Study of equilibrium,kinetic and thermodynamic parameters about methylene blue adsorption onto natural zeolite

Adsorption equilibrium and kinetic of methylene blue (MB) onto natural zeolite was studied in a batch system. Variables of the system include contact time, pH, salt concentration, temperature, and initial MB concentration. The increase in temperature resulted in a higher MB loading per unit weight of the zeolite. Langmuir, Freundlich, Redlich–Peterson, Koble–Corrigan and Temkin isotherm models were applied to experimental equilibrium data of MB adsorption depending on temperature. The effect of contact time at different temperatures and initial concentration were fitted to pseudo-second-order kinetic model. Linear regressive method and nonlinear regressive method were used to obtain the relative parameters. The error analysis was conducted to find whether linear method or nonlinear method was better to predict the experimental results and which model was better to fit the experimental data. Both methods were suitable to obtain the parameters. The Redlich–Peterson equation was best to fit the equilibrium data. The pseudo-second-order kinetic model can be used to describe the adsorption behavior. The nonlinear method may be better with the absolute error as limited condition. The adsorption process was spontaneous and endothermic.     

改性MCM-41分子筛的合成与亚甲基蓝吸附性能

选用TEOS（正硅酸乙酯）做为硅源,CTAB（十六烷基三甲基溴化铵）做为表面活性剂,在碱性条件下水热合成MCM-41。实验采用3-氨丙基三甲基硅烷对MCM-41进行改性,成功得到氨基改性介孔材料NH₂-MCM-41吸附剂,并使用X射线衍射（XRD）对其做了表征。考察了各种实验条件下,比如温度、吸附剂的量、pH、亚甲基蓝初始浓度等条件下MCM-41和NH₂-MCM-41对水溶液中亚甲基蓝（MB）的吸附能力。MCM-41和氨基改性介孔材料NH₂-MCM-41均为平面六方介孔结构。结果表明,温度和pH是影响MCM-41和NH₂-MCM-41对亚甲基蓝吸附的最主要的因素。随着温度的升高,材料吸附能力增强,而过高或者过低的pH都会降低MCM-41和NH₂-MCM-41对亚甲基蓝的吸附能力。     

Characterization of modified sawdust, kinetic and equilibrium study about methylene blue adsorption in batch mode

Methylene blue (MB) biosorption by citric acid modified pine sawdust (Pinus tabulaeformis) was studied from aqueous solutions. Batch experiments were conducted to determine the biosorption properties of the biomass. The Langmuir isotherm equation could fit the equilibrium data. The maximal equilibrium quantity of MB from Langmuir model was 111.46 mg g^?1 at 293 K. The Elovich model adequately described the kinetic data in comparison to the pseudo-first-order model and pseudo-second-order model; the process involving rate-controlling step is very complex involving both boundary layer and intra-particle diffusion processes. The effective diffusion parameter D _i and D _f values were estimated at different initial concentration, and the average values were determined to be 5.76×10^?8 and 2.12× 10^?7 cm² s^?1. Thermodynamic parameters showed that the adsorption of methylene blue onto pine sawdust biomass was feasible, spontaneous and endothermic under studied conditions. The physical and chemical properties of the biosorbent were determined by SEM, TG-DSC, XRD, and the point of zero charge (pH _pzc ) and the nature of biomass-dye interactions were evaluated by FTIR analysis, which showed the participation of COOH, OH and NH₂ groups in the biosorption process. Biosorbents could be regenerated using 0.01 mol L^?1 HCl solution at least three cycles, with up to 90% recovery. Thus, the biomass used in this work proved to be effective for the treatment of MB bearing aqueous solutions.     

MCM-41介孔分子筛吸附性能的热力学和动力学分析

实验以亚甲基蓝作为模型吸附质,探讨了MCM-41介孔分子筛对模型吸附质亚甲基蓝的吸附性能,并对其吸附过程进行了热力学和动力学分析。结果表明,MCM-41介孔分子筛的吸附率高达94%,对亚甲基兰的吸附符合二级吸附动力学,MCM-41对亚甲基兰的吸附行为属于Freundlich等温吸附,整个吸附过程属于放热反应。     

Removal of methylene blue from aqueous solutions by adsorption onto chemically activated halloysite nanotubes

This study examines the adsorption behavior of methylene blue (MB) from aqueous solutions onto chemically activated halloysite nanotubes. Adsorption of MB depends greatly on the adsorbent dose, pH, initial concentration, temperature and contact time. The Langmuir and Freundlich models were applied to describe the equilibrium isotherms and the Langmuir model agrees very well with experimental data. The maximum adsorption capacities for MB ranged from 91.32 to 103.63 mg·g⁻¹ between 298 and 318 K. A comparison of kinetic models applied to the adsorption data was evaluated for pseudo-first-order, pseudo-second-order, Elovich and intra-particle diffusion equation. The results showed the adsorption process was well described by the pseudo-second-order and intra-particle diffusion mode. Thermodynamic parameters suggest that the adsorption is spontaneous and endothermic. The obtained results indicated that the product had the potential to be utilized as low-cost and effective alternative for dye removal in wastewater.     

Removal of methylene blue from coloured effluents by adsorption onto SBA‐15

Adsorption has been proven to be the most efficient method for quickly lowering the concentration of dissolved dyes in an effluent. In this regard, activated carbon is the most widely used adsorbent for removal of dyes from aqueous solution. However, the high cost of production and regeneration make it uneconomical. Therefore, inorganic adsorbents (e.g. zeolites) with high surface areas have been used as alternatives to carbon adsorbents. Microporous zeolites ZSM‐5, NH₄‐Beta, MCM‐22 and mesoporous materials MCM‐41 have been investigated for the removal of dyes from aqueous solutions and they show effective adsorption performance. SBA‐15 possesses a larger pore size and pore wall thickness than MCM‐41. As a result, SBA‐15 has greater potential for the adsorption of methylene blue with larger molecule size and higher hydrothermal stability than the M41S family. SBA‐15 is an excellent adsorbent for methylene blue (MB), exhibiting 280 mg g^?1 adsorption capacity and about 100% fading rate for MB. The adsorptive process is so fast that adsorption equilibrium is achieved in 5 min. In addition, SBA‐15 can be effectively recovered by calcination and reused 10 times without significant loss in removal of MB from aqueous solution. The efficient adsorption of MB molecules onto SBA‐15 was ascribed to MB adsorbed into the pore channels of SBA‐15, which was confirmed by nitrogen physisorption analysis of the adsorbent before and after adsorption. The long reuse life of the adsorbent suggests a high potential for application in industry. Copyright © 2010 Society of Chemical Industry     

Kinetics and equilibrium studies from the methylene blue adsorption on diatomite treated with sodium hydroxide

Diatomite was treated with sodium hydroxide to remove impurity in order to improve its performance as an adsorbent. The raw diatomite and purified diatomite were characterized by scanning electron microscopy, energy dispersive X-ray analysis and Brunauer–Emmett–Teller adsorption. It was found that the surface area was in order of 15.87 m² g^− 1 for raw diatomite and 31.35 m² g^− 1 for purified diatomite. Scanning electron microscopy images showed the well-developed porous structure of purified diatomite. Purified diatomite improved a more than tenfold increase in adsorption amount from 1.72 mg g^− 1 to 18.15 mg g^− 1 and removal efficiency from 8.60% to 90.75% for methyelen blue initial concentration 100 ppm respectively. The kinetics studies showed that experiment data followed pseudo-second-order model better. The equilibrium data was fitted to Langmuir and Freundlich adsorption isotherms and was found that Langmuir model presented the best fit, showing maximum monolayer adsorption capacity of 27.86 mg g^− 1. The thermodynamic parameters such as the standard enthalpy, standard entropy and standard free energy were evaluated. The obtained results indicated the adsorption of methylene blue onto diatomite treated with sodium hydroxide is endothermic and spontaneous process and confirmed the applicability of this purified inorganic material as an efficient adsorbent for basic dyes.     

不同负载方式Fe/改性MCM-41催化剂的制备及其降解亚甲基蓝性能研究

以自制二元共聚物聚[苯乙烯—3-（甲基丙烯酰氧）丙基三甲氧基硅烷]改性MCM-41,并以其为载体分别采用浸渍负载活性金属、原位负载活性金属和NaBH₄还原负载活性金属的方式制备铁基异相催化剂。研究了3类催化剂降解亚甲基蓝的性能差异。结果显示,在3种催化剂中,浸渍负载活性金属制备的催化剂具有最好的催化活性,25 min时亚甲基蓝去除率为81.2%。同时采用XRD、TEM、FTIR、XPS、压汞测试等手段分析了催化剂具有优异性能的原因。表征结果表明:Fe与改性MCM-41间的相互作用及催化剂孔结构,两者的协同作用是催化剂具有优异性能的原因。     

Adsorption behavior of methylene blue onto titanate nanotubes

Calcined titanate nanotubes were synthesized with hydrothermal treatment of the commercial TiO₂ (Degussa P25) followed by calcination. The morphology and structures of as-prepared samples were investigated by transmission electron microscopy, X-ray diffraction and N₂ adsorption/desorption. The samples exhibited a tubular structure and a high surface area of 157.9 m²/g. The adsorption of methylene blue onto calcined titanate nanotubes was studied. The adsorption kinetics was evaluated by the pseudo-first-order, pseudo-second-order and Weber's intraparticle diffusion model. The pseudo-second-order model was the best to describe the adsorption kinetics, and intraparticle diffusion was not the rate-limiting step. The equilibrium adsorption data were analyzed with three isotherm models (Langmuir model, Freundlich model and Temkin model). The best agreement was achieved by the Langmuir isotherm with correlation coefficient of 0.993, corresponding to maximum adsorption capacity of 133.33 mg/g. The adsorption mechanism was primarily attributed to chemical sorption involving the formation of methylene blue-calcined titanate nanotubes nanocomposite, associated with electrostatic attraction in the initial bulk diffusion.     

Methylene blue adsorption onto an eco-friendly modified polyacrylamide/graphite composites: Investigation of kinetics,equilibrium, and thermodynamic studies

ABSTRACT

Batch adsorption system using eco-friendly glucose and glucosamine grafted polyacrylamide/graphite composites were investigated to eliminate methylene blue (MB) dye from aqueous solution. The effect adsorption parameters reveal that pseudo-second order and Langmuir model exhibited good correlation with the adsorption kinetic and isotherm data for pollutant, respectively. Furthermore, an increase in pH from 2 to 11 was accompanied by an approximately fourfold increase in the amount of dye adsorbed. The maximum removal efficiency of MB was 96.23% under optimum conditions with equilibrium time of 40 min. The thermodynamic data supported its spontaneous and endothermic property of adsorption process. A possible adsorption mechanism has been proposed, where H-bonding and electrostatic interactions dominated the adsorption of dye.     

Comparative study of methylene blue dye adsorption onto activated carbon,graphene oxide,and carbon nanotubes

Three different carbonaceous materials, activated carbon, graphene oxide, and multi-walled carbon nanotubes, were modified by nitric acid and used as adsorbents for the removal of methylene blue dye from aqueous solution. The adsorbents were characterized by N₂ adsorption/desorption isotherms, infrared spectroscopy, particle size, and zeta potential measurements. Batch adsorption experiments were carried out to study the effect of solution pH and contact time on dye adsorption properties. The kinetic studies showed that the adsorption data followed a pseudo second-order kinetic model. The isotherm analysis indicated that the adsorption data can be represented by Langmuir isotherm model. The remarkably strong adsorption capacity normalized by the BET surface area of graphene oxide and carbon nanotubes can be attributed to π–π electron donor acceptor interaction and electrostatic attraction.     

亚甲基蓝在石棉尾矿酸浸渣上的吸附行为

采用XRD、FT-IR等手段分别对石棉尾矿和石棉尾矿酸浸渣进行表征。利用活化煅烧的石棉尾矿酸浸渣对亚甲基蓝(MB)进行静态吸附研究, 探讨了吸附剂投加量、吸附时间、pH值、离子强度和温度等因素对吸附作用的影响。结果表明:pH值、离子强度和温度对亚甲基蓝在石棉尾矿酸浸渣上的吸附影响较大。当pH<4.5时, 吸附量随着pH值的增大而增大, 随后pH值增大, 吸附量基本不变;亚甲基蓝在石棉尾矿酸浸渣上的吸附随离子强度的增大而降低;通过相关热力学研究计算吸附过程为吸热过程, 即高温利于吸附;亚甲基蓝在石棉尾矿酸浸渣上的吸附动力学符合Lagrange准二级方程;热力学符合Langmuir等温线方程。     

The adsorption of methylene blue by active carbon

The extent of adsorption of methylene blue from an aqueous solution is a convenient indicator in the evaluation of active carbons. The adsorption process is, however, complicated by factors inherent in the structures of both the methylene blue solution and the active carbon. These factors include the tendency of methylene blue to form molecular aggregates in solution, molecular sieving imposed by the pore size distribution of the carbon and the heterogeneous nature of the energies of adsorption sites. Temperature variation of adsorption and calorimetric experiments show, however, that the results obtained can be rationalized on the basis of these structural factors and the kinetic effects which result from them.     

吸附法处理亚甲基蓝研究

处理亚甲基蓝的方法很多,吸附法是其中之一。吸附法属于物理化学法,具有操作简单、费用低、处理效果较好等优点,历来受到研究者和使用者的重视。重点介绍了近年来采用吸附法处理亚甲基蓝的研究进展,特别是新型吸附剂以及吸附动力学与热力学等领域的研究进展。结果表明,吸附法处理亚甲基蓝有一定优势,在应用中要根据废水实际情况和生产状况选择最佳处理和回收工艺。     

高岭土对亚甲基蓝的吸附性能和等温吸附模型研究

以高岭土为吸附剂,研究了其对亚甲基蓝模拟废水的吸附行为、等温吸附模型和吸附动力学。探讨了吸附时间、高岭土投加量、亚甲基蓝初始浓度、盐浓度、p H值等因素对亚甲基蓝吸附效果的影响。结果表明,吸附时间120 min,高岭土投加量10 g/L,低温、碱性条件下就能达到更好的亚甲基蓝吸附效果。高岭土对亚甲基蓝吸附符合Langmuir和Freundlich等温吸附模型,吸附动力学符合准二级动力学模型。     

高岭土对亚甲基蓝的吸附性能和等温吸附模型研究

以高岭土为吸附剂,研究了其对亚甲基蓝模拟废水的吸附行为、等温吸附模型和吸附动力学。探讨了吸附时间、高岭土投加量、亚甲基蓝初始浓度、盐浓度、p H值等因素对亚甲基蓝吸附效果的影响。结果表明,吸附时间120 min,高岭土投加量10 g/L,低温、碱性条件下就能达到更好的亚甲基蓝吸附效果。高岭土对亚甲基蓝吸附符合Langmuir和Freundlich等温吸附模型,吸附动力学符合准二级动力学模型。     

Preparation of reusable glass hollow fiber membranes and methylene blue adsorption

In this work, the PVDF/glass as-prepared composite membrane was prepared through phase-inversion method and used to adsorb methylene blue dye. The results of SEM and BET showed that the membrane had an asymmetric nanoscale porous structure. The electronegativity on the surface of membrane was determined through zeta potential test. The adsorption properties of as-prepared composite membrane and glass membrane were studied through testing the removal ratio of methylene blue from aqueous solution. Then the effects of membranes dose, pH value, temperature and initial concentration on the removal ratio were systematically studied. The adsorption mechanism was also studied. The adsorption kinetics and adsorption isotherm fitted well with the pseudo-second-order model and Freundlich model, respectively. In addition, the adsorption efficiency of glass membrane basically remained 85% after eight repeated adsorption-calcination cycles. The obtained membranes could be reused for methylene blue removal with high efficiency for multiply times.     

Removal of methylene blue from aqueous solution by adsorption onto zeolite synthesized from coal fly ash and its thermal regeneration

BACKGROUND: The removal of cationic dyes from wastewater is of great importance. Three zeolites synthesized from coal fly ashes (ZFAs) were investigated as adsorbents to remove methylene blue (MB), a cationic dye, from aqueous solutions. Experiments were conducted using the batch adsorption technique under different conditions of initial dye concentration, adsorbent dose, solution pH, and salt concentration. RESULTS: The adsorption isotherm data of MB on ZFAs were fitted well to the Langmuir model. The maximum adsorption capacities of MB by the three ZFAs, calculated using the Langmuir equation, ranged from 23.70 to 50.51 mg g^?1. The adsorption of MB by ZFA was essentially due to electrostatic forces. The measurement of zeta potential indicated that ZFA had a lower surface charge at alkaline pH, resulting in enhanced removal of MB with increasing pH. MB was highly competitive compared with Na⁺, leading to only a < 6% reduction in adsorption in the presence of NaCl up to 1.0 mol L^?1. Regeneration of used ZFA was achieved by thermal treatment. In this study, 90–105% adsorption capacity of fresh ZFA was recovered by heating at 450 °C for 2 h. CONCLUSION: The experimental results suggest that ZFA could be employed as an adsorbent in the removal of cationic dyes from wastewater, and the adsorptive ability of used ZFA can be recovered by thermal treatment. Copyright © 2010 Society of Chemical Industry     

一种生物质活性炭的制备及其对亚甲基蓝的吸附性能

以磷酸为活化剂,将稻壳、柚子皮分别与核桃壳按一定质量比混合,进行热解,制备了高吸附性能的生物质活性炭。研究结果表明:以柚子皮+核桃壳制备的生物质活性炭吸附亚甲基蓝2 h即可达平衡;比商品活性炭具有较优的吸附性能,对亚甲基蓝的吸附值达574.6 mg/g,吸附过程符合准二级动力学方程,等温吸附满足Langmuir等温吸附模型,属于自发进行的良性吸附。研究利用生物质废弃物,将其再利用并制备对染料吸附性能优良的生物质活性炭,可望成为环境友好型活性炭,并为生物质热解产物的资源化利用提供了应用前景。