Siloxanes removal from biogas by high surface area adsorbents

Biogas utilized for energy production needs to be free from organic silicon compounds, as their burning has damaging effects on turbines and engines; organic silicon compounds in the form of siloxanes can be found in biogas produced from urban wastes, due to their massive industrial use in synthetic product, such as cosmetics, detergents and paints.Siloxanes removal from biogas can be carried out by various methods (Mona, 2009, Ajhar et al., 2010, Schweigkofler and Niessner, 2001); aim of the present work is to find a single practical and economic way to drastically and simultaneously reduce both the hydrogen sulphide and the siloxanes concentration to less than 1 ppm. Some commercial activated carbons previously selected (Monteleone et al., 2011) as being effective in hydrogen sulfide up taking have been tested in an adsorption measurement apparatus, by flowing the most volatile siloxane (hexamethyldisiloxane or L2) in a nitrogen stream, typically 100–200 ppm L2 over N₂, through an activated carbon powder bed; the adsorption process was analyzed by varying some experimental parameters (concentration, grain size, bed height). The best activated carbon shows an adsorption capacity of 0.1 g L2 per gram of carbon. The next thermogravimetric analysis (TGA) confirms the capacity data obtained experimentally by the breakthrough curve tests.The capacity results depend on L2 concentration. A regenerative carbon process is then carried out by heating the carbon bed up to 200 °C and flushing out the adsorbed L2 samples in a nitrogen stream in a three step heating procedure up to 200 °C. The adsorption capacity is observed to degrade after cycling the samples through several adsorption–desorption cycles.     

Differences in volatile methyl siloxane (VMS) profiles in biogas from landfills and anaerobic digesters and energetics of VMS transformations

The objectives of this study were to compare the types and levels of volatile methyl siloxanes (VMS) present in biogas generated in the anaerobic digesters and landfills, evaluate the energetics of siloxane transformations under anaerobic conditions, compare the conditions in anaerobic digesters and municipal solid waste (MSW) landfills which result in differences in siloxane compositions. Biogas samples were collected at the South District Wastewater Treatment Plant and South Dade Landfill in Miami, Florida. In the digester gas, D4 and D5 comprised the bulk of total siloxanes (62% and 27%, respectively) whereas in the landfill gas, the bulk of siloxanes were trimethylsilanol (TMSOH) (58%) followed by D4 (17%). Presence of high levels of TMSOH in the landfill gas indicates that methane utilization may be a possible reaction mechanism for TMSOH formation. The free energy change for transformation of D5 and D4 to TMSOH either by hydrogen or methane utilization are thermodynamically favorable. Either hydrogen or methane should be present at relatively high concentrations for TMSOH formation which explains the high levels present in the landfill gas. The high bond energy and bond distance of the Si–O bond, in view of the atomic sizes of Si and O atoms, indicate that Si atoms can provide a barrier, making it difficult to break the Si–O bonds especially for molecules with specific geometric configurations such as D4 and D5 where oxygen atoms are positioned inside the frame formed by the large Si atoms which are surrounded by the methyl groups.     

Development of on-line measurement techniques for siloxanes and other trace compounds in biogas

This paper focuses on the development of an on-line measurement method for siloxanes and other biogas trace compounds impeding the energy utilisation of biogas, as well as the main gas components, methane and carbon dioxide. The method is based on gas chromatography and FT-IR-analysis. The level of siloxane, hydrogen sulphide and halogens in biogas generated in a number of landfills and digesters in Finland is also presented and factors affecting the concentrations discussed. Generally, the level of biogas trace compounds hampering electricity production was lower than those measured at comparable sites in Central Europe and the US. Moreover, the paper discusses the significance of on-line monitoring of siloxane in connection to biogas-to-electricity applications and points out with activated carbon as an example the benefits of on-line siloxane measurement in the control of siloxane removal technology.     

Removal of Cr6 + and Ni2+ from aqueous solution using bagasse and fly ash

Raw bagasse and fly ash, the waste generated in sugar mills and boilers respectively have been used as low-cost potential adsorbents. Raw bagasse was pretreated with 0.1N NaOH followed by 0.1N CH3COOH before its application. These low-cost adsorbents were used for the removal of chromium and nickel from an aqueous solution. The kinetics of adsorption and extent of adsorption at equilibrium are dependent on the physical and chemical characteristics of the adsorbent, adsorbate and experimental system. The effect of hydrogen ion concentration, contact time, sorbent dose, initial concentrations of adsorbate and adsorbent and particle size on the uptake of chromium and nickel were studied in batch experiments. The Sorption data has been correlated with Langmuir, Freundlich and Bhattacharya and Venkobachar adsorption models. The efficiencies of adsorbent materials for the removal of Cr(VI) and Ni(II) were found to be between 56.2 and 96.2% and 83.6 and 100%, respectively. These results were obtained at the optimized conditions of pH, contact time, sorbent dose, sorbate concentration of 100 mg/l and with the variation of adsorbent particles size between 0.075 and 4.75 mm. The order of selectivity is powdered activated carbon > bagasse > fly ash for Cr(VI) removal and powdered activated carbon > fly ash > bagasse for Ni(II) removal.     

Experimental study on flue gas purifying of MSW incineration using in-pipe jet adsorption techniques

This paper presents the experimental research process and results about flue gas purifying of municipal solid wastes (MSW) incineration using in-pipe jet adsorption techniques. MSW incineration was carried out in a fluidized bed test rig, and the flue gas purifying was carried out in an in-pipe jet adsorption test rig. The experimental results are as follows: when the feedstock of activated carbon is 1.6g/Nm(3), the desulfurization efficiency is 83%, the denitrification efficiency is 41%, and the dechlorination efficiency is 27%. The order of purifying effect of the three kinds of adsorbents on acidic gases from MSW incineration is activated carbon>activated bauxite>kaolin. Comparison of adsorption capabilities of the three kinds of adsorbents to heavy metals shows that activated carbon is the best additive to remove Cd, Pb and Cu, kaolin is inferior, and activated bauxite is the worst one. However, activated bauxite is the best additive to remove Hg, and it can remove Cd effectively. PAHs in fly ash are dominated by three-, four-, and five-ringed PAHs, and PAHs in the flue gas mainly include three- and four-ringed PAHs. When the injected quantity of additive is constant, the order of cleaning effect on PAHs is kaolin>activated carbon>activated bauxite. These three kinds of adsorbents have different purifying effects on acidic gases, heavy metals and PAHs in the flue gas from MSW incineration. In general, activated carbon has a better adsorption capability.     

Activated carbon from Ceiba pentandra hulls, an agricultural waste, as an adsorbent in the removal of lead and zinc from aqueous solutions

The ability of low-cost activated carbon prepared from Ceiba pentandra hulls, an agricultural waste material, for the removal of lead and zinc from aqueous solutions has been investigated. In the batch tests experimental parameters were studied, including solution pH, contact time, adsorbent dose and initial metal ions concentration. The adsorbent exhibited good sorption potential at pH 6.0. Maximum removal of lead (99.5%) and of zinc (99.1%) with 10 g/l of sorbent was observed at 50 mg/L sorbate concentration. Removals of about 60-70% occurred in 10 min, and equilibrium was attained at around 50 min for both metals. The functional groups (CO, SO,-OH) present on the carbon surface were responsible for the adsorption of metal ions. The adsorption parameters were analysed using both the Freundlich and Langmuir models. The data are better fitted by the Freundlich isotherm as compared to Langmuir model, and the adsorption capacities for lead and zinc were 25.5 and 24.1 mg/g, respectively. Kinetics of adsorption obeyed a second order rate equation and the rate constant was found to be 2.71 x 10(-2) and 2.08 x 10(-2) g/mg/min for lead and zinc, respectively. The desorption studies were carried out using dilute HCl, and the effect of HCl concentration on desorption was studied. Maximum desorptions of 85% for lead and 78% for zinc were attained with 0.15 M HCl.     

生物炭对铅离子的吸附性能

以废弃松木屑为原料,采用控制热分解法制备了生物炭。运用BET和FTIR等技术对生物炭进行了表征,考察了生物炭对铅离子的吸附效果,并探讨了吸附机理。表征结果显示,700℃氨气处理的生物炭,其比表面积和总孔体积显著增大。实验结果表明:生物炭对铅离子的吸附效果优于普通活性炭,且以700℃氨气处理的生物炭为最佳;随溶液pH的升高生物炭对铅离子的去除率增大,当pH为4~6时去除效果较好;在溶液pH为6、初始铅离子质量浓度为50 mg/L、吸附剂加入量为1 g/L、吸附时间为6 h的条件下,700℃氨气处理的生物炭对铅离子的去除率达99%以上;700℃氨气处理的生物炭的Langmuir吸附常数和Freundlich吸附常数远大于普通活性炭和其他工艺的生物炭;铅离子在生物炭上的吸附过程符合拟二级动力学方程。     

中孔活性炭对水溶液中Cr3+的吸附

采用模板法和氢氧化钾化学活化法制备出不同中孔率的中孔活性炭并用于水中Cr3+的静态吸附,探讨了中孔活性炭吸附Cr3+的影响因素.实验结果表明,当溶液pH为6.0、吸附温度为50℃、吸附时间为120min、活性炭加入量为2.0g/L以及活性炭中孔率为80.0％～90.0％时.中孔活性炭对溶液中Cr3+的去除率达到98.5％.分别采用Langmuir和Freundlich方程拟合活性炭对Cr3+吸附的等温线,发现Langmuir等温吸附模型对活性炭吸附Cr3+拟合程度更好.活性炭中孔率的增大有利于提高Cr3+的平衡吸附量,但同时还受到活性炭表面酸总量的影响.吸附Cr3+前、后活性炭的FTIR谱图表明,Cr3+与活性炭表面含氧官能团发生了离子交换反应.     

粉煤灰的改性及对刚果红的吸附

分别采用沸水浸泡、酸浸、碱浸和加热的方法对粉煤灰进行改性处理，利用FTIR仪和XRD仪对改性粉煤灰的成分和官能团进行了分析，并利用改性粉煤灰对模拟刚果红废水进行脱色。实验结果表明：碱改性粉煤灰中含有大量官能团，以及NaPl型沸石类物质，能够明显提高粉煤灰对刚果红的吸附性能；与活性炭相比，碱改性粉煤灰具有更高的性价比；在初始刚果红质量浓度为20mg/L、碱改性粉煤灰加入量为50g/L的条件下，废水的脱色率可达87.52%；碱改性粉煤灰对刚果红的吸附过程遵循二级反应动力学，较好地符合Langmuir等温式和Freundlich等温式。     

Adsorption of malachite green on groundnut shell waste based powdered activated carbon

In the present technologically fast changing situation related to waste management practices, it is desirable that disposal of plant waste should be done in a scientific manner by keeping in view economic and pollution considerations. This is only possible when the plant waste has the potential to be used as raw material for some useful product. In the present study, groundnut shell, an agricultural waste, was used for the preparation of an adsorbent by chemical activation using ZnCl2 under optimized conditions and its comparative characterisation was conducted with commercially available powdered activated carbon (CPAC) for its physical, chemical and adsorption properties. The groundnut shell based powdered activated carbon (GSPAC) has a higher surface area, iodine and methylene blue number compared to CPAC. Both of the carbons were used for the removal of malachite green dye from aqueous solution and the effect of various operating variables, viz. adsorbent dose (0.1-1 g l(-1)), contact time (5-120 min) and adsorbate concentrations (100-200 mg l(-1)) on the removal of dye, has been studied. The experimental results indicate that at a dose of 0.5 g l(-1) and initial concentration of 100 mg l(-1), GSPAC showed 94.5% removal of the dye in 30 min equilibrium time, while CPAC removed 96% of the dye in 15 min. The experimental isotherm data were analyzed using the linearized forms of Freundlich, Langmuir and BET equations to determine maximum adsorptive capacities. The equilibrium data fit well to the Freundlich isotherm, although the BET isotherm also showed higher correlation for both of the carbons. The results of comparative adsorption capacity of both carbons indicate that groundnut shell can be used as a low-cost alternative to commercial powdered activated carbon in aqueous solution for dye removal.     

A comparative adsorption/biosorption study of mono-chlorinated phenols onto various sorbents

The potential use of dried activated sludge and fly ash as a substitute for granular activated carbon for removing mono-chlorinated phenols (o-chlorophenol and p-chlorophenol) was examined. The pollutant binding capacity of the adsorbent/biosorbent was shown to be a function of substituted group, initial pH and initial mono-chlorinated phenol concentration. The working sorption pH value was determined as 1.0 and the equilibrium uptake increased with increasing initial mono-chlorinated phenol concentration up to 500 mg dm(-3) for all the mono-chlorinated phenol-sorbent systems. The suitability of the Freundlich, Langmuir and Redlich-Peterson adsorption models to the equilibrium data were investigated for each mono-chlorinated phenol-sorbent system. The results showed that the equilibrium data for all the mono-chlorinated phenol-sorbent systems fitted the Redlich-Peterson model best within the concentration range studied.     

活性污泥吸附废水中的铍

探讨了活性污泥吸附处理含铍废水的吸附动力学特性及吸附模型，研究了吸附后铍在活性污泥上的存在形态。实验结果表明，铍离子在活性污泥上的吸附行为遵循二级动力学规律，活性污泥在溶液中的分散性非常好，污泥微孔内扩散效应不是吸附过程的主要控制步骤，扩散速率主要由液相向固相的传质速率所控制，铍在污泥上的吸附主要为快速的表面吸附。铍在活性污泥上的吸附数据既可用Freundlich方程描述，也符合Langmuir吸附规律，Langmuir曲线的相关性还较Freundlich曲线高，吸附过程受温度影响不大，通过对处理后污泥的连续提取实验研究可知，处理后的活性污泥中铍的主要存在形态为有机结合态、残渣态和交换态。     

煤矸石的改性及其对稀土生产废水中氨氮的吸附

采用热改性、盐酸改性、硫酸改性、碱改性的方法分别制备了4种改性煤矸石吸附剂,研究了吸附工艺条件对4种改性煤矸石吸附剂对稀土生产废水中氨氮去除效果的影响以及吸附机理.实验结果表明:4种改性煤矸石吸附剂吸附氨氮的最佳工艺条件为:吸附剂加入量0.02 g/mL,振荡时间2.5 h,废水pH 7～8;4种吸附剂氨氮去除率大小顺序为:碱改性煤矸石＞硫酸改性煤矸石＞盐酸改性煤矸石＞热改性煤矸石;碱改性煤矸石的氨氮去除率最高,为59.19％;碱改性煤矸石吸附剂对含氨废水中氨氮的吸附较好地符合Langmuir方程和Freundlich方程,在一定程度上符合Temkin方程.     

Investigation of the Thermosensitive Nanosphere Polymer in Removing Organophosphorus Pesticides from Water and Its Isotherm Study (Case Study: Diazinon)

In this research, a novel thermosensitive nanosphere polymer (TNP) was synthesized by copolymerization of N-isopropylacrylamide with 3-allyloxy-1,2-propanediol for the removal of diazinon from water. The characterization of the synthesized adsorbent has been performed by Fourier transform infrared spectrometer, scanning electron microscopy and elemental analysis. Batch adsorption method was performed to investigate the influences of various parameters like pH, temperature and contact time on the adsorption of diazinon. The equilibrium adsorption data of diazinon by TNP was studied by Langmuir, Freundlich, Temkin and Redlich–Peterson model. According to equilibrium adsorption results, the Langmuir, Freundlich and Temkin constants were evaluated to be 0.912 (L/mg), 7.916 (mg/g) (L/mg)^1/n and 2.494 respectively at pH 7 and room temperature. Based on Redlich–Peterson model analysis, the equilibrium data for the adsorption of diazinon was conformed well to the Langmuir isotherm model. This method was successfully applied for removal of diazinon from environmental samples. Moreover, in reusing of TNP, the sorption capacity was maintained without any significant change after 10 cycles of sorption–desorption process.     

The Removal of Acid Violet 90 from Aqueous Solutions Using PANI and PANI/Clinoptilolite Composites: Isotherm and Kinetics

Polyaniline (PANI) and polyaniline/Gördes-clinoptilolite (PANI/GC) composite materials were synthesized by the chemical oxidative polymerization technique and used in the adsorption of Acid Violet 90 metal-complex dye (AV 90). The samples were characterized by X-ray diffractions, nitrogen adsorption–desorption isotherms, scanning electron microscopes and Fourier transform infrared. The effect of initial pH (2–8), sorbent dosage (0.5–4.0 g/L) and initial dye concentrations (50–400 mg/L) on adsorption onto PANI and PANI/GC were examined in a batch system. Langmuir, Freundlich and Temkin isotherm models were used to investigate the adsorption mechanism of AV 90 on PANI and PANI/GC. Langmuir isotherm model for PANI/GC and Freundlich isotherm model for PANI were fitted well with the experimental data. The highest dye uptake capacities were obtained with Langmuir isotherm model as 153.85 mg/g and 72.46 mg/g for PANI and PANI/GC, respectively. In order to determine the adsorption kinetics, pseudo first-order and second-order kinetic models were studied. As a result, the adsorption of AV 90 dye on PANI and PANI/GC was better identified with Pseudo second-order kinetic model than the first one.     

Study on desulfurization performance of MnO<Subscript>2</Subscript>-based activated carbon from waste coconut shell for diesel emissions control

Increasing concern about the air pollution caused by sulfur dioxide (SO₂) from diesel exhaust has resulted in the improvement of low-temperature desulfurization materials for the combined SO₂ trap. In this study, coconut shell activated carbon (AC) is pretreated by nitric acid to prepare MnO₂-based activated carbon materials for SO₂ removal. The prepared materials are characterized intensively by SEM, TEM, BET, XRD, FTIR, and XPS. The SO₂ capture capacity of these materials are measured at low temperature by thermogravimetry, and the SO₂ equilibrium adsorption characteristic is also investigated. The results show that the concentrations of nitric acid do not significantly change the textural properties of MnO₂-based AC materials. The content of surface-oxygenated groups (carbonyl carbon and transition) initially increases with the HNO₃ concentration rising and reaches the maximum value when the HNO₃ concentration is 10 mol/L, resulting in the enhancement of the SO₂ capture capacity. SO₂ capture capacity of MnO₂-based activated carbon decreases after regeneration and keeps stable after several cycles of thermal regeneration. The experimental data for SO₂ adsorption on MnO₂-based AC composite can fit the Freundlich model well in comparison with Langmuir model.     

Bisolute Equilibrium Studies for the Sorption of Basic Dyes on a GAC from Almond Shells: A Nonlinear Approach

Aqueous phase adsorption of three textile dyes onto a granular activated carbon produced from acid activation of almond shells is presented. Primarily, the sorption of three basic dyes, methylene blue, rhodamine b, and malachite green oxalate were studied. Four models, the Freundlich, the Langmuir, the Redlich-Peterson, and the Toth isotherms were compared for their quality of fit to the single-solute sorption data. Next, sorption of the three likely binary systems was examined. Four bi-solute models, the extended Langmuir with and without an interaction term, the extended Redlich-Peterson with an interaction term, and the empirical extended Freundlich model were used to predict sorption in the binary systems. Nonlinearly determined constants of the corresponding single-solute isotherms were used in the binary models to compare with experimental binary sorption data. For the single-solute system, the three-parameter models of the Redlich-Peterson and the Toth isotherms outperformed the Langmuir and Freundlich models. The empirical extended Freundlich model produced the closest comparison to the binary data in each system. In general, the nonlinear method provided a simple and computationally effective technique of producing optimal fitting parameters for the bi-solute sorption models.     

Removal of ammoniacal nitrogen (N-NH3) from municipal solid waste leachate by using activated carbon and limestone.

The presence of ammoniacal nitrogen (N-NH3) in leachate is one of the problems normally faced by landfill operators. Slow leaching of wastes producing nitrogen and no significant mechanism for transformation of N-NH3 in the landfills causes a high concentration of ammoniacal nitrogen in leachate over a long period of time. A literature review showed that the removal of ammoniacal nitrogen from leachate was not well documented and to date, there were limited studies in Malaysia on this aspect, especially in adsorption treatment. The main objective of the present study was to investigate the suitability of activated carbon, limestone and a mixture of both materials as a filtering medium, in combination with other treatments capable of attenuating ammoniacal nitrogen which is present in significant quantity (between 429 and 1909 mg L(-1)) in one of the landfill sites in Malaysia. The results of the study show that about 40% of ammoniacal nitrogen with concentration of more than 1000 mg L(-1) could be removed either by activated carbon or a mixture of carbon with limestone at mixture ratio of 5:35. This result shows that limestone is potentially useful as a cost-effective medium to replace activated carbon for ammoniacal nitrogen removal at a considerably lower cost.     

Poultry litter-based activated carbon for removing heavy metal ions in water

Utilization of poultry litter as a precursor material to manufacture activated carbon for treating heavy metal-contaminated water is a value-added strategy for recycling the organic waste. Batch adsorption experiments were conducted to investigate kinetics, isotherms, and capacity of poultry litter-based activated carbon for removing heavy metal ions in water. It was revealed that poultry litter-based activated carbon possessed significantly higher adsorption affinity and capacity for heavy metals than commercial activated carbons derived from bituminous coal and coconut shell. Adsorption of metal ions onto poultry litter-based carbon was rapid and followed Sigmoidal Chapman patterns as a function of contact time. Adsorption isotherms could be described by different models such as Langmuir and Freundlich equations, depending on the metal species and the coexistence of other metal ions. Potentially 404 mmol of Cu²⁺, 945 mmol of Pb²⁺, 236 mmol of Zn²⁺, and 250–300 mmol of Cd²⁺ would be adsorbed per kg of poultry litter-derived activated carbon. Releases of nutrients and metal ions from litter-derived carbon did not pose secondary water contamination risks. The study suggests that poultry litter can be utilized as a precursor material for economically manufacturing granular activated carbon that is to be used in wastewater treatment for removing heavy metals.     

Experimental and Modeling Studies for the Removal of Crystal Violet Dye from Aqueous Solutions using Eco-friendly <Emphasis Type="Italic">Gracilaria corticata</Emphasis> Seaweed Activated Carbon/Zn/Alginate Polymeric Composite Beads

This research article describes, an eco-friendly activated carbon prepared from the Gracilaria corticata seaweeds which was employed for the preparation of biodegradable polymeric beads for the efficient removal of crystal violet dye in an aqueous solution. The presence of chemical functional groups in the adsorbent material was detected using FTIR spectroscopy. The morphology and physical phases of the adsorbent materials were analyzed using SEM and XRD studies respectively. Batch mode dye adsorption behavior of the activated carbon/Zn/alginate polymeric beads was investigated as a function of dosage, solution pH, contact time, initial dye concentration and temperature. Maximum dye removal was observed at a pH of 5.0, 1 g of adsorbent dosage with 60 mg/L dye concentration, 50 min of contact time and at 30 °C. The equilibrium modeling studies were analyzed with Freundlich and Langmuir adsorption isotherms and the adsorption dynamics was predicted with Lagergren’s pseudo-first order, pseudo-second order equations and intra particle diffusion models. The process of dye removal followed a pseudo second-order kinetics rather than pseudo first order. The thermodynamic parameters like standard Gibbs free energy change (ΔG°), enthalpy change (ΔH°) and entropy change (ΔS°) were determined and the results imply that the adsorption process was spontaneous, endothermic and increases the randomness between the adsorbent and adsorbate. The results from the experimental and correlation data reveal that the Gracilaria corticata activated carbon/Zn/alginate polymeric beads have proved to be an excellent adsorbent material for the removal of CV dye.