Removal of Hazardous Anions from Aqueous Solutions by La(lll)- and Y(lll)-lmpregnated Alumina

Abstract

New adsorbents, La(III)- and Y(III)-impregnated alumina, were prepared for the removal of hazardous anions from aqueous solutions. A commercially available alumina was impregnated with La(III) or Y(III) ions by the adsorption process. The change in the surface charge due to the impregnation was measured by acid/base titration. The adsorption rate and the capacity of the alumina for La(III) and Y(III) ions were determined. The adsorption characteristics of the La(III)- and Y(III)-impregnated alumina and the original alumina for fluoride, phosphate, arsenate and selenite ions were analyzed under various conditions. The pH effect, dose effect, and kinetics were studied. The removal selectivity by the impregnated alumina was in the order fluoride > phosphate > arsenate > selenite. The impregnated alumina has been successfully applied for the removal of hazardous anions from synthetic and high-tech industrial wastewaters.     

Defluoridation of drinking water using chemically modified bentonite clay

Adsorption potential of metal oxide (lanthanum, magnesium and manganese) incorporated bentonite clay was investigated for defluoridation of drinking water using batch equilibrium experiments to gain insight of adsorption behavior, kinetics and mechanisms of adsorption of fluoride ion. The effect of various physico-chemical parameters such as pH, adsorbent dose, initial fluoride concentration and the presence of interfering co-ions on adsorption of fluoride has been investigated. The 10%La-bentonite shows higher fluoride uptake capacity for defluoridation of drinking water as compared to Mg-bentonite, Mn-bentonite and bare bentonite clay. The uptake of fluoride in acidic pH was higher as compared to alkaline pH. The equilibrium adsorption data fitted reasonably well in both Langmuir and Freundlich isotherm models. It was also observed that in the presence of certain co-existing ions can have positive effect on removal of fluoride, while carbonate and bicarbonate anions show deleterious effect. The rate of adsorption was reasonably rapid and maximum fluoride uptake was attained within 30 min. The modified adsorbent material shows better fluoride removal properties for actual field water, which could be due to the positive effect of other co-ions present in the field water.     

Preparation and characterization of charcoals that contain dispersed aluminum oxide as adsorbents for removal of fluoride from drinking water

Charcoals adsorbents that contain dispersed aluminum and iron oxides have been synthesized by impregnating wood with salt solutions followed by carbonization at 500 °C, 650 °C or 900 °C. The adsorbents were characterized and their performance for fluoride removal from aqueous solution was evaluated. Aluminum and iron oxides were well dispersed into the porous charcoals. The carbons were amorphous and highly porous. XRD of the adsorbents showed crystalline iron oxide but did not show any form of crystalline aluminum oxides. All the adsorbents showed acidic surface properties. The efficiency of defluoridation was found to depend on the carbonization temperature, the pH of point of zero charge (pHPZC), and the co-existing ions. Substrates prepared at 650 °C with aluminum and iron oxides exhibited the best efficiency with a fluoride sorption capacity of 13.64 mg g⁻¹. More than 92% removal of fluoride was achieved within 24 h from a 10 mg L⁻¹ solution at neutral pH. Fluoride adsorption kinetic was well fitted by a pseudo-second order model. The amounts of residual Al and Fe in treated solution were pH dependant. At neutral pH, the amounts of dissolved Al and Fe were found to be 0.67 and 1.8 mg L⁻¹, respectively.     

煤系高岭土合成Al-MCM-41及镧改性后有效脱除磷

用煤系高岭土作为硅源和铝源合成介孔分子筛Al-MCM-41,然后浸渍镧获得一种具有高吸附容量和磷去除率的新型磷酸根吸附剂。分别考察了载体和镧负载量对吸附磷酸根性能影响。 硅铝比为48的介孔分子筛Al₄₈-MCM-41具有非常规整的一维孔道结构,作为载体为负载镧氧化物提供一个好的空间结构。负载量为15%的 La₁₅-Al₄₈-MCM-41磷酸根吸附量吸附时间先呈线性增长,后缓慢增加,最后趋于平衡,饱和吸附量为60.43 mg/g,投加量为0.12 g时磷去除率96.01%。通过比较不同初始pH值条件下吸附过程中的pH值变化情况,发现吸附剂表面上的羟基和磷酸根之间的离子交换是去除磷酸盐的主要原因。     

Static and dynamic adsorption of fluoride using La(Ⅲ)-loaded chitosan beads crosslinked with EGDE

利用乙二醇二缩水甘油醚(EGDE)替代戊二醛对壳聚糖微球进行交联,然后负载稀土镧离子La(Ⅲ),制备得到新型的除氟剂（CEB-La）。研究了CEB-La对F^-的静态和动态吸附性能。静态吸附实验结果表明：该除氟剂的静态吸附条件为pH7.0、温度50℃、吸附时间60 min、振荡频率120 r·min^-1;当CEB-La用量3 g·L^-1时,对浓度10 mg·L^-1含氟水的除氟率可达92.9%;CEB-La对F^-的吸附过程符合Langmuir和Freundlich吸附等温线,饱和吸附容量为25.7 mg·g^-1;拟二级动力学方程能较好地描述CEB-La对F^-的吸附动力学过程;CEB-La吸附饱和后,经NaOH溶液处理后再与镧离子螯合,可有效再生;共存阴离子特别是CO ^{2 -}₃ 和HCO^-₃对CEB-La的除氟性能有不利影响。动态吸附实验结果表明：进水流量3 ml·min^-1时,CEB-La适于处理F^-浓度2～15 mg·L^-1的含氟水;利用Thomas模型可较好地描述CEB-La对F^-的动态吸附特征,动态饱和吸附容量为3.67 mg·g^-1。因此,CEB-La的除氟性能优越,再生方法简单,使用成本较低,具有较好的应用前景。     

PREPARATION AND ADSORPTION PROPERTIES OF THE POLYSTYRENE RESIN HAVING DIETHYLENETRIAMINE-N,N′- BIS(METHYLENEPHOSPHONATE) GROUP

Styrene-divinylbenzene copolymer beads containing diethylenetriamine-N,N′-bis(methylenephosphonate) group have been synthesized. The adsorption properties, of the present resin for some trivalent and bivalent metal ions have been examined. The selectivity sequence of the present resin at pH lower than 2.0 is as follows: Ga(III)> A1(III)> Sm(III)>Cu(II)>Co(II)>Zn(II)>Ca(II). The present resin reveals remarkable selectivity for the trivalent metal ions. The selective concentration of In(III) Ga(III) and Sm(III) from an acidic aqueous solution has been demonstrated by using a column of the present resin.     

Effective Removal of Arsenic with Lanthanum(III)- and Cerium(III)-loaded Orange Waste Gels

Abstract

Orange waste has been chemically modified and loaded with lanthanum(III) and/or cerium(III) to examine its adsorption behavior to both As(V) and As(III). Arsenate removal was found to be favored over a pH range of 6 ～ 9.5 while arsenite removal took place at pH values ranging from 9 to 11. The maximum sorption capacity of the gel for As(III) removal was evaluated as 43 mg/g, while that for As(V) was 42 mg/g. Column-mode tests using the La(III)-loaded gel confirmed a complete removal of As(V). A reasonably high adsorption potential within the design criteria makes the present gel an alternative choice for arsenic removal.     

载镧活性炭对水中氟离子的吸附性能研究

通过酸改性和负载镧改性,制备出一种载镧活性炭吸附材料。采用静态吸附试验研究了该材料对水中氟离子的吸附行为。研究结果表明,该载镧活性炭吸附材料对氟离子的去除率可达到96%以上,较低的pH值有利于吸附,吸附行为符合Langmuir型吸附等温式,最大吸附容量为21.4 mg/g。     

Preparation of porous resin loaded with crystalline hydrous zirconium oxide and its application to the removal of arsenic

A porous resin loaded with monoclinic or cubic hydrous zirconium oxide was prepared by incorporation of ZrOCl₂·8H₂O into porous spherical polymer beads followed by hydrolysis and hydrothermal treatment of the zirconium salt. Hydrous zirconium oxide appeared to deposit inside the pores with relatively large diameter. The adsorption capacity and distribution coefficients for As(III) and As(V) were determined by batch procedures. The hydrous zirconium oxide-loaded resin (Zr resin) showed a strong adsorption for As(V) at slightly acidic to neutral pH region while As(III) was favorably adsorbed at pH around 9 to 10. The removal of low concentrations of arsenic from the model effluents to meet the demand of Japanese industrial effluent standard (0.1 ppm) was successfully achieved by the column operation packed with the Zr resin. The Zr resin was regenerated by treatment of the column with 1 M sodium hydroxide followed by conditioning with 0.2 M acetate buffer solution. The amount of zirconium leached out during the adsorption and regeneration cycles was negligibly small and the column can be used repeatedly.     

Dye sorption characters of gamma irradiated foamed ethylene propylene diene monomer (EPDM) rubber/clay composites

Composites based on gamma irradiated ethylene propylene diene monomer rubber in foam structure, loaded with different types of clays were used as adsorbents for different classes of dyestuffs (basic, acid, reactive and disperse) from aqueous solutions. The clays under investigation were Aswan clay (ASC) and sodium montmorillonite (Na-MMT). The effect of adsorbent composition, irradiation dose, pH and contact time on dye sorption was studied. It was found that the rubber composites loaded by Na-MMT gave maximum adsorption of the basic dye (～42%) in aqueous solution, while the rubber composites loaded by AS clay gave maximum adsorption (～28%) of the acidic dye. On the other hand, both type of clays did not show no affinity toward reactive and disperse dyes. The efficiency of dye removal was found to increase with increasing the pH and contact time. It was also observed that the irradiation dose (50 kGy) was the optimum dose for the removal of dyes for all rubber composites.     

Uptake of Fluoride by Al3+ Pretreated Low‐Silica Synthetic Zeolites: Adsorption Equilibrium and Rate Studies

Abstract

The removal of fluoride from single component aqueous solution using Al³⁺‐ pretreated low‐silica synthetic zeolites (Al‐Na‐HUD, Al‐HUD, Al‐F9, and Al‐A4) was studied. The effects of adsorbent mass, initial solution pH, and initial concentration on fluoride removal in a batch system were evaluated. Equilibrium data were simulated using simple isotherms such as the Freundlich (F), Langmuir‐Freundlich (LF), Redlich‐Peterson (RP) and Dubinin‐Radushkevitch (DR) isotherms. From the DR model, initial pH effects and desorption studies, it was considered that the fluoride adsorption onto the zeolites proceeded by ion‐exchange or chemisorption mechanism. In interpreting the kinetic results, reaction kinetics (using Elovich equation) and mass transfer processes (both external mass transfer and intraparticle diffusion) were considered. Equilibrium and kinetic results of fluoride adsorption onto the adsorbents demonstrated the following order of performance: Al‐Na‐HUD>Al‐F9> Al‐HUD>Al‐A4.     

镧改性材料对水中磷酸盐去除的研究进展

在各种除磷技术中,吸附法因其成本低、操作简单、设计简单而受到广泛关注;稀土镧由于对磷酸盐具有特异性而被广泛运用于复合吸附剂中,以增强吸附磷酸盐的能力。文中综述了近几年来用于磷酸盐去除的镧改性复合材料吸附剂的研究进展,主要包括镧氧化物/氢氧化物、镧改性铝/铁、镧改性黏土矿物、镧改性碳材料和镧改性其他材料,考虑了镧改性后吸附剂的吸附容量、pH及回收情况等。在进一步的研究中,应考虑镧改性复合材料吸附剂在复杂条件下的稳定性和潜在风险,以及其高效分离和再生的能力。     

Fluoride removal from water by adsorption on china clay

China clay has been used as adsorbent for removal of fluoride from water at different concentrations, temperatures and pH. Kinetics of adsorption as well as adsorption isotherms at different temperatures for the present system have been investigated. Fluoride removal is favoured by low concentration, high temperature and acidic pH. The alumina constituent of china clay is responsible for maximum adsorption of fluoride in the pH range of interest.     

EGDE交联的载镧壳聚糖微球对氟离子的静态和动态吸附

利用乙二醇二缩水甘油醚(EGDE)替代戊二醛对壳聚糖微球进行交联,然后负载稀土镧离子La(Ⅲ),制备得到新型的除氟剂(CEB-La).研究了CEB-La对F-的静态和动态吸附性能.静态吸附实验结果表明:该除氟剂的静态吸附条件为pH7.0、温度50℃、吸附时间60 min、振荡频率120 r·min-1;当CEB-La用...     

Next-generation organometallic adsorbents for safe removal of excessive fluoride from aqueous systems

The presence of excessive fluoride contamination in aquatic environments causes large-scale health problems affecting about 260 million people across the globe. Here we have investigated a novel method to develop zirconium-based organometallic nanoadsorbents (ZrAN) for the removal of fluoride from aqueous systems. A series of ZrAN adsorbents composed of zirconyl methacrylate (ZrDMA) and acrylonitrile (AN) have been developed by varying the relative amounts of crosslinker, porogen, and comonomers. The spherical adsorbents have high porosity and excellent mechanical stability, properties that prevent material breakage and mass loss during practical use. Experimental factors such as effects of pH, initial fluoride concentration, adsorbent dose, coexisting anions, pH_pzc, isotherm models, and surface chemistry were investigated to clarify the adsorption properties of ZrAN. A high adsorption capacity of 46 mg/g was recorded with a high fluoride concentration of 60 mg/L, which outperformed many other reported adsorbents. Moreover, the ZrAN adsorbent performed well over a considerable pH range of 2–10 with significant removal at pH 6–8, which is the preferred range for groundwater applications. Additionally, the results of the toxicity characteristics leaching procedure suggested the ZrAN adsorbents were inert, do not leach out any contaminants (Zr, F⁻), and deliver safe and potable treated water. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 46993.     

Comparison of different sorbents (inorganic and biological) for the removal of Pb2+ from aqueous solutions

In an attempt to evaluate the suitability of activated sludge for Pb²⁺ removal, a comparative study was carried out using several chemical adsorbents and three types of biomass. The order of Pb²⁺ removal capacities for chemical adsorbents was found to be: ion exchange resin > zeolite > granular activated carbon (GAC) > powdered activated carbon (PAC), while for biomass the order was Aureobasidium pullulans > Saccharomyces cerevisiae > activated sludge. Although Pb²⁺ removal capacity (mg Pb²⁺ g⁻¹) of the activated sludge (30.9) was lower than those of the ion exchange resin (167.7) and other pure cultures of A pullulans (170.4) and S cerevisiae (95.3), it was higher than those of other chemical adsorbents such as GAC (26.0), PAC (2.1), and zeolite (30.2). The initial Pb²⁺ removal rates for the chemical adsorbents were in the order of PAC > GAC > zeolite > ion exchange resin, while for the biomass samples it was A pullulans > activated sludge > S cerevisiae. The initial Pb²⁺ removal rate of activated sludge was higher than those of GAC, zeolite, ion exchange resin and S. cerevisiae cells. Therefore, it was concluded that activated sludge that has been used in a municipal wastewater facility can be effectively used in heavy metal removal processes, in situ. © 2000 Society of Chemical Industry     

新型除氟载铁(Fe~(3+))聚丙烯酰胺凝胶的性能研究

以Fe3+溶液在30℃,pH=1.75条件下对聚丙烯酰胺凝胶改性2 h,得到载铁凝胶。运用载铁凝胶进行除氟实验,考察pH值、反应温度、反应时间、初始F-浓度以及干扰离子等因素对载铁凝胶的除氟效果的影响。结果表明,载铁聚丙烯酰胺凝胶适于氟离子浓度为5 mg/L的含氟溶液在30℃,pH=8条件下反应2 h,除氟率可达69.32%。Na2SO4、Na2CO3、CaCl2和KCl等干扰离子对除氟效果的影响较大,而且干扰离子含量越多影响越大,除氟率越低,故用凝胶进行除氟时应先除去干扰离子。     

Ion Exchange Resins for Gold Cyanide Extraction Containing a Piperazine Functionality, 2. Study of the Gold Extraction Reaction

Ion exchange technology is offered as an alternative to activated carbon for gold cyanide recovery. A new type of ion‐exchange resin (PS‐PIP) incorporating a piperazine group, linked to a styrene‐divinylbenzene macroporous network, is described. The extraction of Au(CN)₂^– and other metal cyanides with the PS‐PIP resin involves three modes of metal extraction: the protonated secondary amine groups of the resin (at acidic pH conditions), the free amine groups of the resin (at neutral and basic pH values) and the small portion of the quaternary ammonium groups participate in the gold extraction mechanism. The gold cyanide extraction reaction on the polymeric piperazine was studied by a combination of metal extraction data, from batch experiments, and IR and XPS spectroscopic analysis of the metal loaded polymers. Extraction isotherms of gold cyanide show that gold binding is possible from 40–60 mg Au/g of resin in alkaline solutions, up to 150 mg Au/g of resin in acidic solutions. Efficient stripping of gold from the resin was achieved using ethanol/water solutions of sodium hydroxide, or 0.5 mol/l thiourea in sulfuric acid solutions.     

Adsorptive removal of tetracycline from water using Fe(III)-functionalized carbonized humic acid

Humic acid (HA) was carbonized at 300, 400 and 500 °C and then functionalized with 1 wt%–12 wt% Fe(III) respectively [CHA300/400/500-Fe(III)]. Adsorption of such Fe(III)-functionalized carbonized HA as adsorbents to aqueous tetracycline (TC: 25 mg·L⁻¹) was studied. The adsorption equilibrium time for CHA400-Fe(III) to TC was 6 h faster and the adsorption removal efficiency (R_e) was two times higher than that of HA/CHA. The adsorption R_e of CHA400-Fe(III) loaded 10% iron [CHA400-(10%)Fe(III)] to TC could reach 99.8% at 8 h and still kept 80.6% after 8 cycles. The adsorption kinetics were well fitted to the pseudo-second-order equation and the adsorption isotherms could be well delineated via Langmuir equations(R² > 0.99), indicating that the homogeneous chemical adsorption of TC occurred on the adsorbents. The main adsorption mechanisms of TC were complexation Fe(III) and hydrophobic distribution. Electropositive and electronegative repulsion between TC and CHA400-(10%)Fe(III) at lowly pH(2) and highly pH(8–10) respectively, leaded to the relatively low adsorption capacity and more notable influence of ion concentration. When the pH was between 4 and 8, TC mainly existed in neutral molecules (TCH₂), so the influence of ion concentration was not obvious. The dynamic adsorption results showed that the CHA400-(10%)Fe(III) could continuously treat about 2.4 L TC(27 mg·L⁻¹) wastewater with the effluent concentration as low as 0.068 mg·L⁻¹. Our study suggested a broad application prospect of a new, effective, low-cost and environment-friendly adsorbent CHA400-(10%)Fe(III) for treatment of low-concentration TC polluted wastewater.     

Implementation of Hybrid Inorganic/Organic Adsorbents for Removal and Preconcentration of Heavy Metals from Industrial Waste and Drinking Waters

Three hybrid inorganic/organic adsorbents based on alumina and phenylazoformic acid 2-phenylhydrazide were synthesized, characterized and examined for their heavy metal sorption properties. The main purpose of this research paper is to study and explore the combined hybrid characters of inorganic/organic sorbents for the selective removal and preconcentration of heavy metals via static and dynamic solid phase techniques from industrial wastewater and drinking tap water samples as well. The hybrid inorganic/organic adsorbents were identified as strongly resistive to leaching in solutions with pH 1–7 and thermally stable up to 350°C. Optimization of heavy metal removal by implementation of newly designed hybrid inorganic/organic adsorbents was studied in presence of various factors as the effect of pH of contact solution and reaction time via determination of the metal sorption capacity and distribution coefficient. The hybrid adsorbents were successfully implemented for the selective removal of Pb(II), Cu(II), Fe(III), and Cr(III) from industrial wastewater samples with recovery values in the range of 91–99 ± 2–3% as well as 98–99 ± 1–3% for the selective preconcentration of Pb(II), Cu(II), and Cr(III) from drinking tap water samples without noticeable interference caused by the matrix effect.