天然斜发沸石吸附去除水中氨氮机理研究

采用天然斜发沸石吸附去除水中氨氮,利用X射线衍射(XRD)和X荧光光谱(XRF)分析沸石的物相组成和化学成分。通过批试验考察p H、氨氮初始浓度和温度对沸石吸附氨氮的影响,通过吸附等温线、吸附热力学和吸附动力学的研究探讨天然斜发沸石吸附氨氮的机理。溶液p H=8时沸石对氨氮的吸附效果最佳。Freundlich吸附等温线较Langmuir能更准确描述天然斜发沸石吸附氨氮的过程,该吸附过程属优惠吸附。对吸附热力学参数计算得到吉布斯自由能变ΔG~00,熵变ΔH~00,说明天然斜发沸石吸附氨氮是自发的吸热过程;熵变ΔS~00说明氨氮在沸石上的分布较在水溶液中的分布倾向无序。吸附动力学符合准二级动力学方程,且随着氨氮初始浓度的增大,吸附反应的优惠程度降低。运用颗粒内扩散模型对实验数据的拟合结果表明吸附过程分为两个阶段:前30分钟主要是外表面吸附,30分钟后主要是颗粒内扩散。     

Removal of Cadmium Ions from Aqueous Solution by Silicate-incorporated Hydroxyapatite

This article reports a preliminary research on silicate-incorporated hydroxyapatite as a new environmental mineral used to remove cadmium ions from aqueous solutions. The silicate-incorporated hydroxyapatite was prepared by coprecipitation and calcining, and silicate was incorporated into the crystal lattice of hydroxyapatite by partial substitution of phosphate. The amount of cadmium ions removed by silicate-incorporated hydroxyapatite was significantly elevated, which was 76% higher than that of pure hydroxyapatite. But the sorption behavior of cadmium ions on silicate-incorporated hydroxyapatite was similar to that of pure hydroxyapatite. Morphological study revealed that silicate incorporation confined the crystal growth and increased the specific surface area of hydroxyapatite, which were in favor of enhancing the cadmium ion sorption capacity of the samples. Incorporation of silicate into hydroxyapatite seems to be an effective approach to improve the environmental property of hydroxyapatite on removal of aqueous cadmium ions.     

天然丝光沸石表面重构改性及其在水中去除重金属的应用

天然丝光沸石作为一种绿色廉价多孔材料广泛应用于环境治理中去除重金属,目前报道的天然沸石对重金属的去除率多在60%～90%,提升其去除效率已成为研究热点。本文采用正硅酸乙酯对天然丝光沸石进行表面重构改性,通过TEM、XRD、BET等手段表征其形貌和结构。结果表明:正硅酸乙酯水解生成的SiO_2可与天然丝光沸石复合形成新颖的"SiO_2/丝光沸石",原沸石表面包覆了新生纳米SiO_2孔结构,同时没有损坏原始沸石的多孔结构,使改性沸石材料兼具了天然丝光沸石和纳米SiO_2孔结构优点,增强了对重金属离子的吸附能力。该改性材料对水中Pb~(2+)、Cd~(2+)、Zn~(2+)和Mn~(2+)的最高吸附率为99. 3%、97. 1%、98. 3%和97. 0%,且极少解吸,性能稳定。考虑经济成本并保证合适吸附率的情况下选择吸附效率最佳的投加量,得到改性材料对初始浓度10 mg/L的Pb~(2+)、Cd~(2+)、Zn~(2+)、Mn~(2+)溶液的最佳投加量分别为0. 5 g/L、2 g/L、2 g/L、5 g/L,可为中试和规模应用提供参考。较之焙烧、酸、碱、盐和有机改性,本改性方式对多种重金属均有高的吸附率,并显现出操作简便、成本低和环境友好等优势,具有较好应用前景。     

天然锰钾矿吸附水溶液中Hg^2＋的实验研究

利用粉碎分级的天然锰钾矿去除水溶液中Hg^2 的实验研究表明：反应平衡时间约为20小时；pH值对其吸附率影响很大，在中性（氯化物在偏碱性）条件下吸附率较高；溶液中阳离子的存在会产生竞争吸附而降低对Hg^2 的吸附量，2价金属离子较1价金属离子对Hg^2 竞争干扰明显；溶液中Cl^-的存在能明显降低对Hg^2 的吸附量。对等温吸附曲线的回归分析得出在浓度为5～350mg/L段能很好地符合Langmuir单吸附位吸附曲线，并计算出在该实验条件下其最大理论吸附量为27.6mg/g。解吸实验结果表明，在无其他电解质参与的条件下解吸量较少，受多种电解质干扰时其解吸率不超过20%。     

响应曲面法优化生物质炭去除水溶液中的阿特拉津

将农业废弃物大豆秆在450℃缺氧条件下热裂解制备生物质炭。采用元素分析仪、扫描电镜(SEM)、傅里叶变换红外光谱(FTIR)、光电子能谱分析(XPS)等手段对生物质炭进行理化性质分析;应用响应曲面法(RSM)下的中心合成设计(CCD)功能研究4个因素(初始pH、吸附剂质量浓度、阿特拉津质量浓度、温度)对阿特拉津去除率的影响;建立二阶模型,并通过方差分析验证二阶方程的有效性。结果表明:生物质炭表面充满孔状结构,且富含C=C、C-C、CHx、-C-OR、-COOR等官能团;吸附阿特拉津后生物质炭在羟基(-OH)的位置产生了新的吸收峰,推测羟基官能团在吸附过程中发挥了重要作用。RSM法优化最佳吸附去除阿特拉津条件为:初始阿特拉津质量浓度为5mg/L、pH=6.67,吸附剂质量浓度为7.75g/L、温度为32℃;在该条件下阿特拉津的吸附去除率达到92.18%。该研究可为评价施加生物质炭土壤中阿特拉津的迁移规律及阿特拉津污染水体修复提供参考。     

Adsorption of Lead (II) and Zinc (II) from Aqueous Solution by Bituminous coal

Activated carbons have been proven to be effective adsorbents for the removal of Pb (II) and Zn (II) dissolved in aqueous media. The study of adsorption of Pb (II) and Zn (II) on two different size fractions from a composite coal sample of Maghara coal mine, C₆₃ (63–125 μm) and C₂₅₀ (125–250 μm) is presented in this paper. C₆₃ and C₂₅₀ were treated in water solutions of 50 mM lead and zinc acetates. X-ray photoelectron spectroscopy (XPS) was used to characterize the starting and treated coal surfaces. The high surface area and surface functional groups (carboxy and phenolic) enable activated bituminous coal of Maghara to act as efficient adsorbents for removing dissolved Pb (II) and Zn (II) in alkaline medium.     

Adsorption of Fe~(3+) Ions from Aqueous Solution by Natural and Synthetic Apatites: Kinetic,Equilibrium and Thermodynamic Study

In this study, the adsorption kinetics, equilibrium and thermodynamics of Fe3+ ions on natural (NAP) and synthetic (HAP) apaties were examined. The adsorption efficiency of Fe3+ onto the NAP and HAP was increased with increasing temperature. The kinetics of adsorption of Fe3+ ions was discussed using three kinetic models, the pseudo-first-order, the pseudo-second-order and the intra-particle diffusion model. The experimental data fitted very well the pseudo-second-order kinetic model. The initial sorption rate and the activation energy were also calculated. The activation energy of the sorption was calculated as 37.15 and 49.84 kJ·mol 1 for NAP and HAP, respectively. Experimental results were also analysed by the Langmuir, Freundlich and Dubinin–Redushkevich (D–R) isotherm equations at different temperatures. RL separation factor for Langmuir and the n value for Freundlich isotherm show that Fe3+ ions are favorably adsorbed by NAP and HAP. Various thermodynamic parameters such as enthalpy (ΔH), Gibbs free energy (ΔG) and entropy (ΔS) changes were computed and the results showed that the adsorption of Fe3+ ions onto NAP and HAP were spontaneous and endothermic in nature.     

Removal of Arsenic(V) from Aqueous Solutions by Lanthanum-loaded Zeolite

A new adsorption process for the removal of As（V） ion from aqueous solutions is studied in this paper using lanthanum-loaded zeolite. The removal efficiency of different adsorbents, activated alumina and activated carbon are obtained in the study for comparison. The results show that lanthanum-loaded zeolite is an effective adsorbent for the removal of As（V） from aqueous solutions. Then, the pH effect and regeneration of modified zeolite on the As（V） removing efficiency are also assessed. It functions with a wide range of pH （2-8）. After adsorption, zeolite adsorbed with As（V） ions can be regenerated successfully with 1 M NaOH. Based on the data obtained, an adsorption mechanism and the possible complex structure are tentatively presented. Compare to other adsorbents, easy availability of this adsorbent, excellent adsorption capacity, wide optimum pH range, and regeneration are expected to be utilized in practical operations.     

煤化工渣高效吸附去除水中全氟辛酸

为高效快速去除水中全氟辛酸,选择工业废物煤化工渣对全氟辛酸进行吸附去除探究。采用不同的处理方法制备了4种煤化工渣（粒径从大到小为CGA1、CGA2、CGA3和CGA4）,研究其在水溶液中的全氟辛酸吸附性能。利用扫描电子显微镜（SEM）、拉曼光谱、傅里叶变换红外光谱（FTIR）和X射线光电子能谱（XPS）对4种煤化工渣的结构特征进行表征分析,并考察了全氟辛酸初始质量浓度和初始pH对吸附进程的影响。实验结果表明：煤化工渣对全氟辛酸有高效的吸附能力,伪二级动力学模型和Langmuir等温模型可以较好地描述4种煤化工渣对全氟辛酸的吸附行为及过程,其中CGA4去除全氟辛酸的最大吸附量为25.51 mg/g;随着全氟辛酸溶液初始质量浓度升高,煤化工渣对全氟辛酸的吸附容量逐渐增加;初始pH对CGA3和CGA4的影响微弱,CGA1和CGA2在酸性条件下显示出更优越的吸附性能。由此得出,4种煤化工材料中粒径最小的CGA4具有最优的全氟辛酸去除能力且基本不受pH限制。FTIR分析表明,吸附过程中氢键的形成占主导地位,XPS和Zeta电位检测结果表明,物理吸附和静电吸附在去除过程中也发挥了重要作用。     

坡缕石粘土对Cu2+的吸附热力学

将坡缕石粘土分离提纯后作为吸附剂,通过对水中Cu2+的静态吸附实验,考察了时间及介质pH值对吸附效果的影响,并对吸附平衡和吸附热力学特征进行了探讨。结果表明:在实验条件下坡缕石粘土对水中的Cu2+离子具有较强的吸附作用,吸附平衡时间约为60 min,pH值对吸附效果有显著的影响,吸附量随pH值的升高而增加,当平衡溶液pH>7时吸附率超过99%;吸附平衡与Langmuir方程的符合程度优于D-R方程和Freundlich方程,由Langmuir方程拟合饱和吸附量为33.0～34.0 mg/g,由D-R方程得平均吸附能Es为13 kJ/mol,吸附过程为离子交换反应;吸附过程吸热,吸附焓为16.97 kJ/mol,吸附Gibbs函数在-27～-24 kJ/mol之间,吸附熵大于零,吸附过程可自发进行。     

季胺盐阳离子插层蒙脱土对铀吸附性能的研究

通过十六烷基三甲基溴化铵（CTMAB）与钠基蒙脱土离子交换制备出季胺盐阳离子插层蒙脱土（CTMA’-M）,采用小角X射线衍射仪、傅里叶变换红外光谱仪和高分辨透射电镜表征微观结构,研究CTMA’的插层量、溶液的初始pH值、初始浓度和其他共存离子对吸附铀性能的影响,考察了CTMA’-M处理铀矿水）台废水的应用性能。结果表明：CTMA’插层后蒙脱土的层间距由1．21nm增加到4．09nm,但仍保持钠基蒙脱土原有的晶体结构。随CTMAB用量的增加,插层到蒙脱土层间的CTMA’量增加,对铀离子的吸附容量逐渐增大,当CTMAB的用量超过阳离子交换容量的1．4倍时,铀吸附容量基本保持不变。溶液pH和接触时间对铀离子吸附性能影响较大．CTMA’-M最佳吸附pH值为6．0,平衡吸附时间为80min,CTMA’插层能够改善蒙脱土对铀离子的选择性吸附。在1L含有15mg／L铀的废水中加入1．5gCTMA’-M时,铀的去除率达到98％以上。     

锰矿石脱硫产物处理含铜废水动态实验研究

氧化型锰矿石脱硫产物含大量硫化锰,利用这种材料装填固定床进行净化水中铜离子的动态试验.在材料粒径0.45～0.9mm、进水pH=5.8、进水滤速4.58 m/h条件下,1 t锰矿石脱硫产物可以处理923 tρ(Cu~(2+))=50 mg/L的含铜废水,出水ρ(Cu~(2+))<0.5 mg/L,低于国家一级排放标准.控制进水pH在4～9之间、降低进水滤速、采用较小粒径的材料有利于提高锰矿石脱硫产物处理含铜废水的容量.利用X射线粉末衍射(XRD)和扫描电镜-能谱分析(SEM-EDS)对材料和产物进行表征,证明锰矿石脱硫产物去除水中铜离子是基于离子交换反应的原理.     

Removal of Lead, Copper, Zinc and Cadmium from Water Using Phosphate Rock

Removal of Pb2 ,Cu~(2 ),Zn~(2 )and Cd~(2 )from aqueous solutions by sorption on a natural phosphate rock(FAP)was investigated.The effects of the contact time and initial metal concentration were examined in the batch method.The percentage sorption of heavy metals from solution ranges generally between 50% and 99%.The amount of sorbed metal ions follows the order Cu>Pb>Cd>Zn. Heavy metal immobilization was attributed to both surface complexation of metal ions on the surface of FAP grains and partial dissolution and precipitation of a heavy metal-containing phosphate.The very low desorption ratio of heavy metals further supports the effectiveness of FAP as an alternative and low-cost material to remove toxic Pb~(2 ),Cu~(2 ),Zn~(2 )and Cd~(2 )from polluted waters.     

Removal of Lead,Copper, Zinc and Cadmium from Water Using Phosphate Rock

Removal of Pb^2＋, Cu^2＋, Zn^2＋ and Cd^2＋ from aqueous solutions by sorption on a natural phosphate rock （FAP） was investigated. The effects of the contact time and initial metal concentration were examined in the batch method. The percentage sorption of heavy metals from solution ranges generally between 50% and 99%. The amount of sorbed metal ions follows the order Cu〉Pb〉Cd〉Zn. Heavy metal immobilization was attributed to both surface complexation of metal ions on the surface of FAP grains and partial dissolution and precipitation of a heavy metal-containing phosphate. The very low desorption ratio of heavy metals further supports the effectiveness of FAP as an alternative and low-cost material to remove toxic Pb^2＋, Cu^2＋, Zn^2＋ and Cd^2＋ from polluted waters.     

pH值对羟基磷灰石除镉行为的影响

介质的pH值是影响羟基磷灰石(Hap)除镉行为最为复杂的因素之一,它决定了水溶液中Cd2+的赋存状态及Hap的溶解特性与表面性质等,而这些因素与Hap的除镉行为密切相关。实验研究表明,强酸(pH<3)条件下Cd2+的去除率随pH值的升高增加较快,但当pH≥3时这种增加变缓。在广泛的pH值范围内,Hap在含镉溶液和空白溶液中均表现为质子催化和非化学计量比的溶解机理。根据络合平衡计算,Cd2+在不同pH值时具有不同的型体及分布系数。Hap在空白溶液中的表面电动电势ζ为负值,且随pH值的增加其电负性增大。由此可知Hap除镉行为的作用机理是表面络合与表面电位吸附,而不存在溶解 沉淀作用。     

用天然碳酸钙除去硫酸钾肥料中游离酸

研究了天然碳酸钙的粒度对除去K2 SO4肥料中游离酸的影响 ,实验表明 ,粒径小于0 1 49mm的天然CaCO3能有效除去游离酸 ,按m(CaCO3)∶m(K2 SO4) =4∶1 0 0的比例控制天然CaCO3的加入量 ,可使K2 SO4中的游离酸酸度小于 0 50 %。     

水热条件下利用微波加热从粉煤灰合成沸石研究

着重选用NaOH水溶液为反应前驱物, 通过改变反应温度、NaOH浓度与合成时间等参数, 在水热条件下利用微波加热直接对粉煤灰进行晶化, 合成得到了浊沸石、菱沸石、NaP1沸石3种沸石.粉煤灰转化为沸石率约15%~40%.研究表明: (1) 反应体系在15min左右即有合成沸石产生, 30min左右合成沸石转化率达到最佳; (2) 为保证沸石晶核生成和晶体的生长, 反应体系的溶液/粉煤灰比不应低于2.5; (3) 在溶液/粉煤灰比为2.5时, 应控制加热时间在30min左右.      

天然磁铁矿化学改性及其在水体除砷中的应用

铁氧化物及其复合氧化物(如菱铁矿、水铁矿)的表面电荷高、比表面积大,在特定条件下对亚砷酸盐和砷酸盐有较强的结合能力和亲和性,以铁氧化物作为吸附剂处理高砷水已经成为研究热点之一。天然磁铁矿的主要成分为Fe_3O_4,但其本身活性较弱,直接应用于处理高砷水的除砷率低。本文对天然磁铁矿采取酸化、碱化、不同温度灼烧、不同灼烧时间等简易的方法进行改性,达到有效去除水中砷的目的。实验结果表明:经0.5 mol/L盐酸浸泡、150℃灼烧10 min的改性磁铁矿分别处理As(Ⅲ)溶液和As(Ⅴ)溶液时,As(Ⅴ)去除率达98%,吸附能力显著增强,达到预期目标;溶液中As(Ⅲ)浓度从1000μg/L下降到250μg/L,去除率达75%,即As吸附能力明显优于未改性的天然磁铁矿,与其他改性铁矿除砷能力相近,而改性方法更加简便、易行。本文研究的改性天然磁铁矿吸附剂为控制高砷水的砷含量提供了一种切实可用的吸附材料。     

Mineral Surface after Reaction with Aqueous Solution at High Temperatures and Pressures

This work presents new experimental results on surface chemistry of reacting minerals and interface kinetics between mineral and aqueous solutions. These experiments were carried out using a flow reactor (packed bed reactor) of an open system as well as a continuous stirred tank reactor, CSTR. The authors measured reaction rates of such minerals as zeolite, albite and carbonate (rhodochrosite, dolomite) in various solutions, and tested corresponding mineral surface by using SEM, XPS, SIMS, etc. This paper mainly presents the experimental results of zeolite dissolution in water and in low pH solutions at room temperature, and dolomite dissolution at elevated temperatures. The results show that the release rates of Si, Al and Na of zeolite are different in most cases. The incongruent dissolution of zeolite is related to surface chemical modifications. The Na, Al and Si release rates for dissolution of albite and zeolite in water and various solutions were measured as a function of temperature, flow veloci     

改性硅藻土对水中DDTs的吸附机理

采用阳离子表面活性剂(十六烷基三甲基溴化铵)对硅藻土进行改性, 并以优选的改性方案为基础, 研究了该有机硅藻土对水中有机氯农药DDTs(p, p'-DDT、p, p'-DDE和p, p'-DDD)的吸附过程及增强机理.结果表明, 十六烷基三甲基溴化铵能有效改变硅藻土的Zeta电位、比表面积和表面疏水性质, 从而提高硅藻土吸附有机氯农药的能力.改性硅藻土对水中3种有机氯农药的吸附能力依次为: p, p'-DDT>p, p'-DDE>p, p'-DDD.基于模型的准确性(R2值)考虑, Redlich-Peterson方程能更好地用于拟合DDTs在改性硅藻土上的等温吸附曲线.