纳米Pd／Fe双金属颗粒对单氯酚及二氯酚的还原脱氯

采用改进液相化学还原法制备纳米Pd／Fe双金属颗粒,研究其钯化率为0．045％和0．135％的条件下分别对3种单氯酚（2-CP、3-CP和4-CP）和3种二氯酚（2,3-DCP、2,4-DCP和2,6-DCP）的脱氯反应。结果表明,合成的纳米Pd／Fe颗粒分散性良好,粒径分布介于25～40nm。纳米Pd／Fe双金属颗粒对单氯酚及二氯酚具有良好的去除效果,3种单氯酚和3种二氯酚的脱氯难易程度分别为2-CP〉4-CP〉3-CP和2,6-DCP〉2,4-DCP〉2,3-DCP,脱氯反应均符合拟一级反应动力学方程。通过还原脱氯实验揭示了分子中氯原子的化学环境对还原脱氯过程具有明显影响。     

Comparison of modified montmorillonite adsorbents. Part II: The effects of the type of raw clays and modification conditions on the adsorption performance

This paper builds on the preceding researches to study the effects of the type of clays (montmorillonites K10, KSF) and modifying conditions on the structure and adsorption behavior of resulting clay adsorbents. The raw clays were modified by polymeric Al/Fe species, hexadecyl-trimethylammonium (HDTMA) surfactant and a complex of polymeric Al/Fe-HDTMA. X-ray diffraction spectra was applied to analyze the structure of the raw and modified clays. After modification, the basal spacing of the clays varied, depending on the types of raw clay and modification conditions. Copper and phenol were selected as adsorbates for evaluating the adsorption performance of various clays, which was affected significantly by the types of raw clay and modification conditions. In general the inorganic contaminant (e.g., Cu) tend to be adsorbed by the polymeric Al/Fe modified clay and the organic impurities (e.g., phenol) will be preferably captured by the surfactant modified clay; both due to the specific surface properties resulting from introducing the modifiers. The complex modified clays possessed the ability of adsorbing both inorganic and organic contaminants. In addition, the d 0 0 1 spacing of modified KSF was greater than that of K10; the adsorption performance with modified KSF was thus greater than that with the modified K10. Finally, the ratio of modifiers to the clay (metal:surfactant:clay) has been observed to affect the adsorption performance; the optimal conditions have been defined.     

Chlorinated naphthalene formation from the oxidation of dichlorophenols

Polychlorinated naphthalenes (PCNs) formed along with dibenzo-p-dioxin and dibenzofuran products in the slow combustion of dichlorophenols (DCPs) at 600 degrees C were identified. Each DCP reactant produced a unique set of PCN products. Major PCN congeners observed in the experiments were consistent with products predicted from a mechanism involving an intermediate formed by ortho-ortho carbon coupling of phenoxy radicals; polychlorinated dibenzofurans (PCDFs) are formed from the same intermediate. Tautomerization of the intermediate and H2O elimination produces PCDFs; alternatively, CO elimination to form dihydrofulvalene and fusion produces naphthalenes. Only trace amounts of tetrachloronaphthalene congeners were formed, suggesting that the preferred PCN formation pathways from chlorinated phenols involve loss of chlorine. 3,4-DCP produced the largest yields of PCDF and PCN products with two or more chlorine substituents. 2,6-DCP did not produce tri- or tetra-chlorinated PCDF or PCN congeners. It did produce 1,8-DCN, however, which could not be explained.     

腐殖酸、细颗粒泥沙对粉末活性炭吸附苯酚特性影响的研究

通过一系列实验,探讨了粉末活性炭吸附水中苯酚时,腐殖酸(HA)浓度和细颗粒泥沙用量对苯酚吸附量和去除率的影响.实验结果表明:在中性条件下,随着HA浓度的增加,粉末活性炭对苯酚的吸附量减少;在不同质量细颗粒泥沙的影响下,苯酚的去除率基本不变;在未加HA时,粉末活性炭对苯酚的吸附行为用Langmuir吸附等温式拟合效果最好,对苯酚的最大吸附量为150.60 mg/g,而在有HA存在时,粉末活性炭对苯酚的吸附行为用Freundlich吸附等温式拟合效果最好,对苯酚的最大吸附量为28.49 mg/g.     

有机粘土矿物对水中低浓度菲的吸附性能和机理

分别选用十六烷三甲基溴化铵(HDTMA-Br)、四甲基溴化铵(TMA-Br)、聚乙二醇(PEG)表面活性剂改性天然粘土矿物,研究其对水中低浓度多环芳烃类难降解有机物菲的吸附性能和机理,并讨论了有机粘土的用量对吸附菲的性能的影响,验证了有机粘土矿物吸附菲后的稳定性.3种有机粘土矿物对菲的吸附等温线均呈中凹型,表现为分配系数(Kp)逐渐增大,表明吸附是分配作用和溶剂化效应共同作用的结果.根据Kp及土样有机碳含量(foc)所得的经有机碳归一化的分配系数(Koc)基本为常数,远远高于天然土壤/沉积物的Koc.在相同实验条件下,3种有机粘土矿物中HDTMA改性粘土矿物对菲的吸附性能最强,PEG改性粘土矿物次之,TMA改性粘土矿物最差.     

木棉基活性炭纤维吸附性能的研究

采用浸渍(NH₄)₂HPO₄化学活化法650℃时制备得到3种新型木棉基活性炭纤维,即只浸渍不预氧化方法处理的AK1(activated kapok),先浸渍后预氧化的AK-2和先预氧化后浸渍的AK-3。利用制备得到的活性炭纤维处理苯酚和亚甲基蓝的模拟废水,AK-2具有苯酚最大吸附量(137.00 mg/g),AK-1具有亚甲基蓝最大吸附量(274.11 mg/g)。吸附苯酚时,在静态平衡实验中,更符合Freundlich吸附等温线;在动力学实验中,更符合准一级反应。吸附亚甲基蓝时,在静态平衡实验中,AK-1更符合Langmuir模型,AK-2 、AK-3更符合Freundlich吸附等温线;在动力学实验中,更符合准二级反应。     

Adsorption of lead onto smectite from aqueous solution

The purpose of this research is to study the effect of a new method of adsorption using membrane filtration to determine the maximum amount of lead adsorbed by clay and investigate the behavior of the clay after adsorption of the said metal. Treatment of wastewater contaminated with heavy metals depends on the characteristics of the effluent, the amount of final discharge, the cost of treatment, and the compatibility of the treatment process. The process of adsorption of heavy metals by clays may be a simple, selective, and economically viable alternative to the conventional physical–chemical treatment. This is justified by the importance of the surface developed by this material, the presence of negative charges on the said surface, the possibility of ion exchange taking place, and its wide availability in nature. The removal of lead from wastewater was studied by using the adsorption technique and using clay as the adsorbent. A method was optimized for adsorption through a membrane approaching natural adsorption. This new method is simple, selective, and the lead adsorption time is about 3 days. The various properties of clay were determined. It was observed that the cation exchange capacity of the clay was 56 meq/100 g of hydrated clay for the raw sample and 82 meq/100 g for the purified sample. The total surface area determined by the methylene blue method was equal to 556 and 783 m²/g for the raw and purified samples, respectively. The adsorption kinetics depends on several parameters. The Pb(II) clay, obeys the Langmuir, Freundlich, and the Elovich adsorption isotherms with high regression coefficients. The use of this adsorbent notably decreases the cost of treatment. It was concluded that clay shows a strong adsorption capacity on Pb(II), the maximum interaction occurring with purified clay treated at high concentration of lead. It is proposed that this adsorption through a membrane be extended for the treatment of effluents containing other metals.     

Preparation and reactivation of magnetic biochar by molten salt method: Relevant performance for chlorine-containing pesticides abatement

Molten salt has been regarded as a versatile and environmental-friendly method for the material preparation and waste destruction. In this work, molten FeCl3 was utilized for the generation of magnetic biochar (MBC) derived from simultaneous activation and magnetization of biomass. The sample characterization indicated that MBC had a rough surface with BET surface area of 404 m2/g and total pore volume of 0.35cm3/g. Highly dispersed Fe3O4 and nitrogen could be deposited on the surface, leading to an excellent magnetization property. The MBC exhibited a great 2,4-Dichlorophenol (2.4-DCP) and atrazine removal performance in solution with the maximum adsorption capacity achieved 298.12 mg/g and 102.17 mg/g. Kinetics results demonstrated that MBC adsorption met the Pseudo-first-order model better. Molten NaOH-Na2CO3 was provided for the re-activation of exhausted MBC. 2,4-DCP was firstly desorbed from the MBC and subsequently destructed by the active species in the melt medium. Chlorine can be captured in the molten alkaline medium from the XRD pattern of residues.The MBC could be easily recovered with a yield of 98.2% and fixed carbon content of 61.0% after the molten salt regeneration process. With no 2,4-DCP detected, 65.5% and 31.69% of initial Cl was found in washing water and residues with the molten NaOH-Na2CO3, respectively. After 4 cycles of regeneration and adsorption, 60.55%-72.22% of initial adsorption capacity can be kept. This preparation and regeneration method can be an effective way to reduce the risk of secondary pollution of chlorinated organic compounds during adsorbent regeneration.

Implications: Molten salt (MS) is a salt or multiple salts with a low melting point, and has been applied in many sectors and is regarded as a crucial role in terms of energy, environmental, and resource sustainability. In our paper, magnetic biochar was prepared by one-step activation and magnetization of fir dust using molten FeCl₃?6H₂O. Meanwhile, a regeneration method using molten alkaline salt was provided. Magnetic biochar generated in our study performed well in the 2,4-dichlorophenol and atrazine adsorption. After four cycles of regeneration and adsorption, 72.2% of initial 2,4-DCP adsorption capacity can be kept.     

Effects of humic substances on the decomposition of 2,4-dichlorophenol by ozone after extraction from water into acetic acid through activated carbon

The objectives of this study are to clarify the behavior of humic substances throughout the processes of 2,4-dichlorophenol (2,4-DCP) adsorption on granular activated carbon (GAC) from water and extraction into acetic acid, and the influence of the extracted humic substances on the decomposition of 2,4-DCP by ozone in the acetic acid. The adsorption capacity of GAC for 2,4-DCP was not influenced by the humic substances preloaded to have equilibrium concentration of 24.9mg Cl(-1) (14.5mg Cg(-1)). The adsorption capacity of GAC for 2,4-DCP decreased to one tenth of new GAC after the first adsorption-extraction step because of only 16% desorption in the first step. However, 2,4-DCP adsorbed on GAC was completely extracted after the second step suggesting that GAC can be used as adsorbent to transfer 2,4-DCP from water to acetic acid. The concentration ratio of 2,4-DCP from water into acetic acid was around 2x10(5), whereas the concentration ratio of humic substances was about 3.5, indicating that 2,4-DCP was selectively adsorbed and extracted by this system. The first order degradation rate constant for 2,4-DCP by ozone in acetic acid increased with the addition of humic substances. The rate constant with 16mg Cl(-1) of humic substances was 2.6 times as high as that without humic substances. Humic substances behaved as a promoter for the degradation of 2,4-DCP by ozone.     

Adsorption of phenols by papermill sludges

In this paper we studied the sorption capacity of paper mill sludges for phenols. Phenol, 2-chlorophenol (2-CP), 3-chlorophenol 3-CP). 4-chlorophenol (4-CP), 2-nitrophenol (2-NP), 4-nitrophenol (4-NP), 2.4-dichlorophenol (2,4-DCP), 3,4-dichlorophenol (3,4-DCP) 3,5-dichlorophenol (3,5-DCP) and 2,4,5-trichlorophenol (2,4,5-TCP) were chosen for the sorption tests. Kinetic experiments showed that substituted-phenol sorption on papermill sludge was rapid (equilibrium was reached after 3 h); conversely, the time taken by the phenol to reach equilibrium conditions was 260 h. Experimental data showed that particle diffusion was involved in the sorption process but was not the only rate-limiting mechanism; several other mechanisms were involved. The adsorption isotherms showed the following order of retention capacity of papermill sludge: 2-NP = 4-NP < < 2-CP < phenol < 4-CP < or = 3-CP < 2,4 DCP<3,4 DCP=2,4,5 TCP<3,5 DCP. In all cases the experimental data showed a good fit with the Hill equation. which is mathemratically equivalent to the Langmuir-Freundlich model obtained by assuming that the surface is homogeneous, and that the adsorption is a cooperative process influenced by adsorbate-adsorbate interactions.     

酚类化合物在2-羧基苯甲酰基修饰的超高交联树脂上的吸附

合成了一种用来吸附和去除水溶液中酚类化合物的 2 羧基苯甲酰基修饰的超高交联吸附树脂 (ZH 0 1) ,并从动力学和吸附容量角度比较了XAD 4、AM 1和ZH 0 1分别吸附浓度为 80 0mg/L苯酚的情况。实验结果表明 ,ZH 0 1吸附剂有利于吸附苯酚、对甲苯酚和对硝基苯酚之类的酚类化合物。动力学和热力学研究都得到了相同的结果 :ZH 0 1对苯酚和对甲苯酚吸附是化学吸附的过渡状态 ,而对对硝基苯酚的吸附是一种物理吸附过程 ,并且显示了ZH 0 1表面均孔特性。苯酚在ZH 0 1上的小柱吸附研究表明了吸附穿透容量和总吸附量分别为 2 .38mmol/g和 3.0 5mmol/g ,溶剂甲醇对吸附在ZH 0 1上苯酚的脱附效果较好。     

Experimental design methodology for the preparation of carbonaceous sorbents from sewage sludge by chemical activation--application to air and water treatments

The objective of this study is to optimize experimental conditions of sorbent preparation from sewage sludge using experimental design methodology. Series of carbonaceous sorbents have been prepared by chemical activation with sulfuric acid. The sorbents produced were characterized, and their properties (surface chemistry, porous and adsorptive properties) were analyzed as a function of the experimental conditions (impregnation ratio, activation temperature and time). Carbonaceous sorbents developed from sludge allow copper ion, phenol and dyes (Acid Red 18 and Basic Violet 4) to be removed from aqueous solution as well as VOC from gas phase. Indeed, according to experimental conditions, copper adsorption capacity varies from 77 to 83 mg g(-1), phenol adsorption capacity varies between 41 and 53 mg g(-1) and VOC adsorption capacities (acetone and toluene) range from 12 to 54 mg g(-1). Each response has been described by a second-order model that was found to be appropriate to predict most of the responses in every experimental region. The most influential factors on each experimental design response have been identified. Regions in which optimum values of each factor were achieved for preparation of activated carbons suitable for use in wastewater and gas treatments have been determined using response surfaces methodology. In order to have a high mass yield and to minimize the energetic cost of the process, the following optimal conditions, 1.5 g of H2SO4 g(-1) of sludge, 700 degrees C and 145 min are more appropriate for use of activated carbon from sludge in water and gas treatments.     

Sorption studies of chloroanilines on kaolinite and montmorillonite

Batch experiments have been performed in order to evaluate the ability of the two reference clays kaolinite (KGa-1) and Na-montmorillonite (SWy-1) to retain three representative chloroanilines: 3-chloroaniline, 3,4-dichloroaniline and 2,4,6-trichloroaniline. Systems containing the clay mineral and the pollutant solution (at concentration levels ranging between 1.0 and 10.0mg/L) were considered and RP-HPLC methods were employed to follow the sorption processes as a function of time. The results indicate that montmorillonite shows a general higher sorption capacity with respect to kaolinite and that for both the reference clays, in the concentration range investigated, the amount of pollutant sorbed increases with concentration. The sorption coefficient K(d) ranges between 0.0030 L/g for the system 3-chloroaniline-kaolinite and 0.0488L/g for the system 2,4,6-trichloroaniline-montmorrillonite. The most lipophilic trichloroaniline shows the greater sorption. X-ray analyses suggest for kaolinite a preferential sorption onto the mineral surface, while for montmorillonite a progressive swelling of the structure is observed, likely due to sorption processes that also take place in the interlayer.     

Photoinduced transformation processes of 2,4-dichlorophenol and 2,6-dichlorophenol on nitrate irradiation

2,4-Dichlorophenol (2,4-DCP) and 2,6-dichlorophenol (2,6-DCP) undergo oxidation, nitrosation and nitration in the presence of nitrate under UV irradiation. Nitration is favoured under acidic conditions, most likely because HNO(2) is formed on nitrate photolysis. The most likely photonitration pathway is the reaction between radiation-excited dichlorophenols (DCP*) and HNO(2). HNO(2) is also able to nitrate DCP in the dark with elevated yields. Irradiation also causes DCP direct photolysis, which is more efficient for the dichlorophenolate anions. The photolysis of the dichlorophenols and that of the dichlorophenolates also produce different intermediates, by dechlorination in the former and ring contraction in the latter case.     

Adsorption of picloram on clays nontronite,illite and kaolinite: equilibrium and herbicide-clays surface complexes

The picloram (PCM) adsorption on nontronite, illite and kaolinite was studied at pH 3, 5 and 7. The adsorption isotherms had well-fitted to Langmuir and Freundlich models equations. The interactions of PCM with the clay mineral surfaces exhibited an anionic profile adsorption, with a decrease in adsorption when the pH increases. The PCM adsorption capacity increases in the following order: kaolinite?<?illite?<?nontronite. The X-ray diffraction (XRD) analysis of PCM-clay samples revealed that the picloram molecule does not enter into the clays basal space. The interaction of PCM with clays surface sites through nitrogen of the pyridine ring was confirmed by X-ray photoelectron spectroscopy (XPS). Due to the anionic form of PCM, the adsorption onto the external and edges surface sites of the clay minerals was proposed.     

褐煤活性炭吸附处理焦化废水

研究褐煤活性炭吸附处理焦化废水的性能,为褐煤活性炭用于废水处理提供理论依据和技术指导。以河南某气化厂的焦化废水为吸附原水,进行褐煤活性炭对酚吸附性能的静态和动态实验。静态实验表明,褐煤活性炭对酚的吸附性能符合弗兰德里希（Freundlich）吸附方程式。在室温条件下,对于150 mL焦化废水,当活性炭的用量为10 g,吸附反应时间为1 h,酚的去除率可达92%以上。动态实验研究表明,当进水酚浓度为3 800 mg/L,吸附1.5 h,活性炭的吸附容量可达21.38 mg/g。水处理的实验研究表明,利用褐煤制备的活性炭,对焦化废水具有良好的处理效果。     

纳米有机膨润土对苯酚的吸附性能研究

通过对天然膨润土改性,制备纳米有机膨润土并用于吸附苯酚,探讨了吸附时间、溶液pH、纳米有机膨润土投加量等因素对苯酚吸附的影响。结果表明,吸附在5 min内快速达到平衡,溶液pH可以影响苯酚在溶液中的状态,是影响苯酚吸附性能的重要因素。纳米有机膨润土吸附苯酚的过程可用伪二级反应动力学方程来描述,伪二级吸附速率常数为1.3 g/(mg.min)。吸附等温线符合Langmuir等温方程,在25℃时,Langmuir理论最大吸附容量可达到536.32 mg/g,吸附热力学参数表明吸附过程是自发的、放热的物理吸附过程。     

淀粉微球对苯酚的吸附性能研究

以可溶性淀粉为原料,N,N’-亚甲基双丙烯酰胺(MBAA)为交联剂,通过反相悬浮聚合得到淀粉微球作为吸附载体,研究了pH、吸附时间、温度对其苯酚吸附性能的影响,以及淀粉微球吸附苯酚的热力学和动力学特性,并利用扫描电镜仪、红外光谱仪对淀粉微球的结构进行了表征。结果表明,淀粉微球粒度分布均匀,表面粗糙多孔,具有相当大的孔容积和比表面积,具有较好的吸附性能;在20℃、pH为5.3时,吸附30 min后,淀粉微球对苯酚的吸附容量达到饱和,最大吸附量为18.71 mg/g;采用准二级吸附动力学方程能更好地描述淀粉微球对苯酚的吸附行为,淀粉微球对苯酚的吸附是以化学吸附为主控步骤的作用过程,淀粉微球对苯酚的吸附主要是通过氢键作用来完成的。     

羽毛不可溶角蛋白海绵膜对Cr（Ⅵ）的吸附性能

通过冷冻干燥,将还原法产生的凝胶状不可溶蛋白制备成具有致密孔隙的海绵膜,无需预处理和无交联剂,并研究了其对Cr（Ⅵ）的吸附性能。结果表明,在60℃、固液比12．5g／L、初始浓度100mg／L下最大吸附量为148．8mg／g,吸附过程符合Langmuir型和Freundlich型等温吸附模型,为吸热过程,物理吸附和化学吸附均起到重要作用。