Zr-Fe双组分复合除砷吸附剂的优化制备及性能评价

实验发现,铁氧化物或铁的羟基氧化物对As(V)有较好的吸附性能,而锆氧化物或锆水合氧化物则对As(Ⅲ)有优异的吸附选择性,但其使用的pH通常要在9的条件下。通过简单的共沉淀法制备了Zr-Fe双组分复合吸附剂,在制备过程中通过优化制备条件如:沉淀剂浓度、金属离子总浓度、金属离子配比、反应温度、反应时间及吸附剂价格等因素,最终合成出了对As(V)和As(Ⅲ)都具有良好吸附能力的吸附剂。这种吸附剂在中性条件下对As(V)和As(Ⅲ)的最大吸附量为62 mg/g和118 mg/g。     

As（V）在金红石TiO2颗粒表面吸附特性及机理

通过静态动力学和热力学吸附实验，研究了温度、共存离子以及溶质的初始浓度对As（V）在金红石TiO2颗粒表面吸附的影响，探讨了As（V）在金红石TiO2颗粒表面吸附特性及机理。结果表明，在As（V）初始浓度为10mg／L，pH为7的条件下，25℃时的吸附量0．41mg／g高于30℃时的吸附量0．31mg／g，As（V）在金红石TiO，上的吸附为放热过程。CaCl2和MgCl2的添加对As（V）在金红石TiO2表面吸附起到明显的促进作用。T=25℃，Ca2＋或Mg2＋浓度为10mmol／L时，As（V）吸附量分别为0．64和0．56mg／g，Ca2＋比Mg2＋对As（V）吸附促进作用强。As（V）在金红石TiO2的吸附等温线符合Frendlich方程，Lagergren二级动力学方程能较好地描述As（V）在金红石TiO2颗粒表面吸附的动力学过程。     

除氟活性铝氧化物（AlOxHy-Fn）的吸附除砷性能

以活性铝氧化物AlOxHy处理某高氟地下水的中试实验获得的吸附剂废料AlOxHy-Fn为对象，考察其对三价砷（As（Ⅲ））和五价砷（As（Ⅴ））吸附去除性能，并对吸附机理进行了探讨。研究显示，AlOxHy-Fn为多孔无定型且具有不规则表面的絮状结构，比表面积为218．88m2／g，零电荷点pHZPC在pH为8左右；AlOxHy-Fn可快速吸附As（Ⅲ）和As（Ⅴ），且反应24h后的平衡吸附量分别为0．60和3．41mg／g，朗格缪尔模型可以很好地描述As（Ⅲ）和As（Ⅴ）在AlOxHy-Fn表面的吸附，且As（Ⅲ）和As（Ⅴ）的最大吸附容量分别为13．63和63．27mg／g；AlOxHy-Fn在pH=4～10范围内对As（Ⅴ）去除率在90％以上，As（Ⅲ）在中性和弱碱性pH范围内吸附效果较好，但去除率仍在32％以下。AlOxHy-Fn表面性质、砷形态分布特征等对As（Ⅲ）与As（Ⅴ）的吸附有重要影响，电负性As（Ⅴ）较电中性As（Ⅲ）更容易吸附在AlOxHy-Fn表面。AlOxHy-Fn吸附除砷过程中，在pH为6时氟溶出量最低（0．40mg／g），过高或过低pH均会导致氟溶出量增大；氟溶出量与As（Ⅴ）吸附量之间有明显正相关关系（R2=0．97），但与As（Ⅲ）吸附量无相关关系；铝溶出量在pH为4～10范围内均很低。将AlOxHy-Fn回用作为除砷吸附剂去除工业含砷废水的砷具有良好的技术经济可行性，且将As（Ⅲ）氧化为As（Ⅴ）是提高去除效果的重要手段。     

铁改性竹炭去除水中的As(Ⅲ)和As(Ⅴ)

利用竹炭负载铁氧化物制备了复合吸附剂,并用粉末X射线衍射对负载的铁进行了表征。通过静态吸附实验,对比研究了改性竹炭对水溶液中As(Ⅲ)和As(Ⅴ)阴离子的吸附特性。结果表明,载铁竹炭对As(Ⅲ)和As(Ⅴ)的最佳吸附pH分别为8和2。改性竹炭对砷阴离子的吸附过程可符合准二级动力。Freundlich等温方程式能很好地描述As(Ⅲ)和As(Ⅴ)在改性竹炭上的吸附。在相同初始浓度和吸附剂投加量下,改性竹炭对As(Ⅴ)的吸附量大于As(Ⅲ)。     

锆、铁氧化物改性活性炭纤维的制备及其除磷性能

利用锆、铁氧化物对活性炭纤维进行改性,制备了一种新型高效除磷吸附剂——负载锆铁氧化物的活性炭纤维(ACF-ZrFe)。综合运用单因素实验与正交实验对吸附剂的制备条件进行优化,同时利用环境扫描电镜和傅里叶变换红外光谱分析对吸附剂表面性质及反应机理进行了探究。实验结果表明,ACF-ZrFe制备的最佳条件为:锆铁摩尔比7∶3,浸渍液中锆铁总浓度0.1mol/L,超声处理时间10min。当pH为4时,ACF-ZrFe对磷的吸附效果最显著。NO_3~-、SO_4~(2-)、F~-和Cl~-等共存阴离子对磷吸附有一定抑制作用,其作用强弱顺序为:F~-NO_3~-Cl~-SO_4~(2-)。Langmuir等温吸附模型很好地描述了ACF-ZrFe对水中磷的等温吸附行为,最大吸附量为27.03mg/g,吸附动力学满足准二级动力学模型,表明化学吸附是该反应的主要限速步骤。红外光谱分析及pH影响实验表明,ACF-ZrFe吸附磷的主要机理为阴离子配位体交换和静电吸附。     

无定型纳米TiO2吸附去除饮用水中的低浓度As(Ⅲ)

研究了纳米无定型TiO2颗粒对饮用水中低浓度的三价砷As(Ⅲ)吸附行为。纳米TiO2颗粒吸附剂的BET表面积为205 m2/g,计算的BJH吸附平均孔径为4.02 nm(4 V/A)。对起始As(Ⅲ)浓度为150μg/L的模拟含砷水,经过5h的吸附处理后残余浓度不足4μg/L,As(Ⅲ)去除率达到97%。反应起始阶段吸附速率较快,84%的As(Ⅲ)能够在20min内去除。As(Ⅲ)吸附动力学较好地符合拟二级动力学模式。最佳As(Ⅲ)吸附pH为9.3,低于此值,随酸性增加吸附速率有所降低;而高于此值的强碱性pH对吸附有强烈抑制作用。在平衡浓度较低的情形下(10～220μg/L),Lang-muir,Freundlich和Dubinin-Radushkevich(D-R)吸附等温式均可较好拟合吸附行为,但中性和弱碱性条件下更符合Fre-undlich吸附等温式;平衡浓度大于220μg/L,吸附容量随平衡浓度增加而迅速增加,最大吸附容量在低浓度下达到4.79 mg/g。     

海藻酸钠微胶囊负载纳米铁吸附水中的As(Ⅴ)

利用本实验所制备的海藻酸钠微胶囊负载纳米零价铁材料(M-NZVI)对水中不同浓度的As(V)进行了吸附去除研究,并比较了不同材料的吸附等温曲线。实验结果表明,2 g/L M-NZVI在pH=6.5±0.1,常温常压条件下对5 mg/L的As(V)的吸附去除率为90.35%,吸附速率较快,在30 min即可达到吸附平衡。通过M-NZVI、Ca-ALG和NZVI的热力学对比实验可知,M-NZVI表现出优越的吸附性能。溶液吸附剂添加量、初始pH值、离子浓度等因素对M-NZVI吸附水中砷离子的效率有一定影响:在其他条件不变的情况下,As(V)的去除率随着添加量的增加而逐渐增大;M-NZVI对As(V)的最佳吸附效果在pH=6~7范围之间;溶液中高浓度Na Cl能对M-NZVI的吸附性产生较强的干扰。同时,对于As(V)≤5mg/L的溶液,M-NZVI可以不做任何处理多次利用3~4次。这些结果显示,M-NZVI是一种用于原位修复重金属污染水体的潜在理想材料。     

As(V)在金红石TiO_2颗粒表面吸附特性及机理

通过静态动力学和热力学吸附实验,研究了温度、共存离子以及溶质的初始浓度对As(V)在金红石TiO2颗粒表面吸附的影响,探讨了As(V)在金红石TiO2颗粒表面吸附特性及机理。结果表明,在As(V)初始浓度为10 mg/L,pH为7的条件下,25℃时的吸附量0.41 mg/g高于30℃时的吸附量0.31 mg/g,As(V)在金红石TiO2上的吸附为放热过程。CaCl2和MgCl2的添加对As(V)在金红石TiO2表面吸附起到明显的促进作用。T=25℃,Ca2+或Mg2+浓度为10 mmol/L时,As(V)吸附量分别为0.64和0.56 mg/g,Ca2+比Mg2+对As(V)吸附促进作用强。As(V)在金红石TiO2的吸附等温线符合Frendlich方程,Lagergren二级动力学方程能较好地描述As(V)在金红石TiO2颗粒表面吸附的动力学过程。     

棘孢曲霉（Aspergillus aculeatus）对Pb^2＋和Cd^2＋的吸附特征

为了研究棘孢曲霉（Aspergillus aculeatus）对溶液中Pb^2＋和Cd^2＋吸附过程的特征，分别从动力学、热力学和吸附等温线三方面进行了实验，同时还研究了pH、温度、时间、重金属离子起始浓度和吸附剂用量对吸附过程的影响。等温吸附过程可以用Langmuir方程来描述。在实验设定条件下，棘孢曲霉对Pb^2＋和Cd^2＋最大吸附量分别为71．2mg／g和59．8mg／g；动力学实验数据很好的符合二级动力学方程，吸附达到平衡的时间为3h；热力学实验数据显示该吸附过程为自发的、吸热的过程。     

交联菌丝体吸附剂的制备及其对Cr^3＋的吸附特性

深入研究了交联菌丝体吸附剂的制备工艺及其对Cr^3＋的吸附特性。交联菌丝体吸附剂制备工艺简单，但在制备过程中，活化剂NaOH和交联剂的用量对吸附特性影响较大。与纯菌丝体吸附剂相比，交联菌丝体吸附剂表观吸附容量提高48％，达到49．83mg／g（pH=2．53，水溶液中的Cr^3＋浓度为600mg／L），同时其机械强度明显增强。交联菌丝体吸附剂对Cr^3＋的吸附特点是将沉淀法与吸附法相结合，将沉淀与吸附两过程合二为一，从而简化了处理工艺，降低了处理成本。     

Fluoride removal performance of a novel Fe-Al-Ce trimetal oxide adsorbent

A trimetal oxide was developed as a fluoride adsorbent by coprecipitation of Fe(II), Al(III) and Ce(IV) salt solutions with a molar ratio of 1:4:1 under alkaline condition. The material retained amorphous structure and maintained relatively stable fluoride adsorption performance at calcination temperatures lower than 600 degrees C. The optimum pH range for fluoride adsorption was 6.0-6.5 and the adsorbent also showed high defluoridation ability around pH 5.5-7.0, which is preferable for actual application. A high fluoride adsorption capacity of 178 mg g(-1) was acquired under an equilibrium fluoride concentration of 84.5 mg l(-1), adsorbent dose of 150 mg l(-1) and pH 7.0. The adsorption isotherm could be better described by the two-site Langmuir model than the one-site model, suggesting the existence of two types of active sites on the adsorbent surface. Coexistence of high concentrations of phosphate or arsenate only led to partial inhibition of fluoride adsorption, which further suggests the existence of heterogeneous adsorption sites. Sulfate and chloride did not affect fluoride adsorption, and nitrate influenced it only when the concentration of NO(3)(-)-N exceeded 50 mg l(-1). A high desorption efficiency of 97% was achieved by treating fluoride loaded Fe-Al-Ce oxide with NaOH solution at pH 12.2. A column experiment using the adsorbent fabricated into 1mm pellets was performed at an initial fluoride concentration of 5.5 mg l(-1), space velocity of 5h(-1) and pH of 5.8, and 2240 bed volumes were treated with the effluent fluoride under 1.0 mg l(-1).     

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。     

Arsenic(V) removal with a Ce(IV)-doped iron oxide adsorbent

The removal of arsenic(V) by a new Ce-Fe adsorbent was evaluated under various conditions. Under an initial As(V) of 1.0 mg l(-1), the adsorption capacity of the Ce-Fe absorbent was constant around a value of 16 mgg(-1) over a wide pH range (3-7), while a maximum adsorption capacity of 8.3 mgg(-1) was obtained over a narrow pH range around 5.5 for activated alumina, a conventional adsorbent. Kinetics of adsorption obeys a pseudo-first-order rate equation with the rate constant K(ad) as 1.84 x 10(-3) min(-1). The pattern of adsorption of As(V) by the adsorbent fitted well both the Langmuir and Freundlich models. A Langmuir Q(0) of 70.4 mgg(-1) was obtained at an initial pH of 5.0 and temperature of 20 degrees C, significantly higher than those of other adsorbents reported. Phosphate seriously inhibited the removal of As(V) while fluoride did not compete with As(V) even at an F/As molar ratio as high as 30, suggesting that the adsorption sites for As(V) and fluoride were different. Salinity, hardness, and other inorganic anions such as Cl(-), NO(3)(-), and SO(4)(2-) had no apparent effect on As(V) adsorption. Fourier transform infrared spectra of Ce-Fe adsorbent before and after As(V) adsorption demonstrated that M-OH groups plays an important role for As(V) ions removal in the adsorption mechanisms of Ce-Fe adsorbent.     

聚（丙烯酸-co-丙烯酰胺）/膨润土/腐植酸钠三维网络凝胶吸附剂对Cd^2＋吸附性能研究

制备了一种聚（丙烯酸-co-丙烯酰胺）/膨润土/腐植酸钠三维网络凝胶吸附剂,重点考察了吸附剂对Cd2＋吸附的pH依赖性、吸附动力学和吸附等温线。结果表明,Cd^2＋溶液pH值对吸附容量有较大影响。在pH=8、吸附时间30 min、Cd^2＋溶液初始浓度0.02 mol/L和吸附剂用量0.10 g的条件下,吸附剂对Cd2＋的饱和吸附量可达294.7 mg/g。与膨润土相比,三维网络凝胶吸附剂具有更高的吸附容量和更快的吸附速率。     

Competitive adsorption and desorption of arsenate,vanadate, and molybdate onto the low-cost adsorbent materials alum water treatment sludge and bauxite

When low-cost adsorbents are being used to remove contaminant ions (e.g. arsenate, vanadate, and molybdate) from wastewater, competitive adsorption/desorption are central processes determining their removal efficiency. Competitive adsorption of As, V, and Mo was investigated using equimolar oxyanion concentrations in single, binary, and tertiary combinations in adsorption isotherm and pH envelope studies while desorption of previously adsorbed oxyanions was examined in solutions containing single and binary oxyanion combinations. The low-cost adsorbent materials used were alum water treatment sludge (amorphous hydroxy-Al) and bauxite ore (crystalline Al oxides). Adsorption isotherm and pH envelope studies showed that Mo had only a small effect in decreasing adsorption of As and V but V and As had substantial and similar effects in reducing adsorption of the other. As had a greater effect than V in reducing adsorption of Mo and it was concluded that the affinity of oxyanions for the surfaces of water treatment sludge and bauxite followed the order As > V >> Mo. In 0.3 M NaCl electrolyte, desorption of previously adsorbed oxyanions amounted to 0.3–3.4% for V and As, and 11–20% for Mo. As had approximately four times greater effect than Mo in increasing desorption of V while V had about three times the effect of Mo in increasing desorption of As. Thus, the order of oxyanions in inducing desorption of the other oxyanions (i.e. As on V and As) was the same as that for adsorption selectivity: As > V >> Mo. Water treatment sludge was a more effective adsorbent than bauxite because it had a greater adsorption capacity for all three anions and, in addition, they were held more strongly so desorption in the background electrolyte was proportionately less. It was concluded that at similar molar concentrations, arsenate would tend to reduce adsorption of vanadate as well as displace vanadate already held on adsorbent surfaces while both anions will compete effectively with molybdate. The limiting factor for simultaneous removal of As, V, and Mo from multielement solutions by adsorption will therefore be the removal of Mo.     

纳米四氧化三铁同步去除水中的Pb（Ⅱ）和Cr（Ⅲ）离子

采用共沉淀方法制备纳米四氧化三铁颗粒（MNPs）,通过扫描电镜（SEM）、X射线衍射（XRD）和光电子能谱分析（XPS）等表征手段对材料进行分析。同时考察了不同MNPs投加量、pH值、温度和初始浓度条件下对纳米四氧化三铁同步去除水中Pb（Ⅱ）和Cr（Ⅲ）离子的影响。结果表明,在pH为6.0、温度为25℃、纳米四氧化三铁的投加量为4.0 g/L下,吸附3 h后,Pb（Ⅱ）-Cr（Ⅲ）复合溶液中Pb的去除率为70.5%,Cr的去除率可达77.4%。pH和温度对去除过程影响较大。SEM和XRD分析证实成功制备了纳米级四氧化三铁,XPS结果表明,复合溶液中Pb（Ⅱ）和Cr（Ⅲ）离子的去除过程为同步吸附。吸附等温线研究说明,Pb（Ⅱ）的吸附是放热过程且为单相吸附;相反Cr（Ⅲ）的吸附是吸热过程且为多相吸附。重复利用实验表明,MNPs利用3次后对Pb和Cr的去除率几乎未受影响。因此,MNPs可用于实际工程中多种重金属离子共存废水的原位处理。     

Mg—Al水滑石对偶氮染料活性艳红X-3B的脱色性能研究

采用共沉淀法合成出一系列镁铝摩尔比不同的碳酸根型水滑石（LDHs），经500℃高温煅烧制备出镁铝复合氧化物CLDH，并用X-射线、红外光谱对它们进行表征。考查了吸附剂投加量、反应时间、初始pH值等因素对LDHs和CLDH处理阴离子染料活性艳红X-3B模拟废水效果的影响，并对吸附机理进行探讨。实验结果表明：以镁铝摩尔比为3：1时制得的水滑石对活性艳红X-3B溶液的脱色效果最好。水滑石LDHs及其焙烧产物CLDH对活性艳红X-3B染料均具有较好的吸附性能，最佳反应时间分别为60min和30min；在较宽的pH范围内二者的脱色性能稳定，且CLDH对该染料的吸附效果要优于LDHs。LDHs及CLDH对活性艳红X-3B的吸附结果符合Langmuir吸附等温式，25℃下饱和吸附量分别为263．77mg／g和875．23mg／g。LDHs及CLDH的吸附机理分别为离子交换和层状结构重建。饱和吸附后的CLDH用高温热解法再生，吸附性能良好，随再生次数增多，脱色率下降。     

Arsenic sorption by red mud-modified biochar produced from rice straw

Red mud-modified biochar (RM-BC) has been produced to be utilized as a novel adsorbent to remove As because it can effectively combine the beneficial features of red mud (rich metal oxide composition and porous structure) and biochar (large surface area and porous structure properties). SEM-EDS and XRD analyses demonstrated that red mud had loaded successfully on the surface of biochar. With the increasing of pH in solution, arsenate (As(V)) adsorption on RM-BC decreased while arsenite (As(III)) increased. Arsenate adsorption kinetics process on RM-BC fitted the pseudo-second-order model, while that of As(III) favored the Elovich model. All sorption isotherms produced superior fits with the Langmuir model. RM-BC exhibited improved As removal capabilities, with a maximum adsorption capacity (Q_max) for As(V) of 5923 μg g^?1, approximately ten times greater than that of the untreated BC (552.0 μg g^?1). Furthermore, it has been indicated that the adsorption of As(V) on RM-BC may be strongly associated with iron oxides (hematite and magnetite) and aluminum oxides (gibbsite) by X-ray absorption near-edge spectroscopy (XANES), which was possibly because of surface complexation and electrostatic interactions. RM-BC may be used as a valuable adsorbent for removing As in the environment due to the waste materials being relatively abundant.