度失活，阻碍反应的进行，使得AF的去除率下降。NaNO₃、K₂Cr₂O₇、EDTA二钠盐与纳米铁发生反应，与AF存在明显的竞争作用。重复利用实验表明，CS-nZⅥ重复利用7次仍具有一定的反应活性。此外，CS-nZⅥ对加标（50 mg/L）实际废水中AF的去除率达到99%以上，表明CS-nZⅥ是一种潜在的环境修复材料。     

Investigation of the complexation of metal-ions by strong ligands in fresh and marine water

SCOPE: The detection and investigation of metal ions bound in strong complexes in natural waters is a difficult task, due to low concentration of the metal ions themselves, and also of the strong ligands, which, moreover, are often not of a well-defined composition. Here, a method is proposed for the investigation of the speciation of metal ions in natural waters. OBJECTIVE AND METHOD: It is based on the sorption of metal ions on strongly sorbing ion exchange resins, i.e. complexing resins. For this reason the method is called Resin Titration. It has been shown in previous investigations that the concentration of metal ion totally sorbed by a particular resin, and its reaction coefficient in the solution phase in the presence of the resin, can be determined from the sorption data using a simple relationship. Here, a data treatment (the Ruzic linearization method) is proposed for also determining the concentration of the ligands responsible for the complex in equilibrium with the resin. RESULTS: The method was applied to data obtained by Resin Titration of a freshwater and a seawater. Copper(II) and aluminium(III) were considered, using Chelex 100 as a titrant, due to its strong sorbing properties towards these metal ions. The results were: the total metal concentration in equilibrium with the resin, the side reaction coefficients, and the concentration of ligands. In all these cases the ligands forming very strong complexes were found to be at concentration lower than that of the metals. CONCLUSION: The Ruzic linearization method allows the determination of the concentration of the ligands forming very strong complexes in equilibrium with Chelex 100. The reaction coefficient was better determined by the calculation method previously proposed for RT. The ligands responsible for the strong complexes were found to be at low concentration, often lower than that of the metal ions considered. The metal in the original sample is partly bound to these ligands, since the complexes are very strong. Only a part of the metal is linked to weaker ligands, or free.     

树脂-气升式环流生物反应器的脱氮性能

为了提高废水生物处理过程的脱氮性能,设计了树脂-气升式环流生物反应器,通过实验考察了该反应器连续抗氨氮冲击的能力,并验证了反应器中吸附铵离子的强酸阳离子树脂生物再生的可行性,分析了生物再生机理。结果表明,原水中铵离子之外的阳离子的存在是实现树脂生物再生的关键。     

Removal of acutely hazardous pharmaceuticals from water using multi-template imprinted polymer adsorbent

Molecularly imprinted polymer adsorbent has been prepared to remove a group of recalcitrant and acutely hazardous (p-type) chemicals from water and wastewaters. The polymer adsorbent exhibited twofold higher adsorption capacity than the commercially used polystyrene divinylbenzene resin (XAD) and powdered activated carbon adsorbents. Higher adsorption capacity of the polymer adsorbent was explained on the basis of high specific surface area formed during molecular imprinting process. Freundlich isotherms drawn showed that the adsorption of p-type chemicals onto polymer adsorbent was kinetically faster than the other reference adsorbents. Matrix effect on adsorption of p-type chemicals was minimal, and also polymer adsorbent was amenable to regeneration by washing with water/methanol (3:1, v/v) solution. The polymer adsorbent was unaltered in its adsorption capacity up to 10 cycles of adsorption and desorption, which will be more desirable in cost reduction of treatment compared with single-time-use activated carbon.     

Removal of phosphate from water by a highly selective La(III)-chelex resin

A new polymer ligand exchanger (PLE) has been developed for the removal of phosphate in wastewater. This PLE, consisting of lanthanum(III) bound to chelex-100 resin, was prepared by passing LaCl3 solution through a column of chelex-100. Uptake of phosphate from water by this La-chelex resin was investigated in the column mode. The La-chelex resin was able to remove phosphate efficiently from water, and the uptake of phosphate was not affected by the presence of large amounts of anions (0.1M) such as chloride and sulfate. The La-chelex resin was also able to efficiently remove phosphate from seawater to <0.1mg-Pl(-1), and regenerated for reuse by removing the sorbed phosphate by eluting with 6M HCl.     

A fingerprint analysis method for characterization of dissolved organic matter in secondary effluents of municipal wastewater treatment plant

Dissolved organic matter (DOM) in wastewater and reclaimed water is related to water quality, safety, and treatability. In this study, DOM was characterized through a fingerprint analysis method for DOM characterization using resin fractionation followed by size exclusion chromatography (SEC). Resin fractionation was used in the first step to divide the DOM in water samples into six resin fractions, namely, hydrophobic acids (HOA), hydrophobic bases (HOB), hydrophobic neutrals (HON), hydrophilic acids (HIA), hydrophilic bases (HIB), and hydrophilic neutrals (HIN). SEC analysis was then performed to separate each resin fraction into several (n) subfractions with different molecular weights (MW). Thus, the total DOM in the water sample was fractionated into 6n subfractions. After quantification of each subfraction by dissolved organic carbon (DOC), a fingerprint graph was constructed to express the distribution of DOM in the subfractions. The fingerprint analysis method was applied to a secondary effluent sample during ozonation. Ozonation (dose of 10 mg L^?1) removed the DOC only by 8 % and reduced UV₂₅₄ of the sample by 36 %. Fingerprint graphs also revealed that the resin fractions changed quite limitedly but transformation of subfractions occurred notably.     

Thermal formation of PBDD/F from tetrabromobisphenol A--a comparison of polymer linked TBBP A with its additive incorporation in thermoplastics

For a long period, polybrominated flame retardants are under discussion because of the formation of polybrominated dibenzo-p-dioxins (PBDD)/dibenzofurans (PBDF) (PBDD/F) in case of thermal stress. Concerning polymer linked tetrabromobisphenol A (TBBP A), formation of PBDD/F was commonly presumed to be sterically hindered because of the covalent fixation into the polymer backbone. Combustion experiments with additively incorporated TBBP A compared with its polymer linkage revealed, that this assumption is incorrect and has to be revised. Under same conditions, similar PBDD/F concentrations in the range of 17.5-19.6 mg PBBD/F per kg TBBP A applied were analyzed. PBDD/F homologue distribution patterns were almost identical predominated by low brominated PBDF. These findings for PBDD/F formation have to be considered in future discussions regarding thermal stress caused by combustion or recycling processes, including other flame retardants bound in polymer matrix, e.g. polybrominated polystyrene (PS), or those with molecular structures showing less analogy to PBDD/F, like hexabromocyclododecane. The second aspect introduced, is the influence of different plastics on the formation rates of PBDD/F. In this context, combustion experiments were performed in an atmosphere consisting of synthetic air and HBr. PBDD/F concentrations were 8.47 mg/kg polyethylene, 1.67 mg/kg PS, 3.92 mg/kg phenolic resin and 18.1 mg/kg epoxy resin. Distribution patterns of PBDD/F homologues could partly be correlated with the occurrence of the precursors polybrominated benzenes and phenols.     

Removal of humic acid using TiO2 photocatalytic process--fractionation and molecular weight characterisation studies

The photocatalytic removal of humic acid (HA) using TiO₂ under UVA irradiation was examined by monitoring changes in the UV₂₅₄ absorbance, dissolved organic carbon (DOC) concentration, apparent molecular weight distribution, and trihalomethane formation potentials (THMFPs) over treatment time. A resin fractionation technique in which the samples were fractionated into four components: very hydrophobic acids (VHA), slightly hydrophobic acids, hydrophilic charged (CHA) and hydrophilic neutral (NEU) was also employed to elucidate the changes in the chemical nature of the HA components during treatment. The UVA/TiO₂ process was found to be effective in removing more than 80% DOC and 90% UV₂₅₄ absorbance. The THMFPs of samples were decreased to below 20 μg l⁻¹ after treatments, which demonstrate the potential to meet increasingly stringent regulatory level of trihalomethanes in water. Resin fractionation analysis showed that the VHA fraction was decreased considerably as a result of photocatalytic treatments, forming CHA intermediates which were further degraded with increased irradiation time. The NEU fraction, which comprised of non-UV-absorbing low molecular weight compounds, was found to be the most persistent component.     

Modelling of the acid-base properties of natural and synthetic adsorbent materials used for heavy metal removal from aqueous solutions

In this paper a comparison about kinetic behaviour, acid-base properties and copper removal capacities was carried out between two different adsorbent materials used for heavy metal removal from aqueous solutions: an aminodiacetic chelating resin as commercial product (Lewatit TP207) and a lyophilised bacterial biomass of Sphaerotilus natans. The acid-base properties of a S. natans cell suspension were well described by simplified mechanistic models without electrostatic corrections considering two kinds of weakly acidic active sites. In particular the introduction of two-peak distribution function for the proton affinity constants allows a better representation of the experimental data reproducing the site heterogeneity. A priori knowledge about resin functional groups (aminodiacetic groups) is the base for preliminary simulations of titration curve assuming a Donnan gel structure for the resin phase considered as a concentrated aqueous solution of aminodiacetic acid (ADA). Departures from experimental and simulated data can be interpreted by considering the heterogeneity of the functional groups and the effect of ionic concentration in the resin phase. Two-site continuous model describes adequately the experimental data. Moreover the values of apparent protonation constants (as adjustable parameters found by non-linear regression) are very near to the apparent constants evaluated by a Donnan model assuming the intrinsic constants in resin phase equal to the equilibrium constants in aqueous solution of ADA and considering the amphoteric nature of active sites for the evaluation of counter-ion concentration in the resin phase. Copper removal outlined the strong affinity of the active groups of the resin for this ion in solution compared to the S. natans biomass according to the complexation constants between aminodiacetic and mono-carboxylic groups and copper ions.     

苯酚分子印迹聚合物的合成、表征及吸附性能研究

以苯酚为模板,2-Vpy为功能单体,EGDMA为交联剂,采用本体聚合方式在氯仿溶剂中合成了一系列分子印迹聚合物,并通过静态吸附实验对聚合物的选择吸附性进行评价.结果显示,以氯仿作为致孔剂,模板分子与功能单体的摩尔比为1∶2时,聚合物对模板分子的印迹因子为3.96,最大表现结合量(Qmax)为120.7 mmol/g,具...     

Chemical modification of montan resin by peracetic acid and agricultural application of its modified products

ABSTRACT

Montan resin (MR) is a by-product produced during the refinement process of montan wax extracted from lignite and has no usage yet. Chemical modification is an effective method to change the material property for expanding or converting the application area of the material itself. Our previous study found that the high hydrophobicity of MR is the primary limiting factor for its utilization in agriculture. Based on this point, this study attempted to chemically modify MR using the oxidation of peracetic acid, resulting that the MR hydrophilicity was significantly improved, and a water-soluble product (WSP) was obtained. The optimized oxidation conditions of MR, including the reaction temperature (X₁), reaction time (X₂), weight ratio of oxidant and montan resin (X₃), and oxidant concentration (X₄), were determined using single-factor experiments and response surface analysis. The modification degree was evaluated using elemental and oil-water partition coefficient analyses, infrared (IR) spectroscopy, and gas chromatography-mass spectrometry (GC-MS), revealing that the oil-water partition coefficient of the modified product decreased and that the number of chemical constituents with oxygen-containing functional groups clearly increased after modification. Furthermore, the WSP was tested its effects on germination and seedling growth of the wheat seed. Compared with the control group, the WSP showed a promoting effect on the growth and germination of wheat. The WSP concentrations of 600 mg·L^?1 and 300 mg·L^?1 had the most substantial effect on the root and seedling growth of wheat, respectively.

Implications: Montan resin, a useless by-product produced from crude montan wax, was chemically modified via oxidation of peracetic acid. Its hydrophilicity was significantly improved, and a water-soluble product was obtained after the chemical modification. The optimized oxidation conditions of montan resin were determined using single-factor experiments and response surface analysis. The amount of chemical constituents with oxygen-containing functional groups increased in the modified products after modification, as determined by IR and GC-MS analysis, among other methods. The water-soluble modified product showed an obvious effect in promoting growth and germination of wheat at 600 mg·L-1 and 300 mg·L-1, respectively.