羟基磷灰石/蔗渣炭复合吸附剂的制备及其对As(Ⅴ)的吸附机理

以甘蔗渣为原料,采用水热合成法制备羟基磷灰石/蔗渣炭复合吸附剂--HBA,通过静态吸附试验研究HBA对As（Ⅴ）的吸附特性,并采用红外光谱和X射线光电子能谱对吸附前后的HBA进行表征,探讨其吸附As（Ⅴ）的机理.结果表明:HBA的比表面积为89.52 m2/g,pH_zpc（零点电荷）=7.2,HBA上的羟基磷灰石的分子式为Ca₁₀（PO₄）₆（OH）₂.HBA吸附As（Ⅴ）的效果最佳pH为5.0~9.0.Langmuir等温吸附模型适合拟合HBA对As（V）的吸附等温线,25℃时Langmuir最大吸附量为6.76 mg/g,是蔗渣炭对As（Ⅴ）最大吸附量的20多倍.红外光谱分析表明,HBA含有的＝C＝O、─OH、─COOH等含氧官能团,可为化学吸附提供充足的吸附位点和提高HBA的吸附能力.XPS分析表明,HBA表面的含氧官能团[如羧基（─O─C＝O,532.2 eV）、羟基（─OH,530.6 eV）]参与了吸附反应,羟基磷灰石能提高HBA吸附As（Ⅴ）的能力,被吸附到HBA表面上的As主要以AsO₄3-和HAsO₄2-形态存在.      

镍锌铁氧体的表征及在肝素提取废水处理中的应用

通过共沉淀法制备了镍锌铁氧体(Ni0.5Zn0.5Fe2O4),FT-IR、SEM、XRD、BET等技术表征后发现,此铁氧体是一种纳米级铁磁性颗粒,平均粒径27.53 nm,其结构疏松多孔且比孔径和表面积均较大。当其用处理肝素提取废水时,发现具有很强的吸附能力,不仅存在表面吸附而且存在磁性吸附,这种吸附能很好地促进废水中污染物的去除,实验发现其处理过程主要分2个过程:污染物先被吸附,然后其中有机物被添加的过氧化氢氧化;无机物、金属离子被笼络到铁氧体的晶格中后通过絮凝过滤而去除,处理后的废水中含盐量去除率在92%以上。UV-Vis分析发现镍锌铁氧体对此种废水的处理能使废水中的特征吸收峰明显降低;它也能促进过氧化氢的氧化,高于芬顿试剂的氧化效果:能使吸收在296 nm处的物质彻底消除。     

原位载铁中孔活性炭吸附As和天然有机物效能

采用配煤、原位浸渍和两步活化法制备了4种原位载铁活性炭（FGL1/2/3/4）,并以空白炭C-GL为基础的表面铁浸渍后改性炭（Fe-GL-2/3/4）为对照,研究了原位载铁炭对水中As和腐植酸（HA）的同步吸附效能.结果表明,炭化料原位载铁促进了比表面积（S_BET）和中孔结构的发育.其中,原位载铁炭FCL4（载铁量6.51%）在45Å~480Å的范围内的中孔容积（V_mes）比C-GL增加了0.1146cm³/g;而后改性载铁则造成S_BET和V_mes的显著降低.原位载铁同时促进了表面碱度的增加,保证了中性条件下更好的As离子吸附能力;FCL4对As（Ⅲ）和As（V）的Langmuir最大吸附量（L-Q_max）分别达到2.566和2.825mg/g.原位载铁炭进一步发育的中孔结构促进了对HA（<10mg DOC/L）的吸附效能,FGL4对HA的Langmuir最大吸附量（Q_HA）达到46.25mg DOC/g.As-HA共存体系内FGL4对各组分的吸附容量有所降低,但As（Ⅲ）和As（V）的吸附容量仍达到2.325和2.675mg/g.     

淀粉稳定Fe3O4纳米粒子对水中As(V)的吸附特性研究

以可溶性淀粉作为稳定剂制备纳米Fe_3O_4粒子,探讨了反应时间、p H值、初始砷浓度和腐殖酸对Fe_3O_4纳米粒子吸附水体中As(V)的吸附效果影响.实验结果表明,淀粉稳定的Fe_3O_4纳米粒子对水体中As(V)的吸附动力学过程符合准二级动力学,吸附等温线符合Langmuir吸附模型;吸附容量随着溶液p H的增加逐渐降低,在p H为8.0的弱碱性水体中对As(V)的最大吸附容量可达202.56 mg·g~(-1);此外,腐殖酸(HA)能降低纳米粒子对As(V)的吸附能力.     

壳聚糖海藻酸钠铁锰泥吸附剂制备与除As(V)研究

将生物除铁除锰水厂反冲洗铁锰泥包埋在壳聚糖海藻酸钠水凝胶中,成功制备了一种具有高机械强度和稳定性的复合除砷吸附剂（CAFB）.表征结果显示,其表面粗糙,铁锰元素含量为69.31%,比表面积达117.20m²/g,且具有介孔结构.吸附动力学数据更符合准二级动力学模型（R²=0.963）.Langmuir等温吸附模型能更好地描述As （V）吸附过程（R²=0.969）,25℃时最大吸附容量为15.80mg/g.酸性条件有利于As （V）的吸附,在pH=3~7范围内As （V）去除率能达到80%以上.H²PO₄^-,SiO₃^2-离子对吸附过程抑制作用明显.用0.1mol/L的NaOH溶液再生4次后吸附量能达到初始值的70.68%,具有在工程上运用的前景.     

新型磁性Mn0.6Zn0.4Fe2O4@CdS纳米复合光催化剂的制备及其吸附和光催化特性

以两步水(溶剂)热法制备了一种新型磁性Mn_(0.6)Zn_(0.4)Fe_2O_4@CdS纳米复合光催化剂,并采用X-射线衍射(XRD)、比表面(S_(BET))、扫描电镜-能谱(SEM-EDX)、紫外漫反射(UV-vis)、透射电镜(TEM)、磁滞回线(VSM)和价带能谱(VB-XPS)等手段对制备的铁氧体、CdS和复合材料进行了表征分析.结果发现,得到的材料元素含量与设计预期值吻合,纯相晶格参数与理论值匹配较高,特征峰证实复合材料中存在尖晶石铁氧体和CdS晶格;高分辨透射电镜(HR-TEM)分析表明,CdS有效地附着在铁氧体上,且在可见光区发生了红移.利用该材料对亚甲基蓝(MB)进行了暗室吸附和光催化活性的系统研究,结果表明,复合物吸附速率较快,适宜用Langmuir模型描述吸附平衡,最大吸附容量q_(max)高达79.6 mg·g~(-1);在测试的3个样品中,复合物光催化活性最高,经5次重复光催化实验,MB的降解率仍可保留在50%以上,且易磁分离回收;此外,通过自由基和空穴捕获实验、光致发光(PL)和电子顺磁共振(ESR)测试分析提出了MB降解机理.     

农田灰钙土中有机质和碳酸钙对Zn吸附-解吸行为的影响

采用序批平衡法,研究了Zn在去除有机质及去除碳酸钙前后灰钙土的吸附-解吸行为.结果表明,在试验土壤中吸附量均随着加入Zn浓度的增加而增加,且去碳酸钙土对Zn吸附固定能力明显低于灰钙土,即有机质对灰钙土Zn的吸附影响小于碳酸钙;去有机质及去碳酸钙前后灰钙土对Zn的吸附过程不适合用 Langmuir方程描述,而 Freundlich方程能够很好地拟合,调整后的决定系数R2￠均大于0.90,达到极显著水平(P<0.01);去除有机质和碳酸钙后灰钙土对Zn的解吸率都升高,且灰钙土去碳酸钙后解吸率略高于去有机质;去除有机质及碳酸钙前后灰钙土的解吸量均随吸附量的升高而升高,且去碳酸钙土解吸量最大,去有机质土次之,灰钙土最小;土壤有机质和碳酸钙对Zn均有较强的络合吸附效应,能有效降低Zn的迁移活性,从而促进吸附,抑制解吸.     

天然菱铁矿改性及强化除砷研究

我国高砷地下水分布广泛,经济、高效地饮用水除砷技术受到广泛关注.静态批实验采用资源丰富、价格便宜的天然菱铁矿为主要原材料,考虑灼烧温度、时间及添加黏合剂等因素确定最优改性条件使除砷效果达到最佳.结果表明,在加铝量为10 mg.g-1、350℃下恒温灼烧90 min后造粒达到强度要求并除砷效果较优.25℃、固液比为0.5 g∶50 mL、As(Ⅲ)和As(Ⅴ)初始浓度为5 mg.L-1时,吸附后溶液中残留As浓度均<10μg.L-1.静态吸附批实验结果表明,25℃时,接触反应时间为12 h可达到吸附平衡,吸附过程较好地符合Lagergren假二级吸附速率方程;最优改性天然菱铁矿对砷的吸附规律可用Langmuir和Freundlich等温吸附模型很好地描述,As(Ⅲ)、As(Ⅴ)饱和吸附容量分别可以达到1 039、1 026μg.g-1.结合XRD、SEM等研究方法和比表面及孔结构分析初步探讨天然菱铁矿改性以及除砷的主要机制.分析表明,改性后天然菱铁矿比表面积大幅度增大,孔径减小,且在表面活化生成一层圆球状的含Fe(Ⅱ)和Fe(Ⅲ)的化合物.改性天然菱铁矿是一种值得进一步研究并实际应用的除砷材料.     

Decoupling the adsorption mechanisms of arsenate at molecular level on modified cube-shaped sponge loaded superparamagnetic iron oxide nanoparticles

In this study, a commercial cube-shaped open-celled cellulose sponge adsorbent was modified by in-situ co-precipitation of superparamagnetic iron oxide nanoparticles (SPION) and used to remove As(V) from aqueous solutions. Fe K-edge X-ray absorption spectroscopy (XAS) and TEM identified maghemite as the main iron phase of the SPION nanoparticles with an average size 13 nm. Batch adsorption experiments at 800 mg/L showed a 63% increase of adsorption capacity when loading 2.6 wt.% mass fraction of SPION in the cube-sponge. Experimental determination of the adsorption thermodynamic parameters indicated that the As(V) adsorption on the composite material is a spontaneous and exothermic process. As K-edge XAS results confirmed that the adsorption enhancement on the composite can be attributed to the nanoparticles loaded. In addition, adsorbed As(V) did not get reduced to more toxic As(III) and formed a binuclear corner-sharing complex with SPION. The advantageous cube-shape of the sponge-loaded SPION composite together with its high affinity and good adsorption capacity for As(V), good regeneration capability and the enhanced-diffusion attributed to its open-celled structure make this adsorbent a good candidate for industrial applications.     

A laboratory scale study on arsenic（Ⅴ） removal from aqueous medium using calcined bauxite ore

The present work deals with the As（Ⅴ） removal from an aqueous medium by calcined refractory grade bauxite （CRB） as a function of solution pH, time, As（Ⅴ） concentration and temperature. The residual As（Ⅴ） was lowered from 2 mg/L to below 0.01 mg/L in the optimum pH range 4.0-7.0 using a 5 g/L CRB within 3 h contact time. The adsorption data fits well with Langmuir isotherm and yielded Langmuir monolayer capacity of 1.78 mg As（Ⅴ）/g of CRB at pH 7.0. Presence of anions such as silicate and phosphate decreased As（Ⅴ） adsorption efficiency. An increase temperature resulted a decrease in the amount of As（Ⅴ） adsorbed by 6%. The continuous fixed bed column study showed that at the adsorbent bed depth of 30 cm and residence time of 168 min, the CRB was capable of treating 340 bed volumes of As（V） spiked water （C0 = 2 mg/L） before breakthrough （Ce = 0.01 mg/L）. This solid adsorbent, although not reusable, can be considered for design of adsorption columns as an efficiency arsenic adsorption media.     

磁性吸附剂CeO2/MZFS去除水中盐酸四环素

利用废碱性电池制备得到尖晶石结构的锰锌铁氧体Mn_0.6Zn_0.4Fe₂O₄（MZF）,利用原位聚合制备得到硅包覆的磁性纳米复合物MZF@SiO₂（MZFS）,采用浸渍法制备得到集磁分离、吸附与类Fenton催化活性于一体的CeO₂/MZFS磁性吸附剂,并对其形貌和磁性能等进行了表征.结果表明,CeO₂/MZFS对水中盐酸四环素（TH）表现出良好的吸附性能,160 min吸附过程可达平衡,TH的去除率达到95%.吸附过程可用准二级动力学方程描述,化学吸附为速控步骤;Freundlich等温吸附模型能较好地描述该吸附过程,热力学计算结果表明,CeO₂/MZFS对TH的吸附是以物理吸附为主的自发吸热过程;利用红外光谱初步揭示了吸附机制.吸附TH后的CeO₂/MZFS可利用其非均相类Fenton催化活性以H₂O₂作为再生剂进行原位再生,6次循环使用后,CeO₂/MZFS对TH仍能保持较高的平衡吸附量.研究结果可为抗生素废水的治理提供理论指导和技术支持.     

Fe(Ⅲ)掺杂Mg/Al-LDO作为氮磷吸附剂的研究

针对污水厂尾水脱氮除磷问题,采用共沉淀法制备了镁铝铁类水滑石（Mg/Al/Fe–LDHs）,在450℃下焙烧3h得到焙烧态类水滑石（Mg/Al/Fe–LDO）.研究了Fe（Ⅲ）掺杂对Mg/Al-LDO吸附氮磷的影响及吸附特性.结果表明,当Mg/Al/Fe物质的量比为3：0.6：0.4时,Mg/Al/Fe-LDO对氮磷吸附性能较好,最大吸附容量分别为28.57mg/g和231.46mg/g.吸附过程均符合Langmuir吸附等温模型,拟合相关系数（R²）达到0.99以上.根据XRD、FTIR的表征结果可以推断,Mg/Al/Fe–LDO是通过“记忆效应”、静电引力作用完成对氮磷的吸附,对磷的吸附还包括离子交换作用.     

Removal of arsenate and arsenite from aqueous solution by waste cast iron

The removal of As(III) and As(V) from aqueous solution was investigated using waste cast iron, which is a byproduct of the iron casting process in foundries. Two types of waste cast iron were used in the experiment: grind precipitate dust (GPD) and cast iron shot (CIS). The X-ray diffraction analysis indicated the presence of Fe0 on GPD and CIS. Batch experiments were performed under different concentrations of As(III) and As(V) and at various initial pH levels. Results showed that waste cast iron was effective in the removal of arsenic. The adsorption isotherm study indicated that the Langmuir isotherm was better than the Freundlich isotherm at describing the experimental result. In the adsorption of both As(III) and As(V), the adsorption capacity of GPD was greater than CIS, mainly due to the fact that GPD had higher surface area and weight percent of Fe than CIS. Results also indicated the removal of As(III) and As(V) by GPD and CIS was influenced by the initial solution pH, generally decreasing with increasing pH from 3.0 to 10.5. In addition, both GPD and CIS were more effective at the removal of As(III) than As(V) under given experimental conditions. This study demonstrates that waste cast iron has potential as a reactive material to treat wastewater and groundwater containing arsenic.     

Binary competitive adsorption of naphthalene compounds onto an aminated hypercrosslinked macroporous polymeric adsorbent

An aminated hypercrosslinked macroporous polymeric adsorbent was synthesized and characterized.Adsorption isotherms for 1-amino-2-naphthol-4-sulfonic acid(1, 2, 4-acid) and 2-naphthol obtained from various binary adsorption environments can be well fitted by Freundlich equation, which indicated a favorable adsorption process in the studied range. Adsorption for !, 2, 4-acid was an endothermic process in comparison with that for 2-naphthol of an exothermic process. 2-naphthol molecules put a little influence on the adsorption capacity for 1, 2, 4-acid. However, the adsorption to 1, 2, 4-acid depressed that to 2-naphthol in a large extent for the stronger electrostatic interaction between 1, 2, 4-acid and adsorbent. The predominant mechanism can be contributed to the competition for adsorption sites. And the simultaneous environment was confirmed to be helpful to the selective adsorption towards 1,2,4-acid based on the larqer selectivity index.     

河口沉积物对砷的吸附性能及影响因素

对比分析了砷在辽东湾营口河口外侧近海域沉积物和河口内侧河流段沉积物上的含量和吸附行为,并探讨了主要影响因素.结果表明,海域沉积物和河流段沉积物中As含量分别为7.5和4.0 mg/kg,相对于As的效应临界浓度TEL值7.2 mg/kg,海域沉积物中有一定的As污染.河口外侧近海域沉积物由于铁锰铝等金属和有机质含量较高...     

Antimony(V) removal from water by iron-zirconium bimetal oxide: Performance and mechanism

A Fe-Zr binary oxide adsorbent has been successfully synthesized using a co-precipitation method. It showed a better performance for antimonate (Sb(V)) removal than zirconium oxide or amorphous ferric oxide. The experimental results showed that the Fe-Zr adsorbent has a capacity of 51 mg/g at an initial Sb(V) concentration of 10 mg/L at pH 7.0. Sb(V) adsorption on the Fe-Zr bimetal oxide is normally an endothermic reaction. Most of the Sb(V) adsorption took place within 3 hr and followed a pseudo second-order rate law. Co-existing anions such as SO₄^2-, NO₃^- and Cl^- had no considerable effects on the Sb(V) removal; PO₃^4- had an inhibitory effect to some extent at high concentration; while CO_₃^2- and SiO₄^4- showed significant inhibitory effects when they existed in high concentrations. The mechanism of Sb(V) adsorption on the adsorbent was investigated using a combination of zeta potential measurements, XPS, Raman, FT-IR observations and SO₄^2- release determination. The ionic strength dependence and zeta potential measurements indicated that inner-sphere surface complexes were formed after Sb(V) adsorption. Raman and XPS observations demonstrated that both Fe-OH and Zr-OH sites at the surface of the Fe-Zr adsorbent play important roles in the Sb(V) adsorption. FT-IR characterization and SO₄^2- release determination further demonstrated that the exchange of SO₄^2- with Sb(V) also could promote the adsorption process. In conclusion, this adsorbent showed high potential for future application in Sb(V) removal from contaminated water.     

载铁(β-FeOOH)球形棉纤维素吸附剂去除地下水As(Ⅴ)的研究

制备了一种载铁(β- FeOOH)球形棉纤维素吸附剂,球珠孔隙度大,强度好,活性成分铁的载入量可高达360mg/mL ,(质量分数达50%) ,活性好.研究表明,当铁含量为220mg/mL时,该吸附剂对As(V)的最大吸附量为15.6mg/mL(33.2mg/g) ,Langmuir和Freundlich方程能很好地描述吸附等温线.吸附速度较快,10h可达到吸附平衡,吸附动力学符合Lagergren二级方程.SiO₃^2- ,SO₄^2-,Cl^-干扰离子均不影响砷的去除.柱吸附实验表明,空床停留时间为5.9min ,进水As(V)浓度为500μg/L时,As(V)的穿透体积为5000BV .吸附剂可以用1.5mol·L^-1 NaOH再生,洗脱和再生效率可达90%以上.活性成分β-FeOOH形态稳定,柱操作和再生时铁无溶出.吸附剂制备方法简单,新颖,对地下水和饮用水砷去除具有较好的应用前景.     

利用新型稀土铈铁复合吸附剂去除水体腐殖质的研究

研究了稀土铈铁复合材料(CFA)对水体中黄腐酸(FA)的去除效能和作用机制.结果表明:CFA在平衡pH3.0～6.5的范围内对FA的去除效果较好,吸附速度快,120min即达到平衡.水体中FA与砷酸根在CFA上有很强的竞争作用,当FA加入量为5mg/L～10mg/L时,砷的饱和吸附量Q_o即丧失40%～50%,表明两者作用于材料相同的活性位点.吸附前后的红外谱图(FTIR)揭示了CFA表面羟基在FA去除中起着重要作用.通过Zeta电位的测定得出材料的等电点为5.6,因而pH偏酸性的条件有利于FA的去除.     

γ-Fe2O3抗As2O3中毒能力的分子模拟

采用密度泛函理论研究了γ-Fe₂O₃表面As₂O₃的吸附以及掺杂改性提高抗As₂O₃中毒性能的作用机理.计算了As₂O₃在完整以及O缺陷γ-Fe₂O₃（001）表面的吸附性能,包括吸附位点、吸附结构、吸附能、PDOS等.同时建立了Mo、Ti、Mg掺杂的γ-Fe₂O₃模型,探讨了助剂掺杂对抗砷中毒能力的作用机制,并考虑了掺杂量的影响.结果表明：As₂O₃倾向于以O端化学吸附在γ-Fe₂O₃（001）表面Fe_oct位,吸附过程发生强烈的相互作用和电荷转移.当表面存在O缺陷时,As₂O₃的吸附能得到提高.Mo、Ti、Mg倾向于掺杂在Fe_oct位,增强了对As₂O₃的吸附能力,并且增大Mo的掺杂量可以强化As₂O₃的吸附.As₂O₃倾向于与活性较强的Mo、Ti、Mg发生反应,从而保护活性Fe位不受砷中毒,Ti和Mg的掺杂还抑制了相邻Fe位对As₂O₃的吸附.Mo、Ti、Mg的掺杂还促进了催化剂表面对NH₃的吸附,增强了表面酸性强度,有利于SCR反应.Mo、Ti、Mg原子的掺杂有利于提高γ-Fe₂O₃催化剂的抗砷中毒性能.     

草酸盐介导下含As(V)黄钾铁矾的相转化过程与As(V)的再分配行为

黄钾铁矾能够通过吸附和共沉淀作用固定酸性矿山废水（AMD）中的重（类）金属（如砷）,降低其迁移性和生物可利用性.草酸盐广泛存在于天然水环境中,其具有的羧酸官能团能改变铁矿物的稳定性,进而影响吸持的重（类）金属的再分配行为.利用水热法合成含As（V）黄钾铁矾,探究其在不同草酸盐浓度与pH条件下的溶解、重结晶和共沉淀As（V）的行为.研究结果表明,草酸盐与含As（V）黄钾铁矾表面Fe（III）活性位点配位形成的可溶性强络合物是促进矿物溶解的第一步和关键;在pH 2.5时,含As（V）黄钾铁矾的溶解速率随草酸盐浓度增加而增加,伴随大量As（V）释放到溶液,反应过程中只有少量As（V）重新吸附到固相上,这是由于草酸盐与As（V）竞争矿物表面的同一活性位点;在pH 6.5条件下,草酸盐促进含As（V）黄钾铁矾的重结晶,经X射线衍射分析表明针铁矿和纤铁矿为主要产物,能有效地吸附释放的As（V）.研究结果有助于揭示在AMD环境下黄钾铁矾沉积物与含羧酸官能团有机酸共存时对As（V）的释放和固定机理,对AMD环境中As（V）污染控制有重要意义.