Application of low-cost adsorbents for dye removal – A review

Dyes are an important class of pollutants, and can even be identified by the human eye. Disposal of dyes in precious water resources must be avoided, however, and for that various treatment technologies are in use. Among various methods adsorption occupies a prominent place in dye removal. The growing demand for efficient and low-cost treatment methods and the importance of adsorption has given rise to low-cost alternative adsorbents (LCAs). This review highlights and provides an overview of these LCAs comprising natural, industrial as well as synthetic materials/wastes and their application for dyes removal. In addition, various other methods used for dye removal from water and wastewater are also complied in brief. From a comprehensive literature review, it was found that some LCAs, in addition to having wide availability, have fast kinetics and appreciable adsorption capacities too. Advantages and disadvantages of adsorbents, favourable conditions for particular adsorbate–adsorbent systems, and adsorption capacities of various low-cost adsorbents and commercial activated carbons as available in the literature are presented. Conclusions have been drawn from the literature reviewed, and suggestions for future research are proposed.     

Removal of phenol from aqueous solutions by adsorption

Experiments have been conducted to examine the liquid-phase adsorption of phenol from water by silica gel, HiSiv 3000, activated alumina, activated carbon, Filtrasorb-400, and HiSiv 1000. Experiments were carried out for the analysis of adsorption equilibrium capacities and kinetics. The adsorption isotherm model of the Langmuir-Freundlich type was the best to describe adsorption equilibrium data for phenol for the adsorbents studied. Results of kinetic experiments indicated that HiSiv 1000 had the highest rate of adsorption among the adsorbents studied and therefore more detailed studies were carried out with this adsorbent. The influence of particle size, temperature, and thermal regeneration on adsorption of phenol by HiSiv 1000 was evaluated. From particle size experiments it appeared that adsorption capacity of HiSiv 1000 did not change by changing the particle size, but the rate of adsorption decreased considerably by increasing the particle size. The effect of temperature on adsorption was studied by determining equilibrium isotherms for HiSiv 1000 at 25, 40, and 55 degrees C. The results showed that adsorption capacity decreased with increasing temperature. Thermal regeneration of HiSiv 1000 was performed at 360 degrees C. It was observed that adsorption capacity of HiSiv 1000 did not change after 14 regeneration cycles. Equilibrium experiments showed that the adsorption capacities of activated carbon and Filtrasorb-400 were several times higher than that of HiSiv 1000.     

Removal of mercury from aqueous solutions using activated carbon prepared from agricultural by-product/waste

Removal of mercury from aqueous solutions using activated carbon prepared from Ceiba pentandra hulls, Phaseolus aureus hulls and Cicer arietinum waste was investigated. The influence of various parameters such as effect of pH, contact time, initial metal ion concentration and adsorbent dose for the removal of mercury was studied using a batch process. The experiments demonstrated that the adsorption process corresponds to the pseudo-second-order-kinetic models and the equilibrium adsorption data fit the Freundlich isotherm model well. The prepared adsorbents ACCPH, ACPAH and ACCAW had removal capacities of 25.88 mg/g, 23.66 mg/g and 22.88 mg/g, respectively, at an initial Hg(II) concentration of 40 mg/L. The order of Hg(II) removal capacities of these three adsorbents was ACCPH > ACPAH > ACCAW. The adsorption behavior of the activated carbon is explained on the basis of its chemical nature. The feasibility of regeneration of spent activated carbon adsorbents for recovery of Hg(II) and reuse of the adsorbent was determined using HCl solution.     

Phenol removal from aqueous environments by natural & chemically modified kaolin clay

Natural, acid and base modified kaolin clays were studied for the sake of phenol and 4-chlorophenol removal from aqueous environments and their application to real ground and industrial wastewater samples. Scanning electron microscope (SEM), infrared spectroscopy (IR), X-ray diffraction (XRD), Thermo Gravimetric Analysis (TGA), Differential Thermal Analysis (DTA), and Surface area analysis were employed for characterization of the adsorbents microstructure. Operating factors such as adsorbent dose, solution pH, initial phenol concentration, and contact time were studied. The experimental data displayed that the increase of the adsorbent dose, contact time, and pH value from 2 to 7 increases the efficiency of the removal process. Optimal conditions for phenolic removal were; contact time of 300 min, primary phenol solution of 25 mg/L, pH 7 and 2.5 g/L as an appropriate adsorbent dose using crude (natural), acid modified and base modified kaolin clays. The higher phenolic removal efficiencies were obtained at 5 mg/L as 90, 97, 96.2%, respectively, for the adsorbents in the previously mentioned order. The adsorption capacity in the removal of phenol and 4-chlorophenol were 7.481 and 4.195, 8.2942 and 3.211, and 8.05185 and 18.565 mg/g, respectively, for the adsorbents in the same mentioned order. The adsorption equilibrium data were fitted and analyzed with four isotherm models, namely, Langmuir, Freundlich, Temkin, and Dubinin–Radushkevich isotherm equations. The adsorption process of phenol on studied adsorbents was exothermic, spontaneous and thermodynamically favorable proved by the negative values of their thermodynamic parameters ΔH° and ΔG°. The correlation coefficient (R²) for all concentrations was higher than 0.94, which indicates that in the studied system, the data suitably fit the first-order kinetics. The % desorption capacity was amounted to 96%, 91.11%, and 87.06% of adsorbed phenol, respectively, for the adsorbents in the previous order using 0.1N NaOH and 10% V/V ethanol solutions as eluents at 25°C, indicating the reusability of the adsorbents. Kaolin and its modified forms can be introduced as eco-friendly and low-cost adsorbents in water remediation implementation.     

Possible Utilization of Silica Gel Sludge for the Removal of Phenol from Aqueous Solutions: Laboratory Studies

This paper discusses the adsorption capacity of silica gel sludge for phenol removal from aqueous solution. Kinetic experiments showed that phenol adsorption was completed after 2 h. Adsorption isotherms were measured for phenol from aqueous solution onto silica gel sludge under various pHs and temperatures. Results showed that the adsorption capacities for phenol was increased as pH decreased from 6.5 to 2. Temperature also was found to affect the adsorption isotherm. As temperature increases from 30 to 50°C, the adsorption capacity increases. The adsorption equilibrium of phenol on silica gel sludge was described by the linear Freundlich and Langmuir models. Furthermore, results showed that the isotherm parameters fit both linearized Langmuir and Freundlich adsorption isotherms. The Freundlich and Langmuir parameters at optimum pH was found as K _f=2.89, 1/n=0.23 and K _d=22.0, q _m=7.98, respectively. Whereas, for those at optimum temperature it was observed as K _f=2.87, 1/n=0.16 and K _d=20.93, q _m=7.91, respectively.     

Removal of copper (II) from aqueous solution by adsorption onto low-cost adsorbents

The use of low-cost adsorbents was investigated as a replacement for current costly methods of removing metals from aqueous solution. Removal of copper (II) from aqueous solution by different adsorbents such as shells of lentil (LS), wheat (WS), and rice (RS) was investigated. The equilibrium adsorption level was determined as a function of the solution pH, temperature, contact time, initial adsorbate concentration and adsorbent doses. Adsorption isotherms of Cu (II) on adsorbents were determined and correlated with common isotherm equations such as Langmuir and Freundlich models. The maximum adsorption capacities for Cu (II) on LS, WS and RS adsorbents at 293, 313 and 333 K temperature were found to be 8.977, 9.510, and 9.588; 7.391, 16.077, and 17.422; 1.854, 2.314, and 2.954 mg g(-1), respectively. The thermodynamic parameters such as free energy (delta G0), enthalpy (delta H0) and entropy changes (delta S0) for the adsorption of Cu (II) were computed to predict the nature of adsorption process. The kinetics and the factors controlling the adsorption process were also studied. Locally available adsorbents were found to be low-cost and promising for the removal of Cu (II) from aqueous solution.     

Application of sludge-based carbonaceous materials in a hybrid water treatment process based on adsorption and catalytic wet air oxidation

This paper describes a preliminary evaluation of the performance of carbonaceous materials prepared from sewage sludges (SBCMs) in a hybrid water treatment process based on adsorption and catalytic wet air oxidation; phenol was used as the model pollutant. Three different sewage sludges were treated by either carbonisation or steam activation, and the physico-chemical properties of the resultant carbonaceous materials (e.g. hardness, BET surface area, ash and elemental content, surface chemistry) were evaluated and compared with a commercial reference activated carbon (PICA F22). The adsorption capacity for phenol of the SBCMs was greater than suggested by their BET surface area, but less than F22; a steam activated, dewatered raw sludge (SA_DRAW) had the greatest adsorption capacity of the SBCMs in the investigated range of concentrations (<0.05 mol L^?1). In batch oxidation tests, the SBCMs demonstrated catalytic behaviour arising from their substrate adsorptivity and metal content. Recycling of SA_DRAW in successive oxidations led to significant structural attrition and a hardened SA_DRAW was evaluated, but found to be unsatisfactory during the oxidation step. In a combined adsorption–oxidation sequence, both the PICA carbon and a selected SBCM showed deterioration in phenol adsorption after oxidative regeneration, but a steady state performance was reached after 2 or 3 cycles.     

挥发性有机废气净化技术研究进展

本文对生物净化技术、等离子体净化技术、吸附和催化氧化技术在控制废气中挥发性有机物的研究进展及应用进行了综述。气体生物净化技术在VOCs混合物和改进设备工艺方面开展的研究工作较多,等离子体净化技术与催化技术的组合越来越受到关注。吸附和催化氧化方面则着重在吸附剂（活性炭和沸石）吸附性能的进一步研究和新型催化剂的研制。     

硫化废气污泥活性炭净化处理技术研究

以污泥厂剩余活性污泥作为原料,采用KOH为活化剂制备污泥活性炭,探讨了活化温度及时间、热解温度、洗涤温度及方式在污泥活性炭制备过程中的最佳工艺条件。以品红吸附量及产率作为污泥活性炭的考察指标,采用单因素实验筛选出了制备污泥活性炭的最佳工艺条件,并对污泥活性炭脱硫剂的脱硫性能进行了实验研究。实验研究结果显示,烟气中O2、水蒸气含量的多少及脱硫温度的高低会影响污泥活性炭脱硫剂的脱硫性能。     

Application of 'waste' wood-shaving bottom ash for adsorption of azo reactive dye

The utilization of wood-shaving bottom ash (WBA) for the removal of Red Reactive 141 (RR141), an azo reactive dye, was investigated. WBA/H(2)O and WBA/H(2)SO(4) were made by treating WBA with water and 0.1M H(2)SO(4), respectively, to increase adsorption capacity. Adsorption of RR141 from reactive dye solution (RDS) and reactive dye wastewater (RDW) by WBA/H(2)O and WBA/H(2)SO(4) involved the BET surface area and pore size diameter. Properties of adsorbents, effect of contact time, initial pH of solution, dissolved metals and elution studies indicated that the decolorisation mechanism involved both chemical adsorption and precipitation with calcium ions. In addition, the WBA/H(2)SO(4) surface might contain sulphate-cation complexes that were specific to enhancing dye adsorption from RDW. The adsorption isotherm had a best fit by the Freundlich model. Freundlich parameters showed that WBA/H(2)O used more heterogeneous surface than WBA/H(2)SO(4) and activated carbon for RDW adsorption. A thermodynamic study indicated that RDW adsorption was an endothermic process. The maximum dye adsorption capacities of WBA/H(2)O, WBA/H(2)SO(4) and activated carbon obtained from a Langmuir model at 30 degrees C were 24.3, 29.9, and 41.5mgl(-1), respectively. In addition, WBA/H(2)O and WBA/H(2)SO(4) could reduce colour and high chemical oxygen demand (COD) of real textile wastewater. According to the difficulty in the elution study, it was an environmentally safe disposal of this waste. Therefore, WBA, a waste from combustion of wood shavings, was suitable to be used as an effective adsorbent for azo reactive dye removal.     

Adsorption of carbon dioxide using impregnated activated carbon promoted by Zinc

The effect of impregnation of activated carbon with Cr₂O and Fe₂O₃ and promotion by Zn²⁺ on its adsorptive properties of carbon dioxide was studied using a volumetric adsorption apparatus at ambient temperature and low pressures. Slurry and solution impregnation methods were used to compare CO₂ capture capacity of the impregnated activated carbon promoted by Zinc. The obtained adsorption isotherms showed that amount of CO₂ adsorbed on the samples impregnated by Cr₂O was increased about 20% in compare to raw activated carbon. The results also showed that Fe₂O₃ was not an effective impregnating species for activated carbon modification. Moreover slurry impregnation method showed higher CO₂ adsorption capacity in comparison with solution impregnation method. Samples prepared by co-impregnation of two metal species showed more adsorption capacity than samples impregnated by just one metal species individually. Washing the impregnated samples by metal oxide resulted in 15% increase in CO₂ adsorption capacities of activated carbons which can be attributed to the metal oxides removal covering the adsorption surface. Decreasing impregnation temperature from 95 to 25 °C in solution method showed a significant increase in CO₂ adsorption capacity. Sips equation was found a suitable model fitting to the adsorption data in the range studied.     

Review of fluoride removal from drinking water

Fluoride in drinking water has a profound effect on teeth and bones. Up to a small level (1–1.5 mg/L) this strengthens the enamel. Concentrations in the range of 1.5–4 mg/L result in dental fluorosis whereas with prolonged exposure at still higher fluoride concentrations (4–10 mg/L) dental fluorosis progresses to skeletal fluorosis. High fluoride concentrations in groundwater, up to more than 30 mg/L, occur widely, in many parts of the world. This review article is aimed at providing precise information on efforts made by various researchers in the field of fluoride removal for drinking water. The fluoride removal has been broadly divided in two sections dealing with membrane and adsorption techniques. Under the membrane techniques reverse osmosis, nanofiltration, dialysis and electro-dialysis have been discussed. Adsorption, which is a conventional technique, deals with adsorbents such as: alumina/aluminium based materials, clays and soils, calcium based minerals, synthetic compounds and carbon based materials. Studies on fluoride removal from aqueous solutions using various reversed zeolites, modified zeolites and ion exchange resins based on cross-linked polystyrene are reviewed. During the last few years, layered double oxides have been of interest as adsorbents for fluoride removal. Such recent developments have been briefly discussed.     

Adsorption of pharmaceuticals to microporous activated carbon treated with potassium hydroxide, carbon dioxide, and steam

Adsorption of sulfapyridine, tetracycline, and tylosin to a commercial microporous activated carbon (AC) and its potassium hydroxide (KOH)-, CO-, and steam-treated counterparts (prepared by heating at 850°C) was studied to explore efficient adsorbents for the removal of selected pharmaceuticals from water. Phenol and nitrobenzene were included as additional adsorbates, and nonporous graphite was included as a model adsorbent. The activation treatments markedly increased the specific surface area and enlarged the pore sizes of the mesopores of AC (with the strongest effects shown on the KOH-treated AC). Adsorption of large-size tetracycline and tylosin was greatly enhanced, especially for the KOH-treated AC (more than one order of magnitude), probably due to the alleviated size-exclusion effect. However, the treatments had little effect on adsorption of low-size phenol and nitrobenzene due to the predominance of micropore-filling effect in adsorption and the nearly unaffected content of small micropores causative to such effect. These hypothesized mechanisms on pore-size dependent adsorption were further tested by comparing surface area-normalized adsorption data and adsorbent pore size distributions with and without the presence of adsorbed antibiotics. The findings indicate that efficient adsorption of bulky pharmaceuticals to AC can be achieved by enlarging the adsorbent pore size through suitable activation treatments.     

生物法处理含酚废水的研究

为了降低炼油厂污水处理场的酚负荷,对催化裂化汽提塔所排含酚废水的预处理进行了研究。进行了煤渣吸附实验,酚的生物降解动力学实验及酚在兼氧条件下的处理实验;采用４－氨基安替比林光度法测定酚浓度。实验结果表明采用煤渣填料－生物膜反应器,酚的去除率可达９０％,酚的生物降解符合一级反应动力学,酚类物质可在兼氧条件下降解     

不同物质对垃圾渗滤液中腐殖酸的吸附研究

垃圾渗滤液是一种有毒有害的高浓度有机废水,其中含大量腐殖酸。腐殖酸具有离子交换能力、吸附能力和脱除杂质能力,因此在很多方面有实用价值。活性碳、土壤、堆肥对废水中的有机物有一定的吸附能力。本文采用正交设计的方法,研究了活性碳、土壤、堆肥在不同温度,液／固,腐殖酸初始浓度的条件下对垃圾渗滤液中腐殖酸的吸附效果。实验结果表明：四种实验因素对吸附剂的吸附能力的影响程度为：吸附剂类型〉腐殖酸的初始浓度〉吸附反应温度〉液固比。在温度为25℃,液固比为50／0．5（mL/g）,腐殖酸初始浓度为41．99（mg／L）,吸附剂类型为活性碳时,腐殖酸吸附量最大,为40．86mg。同时分析了响应指标随因素的变化趋势。     

Utilization of powdered waste sludge (PWS) for removal of textile dyestuffs from wastewater by adsorption

Acid pre-treated powdered waste sludge (PWS) was used for removal of textile dyestuffs from aqueous medium by adsorption as an alternative to the use of powdered activated carbon (PAC). The rate and extent of dysetuff removals were determined for four different dyestuffs at different PWS concentrations varying between 1 and 6 gl(-1). Biosorbed dyestuff concentrations at equilibrium decreased with increasing PWS concentration for all dyestuffs tested. PWS was more effective for adsorption of Remazol red RR and Chrisofonia direct yellow 12 as compared to the other dyestuffs tested. More than 80% percent dyestuff removal was obtained for all dyestuffs at PWS concentrations above 4 gl(-1) after 6h of incubation. Similar to percent dyestuff removal, the rate of adsorption was maximum at a PWS concentration of 4 gl(-1). Kinetics of adsorption of dyestuffs was investigated by using the first- and second-order kinetic models and the kinetic constants were determined. Second-order kinetics was found to fit the experimental data better than the first-order model for all dyestuffs tested. Adsorption isotherms were established for all dyestuffs used and the isotherm constants were determined by using the experimental data. Langmuir and the generalized adsorption isotherms were found to be more suitable than the Freundlich isotherm for correlation of equilibrium adsorption data. Acid pre-treated PWS was proven to be an effective adsorbent for dyestuff removal as compared to the other adsorbents reported in literature studies.     

Quaternized agricultural by-products as anion exchange resins

The objectives of this study were the chemical modification of readily available, low-cost agricultural by-products to anion exchange resins and the selection of the best modified by-product for further use in anion removal. Resins were prepared through the quaternization of a series of 12 agricultural by-products with N-(3-chloro-2-hydroxypropyl) trimethylammonium chloride (CHMAC). Phosphate ion adsorption assays were conducted at pH 7 in order to compare adsorption properties among the by-products. Quaternized corn stover showed the highest phosphorus adsorption at 0.66 mmole/g. Since corn stover exhibited the best uptake of phosphate ion, it was compared to a commercially available, cellulose-based anion exchange resin. Additionally, adsorption capacities of quaternized corn stover for arsenate, chromate, and selenate were evaluated and adsorption efficiencies were determined in simulated wastewater samples. Our results indicate that modified corn stover demonstrates good adsorption uptake for arsenate and selenate and especially for chromate.     

A two stage batch adsorber design for methylene blue removal to minimize contact time

The adsorption of methylene blue onto bentonite in a batch adsorber has been studied. Three kinetic models, the intraparticle diffusion equation and the pseudo first and second order equations, were selected to follow the adsorption process. Kinetic parameters, rate constants, equilibrium adsorption capacities and related correlation coefficients for each kinetic model were calculated and discussed. It was shown that the adsorption of methylene blue onto bentonite could be described by the pseudo second order equation. Adsorption of methylene blue onto bentonite followed the Langmuir isotherm. A model has been developed for the design of a two stage batch adsorber based on pseudo second order adsorption kinetics. The model has been optimized with respect to operating time in order to minimize total contact time to achieve a specified amount of methylene blue removal using a fixed mass of adsorbent. The results of two stage batch adsorber design studies showed that the required times for specified amounts of methylene blue removal significantly decreased. This design is particularly suitable for low-cost adsorbents/adsorption systems when minimising contact time is a major operational and design criterion and a significant volume of effluent needs to be treated in the minimum amount of time.     

Loofa egyptiaca as a novel adsorbent for removal of direct blue dye from aqueous solution

In this paper, Loofa egyptiaca (LE), an agricultural plant cultivated in Egypt, was used to prepare low-cost activated carbon (LE_C1 and LE_C2) adsorbents. The adsorbents (LE, LE_C1 and LE_C2) were evaluated for their ability to remove direct blue 106 dye from aqueous solutions. Batch mode experiments were conducted using various parameters such as pH, contact time, dye concentration and adsorbent concentration. The surface chemistry of LE, LE_C1 and LE_C2 was analyzed by scanning electron microscopy (SEM). The experimental data were examined using Langmuir, Freundlich, Temkin and Harkins–Jura isotherms. The results showed that the adsorption of direct blue 106 was maximal at the lowest value of pH (pH = 2). Removal efficiency was increased with an increase in dye concentration and a decrease in amount of adsorbent. Maximum adsorption capacity was found to be 57.14, 63.3 and 73.53 mg/g for LE, LE_C1 and LE_C2 respectively. Kinetics were also investigated using pseudo-first-order, pseudo-second-order and intra-particle diffusion models. The experimental data fitted very well with the pseudo-first-order and pseudo-second-order kinetic models. The results indicate that LE, LE_C1 and LE_C2 could be employed as adsorbents for the removal of direct blue dye from aqueous solutions.     

The thief process for mercury removal from flue gas

The Thief Process is a cost-effective variation to activated carbon injection (ACI) for removal of mercury from flue gas. In this scheme, partially combusted coal from the furnace of a pulverized coal power generation plant is extracted by a lance and then re-injected into the ductwork downstream of the air preheater. Recent results on a 500-lb/h pilot-scale combustion facility show similar removals of mercury for both the Thief Process and ACI. The tests conducted to date at laboratory, bench, and pilot-scales demonstrate that the Thief sorbents exhibit capacities for mercury from flue gas streams that are comparable to those exhibited by commercially available activated carbons. A patent for the process was issued in February 2003. The Thief sorbents are cheaper than commercially-available activated carbons; exhibit excellent capacities for mercury; and the overall process holds great potential for reducing the cost of mercury removal from flue gas. The Thief Process was licensed to Mobotec USA, Inc. in May of 2005.