咪唑类［PF6］-型离子液体萃取胺类化合物

以咪唑类[PF6]-型离子液体1-丁基-3-甲基咪唑六氟磷酸盐([Bmim][PF6])、1-己基-3-甲基咪唑六氟磷酸盐([Hmim][PF6])和1-辛基-3-甲基咪唑六氟磷酸盐([Omim][PF6])对苯胺、对氯苯胺等7种胺类化合物的萃取,考察了溶液初始浓度、相比、盐类、pH及离子液体咪唑基团上取代烷基对萃取平衡的影响,并研究了萃取过程的热效应.实验结果表明:溶液初始浓度对分配系数影响较小;相比10:1是离子液体对胺类化合物的溶解饱和临界点,当相比大于10:1时,分配系数降低;NaCl、K2SO4可以增大萃取分配系数,ZnSO4对分配系数几乎没有影响;pH增加,分配系数增大;离子液体对不同取代基的胺类萃取能力有较大的差异,咪唑基团上取代烷基的长度对不同胺类物质的分配系数影响较显著;萃取过程属于焓增大的吸热过程.     

咪唑类[PF6]^-型离子液体萃取胺类化合物

以眯唑类[PF6]^-型离子液体1-丁基-3-甲基咪唑六氟磷酸盐（[Bmim][PF6]）、1-己基-3-甲基咪唑六氟磷酸盐（[Hmim][PF6]）和1-辛基-3-甲基咪唑六氟磷酸盐（[Omim][PF6]）对苯胺、对氯苯胺等7种胺类化合物的萃取，考察了溶液初始浓度、相比、盐类、pH及离子液体眯唑基团上取代烷基对萃取平衡的影响，并研究了萃取过程的热效应。实验结果表明：溶液初始浓度对分配系数影响较小；相比10：1是离子液体对胺类化合物的溶解饱和临界点，当相比大于10：1时，分配系数降低；NaCl、K2SO4可以增大萃取分配系数，ZnSO4对分配系数几乎没有影响；pH增加，分配系数增大；离子液体对不同取代基的胺类萃取能力有较大的差异，咪唑基团上取代烷基的长度对不同胺类物质的分配系数影响较显著；萃取过程属于焓增大的吸热过程。     

针铁矿对Pb~(2+)的吸附特征及影响因素研究

通过恒温振荡平衡法研究了Pb~(2+)在针铁矿上的等温吸附和吸附动力学特征,探讨了吸附的影响因素.结果表明:(1)随Pb~(2+)平衡浓度和pH的增大,针铁矿对Pb~(2+)的吸附量逐渐增大.(2)针铁矿对Pb~(2+)的等温吸附可用Freundlich和Langmuir方程较好地拟合.(3)在相同温度和pH下,随离子强度的提高,针铁矿对Pb~(2+)的吸附量增大.(4)在相同离子强度和pH下,针铁矿对Pb~(2+)的吸附量总体随温度升高而增大.针铁矿对Pb~(2+)的吸附是自发进行的吸热反应.(5)针铁矿吸附Pb~(2+)的过程可分为初始的快吸附和随后的慢吸附2个阶段.pH影响吸附反应快慢,随pH增大吸附速率增大;随着pH的增大,达到平衡吸附的时间缩短.吸附动力学方程用Elovich方程拟合最佳.     

冠醚-离子液体体系对水相中铀酰离子的萃取

以二环己基-18-冠醚-6(DCH18C6)为萃取剂,一系列离子液体为溶剂的冠醚-离子液体萃取体系对水相中铀酰离子(UO2+2)进行萃取实验。结果表明:UO2+2在1-丁基-3-甲基咪唑双三氟磺酰亚胺盐([C4min]NTf2)体系的去除效率明显高于六氟磷酸盐类(PF-6)离子液体。在水相中当硝酸浓度在3 mol·L~(-1)左右时萃取效率最高,体系的萃取效率随着萃取剂浓度的增加而变大,共存离子的加入会降低体系的萃取效率,但是当加入的是硝酸根离子时,萃取率会相应增大。根据实验结果分析可以判断此萃取体系主要为阳离子交换过程。     

多孔水凝胶P（HEA/AMPS）对水溶液中Fe（Ⅲ）的吸附

以2-丙烯酸羟乙酯（HEA）和2-丙烯酰胺基-2-甲基丙磺酸（AMPS）为单体合成了聚合物水凝胶（PHEA/AMPS）,采用水凝胶对水溶液中Fe（Ⅲ）的吸附行为进行了研究。实验主要考察了聚合物组分、溶液pH、初始Fe（Ⅲ）浓度和吸附时间对水凝胶吸附作用的影响,并通过FT-IR和XPS分析了吸附前后水凝胶的变化。结果表明,当单体摩尔比AMPS∶HEA=1∶1,pH=2时,水凝胶对Fe（Ⅲ）的吸附容量最大。水凝胶对水溶液中Fe（Ⅲ）的吸附容量随着溶液中初始Fe3＋浓度的增加而增加,但当初始Fe3＋的浓度达到1 g/L时,吸附容量基本达到饱和。吸附等温线符合Langmuir等温线方程,吸附动力学符合准二级模型。FI-IR和XPS的分析表明,水凝胶的磺酸基和酰胺基是吸附Fe3＋的有效功能性基团,吸附机理为螯合和离子交换。     

多孔水凝胶P(HEA/AMPS)对水溶液中 Fe(Ⅲ) 的吸附

以2-丙烯酸羟乙酯(HEA)和2-丙烯酰胺基-2-甲基丙磺酸(AMPS)为单体合成了聚合物水凝胶(PHEA/AMPS),采用水凝胶对水溶液中Fe(Ⅲ)的吸附行为进行了研究。实验主要考察了聚合物组分、溶液pH、初始Fe(Ⅲ)浓度和吸附时间对水凝胶吸附作用的影响,并通过FT-IR和XPS分析了吸附前后水凝胶的变化。结果表明,当单体摩尔比AMPS∶HEA=1∶1,pH=2时,水凝胶对Fe(Ⅲ)的吸附容量最大。水凝胶对水溶液中Fe(Ⅲ)的吸附容量随着溶液中初始Fe3+浓度的增加而增加,但当初始Fe3+的浓度达到1 g/L时,吸附容量基本达到饱和。吸附等温线符合Langmuir等温线方程,吸附动力学符合准二级模型。FI-IR和XPS的分析表明,水凝胶的磺酸基和酰胺基是吸附Fe3+的有效功能性基团,吸附机理为螯合和离子交换。     

虾壳粉对水溶液中阴、阳离子型染料的吸附

采用废弃虾壳制备吸附剂处理含刚果红或亚甲基蓝的溶液。考察了温度、吸附时间、初始浓度、吸附剂投加量和初始溶液pH对吸附效果的影响并构建了去除率预测模型,并对吸附等温线、吸附动力学和吸附热力学进行系统研究。结果表明:虾壳粉对刚果红和亚甲基蓝的吸附分别在24 h和4 h时达到平衡,平衡吸附量随吸附时间、初始浓度及吸附剂投加量的增加而增大;刚果红平衡吸附量随pH升高而增大,亚甲基蓝平衡吸附量几乎不随pH变化。在15℃下,吸附剂投加量为1 g·L~(-1),刚果红吸附的最优条件为接触时间24 h、pH=4,在该条件下,虾壳粉对刚果红的饱和吸附量为276.64 mg·g~(-1);亚甲基蓝吸附的最优条件为接触时间4 h、pH=12,在该条件下,虾壳粉对刚果红的饱和吸附量为1.44 mg·g~(-1);虾壳粉对2种染料的吸附过程以物理吸附为主,符合准二级动力学方程。虾壳粉对阴离子型染料的吸附效果较优,对阳离子型染料有一定吸附性能,是一种经济高效的染料废水吸附材料。     

木粉/壳聚糖接枝丙烯酸-丙烯酰胺吸附树脂对二元重金属离子溶液中Pb2+的吸附

采用自制木粉/壳聚糖接枝丙烯酸-丙烯酰胺吸附树脂R1、R2、R3对二元金属离子Cu2 +/pb2和Zn2+/pb2+溶液中的吸附性能进行了较系统考察.pb2+离子溶液中存在竞争离子Cu2+、Zn2+时,随竞争离子浓度增加,3种吸附树脂R1、R2、R3对pb2+的吸附量明显下降,而竞争离子吸附量显著增加.二元溶液中各金属离子浓度相同时,3种树脂对竞争离子Cu2+、Zn2+的吸附量大于对pb2+的吸附量;各溶液中分别加入NaCl及NaNO3、尿素后,对pb2+离子的吸附量下降迅速.随吸附树脂用量增加,竞争离子Cu2+、Zn2+的吸附量逐渐减小,pb2+的吸附量在吸附树脂用量0.10 g/L(Zn2 +/pb2+溶液)或0.15 g/L(Cu2+/pb2+溶液)时出现最大值.溶液pH值对树脂吸附性能有显著影响.3.0＜pH＜5.O时,3种树脂对竞争离子和pb2+的吸附量快速增大;5＜ pH ＜9时,树脂对竞争离子和pb2+的吸附量基本不变;9＜pH＜ll时,树脂对pb2+的吸附量减小,而对竞争离子的吸附量或增大或减小.     

褐煤对废水中酸性红B的吸附去除

选用褐煤作为廉价吸附剂,脱除模拟废水中染料酸性红B。研究了褐煤对废水中酸性红B的吸附动力学、等温吸附模式,考察了pH、褐煤投加量以及离子强度(NaCl)对吸附效果的影响。结果表明,吸附动力学较好地符合准二级速率方程(R2=1.000),并且以化学吸附为主;吸附等温式满足Langmuir方程(R2=0.986),最大单分子层吸附量为42 mg/g;废水中染料的去除率随溶液pH的减小而明显增加,在pH=1时,去除效果最好,证实吸附过程存在静电吸引及化学键合;在一定条件下,溶液中酸性红B的去除率随褐煤投加量增加而增加;吸附效果随溶液中离子强度(NaCl)的增加而增强。说明褐煤可以作为一种廉价吸附材料,用于处理含染料废水。     

光催化法与生物法结合降解咪唑类离子液体

采用纳米TiO2光催化与生物降解相结合的方法,考察了3种1,3-二烷基咪唑类氯型离子液体的降解过程,并用HPLC-MS方法鉴定了光催化降解的碎片和可能的结构。结果表明,在相同条件下3,种离子液体光催化降解的速率次序为1-丁基-3-甲基咪唑氯盐（BmimCl）〉1-己基-3-甲基咪唑氯盐（HmimCl）≈1-辛基3-甲基咪唑氯盐（OmimCl）。BmimCl的光催化降解曲线符合一级动力学方程,最佳催化剂用量为0.5 g/L。HPLC-MS分析表明,光催化降解是咪唑开环氧化的过程,生成众多部分氧化碎片。离子液体水溶液的光催化预处理有利于提高其后续的活性污泥生物降解性能。     

离子液体负载型分子筛的制备及对染料的吸附

为了有效地处理活性黑染料废水,对离子液体负载型分子筛去除水中的活性黑染料进行了研究。首先制备了离子液体负载型吸附材料,分别考察了分散剂种类、离子液体加入量、浸渍时间3种因素对离子液体负载率的影响,确定负载工艺条件为:二氯甲烷作为分散剂、[OMim]BF4离子液体与分子筛质量比1∶2,浸渍时间12 h。其次研究了负载型吸附材料对染料废水的处理效果,考察了吸附材料添加量、溶液pH值、吸附时间对模拟废水活性黑染料去除率的影响,确定吸附工艺条件为:[OMim]BF4离子液体为最佳离子液体、吸附材料添加量0.40 g、pH=6、吸附时间12 h。在此最佳工艺条件下,染料去除率达98.23%。     

Differences in herbicide adsorption on soil using several soil ph modification techniques

Abstract

Effects of soil pH on weak acid and weak base herbicide adsorption by soil are often determined by modifying soil pH in the laboratory. Modification of soil pH with acidic or basic amendments such as HCl or NaOH can cause changes in the soil‐solution system that may affect pesticide adsorption. The partition coefficients (K_d) for atrazine and dicamba by Waukegan, Piano, and Walla Walla silt loam soils stabilized in the field at different pH levels were compared to the K_d obtained when the soil pH was adjusted with acidic or basic amendments before herbicide addition. NaOH addition to raise soil pH generally increased the soluble soil organic carbon (SSOC) concentration in solution compared to field soils at the same pH and to soil treated with Ca(OH)₂. NaOH decreased the soil solution ionic strength slightly. Acidifying soils increased the soil solution ionic strength, when compared to field soils at the same pH and had no effect on SSOC concentration. Dicamba adsorption to soil was minimal (K_d < 0.22) and not influenced by soil pH in the range of 4.1 to 6.0; adsorption by laboratory amended soils in some cases underestimated adsorption compared to nonamended soils. Atrazine adsorption increased with decreased pH in all soils, and was overestimated slightly by several laboratory treatments to reduce pH compared to adsorption by field soils. Treatments to raise the pH did not affect atrazine adsorption. Overall, herbicide adsorption differences due to pH modification were small (<30%), and were not affected by soil solution ionic strength, saturating cation, or SSOC concentration in solution.     

Sorption of polycyclic aromatic hydrocarbons (PAHs) on glass surfaces

Sorption of polycyclic aromatic hydrocarbons (PAHs) to glass commonly used in laboratories was studied. Sorption coefficients (K_d) of five selected PAHs to borosilicate glass surfaces were measured using column chromatography. A linear relationship between log K_d and the corresponding water solubility of the subcooled liquid (log S_w) of the investigated PAHs was observed. Based on the determined sorption coefficients our data revealed that mass loss caused by sorption on glass walls strongly depends on the ratio of solution volume to contacted surface area (V/S). The influence of solution chemistry such as ionic strength, solution pH, presence of cosolvent, and the influence of temperature on the sorption process were investigated. In the presence of ionic strength, sorption coefficients concurrently increased but less than a factor of 2 up to 0.005 M calcium chloride concentration. However, further increasing ionic strength had no influence on K_d. The cosolvent reduced sorption at a concentration of methanol in water above 0.5% (v/v); however, for benzo[a]pyrene even with 10% (v/v) methanol the mass loss would be still higher than 10% (with a V/S ratio less than 0.25). Significant effects of the solution pH and temperature were not observed. These results suggest that van der Waal’s forces dominate the sorption process. In the analysis of highly hydrophobic PAHs in aqueous samples, mass loss due to sorption on glass walls should be accounted for in the final result if untreated glass is used. The presented relationship between log K_d and log S_w may help to decide if such a correction is necessary. Furthermore, the frequently used silanization of glass surfaces may not be sufficient to suppress sorption for large PAHs.     

Decomposition of phenylarsonic acid by AOP processes: degradation rate constants and by-products

The paper presents results of the studies photodegradation, photooxidation, and oxidation of phenylarsonic acid (PAA) in aquatic solution. The water solutions, which consist of 2.7 g dm^?3 phenylarsonic acid, were subjected to advance oxidation process (AOP) in UV, UV/H₂O₂, UV/O₃, H₂O₂, and O₃ systems under two pH conditions. Kinetic rate constants and half-life of phenylarsonic acid decomposition reaction are presented. The results from the study indicate that at pH 2 and 7, PAA degradation processes takes place in accordance with the pseudo first order kinetic reaction. The highest rate constants (10.45?×?10^?3 and 20.12?×?10^?3) and degradation efficiencies at pH 2 and 7 were obtained at UV/O₃ processes. In solution, after processes, benzene, phenol, acetophenone, o-hydroxybiphenyl, p-hydroxybiphenyl, benzoic acid, benzaldehyde, and biphenyl were identified.     

改性甘蔗渣吸附废水中低浓度Cu2+的研究

利用离子液氯化-1-己基-3-甲基咪唑对甘蔗渣进行改性,利用改性甘蔗渣吸附去除模拟废水中低浓度的Cu2+,并对比了较优条件下甘蔗渣改性前后的Cu2+吸附性能.结果表明,溶液pH、改性甘蔗渣投加量、吸附时间对改性甘蔗渣吸附Cu2+均有一定的影响,较佳的溶液pH为5.41、改性甘蔗渣投加量为0.30 g、吸附时间为130 min;吸附温度升高Cu2+吸附率反而降低,因此选择在室温下进行吸附反应为宜;在以上较优条件下,改性甘蔗渣和甘蔗渣的Cu2+吸附率分别为83.20％和53.83％,前者的Cu2+吸附率提高了30.35％.     

Adsorption of ammonium on biochar prepared from giant reed

Giant reed was used as precursor for making biochar in order for the adsorption of NH₄ ⁺–N from aqueous solution. And the adsorption of the product to NH₄ ⁺–N was examined. The surface features of biochar were investigated by Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy/energy dispersive spectrometer (SEM-EDS), and X-ray diffraction (XRD). XRD patterns showed several peaks and correspond to the high amount of crystalline material. The crystals contain KCl, K₂O, CaO, MgO, and SiO and possess high surface area which enhances adsorption. The influence of different parameters such as initial concentration, adsorption time, pH, and ionic strength has been carried out. The adsorption could reach equilibrium through 24 h reaction and had the best adsorption amount at the solution pH values from 7 to 9. The cation has great influence on the adsorption of NH₄ ⁺–N, whereas the anion exerted a weaker effect. The adsorption followed pseudo-first-order and pseudo-second-order models. And the intraparticle diffusion and desorption studies further elucidated that the mechanism of adsorption on the product was ion exchange. The product equilibrium data was well described by the Langmuir and Freundlich model. The maximum adsorption capacities were 1.490 mg/g. Biochar derived from giant reed at 500 °C was suggested as a promising adsorbent for the removal of NH₄ ⁺–N from slightly polluted wastewater.     

Kinetics of the oxidation of hydrogen sulfite by hydrogen peroxide in aqueous solution:: ionic strength effects and temperature dependence

Conductometry was used to study the kinetics of the oxidation of hydrogen sulfite, HSO⁻₃, by hydrogen peroxide in aqueous non-buffered solution at the low concentration level of 10⁻⁵–10⁻⁶ M, typically found in cloud water. The kinetic data confirm that the rate law reported for the pH range 3–6 at higher concentration levels, rate=k_H·[H⁺]·[HSO⁻₃]·[H₂O₂], is valid at the low concentration level and at low ionic strength I_c. At 298 K and I_c=1.5×10⁻⁴ M, third-order rate constant k_H was found to be k_H=(9.1±0.5)×10⁷ M⁻² s⁻¹. The temperature dependence of k_H led to an activation energy of E_a=29.7±0.9 kJ mol⁻¹. The effect of the ionic strength (adjusted with NaCl) on rate constant k_H was studied in the range I_c=2×10⁻⁴–5.0 M at pH=4.5–5.2 by conductometry and stopped-flow spectrophotometry. The dependence of k_H on I_c can be described with a semi-empirical relationship, which is useful for the purpose of comparison and extrapolation. The kinetic data obtained are critically compared with those reported earlier.     

Characterization and lead(II), cadmium(II), nickel(II) biosorption of dried marine brown macro algae Cystoseira barbata

Purpose

The objectives of this research are to identify the functional groups and determine corresponding pK _a values of the acidic sites on dried brown algae Cystoseira barbata using FTIR and potentiometric titrations, and to investigate the biosorption ability of biomass towards divalent nickel, cadmium, and lead ions. Adsorption was studied as a function of solution pH and contact time, and experimental data were evaluated by the Langmuir isotherm model.

Methods

CaCl₂ pretreatment was applied to the sorbent for enhancing the metal uptake capacity. The effect of solution pH on biosorption equilibrium was investigated in the pH range of 1.5?C5.0. Individual as well as competitive adsorption capacity of the sorbent were studied for metal cations and mixtures.

Results

The retention of the tested metal ions was mostly influenced from pH in the range of 1.5?C2.5, then stayed almost constant up to 5.0, while Ni(II) uptake showed the highest variation with pH. Potentiometric titrations were performed to find the number of strong and weak acidic groups and their acidity constants. The density of strong and weak acidic functional groups in the biomass were found to be 0.9 and 2.26?mmol/g, respectively. The FTIR spectra of the sorbent samples indicated various functionalities on the biomass surface including carboxyl, hydroxyl, and amino and sulphonate groups which are responsible for the binding of metal ions.

Conclusions

The capacity of the biomass for single metal ions (around 1?mmol/g) was increased to 1.3?mmol/g in competitive adsorption, Pb(II) showing the highest Langmuir intensity constant. Considering its extremely high abundance and low cost, C. barbata may be potentially important in metal ion removal from contaminated water and industrial effluents.