Adsorption of reactive dyes from aqueous solutions by layered double hydroxides

BACKGROUND: Water‐soluble reactive azo dyes are the most problematic dye house effluents, as they tend to pass through conventional treatment systems unaffected. The release of these compounds into the environment is undesirable and their removal becomes environmentally important. In this work, synthesis, characterization and sorption properties of hydotalcite‐like compounds (Mg/Al and Mg/Fe), calcined and uncalcined, were investigated for the removal of the reactive azo dye Remazol Red 3BS. RESULTS: The calcined compounds present higher surface area than the uncalcined. The optimum pH for sorption was found to be 6. Thermodynamic analysis reveals that the sorption is spontaneous and endothermic. Equilibrium data were fitted by a Langmuir model, and kinetic data by a second‐order model. The calcined Mg/Al compound showed the highest sorption capacity, at 0.125 mmol g^?1. Regeneration of dye loaded derivative is achieved using the surfactant SDS. CONCLUSIONS: The prepared hydotalcite‐like compounds and especially calcined Mg‐Al exhibited significant adsorption capacity, kinetics, and regenerative ability. Its potential applicability as sorbent should be tested in a large‐scale implementation. Copyright © 2011 Society of Chemical Industry     

Adsorption of phosphate by layered double hydroxides in aqueous solutions

Adsorption of phosphate by various calcined layered double hydroxides (LDHs) such as Mg–Al, Zn–Al, Ni–Al, Co–Al, Mg–Fe, Zn–Fe, Ni–Fe and Co–Fe was investigated. LDHs were found to have high anion exchange capacity that enhances their capability to remove anionic contaminants from aqueous system. The nature and content of di- and trivalent cations in LDH have strong influence on the adsorption process. Calcined Mg–Al LDH (CLDH) with Mg–Al molar ratio of 2.0 showed higher adsorption capacity compared to other calcined LDHs as it possessed higher Al³⁺ content. Results indicate that the adsorption isotherm could be fitted to a linearised form of Langmuir and Freundlich equations. The adsorption phenomenon has been well supported by XRD study. The adsorption process was spontaneous and exothermic in nature and followed first order kinetics. Competitive anions were found to have detrimental effect on the percentage of adsorption.     

Removal of Pb2+ from the aqueous solution by tartrate intercalated layered double hydroxides

Adsorption of Pb²⁺ ion by a tartrate intercalated MgAl layered double hydroxides (MgAl-TA LDHs) was studied. The adsorption isotherms and kinetics were investigated as a function of various experimental parameters using batch adsorption experiments. The results indicated that the adsorption isotherm was well described by Sips model. The kinetic adsorption data were fitted well to the pseudo-second-order kinetic equation. The adsorption of Pb²⁺ was controlled mainly by the chemical process combined with intraparticle diffusion. Parameters of adsorption thermodynamic suggested that the interaction of Pb²⁺ adsorbed by MgAl-TA LDHs adsorbents was thermodynamically spontaneous and endothermic.     

Removal of Acid Red G dye from aqueous solutions by adsorption to MCM-41-layered double hydroxides composite

MCM-41 supported layered double hydroxides (LDH) composite materials (ML) were synthesized and studied for removal of Acid Red G (ARG), an anionic dye, with the adsorption method. ML was prepared using in situ synthesis procedure for the low supersaturation coprecipitation method, and ML10 and ML20 presented promising application towards ARG dye adsorption capacity in industrial wastewater. Powder samples were characterized by Xray diffraction, FTIR spectroscopy, scanning electron microscopy and energy dispersive spectrometry. The effects of different reaction time, initial solution pH and temperature on the dye adsorption capacity were investigated. Adsorption process was well described by pseudo-second-order kinetic model and Langmuir isotherm model. The fitting curves showed that ML10 and ML20 had higher adsorption rates and maintained a certain theoretical saturated adsorption capacity (92.19807mg/g and 96.41947mg/g, respectively) compared with LDH.     

Heteropoly blue-intercalated layered double hydroxides for cationic dye removal from aqueous media

Heteropoly blue-intercalated layered double hydroxide (HB-LDH) was obtained by aqueous ion exchange of a Zn–Al LDH precursor in nitrate form with the reduced polyoxometalate anions [PW₁₀Mo₂O₄₀]^5?. The physicochemical properties of the product were characterized by the methods of powder X-ray diffraction, infrared spectroscopy, and cyclic voltammetry. The HB-LDH has been used for the removal of cationic dye methylene blue (MB) from aqueous solutions via adsorption. The intercalation of large cluster anion [PW₁₀Mo₂O₄₀]^5? into LDH could induce the adsorption to cationic dye of MB, obviously. The HB-LDH shows much higher cationic dye adsorption capacity than pure LDH and the maximum adsorption capacity Q_max of MB onto ZnAl–PW₁₀Mo₂ is 30.87 mg/g.     

Effective concentration of dichromate anions using layered double hydroxides from acidic solutions

Chromate anion was effectively concentrated on an anion exchanger, layered double hydroxide (LDH), from aqueous solution. The LDHs used in this study were synthesized by hydrothermal reactions using urea hydrolysis as reported previously (Ogawa and Kaiho, 2002). The ion exchange was conducted at pH = 3 to concentrate larger amount of dichromate (Cr₂O₇^2 −). The adsorption isotherms indicated the strong interactions of chromate anions with LDHs. Among the tested LDHs (MgAl, NiAl, CoAl, and LiAl-LDHs), LiAl-LDH gave the best result in terms of the adsorbed Cr amount. Since the reaction was started from carbonate forms of layered double hydroxides, only the carbonate anions are released to the environment after the anion exchange. All these facts indicated that the present layered double hydroxides are promising materials for the environmental remediation from Cr contaminated water. If compared with commercially available LDHs and those synthesized by the conventional co-precipitation methods, the LDHs synthesized by hydrothermal reaction using urea hydrolysis were shown to be superior because of the stability and the ease of solid–liquid separation after the ion exchange.     

Controlling the reaction kinetics of sodium carbonate-activated slag cements using calcined layered double hydroxides

In this study, Na₂CO₃-activated slag cements were produced from four different blast furnace slags, each blended with a calcined layered double hydroxide (CLDH) derived from thermally treated hydrotalcite. The aim was to expedite the reaction kinetics of these cements, which would otherwise react and harden very slowly. The inclusion of CLDH in these Na₂CO₃-activated cements accelerates the reaction, and promotes hardening within 24 h. The MgO content of the slag also defines the reaction kinetics, associated with the formation of hydrotalcite-type LDH as a reaction product. The effectiveness of the CLDH is associated with removal of dissolved CO₃^2 − from the fresh cement, yielding a significant rise in the pH, and also potential seeding effects. The key factor controlling the reaction kinetics of Na₂CO₃-activated slag cements is the activator functional group, and therefore these cements can be designed to react more rapidly by controlling the slag chemistry and/or including reactive additives.     

焙烧型镁铝双金属氢氧化物对水中苯甲酸的吸附行为

采用共沉淀法制备镁铝双金属氢氧化物(LDHs)功能材料,并在500℃焙烧得到改性的层状氢氧化镁铝(LDO),利用XRD和FTIR对改性前后的产物结构进行表征。以LDO为吸附剂、水中苯甲酸为研究对象,具体考察了吸附剂的投加量、p H、吸附平衡时间及恒温水浴振荡温度等实验条件对苯甲酸脱除效果的影响。结果表明,在25 m L质量浓度为0.6 g/L的苯甲酸溶液中,吸附剂投加量0.8 g,p H=8.0,吸附60 min,(25±0.5)℃的条件下脱除效果较佳,脱除率可达到77.9%。此外,吸附反应较符合Langmuir吸附等温模型,该吸附是一个自发放热反应,吸附热为-17.01 k J/mol。     

ZnAlLa类水滑石对污泥脱水液中磷酸根的吸附

通过共沉淀法合成了ZnAlLa三元类水滑石,并考察了其结构特征和对磷酸根的吸附性能。结果表明,在保持类水滑石层状结构的条件下,La的适量掺杂可增强吸附剂对磷酸根的吸附。当Zn∶Al∶La摩尔比为2.00∶0.90∶0.10时,ZnAlLa类水滑石在24h内对污泥脱水液中磷酸根的吸附量为35.15mgP.g-1,比无La时的吸附量提高了41.9%。300℃焙烧处理后,ZnAlLa样品转化为亚稳态的复合金属氧化物,同时比表面积明显增加,其磷酸根吸附量约为焙烧前的1.48倍。ZnAlLa对磷酸根的吸附在pH变化及竞争离子存在时表现出较强的稳定性。该吸附剂对污泥脱水液中磷酸根的吸附符合假二级吸附动力学;吸附等温线表现为Langmuir型。     

Perchlorate uptake by synthetic layered double hydroxides and organo-clay minerals

The perchlorate uptake of hydrotalcite- and hydrocalumite-type layered double hydroxides (LDHs), and surfactant modified clay minerals were compared. Perchlorate uptake by both hydrotalcite- and hydrocalumite-type LDHs was in the range of 0.011 to 0.197 meq/g from a 2 mM perchlorate solution. The nitrate form of Mg:Al LDH had the highest uptake of 0.197 ± 0.033 meq/g, and the carbonate form of LDH the lowest uptake of 0.011 ± 0.003 meq/g. Octadecyltrimethylammonium (ODTMA), Dodecyltrimethylammonium (DoDTMA), and hexadecyltrimethylammonium (HDTMA) clay minerals removed perchlorate in the range of 0.025 to 0.348 meq/g from a 2 mM perchlorate solution. Synthetic HDTMA (5.0 CEC) Na-1-mica exhibited the highest adsorption of perchlorate with 0.348 ± 0.011 meq/g, while DoDTMA montmorillonite had the lowest adsorption with 0.025 ± 0.009 meq/g. Tested under the same conditions, a surfactant modified carbon showed an uptake of 0.303 ± 0.005 meq/g and this carbon is currently being used for filtration of drinking water.Hydrophobic organo-clay minerals with larger interlayer distance resulted in higher perchlorate uptake by exchange/adsorption on the residual charge of the cationic surfactants. The uptake by LDH was by anion exchange on the surfaces and, for the nitrate form of hydrotalcite, also from the interlayer spaces. The mechanisms of uptake were confirmed by X-ray diffraction (XRD) and scanning electron microscopy. This study indicated that cationic surfactant containing organo-clay minerals may be useful materials for the removal of perchlorate from water and could serve as alternatives to surfactant modified-activated carbons.     

Deintercalation of carbonate ions from carbonate-type layered double hydroxides (LDHs) using acid-alcohol mixed solutions

Because of the high affinity of carbonate ions (CO₃²⁻) for LDHs (layered double hydroxides), their decarbonation—deintercalation of carbonate ions and conversion into LDHs containing other anions—has been considered difficult. So far, dilute acids have been used for decarbonation with additional salt to enhance the reaction. We found that the acid resistance of the LDHs is much higher in alcohols such as methanol and ethanol than in water, and complete decarbonation was attained, yielding LDHs containing the conjugated base anions of the acids used for the decarbonation. The carbonate ions were very rapidly deintercalated (0.5-1 h) from the CO₃²⁻LDHs at room temperature (15-25 °C) without any weight loss or any appreciable selective dissolution of the metal components of the LDH layer. In contrast to decarbonation in water, for which an additional supply of anions from a neutral salt is needed, when using an acid-alcohol mixed solution, decarbonation proceeded almost quantitatively, and any additional salts were not required. Use of other polar organic solvents such as acetone, THF (tetrahydrofuran), led to similar quantitative decarbonation, but acid resistance of LDHs was less in these solvents than in alcohols.     

A new approach to improve sulfate uptake from contaminated aqueous solution: Metal layered double hydroxides functionalized metasomatic rock

In this study, waste rock of iron ore mine (metasomatic rocks) has been modified and utilized as a sulfate adsorbent to enhance sulfate removal from contaminated aqueous solution. The modification generating from the assembly of Mg–Al and Ni–Al layered double hydroxides and metasomatic rocks. The sulfate adsorption onto both adsorbents was performed favorably as a monolayer adsorption in homogeneous condition. The kinetic studies identify the chemisorption mechanism of sulfate adsorption process onto both adsorbents with the combination of the film-mass transfer and internal diffusion. Thermodynamic studies indicate that sulfate adsorption process onto both adsorbents was exothermic and spontaneous.     

Intercalation of layered double hydroxides by poly(oxyalkylene)-amidocarboxylates: tailoring layered basal spacing

Mg-Al layered double hydroxides (LDHs) were intercalated with various molecular-weight poly(oxypropylene)-bis-amidoacid salts (POP-acid), synthesized from polyoxyalkylene-diamines and maleic anhydride. The intercalation involves an ionic exchange reaction of LDHs at 120 °C and under N₂ atmosphere in an autoclave to afford a series of organoclays with a maximal basal spacing of 92 Å, revealed by X-ray diffraction and transmission electron microscopy analyses. The unusually wide interlayer spacing was ascribed to the self-alignment of the hydrophobic POP backbone in the layer confinement. In contrast, the intercalation of poly(oxyethylene)-bis-amidoacids (POE-acid) afforded a low basal spacing (7.8 Å) due to their oxyethylene-backbone interaction with the layered surface. The resultant POP- and POE-acid intercalated LDHs also exhibited different dispersing properties in toluene or water. Particularly, the organically-modified and space-enlarged hybrids with a proper amount of the embedded POPs possessed an amphiphilic property of lowering the toluene/water interfacial tension.     

硝酸根型镁铁水滑石的合成及其离子交换性能研究

采用共沉淀法合成出了层间阴离子为NO-3的镁铁水滑石(MgFe-NO3-LDHs),当滴料终点pH值为9.5,反应温度为100℃,反应时间为4h时,可得到晶体结构规整的层状结构产物。通过离子交换将有机阴离子CH2CHC6H4SO-3和CH3(CH2)11SO-3引入层间,形成以双分子层垂直于层板的交错有序的排布结构模式。     

Size control and optimisation of intercalated layered double hydroxides

Two types of organo-layered double hydroxides (LDH), with adipate or dodecyl sulfate in the interlayer space, have been prepared by the coprecipitation. In order to improve the homogeneity and to obtain well crystallised solids, the samples were submitted to microwave (MW) irradiation. Hydrotalcite (HT)-like compounds were obtained in all cases. The TEM and particle size distribution point out that even short irradiation times led to homogeneous and well defined solids with small particle size.     

镁铝钡三元水滑石的制备及吸附性能研究

以Al(NO3)3·9H2O、Mg(NO3)2·6H2O、Ba(NO3)2为原料,用共沉淀法制备了Mg/Al/Ba三元水滑石(Mg/Al/Ba-LDHs),经过傅里叶红外光谱仪和比表面及孔径分析仪进行表征。考察了该水滑石对重金属铬离子(Ⅲ)的吸附行为及干扰离子,优化了浓度、时间、温度、酸度(pH)等因素对Mg/Al/Ba-LDHs吸附性能的影响。结果表明,在最佳浓度13mg/mL、时间150 min、温度30℃、pH=6时吸附容量最大达到400mg/g。     

New sulfur adsorbents derived from layered double hydroxides: I: Synthesis and COS adsorption

Mixed oxides, prepared via the thermal decomposition of layered double hydroxides (LDHs), were screened gravimetrically for their ability to adsorb carbonyl sulfide (COS). Based on promising results obtained for Ni/Mg/Al, Ni/Mg/Fe and Co/Mg/Al mixed oxides, a study was undertaken to optimize the composition of these materials for COS adsorption. To investigate the effect of the M(II):M(III) ratio, LDHs of the type [M_zMg_yAl_x(OH)₂](CO₃)_x/2·0.5H₂O (where M = Ni or Co, and x + y + z = 1) were prepared at values of x corresponding to 0.33 and 0.20. Simultaneously, the elemental ratio of transition metal to magnesium (z/y) was varied. Mixed oxides obtained from the resulting LDHs were tested in fixed bed mode with a feed of 100 ppm COS in N₂ to determine breakthrough capacity. In general Ni/Mg/Al mixed oxides showed the best performance, a composition with Ni/Mg/Al = 0.32/0.48/0.20 showing the best adsorption capacity. Treatment of the spent adsorbent under an atmosphere of 5% H₂ in N₂ at 450 °C was found to provide an effective means of restoring the adsorption capacity over two cycles of adsorption and regeneration, although after three such cycles, adsorption capacity decreased.     

Removal of phenol from aqueous solutions by continuous RF-pertraction

Water dephenolation was studied using a multistage Rotating Film Pertractor (RFP). This relatively new liquid membrane technique allows the use of almost water-insoluble liquids as intermediate organic ‘membranes’. The effects of the main processing parameters such as disc rotation velocity, temperature and phase flowrate, on removal efficiency were studied. A mathematical model describing the process of dephenolation in a counter-current multistage cascade of n-RFP contactors was proposed for the prediction of phenol removal.     

层状双氢氧化物的可控合成及功能化研究进展

层状双氢氧化物（LDHs）作为一种低成本、表面带正电荷、结构与组成高度可调变并能进行插层反应的二维无机材料备受关注。目前合成出分散性良好、粒径分布范围窄以及可调结构和组成的LDHs具有一定挑战性,再加上为了满足不同应用的实际需求,需要将其他功能组分与含有复杂结构（化学修饰）的LDHs进行组装形成功能化LDHs材料,这对其结构设计和制备方法的策略提出了新的挑战。因此,本文将目光聚焦在LDHs的可控合成、表面化学修饰、功能化复合材料方面的研究上,归类总结了研究者们在设计制备功能化LDHs方面所做的贡献,分析了功能化LDHs复合材料在不同领域应用的特点和作用,提出进行创新结构设计和合成方案简易化将是今后构建功能化LDHs复合材料的研究重点。