改性粉煤灰净化水中的磷

研究了粉煤灰的浓硫酸改性以及改性后的粉煤灰从水中净化磷的过程.通过实验发现粉煤灰改性后对水中磷的净化效果有显著提高.粉煤灰用浓硫酸进行改性后比表面积从8.8m2/g增加到32.5m2/g.而且用浓硫酸改性后,粉煤灰中的金属离子在酸性条件下部分溶解或完全溶解,导致净化过程中水溶液中金属离子浓度增大.改性粉煤灰净化含磷废水的过程中,存在吸附机理和沉淀机理,但沉淀对磷的净化起主要作用.实验结果表明,改性粉煤灰对磷的净化过程速度较快,5min可以达到最大净化率.在pH 5-9范围内磷净化过程影响不显著.通过实验还发现磷的净化率随吸附剂用量的增加而增加.改性粉煤灰对磷的吸附过程比较符合Langmuir吸附等温线,Langmuir常数Q0为9.15mg·g-1.从吸附磷后的改性粉煤灰的XRD图和SEM图可以发现在磷的净化过程中生成了CaHPO4·2H2O,此外磷也与铁和铝反应形成沉淀.     

原子吸收光谱法比较研究3种不同改性吸附剂对Cr(Ⅵ)离子的吸附

从吸附时间、pH值、吸附剂加入量、铬离子初始浓度4个方面,通过原子吸收光谱法比较了改性甘蔗渣、改性花生壳和改性梨渣的吸附特性.在铬离子浓度100mg·L-1、吸附剂投量15g·L-1、最佳pH值、吸附时间120min的实验条件下,三者吸附率不同,改性甘蔗渣的吸附率达86.7％以上,改性花生壳吸附率达64.8％,改性梨渣的吸附率达60.8％.3种改性吸附剂对Cr(Ⅵ)离子的吸附均符合Langmuir等温模型,其最大吸附能力分别为23.92、22.09、20.47mg·g-1.准一级反应动力学方程可描述3种改性吸附剂对Cr(Ⅵ)离子的吸附过程.     

分光光度法研究改性粉煤灰对有机磷的吸附性能

常温下,用硫酸铝为改性剂制得改性粉煤灰,以此作为有机磷废水的吸附剂,用分光光度法分析改性粉煤灰对有机磷的吸附性能,并通过XRD对其结构进行表征。结果表明:改性时,盐灰质量比为1∶12;吸附时,改性粉煤灰用量为35g/L、溶液的pH值为8、振荡时间为30min、吸附温度为30℃时,磷的去除率可达97.0%。     

La/酸化膨润土吸附剂的表征与除磷性能

以酸化改性膨润土为载体,采用浸泡法制备了稀土La掺杂的La/酸化膨润土吸附剂.通过XRD和FTIR对其结构进行了表征,探讨了膨润土的改性机理,研究了该吸附剂对废水的除磷性能.结果表明：酸化过程洗掉了膨润土中的杂质和氧化铝,稀土镧的掺杂在膨润土层间及表面引入了一定数量的羟基化合物,改善了膨润土的层间结构并生成了新的La-O-Si键,实现了La与膨润土的复合,提高了膨润土的吸附性能.     

液溴改性非碳基吸附剂对单质汞吸附的实验研究

为了获得性能高效的非碳基吸附剂脱除燃煤烟气中排放的Hg,采用液溴浸渍的方法,对吸附剂进行了改性。通过固定床和沉降炉吸附实验,发现高岭土、沸石和石灰石改性后对单质汞的吸附能力有较大提高。改性后的吸附能力提高的原因在于化学吸附的增强。     

柠檬渣吸附污水中Hg~(2+)的动力学研究

由于农业废弃物价格低廉,改性后吸附性能优越等优点,目前利用农业废弃物制作吸附剂吸附污水中的重金属逐渐成为研究热点。为了研究柠檬渣对污水中Hg2+的吸附动力学,利用15%硫酸对柠檬渣进行了改性,测试了吸附剂的孔容与孔径等性能,并利用差热分析、红外光谱、电镜和能谱对样品进行了表征。结果表明改性柠檬渣吸附Hg2+的吸附速率由膜扩散控制,符合膜扩散中Lagergren一级动力学方程,该吸附过程主要为物理吸附。改性后的柠檬渣吸附性能有较大改善,孔径分布主要是中孔;有三个失重过程,在66℃左右有一个吸热峰,在316和494℃左右有两个放热峰。吸附前后并柠檬渣的基本框架没改变;样品属于无定型结构。改性柠檬渣表面疏松、多孔,能有效吸附Hg2+。     

外加阴离子吸附剂对复合污染黄土淋洗过程养分淋失的减缓机制(Ⅱ)

化学淋洗法是常用的污染场地修复方法,其经济性、简便性、安全性等指标较其他方法有较大优势。化学淋洗法存在的弊端之一是淋洗过程土壤伴存养分的同步淋失,若能在此瓶颈问题上有所突破,将会大大促进淋洗法场地修复的应用进程。本文研究的目标在于揭示合成秸秆基阴离子吸附剂对养分淋失的减缓机制,采用吸附平衡模式(等温线和动力学)与光谱分析技术(SEM和FT-IR)相结合,力图从微观层面验证宏观研究结果。Langmuir和准二级动力学方程能更好地描述硝酸根和磷酸根的吸附行为,由Langmuir方程计算得出q_m分别为7.507 5和4.194 6 mg·g-1,吸附反应为单层吸附和优惠吸附过程,主要控速步骤为化学吸附。阴离子吸附剂对硝酸根和磷酸根的吸附活化能(298 K)E_a分别为42.25和39.38 kJ·mol-1,吸附反应自发、吸热。纯净水和KOH能够实现阴离子吸附剂的再生,超声辅助和延长解吸时间对于解吸效果略有促进作用。吸附后阴离子吸附剂表面被点状分布的细微颗粒物覆盖,解吸后仅有少量枝状物零星分布。吸附前后FTIR图谱的主要波峰红移或蓝移,证实阴离子吸附剂表面及内部官能团通过静电作用与硝酸根和磷酸根结合。阴离子吸附剂对硝酸根和磷酸根的吸持固定是物理吸附和化学吸附共同作用的结果。     

质子化改性壳聚糖吸附硫酸根行为及其光谱分析

壳聚糖(CTS)具有活性基团氨基和羟基,可用作吸附剂。在酸性介质中其氨基容易质子化形成氨基正离子,具有吸附阴离子的能力,同时也导致吸附剂的溶解流失;进行交联处理可提高吸附剂的酸稳定性,但也导致吸附性能的下降。因此可进行氨基保护后进行交联以改善其酸溶液稳定性,再脱去氨基保护剂进行质子化处理以获得较好的对阴离子的吸附性能。以甲醛为氨基保护剂,戊二醛为交联剂,通过反相悬浮法制得交联壳聚糖(CCTS),对其进行质子化制得质子化改性壳聚糖吸附剂(P-CCTS),并首次将该吸附剂用于处理水溶液中的硫酸根离子。通过静态吸附实验,考察了质子化改性壳聚糖对硫酸根的吸附性能;利用X射线能谱元素分析(EDS)和红外光谱分析(FTIR)对该吸附剂的制备以及对硫酸根离子的吸附过程进行了表征,探索了交联反应和吸附反应的发生机理。实验结果表明：质子化改性壳聚糖吸附剂与交联壳聚糖相比,其对硫酸根离子的吸附性能提高了约10倍;甲醛、戊二醛的醛基与壳聚糖的交联反应主要发生在的氨基(—NH₂)和部分一级羟基(C₆—OH)上;质子化过程中交联壳聚糖的氨基与质子化剂形成了氯化壳聚糖氨盐;对硫酸根离子的吸附则主要是质子化氨基上氯离子与硫酸根离子的交换作用。     

磷酸酯化改性梨渣吸附污染水体中锌离子的研究

以砀山梨渣为原料,经磷酸酯化改性,制备一种酯化梨渣阳离子吸附剂,用批次实验法研究了其在不同实验条件下（pH值、吸附剂量、吸附质浓度和吸附时间）对金属锌离子的吸附性能。结果表明,溶液pH=3.5时,锌离子吸附达到最大值;酯化梨渣≥5g.L-1能除去锌离子为100mg.L-1溶液中的96%锌离子。改性梨渣对锌离子的吸附符合Langmuir吸附等温线模型,最大吸附能力为28.986mg.g-1。锌离子达到吸附平衡的时间为30min;准一级反应动力学方程y=-0.0615x＋2.4437（r2=0.9921）描述锌离子在改性梨渣上的吸附过程。     

过渡金属卤化物改性非碳基吸附剂脱汞研究

以6种大比表面积非碳基成分为载体,经过渡金属卤化物改性处理后制成汞吸附剂,并对其不同烟气气氛和温度下的汞吸附性能及汞氧化率进行了研究。CuCl_2改性氧化铝在各种烟气条件下均表现出较好的汞吸附性能。FeCl_3改性沸石的汞脱除率相对略低,但它制作成本较低。这两种非碳基吸附剂在未来有较好的应用前景。改性吸附剂的最适宜反应温度100～200℃。     

Thermodynamic and kinetic parameters of ciprofloxacin adsorption onto modified coal fly ash from aqueous solution

Batch adsorption experiments were carried out for the removal of ciprofloxacin from aqueous solution using modified coal fly ash as adsorbent. The effects of various parameters such as contact time, initial solution concentration and temperature on the adsorption system were investigated. The optimum contact time was found to be 100 min. The isotherm adsorption data fit well with the Langmuir model, and the kinetic data fit well with the pseudo-second order and the intra-particle diffusion model. Intra-particle diffusion analysis demonstrates that ciprofloxacin diffuses quickly among the particles at the beginning of the adsorption process, and then the diffusion slows down and stabilizes. Thermodynamic parameters such as ΔG, ΔH and ΔS were also calculated. The negative Gibbs free energy change and the positive enthalpy change indicated the spontaneous and endothermic nature of the adsorption, and the positive entropy change indicated that the adsorption process was aided by increased randomness.     

Influence of conductive surface on adsorption behavior of ultrafiltration membrane

In this research the influence of conductivity on adsorptive behavior of PM30 ultrafiltration membrane was investigated using BSA solution as the feed. The conductive membrane was prepared from the originally nonconductive membrane by chemical polymerization of pyrrole as the conducting media on the membrane surface. Both Langmuir and Redlich-Peterson isotherms properly describe the quasi-equilibrium adsorption data which are produced using experimental results of flux and rejection. Higher capacity of protein adsorption was achieved using nonconductive in comparison with conductive membrane. Using nonconductive membrane, an excessive feasibility and spontaneity of BSA adsorption was observed based on the greater negative value of Gibbs free energy change () which is a criterion for spontaneity of adsorption. Determination of filtration mechanism was conducted for elucidation the dominant adsorption region within the membranes i.e. membrane surface or internal pores. The filtration mechanisms for BSA solution using nonconductive and conductive membranes were surface cake deposition and intermediate (partial) blocking, respectively. First-order-kinetic model versus second-order-kinetic model indicated a superior interpretation of adsorption kinetics for both membranes; however, the required time to reach to the equilibrium for nonconductive membrane was slightly higher. All the distinctions in adsorption behavior of the conductive membrane originate from the repulsive potential field appears on the surface of the membrane during preparation. This electrostatic field acts as a barrier against the passage of the negatively charged proteins. Moreover, the partial coverage of membrane surface and internal pores with poly(pyrrole) may reduce the quantity of the active adsorptive sites on the membrane surface and matrix or presumably deactivates a part of the sites.     

Adsorptive removal of congo red dye from aqueous solution using bael shell carbon

This study investigates the potential use of bael shell carbon (BSC) as an adsorbent for the removal of congo red (CR) dye from aqueous solution. The effect of various operational parameters such as contact time, temperature, pH, and dye concentration were studied. The adsorption kinetics was modeled by first-order reversible kinetics, pseudo-first-order kinetics, and pseudo-second-order kinetics. The dye uptake process obeyed the pseudo-second-order kinetic expression at pH 5.7, 7 and 8 whereas the pseudo-first-order kinetic model was fitted well at pH 9. Langmuir, Freundlich and Temkin adsorption models were applied to fit adsorption equilibrium data. The best-fitted data was obtained with the Freundlich model. Thermodynamic study showed that adsorption of CR onto BSC was endothermic in nature and favorable with the positive ΔH° value of 13.613 kJ/mol.     

Adsorption of phosphorus by different biochars

In many areas of the world, leaching of phosphorus in the soil causes serious water pollution. The purpose of this research was to decrease the phosphorus loss in soil by the adsorption behavior of biochars with special structural characteristics. In this study, a series of analysis methods including scanning electron microscopy, infrared spectroscopy, elemental composition, thermogravimetric, and X-ray diffractometer analysis have been used to investigate the properties and structures of different sources of biochars. The adsorption of phosphorus by maize-straw biochar, rice-hull biochar, and pine biochar was quantified by the balance method in this research. The results show that pine biochar has more structural and thermal stability than maize-straw biochar and rice-hull biochar. Different sources of biochar have significantly different phosphate adsorption capabilities. Pine biochar has the best phosphorus adsorption capacity; the actual maximum adsorption capacity was 13.898?mg?g^?1; however, the phosphorus adsorption capacity of maize-straw biochar was minimum, the actual maximum adsorption capacity was 8.809?mg?g^?1. The volume of phosphorus adsorption on biochars increases with increasing concentration of phosphorus added to the solution, but the rate of increase gradually decreases. The phosphorus adsorption curve agreed well with the Langmuir isotherm equation.     

氢氧化铝对重金属离子的吸附性能研究

氢氧化铝对重金属的吸附速率大小顺序为锌铬铅铜镉。5种元素的吸附速率在反应的前几小时内变化很快,之后逐渐趋于平衡。在这些金属中,铜元素在吸附反应初期存在一个峰值变化。氢氧化铝对镉、锌、铜、铅、铬的吸附,在实验浓度范围内,都很好地符合Freundlich型等温式,吸附指数(1/n)在0.1—0.5之间,吸附反应容易进行。氢氧化铝对锌的吸附能力要更强一些。镉、锌、铜、铅、铬的吸附等温线方程分别为qe=14.13Ce1/1.45(20.0±0.5℃)、qe=20.36Ce1/1.70(21.0±0.5℃)、qe=5.10Ce1/1.16(23±1℃)、qe=16.21Ce1/1.01(24.0±0.5℃)、qe=7.76Ce1/1.22(24.0±0.5℃)。在金属离子的初始浓度较低时,吸附量随着金属离子初始浓度的增大而增大;在初始浓度达到一定值时,吸附量出现吸附平衡。     

Nanofibrous membrane of polyacrylonitrile with efficient adsorption capacity for cadmium ions from aqueous solution: Isotherm and kinetic studies

The nanofibrous membrane of polyacrylonitrile (NMP) was successfully synthesized after NaOH and NaHCO₃ treatment aiming its functionalization using electrospinning for cadmium ion (Cd²⁺) adsorption. Field emission scanning electron microscopy (FE-SEM) revealed that small particles attached to the surface of functionalized PAN nanofibers. Equilibrium was attained after 60 min following a rapid uptake of Cd²⁺ with maximum adsorption capacity and percentage removal at an optimum solution pH of 7.0. The adsorbent dose of 0.3 g and 90 mg L⁻¹ of initial Cd²⁺ concentration yielded the maximum adsorption capacity. The pseudo-second-order kinetic model was the best fitted to the adsorption data, indicating that the chemisorption is the controlling mechanism of adsorption. The physisorption was proposed based on the calculated values of the mean free energy of adsorption from the D–R isotherm (E < 8 kJ mol⁻¹). Furthermore, three-parameter isotherm models indicated the homogeneous and heterogeneous Cd²⁺ adsorption onto NMP adsorbent.     

Electronic structures and magnetic properties of rare-earth-atom-doped BNNTs

Stable geometries, electronic structures, and magnetic properties of (8,0) and (4,4) single-walled BN nanotubes (BNNTs) doped with rare-earth (RE) atoms are investigated using the first-principles pseudopotential plane wave method with density functional theory (DFT). The results show that these RE atoms can be effectively doped in BNNTs with favorable energies. Because of the curvature effect, the values of binding energy for RE-atom–doped (4,4) BNNTs are larger than those of the same atoms on (8,0) BNNTs. Electron transfer between RE-5d, 6s, and B-2p, N-2p orbitals was also observed. Furthermore, electronic structures and magnetic properties of BNNTs can be modified by such doping. The results show that the adsorption of Ce, Pm, Sm, and Eu atoms can induce magnetization, while no magnetism is observed when BNNTs are doped with La. These results are useful for spintronics applications and for developing magnetic nanostructures.     

光度法对不同水期黄河甘宁蒙段表层沉积物中磷积累程度和交换能力的比较研究

磷是水体富营养化的主要控制因素,在外源磷输入逐步得到控制后,作为内源磷主要来源的表层沉积物对黄河水体水质的影响作用不容忽视。掌握表层沉积物中磷的积累程度以及沉积物-水界面磷的交换能力,对区域内水环境的治理和磷负荷的调控具有重要的意义。选择黄河甘宁蒙段作为研究区域,分别采集丰水期(2011.07)、枯水期(2014.05)和平水期(2014.10)表层沉积物样品,使用标准测试程序(SMT)和钼锑抗分光光度法测定样品中磷赋存形态,并在实验条件下模拟表层沉积物对磷的等温吸附及吸附动力学过程。研究发现：(1) 相比于国内主要河流表层沉积物中磷的形态特征,黄河甘宁蒙段表层沉积物中有机磷(OP)和铁/铝结合态磷(NaOH-P)含量相对较低,钙结合态磷(HCl-P)含量较高;各形态磷含量的平均值均在丰水期最高,表明丰水期表层沉积物中磷的积累程度最高,黄河甘宁蒙段水环境受到沿程农业发展的冲击较大。因此,合理使用含磷化肥和优化灌渠退水水质是未来降低黄河水体磷污染风险的发展方向。(2) 基于低磷浓度下等温吸附中各采样点表层沉积物吸附-解吸平衡浓度(EPC₀)与判断水体发生富营养化的磷浓度阈值的比较发现,研究区域所有水期大多数采样点表层沉积物发挥着“磷源”的作用,存在向上覆水释放磷的趋势,且枯水期中多数采样点的EPC₀值较高,“磷源”作用更加明显;基于L模型和F模型对高磷浓度下等温吸附的拟合参数,显示丰水期表层沉积物对磷的持留能力最强,枯水期次之,平水期最小,所有采样点表层沉积物对磷的吸附过程均易发生;基于吸附动力学曲线的变化趋势可知,所选择的各采样点磷吸附量在反应开始的12 h内迅速增大,12~48 h内吸附量逐渐增加并趋于稳定;基于伪二级动力学方程对吸附动力学过程的拟合结果,表明表层沉积物对磷吸附过程的反应速率受化学吸附控制为主;从同一水期不同采样点吸附过程中的限速步骤不同及不同水期邻近采样点吸附过程中限速步骤均为微孔扩散的结果发现,表层沉积物组成和理化性质的差异对磷吸附速率的影响大于不同水期条件下上覆水流速和流量的变化。     

光度法研究太湖表层沉积物中磷形态分布及动力学特征

表层沉积物是水体污染物的源和汇。研究表明,太湖地区特别是梅梁湾和东太湖表层沉积物中磷等营养元素污染严重。采用SMT法(standards measurements and testing)和钼锑抗分光光度法对太湖18个采样点表层沉积物样品进行前处理和磷形态分析,结合我国、加拿大和美国标准对总磷进行污染评价。通过拟合建立了吸附-解吸动力学特征方程,并在不同pH、水土比的环境条件下获得磷的吸附特性。同时也在不同温度和pH下对磷进行解吸特征研究。结果表明： S₉采样点总磷、无机磷、有机磷和酸磷含量均最高,S₁₁采样点碱磷含量最高。对于所有采样点,各形态磷平均值大小排序为(μg·g-1)： 无机磷(401.43)>酸磷(377.81)>有机磷(175.37)>碱磷(25.53)。污染评价结果表明： 除S₁₂,S₁₄~S₁₆及S₁₈采样点外,其余采样点均有不同程度的污染。表层沉积物对磷的吸附-解吸过程均符合伪二级动力学方程。吸附过程最佳水土比为25∶1,且pH值对吸附和解吸有不同程度的影响。研究结果为掌握太湖梅梁湾和东太湖区域磷的污染现状提供理论依据,同时为研究磷在沉积物-水界面的迁移规律提供可信的实验数据。     

Adsorption of methylene blue onto sonicated sepiolite from aqueous solutions

The aim of the present study is to enhance the methylene blue (MB) adsorption of sepiolite by ultrasonic treatment. The natural sepiolite was pretreated by sonication to improve the surface characteristics and enhance the dye uptake capacity. Sonication process resulted in a significant increase in the specific surface area (SSA) of sepiolite. The FTIR spectrum of the sonicated sepiolite indicates that the tetrahedral sheet is probably distorted after sonication process. The effect of various parameters such as sonication, pH, initial dye concentration and temperature on dye adsorption has been investigated. The adsorbed amount of MB on sepiolite increased after sonication as well as with increasing pH and temperature. The experimental data were evaluated by applying the pseudo-first- and second-order, and the intraparticle diffusion adsorption kinetic models. Adsorption process of MB onto sepiolite followed the pseudo-second-order rate expression. The experimental data were analyzed by Langmuir and Freundlich isotherms, and found that the isotherm data were reasonably well correlated by Langmuir isotherm. Maximum monolayer adsorption capacity of sepiolite for MB increased from 79.37 to 128.21 mg/g after the sonication. Various thermodynamic parameters, such as ΔG⁰, ΔH⁰ and ΔS⁰ were calculated. The thermodynamics of MB/sepiolite system indicated spontaneous and endothermic nature of the process. Adsorption measurements showed that the process was very fast and physical in nature.