Application of 'waste' metal hydroxide sludge for adsorption of azo reactive dyes

The capacity and mechanism of metal hydroxide sludge in removing azo reactive dyes from aqueous solution was investigated with different parameters, such as charge amount of dyes, system pH, adsorbent particle size, and adsorbent dosage. The three anionic dyes used were CI Reactive Red 2, CI Reactive Red 120, and CI Reactive Red 141, increasing in number of sulfonic groups, respectively. Only 0.2% (w/v) of powdered sludge (<75microm) achieved color removal from 30 mg l(-1) reactive dye solutions within 5 min without pH adjustment. The larger the charge amount of the dyes, the greater the adsorption (>90%) on the metal hydroxide sludge. The system pH played a significant role in the adsorption on metal hydroxides and formation of dye-metal complexes. The optimum system pH for dye adsorption was 8-9 which was close to the pH(zpc) of the sludge while the precipitation of dye-metal complexes occurred at system pH 2. The maximum adsorption capacity (Q degrees ) of the sludge for the reactive dyes was 48-62 mg dye g(-1) adsorbent. The Langmuir and Freundlich models showed that the higher charged dyes had a higher affinity of adsorption. The smaller particle size and the greater amount of adsorbent showed the faster process, due to an increase in surface area of adsorbent. Desorption studies elucidated that metal hydroxide sludge had a tendency for ion exchange adsorption of sulfonated azo reactive dyes. Leaching data showed that the treated water was nontoxic at a system pH above 5 or a solution pH above 2.     

Characteristics of adsorbents made from biological, chemical and hybrid sludges and their effect on organics removal in wastewater treatment

Meso-macropore adsorbents were prepared from biological sludge, chemical sludge and hybrid sludge of biological and chemical sludges, by chemically activating with 18.0 M H₂SO₄ in the mass ratio of 1:3, and then pyrolyzing at 550 °C for 1 h in anoxic atmosphere. The physical and chemical characteristics of the sludge-based adsorbents were examined in terms of surface physical morphology, specific surface area and pore size distribution, aluminum and iron contents, surface functional groups and crystal structure. Furthermore, the adsorption effect of these adsorbents on the organic substances in wastewater was also investigated. The results indicated that the adsorption capacities of the sludge-based adsorbents for UV₂₅₄ were lower than that of commercial activated carbon (AC), whereas the adsorption capacities of the adsorbents prepared from hybrid sludge (HA) and chemical sludge (CA) for soluble COD_Cr (SCOD_Cr) were comparable or even higher than that of the commercial AC. The reasons might be that the HA and CA possessed well-developed mesopore and macropore structure, as well as abundant acidic surface functional groups. However, the lowest adsorption efficiency was observed for the biological sludge-based adsorbent, which might be due to the lowest metal content and overabundance of surface acidic functional groups in this adsorbent.     

Sewage sludge-based adsorbents: A review of their production, properties and use in water treatment applications

The imposition of more stringent legislation governing the disposal and utilisation of sewage sludge, coupled with the growth in its generation and the loss of traditionally accepted disposal routes, has prompted a drive for alternative uses for sewage sludge. One option that exhibits especial promise, due to its potential to valorise the sludge, is the conversion of the sludge into adsorbents. This paper seeks to review the published research in this field: it covers the means of production, the characteristics and the potential applications of sewage sludge-based adsorbents (SBAs). The literature has indicated that chemical activation utilising alkali metal hydroxides is the most effective technique for producing high surface area SBAs. In addition, acid washing is highly effective at raising the BET surface area of SBAs, especially when coupled with physical activation. Due to their relatively low microporosity, the phenol uptake of SBAs produced by physical activation is low, but through a combination of their favourable surface chemistry and relatively high mesoporosity, the best of these adsorbents can attain high uptakes of organic dyes. The SBAs produced by carbonisation, through their high cation exchange capacity, generally exhibit a high metal cation capacity. For further research, the following investigations are recommended: the utilisation of alternative chemical activation reagents; the optimisation of the most effective chemical activation techniques; the combined utilisation of different activation and surface chemistry modification techniques to produce application-specific adsorbents.     

Crab shell for the removal of heavy metals from aqueous solution

The ability of crab shell to remove heavy metals from aqueous solution was evaluated by comparing with that of several sorbents (cation exchange resin, zeolite, granular activated carbon, powdered activated carbon). All experiments were conducted using several heavy metal ion solutions (Pb, Cd, Cu, Cr). The orders of heavy metal removal capacity and initial heavy metal removal rate were found as crab shell > cation exchange resin > zeolite > powdered activated carbon>granular activated carbon. Therefore, crab shell is satisfactory as a good biosorbent for the heavy metal removal. The study indicates that the removal of these heavy metals is selective, with Pb and Cr being removed in preference to Cd and Cu. The sorption equilibrium of heavy metal ions on sorbents was modeled on the applications of Langmuir and Freundlich.     

Kinetic and equilibrium studies of fluoride adsorption by a carbonaceous material from pyrolysis of waste sludge

The efficiency of the adsorption for fluoride by sludge from the treatment of starch industry wastewater was investigated. Batch experiments were conducted in order to determine the parameters that affect the adsorption process. The activation for waste sludge and specific surface area and porosity effects in enhancing the pyrolysis conditions were determined. The adsorption parameters of initial fluoride concentration, pH and adsorbent dosage were investigated with carbonaceous material. As a result of pyrolysis of samples treated with ZnCl₂ 1196 m²/g, the specific surface area was reached. Correlation coefficient of 0.99 and 12.75 mg/g adsorption capacity and adsorption isotherm model were revealed as convenient. Experimental results show that the adsorption of fluoride waste sludge will be effective in many ways in which the adsorbent is applied.     

Removal of Cu(II) and Cd(II) from aqueous solution by seafood processing waste sludge

Dried waste slurry generated in seafood processing factories has been shown to be an effective adsorbent for the removal of heavy metals from dilute solutions. Characterization of the sludge surface with scanning electron microscope and X-ray microanalyzer were carried out to evaluate the components on the sludge surface that are related to the adsorption of metal ions. Aluminum and calcium, as well as organic carbon are distributed on the surface of sludge. Alkalimetric titration was used to characterize the surface acidity of the sludge sample. The surface acidity constants, pKa1s and pKa2s, were 5.80 and 9.55, respectively. Batch as well as dynamic adsorption studies were conducted with 10(-5) to 5 x 10(-3) M Cu(II) and Cd(II). A surface complexation model with the diffuse layer model successfully predicted Cu(II) and Cd(II) removals in single metal solutions. Predictions of sorption in binary-adsorbate systems based on single-adsorbate data fits represented competitive sorption data reasonably well over a wide range of conditions. The breakthrough capacity found from column studies was different for each metal ion and the data reflect the order of metal affinity for the adsorbent material very well.     

Pesticides removal from waste water by activated carbon prepared from waste rubber tire

Waste rubber tire has been used for the removal of pesticides from waste water by adsorption phenomenon. By applying successive chemical and thermal treatment, a basically cabonaceous adsorbent is prepared which has not only a higher mesopore, macropore content but also has a favorable surface chemistry. Presence of oxygen functional groups as evidenced by FTIR spectra along with excellent porous and surface properties were the driving force for good adsorption efficiency observed for the studied pesticides: methoxychlor, methyl parathion and atrazine. Batch adsorption studies revealed maximum adsorption of 112.0 mg g⁻¹, 104.9 mg g⁻¹ and 88.9 mg g⁻¹ for methoxychlor, atrazine and methyl parathion respectively occurring at a contact time of 60 min at pH 2 from an initial pesticide concentration of 12 mg/L. These promising results were confirmed by column experiments; thereby establishing the practicality of the developed system. Effect of various operating parameters along with equilibrium, kinetic and thermodynamic studies reveal the efficacy of the adsorbent with a higher adsorption capacity than most other adsorbents. The adsorption equilibrium data obey Langmuir model and the kinetic data were well described by the pseudo-first-order model. Applicability of Bangham’s equation indicates that diffusion of pesticide molecules into pores of the adsorbent mainly controls the adsorption process. Spontaneous, exothermic and random characteristics of the process are confirmed by thermodynamic studies. The developed sorbent is inexpensive in comparison to commercial carbon and has a far better efficiency for pesticide removal than most other adsorbents reported in literature.     

Stabilization of heavy metals in sludge ceramsite

This paper attempts to investigate the stabilization behaviours of heavy metals in ceramsite made from wastewater treatment sludge (WWTS) and drinking-water treatment sludge (DWTS). Leaching tests were conducted to find out the effects of sintering temperature, (Fe₂O₃ + CaO + MgO)/(SiO₂ + Al₂O₃) (defined as F/SA ratios), pH, and oxidative condition. Results show that sintering exhibits good binding capacity for Cd, Cr, Cu, and Pb in ceramsite and leaching contents of heavy metals will not change above 1000 °C. The main crystalline phases in ceramsite sintered at 1000 °C are kyanite, quartz, Na-Ca feldspars, sillimanite, and enstatite. The main compounds of heavy metals are crocoite, chrome oxide, cadmium silicate, and copper oxide. Leaching contents of Cd, Cu, and Pb increase as the F/SA ratios increase. Heavy metals in ceramsite with variation of F/SA ratios are also in same steady forms, which prove that stronger chemical bonds are formed between these heavy metals and the components. Leaching contents of heavy metals decrease as pH increases and increase as H₂O₂ concentration increases. The results indicate that when subjected to rigorous leaching conditions, the crystalline structures still exhibit good chemical binding capacity for heavy metals. In conclusion, it is environmentally safe to use ceramsite in civil and construction fields.     

Effects of chromium on activated sludge and on the performance of wastewater treatment plants: A review

Chromium is a heavy metal of commercial importance, thus significant amounts are released in wastewaters. Chromium in wastewaters and in the aquatic environment is primarily encountered in oxidation stages +3 (Cr^(III)) and +6 (Cr^(VI)). Recent publications suggest that Cr^(VI) compounds are more toxic than Cr^(III) ones, while Cr^(III) has been identified as trace element, at least for complex organisms. With respect to chromium species mobility, Cr^(VI) can cross cellular membranes, which then may be oxidized to Cr^(III) and react with intracellular biomolecules. Clear conclusions cannot be derived about the critical chromium concentrations that affect activated sludge growth, as the latter is a function of a number of factors. Broadly, may be supported that activated sludge growth is stimulated at Cr^(III) concentrations up to 15 mg L⁻¹, above which is inhibited, with lethal doses lying above 160 mg Cr^(III) L⁻¹. On the other hand, literature data on Cr^(VI) effects on activated sludge are even more controversial. A number of reports support that Cr^(VI) is toxic to activated sludge at concentrations above 5 mg L⁻¹, while others report growth stimulation at concentrations up to 25 mg L⁻¹. However, all reports agree that Cr^(VI) is definitely an activated sludge growth inhibitor at higher concentrations, while 80 mg Cr^(VI) L⁻¹ have been identified as lethal dose. A number of factors have been identified to influence chromium toxicity on activated sludge, such as, pH, biomass concentration, presence of organic substances or other heavy metals, acclimation process, exposure time, etc. Naturally, the presence of chromium species in wastewaters may affect the performance of wastewater treatment plants often causing malfunctions, particularly for industrial wastewaters containing relatively high chromium concentrations. The present work reviews in a critical way the published literature on chromium effects on activated sludge, and on the operation of wastewater treatment plants.     

Comparisons of low-cost adsorbents for treating wastewaters laden with heavy metals

In this article, the removal performance and cost-effectiveness of various low-cost adsorbents derived from agricultural waste, industrial by-product or natural material are evaluated and compared to those of activated carbon for the removal of heavy metals (Cd(II), Cr(III), Cr(VI), Cu(II), Ni(II) and Zn(II)) from metals-contaminated wastewater. To highlight their technical applicability, selected information on pH, dose required, initial metal concentration, adsorption capacity and the price of the adsorbents is presented. It is evident from the survey of 102 published studies (1984-2005) that low cost adsorbents derived from agricultural waste have demonstrated outstanding capabilities for the removal of heavy metal (Cr(VI): 170 mg/g of hazelnut shell activated carbon, Ni(II): 158 mg/g of orange peel, Cu(II): 154.9 mg/g of soybean hull treated with NaOH and citric acid, Cd(II): 52.08 mg/g of jackfruit), compared to activated carbon (Cd(II): 146 mg/g, Cr(VI): 145 mg/g, Cr(III): 30 mg/g, Zn(II): 20 mg/g). Therefore, low-cost adsorbents can be viable alternatives to activated carbon for the treatment of metals-contaminated wastewater. It is important to note that the adsorption capacities presented in this paper vary, depending on the characteristics of the individual adsorbent, the extent of surface modification and the initial concentration of the adsorbate. In general, technical applicability and cost-effectiveness are the key factors that play major roles in the selection of the most suitable adsorbent to treat inorganic effluent.     

Comparison of dried sludge and sludge ash for phosphorus recovery with acidic and alkaline leaching

Nowadays, the recovery of phosphorus has been in the spotlight due to its importance for food security and depleting sources. In this study, phosphorus recovery from dried sewage sludge and sludge ash by acid and alkaline leaching was evaluated. Optimum extraction time and temperature were determined as two hours and ambient temperature. Results showed the superiority of strong acidic conditions for leaching; 75 ml/g with 0.4N HCl and 25 ml/g with 0.6N HCl were determined as optimum conditions to achieve efficient phosphorus dissolution from sludge ash (94.6%) and dried sludge (91.1%), respectively, with the lower heavy metal concentrations. Lower L/S ratio put forward the dried sludge as a more advantageous resource for phosphorus extraction. Besides, by alkaline leaching of sludge ash and dried sludge, 60.3 and 70.3% phosphorus dissolutions were achieved with 75 ml/g and 1N NaOH; and the leachate was a suitable product for phosphorus precipitation due to its high pH.     

微波法制备污泥吸附剂的性能优化研究

通过向污泥中添加吸收微波能的物质实现了微波热解法制备污泥吸附剂,并考察了不同制备条件对污泥吸附剂性能的影响.结果表明,当污泥用量为35 g时,微波法制备污泥吸附剂的最佳务件:微波功率为1.2 kW、辐照时间为10 min、微波能吸收物质的用量为10 g,制得的污泥吸附剂的碘吸附值达585.95 mg/g.采用扫描电镜分析污泥吸附剂的表观结构可知,适宜的微波辐射通过有效热解污泥中的有机质可形成以炭骨架为主体的污泥吸附剂,该吸附剂可有效吸附酸、碱染料,但吸附量与商业活性炭仍存在一定差距.     

Removal of estrone and 17beta-estradiol from water by adsorption

Endocrine disrupting chemicals (EDCs) are the focus of current environment concern, as they can cause adverse health effects in an intact organism, or its progeny, subsequent to endocrine function. The paper reports on the removal of estrone (E1) and 17beta-estradiol (E2) from water through the use of various adsorbents including granular activated carbon (GAC), chitin, chitosan, ion exchange resin and a carbonaceous adsorbent prepared from industrial waste. The results show that the kinetics of adsorption were adsorbent and compound-dependent, with equilibration being reached within 2 h for a waste-derived carbonaceous adsorbent to 71 h for an ion-exchange resin for E1, and within 7 h for the waste-derived carbonaceous adsorbent to 125 h for GAC for E2. Of all the adsorbents tested, the carbonaceous adsorbent showed the highest adsorption capacity, with a maximum adsorption constant of 87500 ml/g for E1 and 116000 ml/g for E2. The GAC also had a very high adsorption capacity for the two compounds, with a maximum adsorption constant of 9290 ml/g for E1 and 12200 ml/g for E2. The effects of some fundamental environmental parameters including adsorbent concentration, pH, salinity and the presence of humic acid and surfactant on adsorption were studied. The results show that adsorption capacity of activated carbon was decreased with an increase in adsorbent concentration and by the presence of surfactant and humic acid. The results have demonstrated excellent performance of a waste derived adsorbent in removing E1 and E2 from water, and indicated the potential of converting certain solid waste into useful adsorbents for pollution-control purposes.     

Magnetic powder MnO-Fe2O3 composite--a novel material for the removal of azo-dye from water

Fine powder adsorbents or catalysts often show better adsorptive or catalytic properties, but they encounter the difficulties of separation and recovery in application. In this study, four inexpensive magnetic powder MnO-Fe2O3 composites used as adsorbent-catalyst materials were prepared and characterized. These materials could be recovered efficiently by a magnetic separation method. Their adsorptive properties for the removal of an azo-dye, acid red B (ARB), from water and the regeneration of adsorbents containing ARB by catalytic combustion was studied. These powder adsorbents showed excellent adsorption towards ARB under acidic conditions. A very fast adsorption rate was observed and could be well described by a pseudo-second-order kinetics model. The adsorption capacity increased with increasing Fe content and surface area of the adsorbent, and the highest adsorption capacity of 105.3 mg/g was obtained at pH 3.5. The adsorption was not affected by the presence of Cl-, but was significantly affected by SO4(2-). The adsorbent containing ARB can be regenerated by catalytic combustion of adsorbed ARB at 400 degrees C in air. Laboratory experiments demonstrated that this material is reusable.     

Leaching techniques to remove metals and potentially hazardous nutrients from trout farm sludge

A fish farm sludge high in P (2-6% w/w as dry matter), Fe (5-7%), C (40-50%) and N (0.8-4%) was subjected to a series of acid leaching treatments using HCl, organic acids, and biologically mediated acid production. Additions of biodegradable organic acid solubilized heavy metals better than HCl, while additions of 1.5% w/v glucose followed by 7 day incubation stabilized the sludge releasing 92% P, 100% Fe. The use of homo-lactic Lactobacillus plantarum starter cultures were more effective than hetero-lactic Lactobacillus buchneri, solubilizing 81.9% P, 92.2% Fe, 93.0% Zn and 96.4% Ca in the sludge. The anaerobic sludge-glucose fermentation using L. plantarum produced a leached sludge that has low heavy metal and nutrient content while affording the recovery of nutrients. The potential of these methods for practical application are briefly discussed.     

Development and tests of lightweight aggregate using sewage sludge for nonstructural concrete

The purpose of this study is to efficiently treat sewage sludge discharged from sewage treatment plants and to evaluate the feasibility of lightweight aggregate made from a large quantity of sewage sludge. Sintered lightweight aggregate from sewage sludge is experimentally manufactured with various mass ratios of clay to sewage sludge by a rotary kiln, and is tested for density, water absorption, abrasion loss, crushing value, impact value and heavy metal leaching. Their physical properties are compared to those of a commercial sintered lightweight aggregate for nonstructural concrete. As a result, an experimentally manufactured lightweight aggregate with a recommendable sewage sludge content is similar or superior in physical properties to the commercial sintered lightweight aggregate. In particular, the water absorption of the lightweight aggregate recommended is about half or less than that of the commercial sintered lightweight aggregate. Because no toxic heavy metals are detected from the tested aggregate, it could be used as an environment-conscious artificial lightweight aggregate.     

The contribution of exopolysaccharides induced struvites accumulation to ammonium adsorption in aerobic granular sludge

Aerobic granular sludge from a lab-scale reactor with simultaneous nitrification/denitrification and enhanced biological phosphorus removal processes exhibited significant amount of ammonium adsorption (1.5 mg NH₄⁺-N/g TSS at an ammonium concentration of 30 mg N/L). Potassium release accompanied ammonium adsorption, indicating an ion exchange process. The existence of potassium magnesium phosphate (K-struvite) as one of potassium sources in the granular sludge was studied by X-ray diffraction analysis (XRD). Artificially prepared K-struvite was indeed shown to adsorb ammonium. Alginate-like exopolysaccharides were isolated and their inducement for struvite formation was investigated as well. Potassium magnesium phosphate proved to be a major factor for ammonium adsorption on the granular sludge. Struvites (potassium/ammonium magnesium phosphate) accumulate in aerobic granular sludge due to inducing of precipitation by alginate-like exopolysaccharides.     

Sorption of perfluorooctane sulfonate and perfluorooctanoate on activated carbons and resin: Kinetic and isotherm study

Perfluorooctane sulfonate (PFOS) and perfluorooctanoate (PFOA) have increasingly attracted global concerns in recent years due to their global distribution, persistence, strong bioaccumulation and potential toxicity. The feasibility of using powder activated carbon (PAC), granular activated carbon (GAC) and anion-exchange resin (AI400) to remove PFOS and PFOA from water was investigated with regard to their sorption kinetics and isotherms. Sorption kinetic results show that the adsorbent size influenced greatly the sorption velocity, and both the GAC and AI400 required over 168 h to achieve the equilibrium, much longer than 4 h for the PAC. Two kinetic models were adopted to describe the experimental data, and the pseudo-second-order model well described the sorption of PFOS and PFOA on the three adsorbents. The sorption isotherms show that the GAC had the lowest sorption capacity both for PFOS and PFOA among the three adsorbents, while the PAC and AI400 possessed the highest sorption capacity of 1.04 mmol g⁻¹ for PFOS and 2.92 mmol g⁻¹ for PFOA according to the Langmuir fitting. Based on the sorption behaviors and the characteristics of the adsorbents and adsorbates, ion exchange and electrostatic interaction as well as hydrophobic interaction were deduced to be involved in the sorption, and some hemi-micelles and micelles possibly formed in the intraparticle pores.     

Development of granular sludge for textile wastewater treatment

Microbial granular sludge that is capable to treat textile wastewater in a single reactor under intermittent anaerobic and aerobic conditions was developed in this study. The granules were cultivated using mixed sewage and textile mill sludge in combination with anaerobic granules collected from an anaerobic sludge blanket reactor as seed. The granules were developed in a single sequential batch reactor (SBR) system under alternating anaerobic and aerobic condition fed with synthetic textile wastewater. The characteristics of the microbial granular sludge were monitored throughout the study period. During this period, the average size of the granules increased from 0.02 ± 0.01 mm to 2.3 ± 1.0 mm and the average settling velocity increased from 9.9 ± 0.7 m h⁻¹ to 80 ± 8 m h⁻¹. This resulted in an increased biomass concentration (from 2.9 ± 0.8 g L⁻¹ to 7.3 ± 0.9 g L⁻¹) and mean cell residence time (from 1.4 days to 8.3 days). The strength of the granules, expressed as the integrity coefficient also improved. The sequential batch reactor system demonstrated good removal of COD and ammonia of 94% and 95%, respectively, at the end of the study. However, only 62% of color removal was observed. The findings of this study show that granular sludge could be developed in a single reactor with an intermittent anaerobic-aerobic reaction phase and is capable in treating the textile wastewater.     

Phosphorus recovery from digested sewage sludge as MAP by the help of metal ion separation

This study was designed to solve metal ion influence problem on phosphorus recovery from digested sewage sludge as MAP. The experimental steps were proceeded to maximize MAP production and its quality. Used experimental steps were:

(a)

Acidic dissolution of phosphorus,

(b)

Removal of metal ions from phosphorus rich water phase,

(c)

Recovery of phosphorus as MAP,

(d)

Separation of MAP.

All digested sewage sludge samples were taken from Stuttgart University sewage treatment plant for research and education (LFKW). Four different forms of LFKW digested sewage sludge were used as feeding sample. These were: original digested sludge, diluted digested sludge, centrifuged digested sludge and incinerated digested sludge.A Donnan membrane unit having a Nafion 117 (DuPont) cation exchange membrane was used to remove metal ions from the samples used. Highest metal ion removal efficiencies, which were 98%, 97%, and 80% for Al, Ca and Fe ions, respectively, were obtained from incinerated digested sludge run.Incinerated digested sludge run was used as preliminary step for MAP production and high quality MAP was produced. Produced MAP fulfils all requirements related with Düngemittelverordnung 2003 and it could be used as a fertilizer in Germany.