Removal of the hazardous dye rhodamine B through photocatalytic and adsorption treatments

This paper reports on photocatalytic and adsorptive treatment of a hazardous xanthene dye, Rohdamine B, in wastewater. The photocatalytic degradation was carried out in the presence of the catalyst TiO(2) and the effects of pH, concentration of the dye, amount of TiO(2), temperature and electron acceptor H(2)O(2) on the degradation process were observed. It was found that photocatalytic degradation by TiO(2) is an effective, economical and faster mode of removing Rohdamine B from aqueous solutions. Attempts were also made to utilize activated carbon and rice husk as potential adsorbents to remove Rhodamine B from wastewater. The adsorption studies were carried out at 40, 50 and 60 degrees C, and the effects of pH, temperature, amount of adsorbents, concentration of adsorbate, etc., on the adsorption were measured. On the basis of adsorption data the Langmuir and Freundlich adsorption isotherm models were also confirmed. The adsorption isotherm constants thus obtained were employed to calculate thermodynamic parameters like Gibb's free energy, change in enthalpy and entropy. In order to observe the quality of wastewater COD measurements were also carried out before and after the treatments. A significant decrease in the COD values was observed, which clearly indicates that both photocatalytic and adsorption methods offer good potential to remove Rhodamine B from industrial effluents.     

Color removal from dye-containing wastewater by magnesium chloride

Color removal by MgCl(2) when treating synthetic waste containing pure dyes was studied. The color removal efficiency of MgCl(2)/Ca(OH)(2) was compared with that of Al(2)(SO(4))(3), polyaluminum chloride (PAC) and FeSO(4)/Ca(OH)(2). The mechanism of color removal by MgCl(2) was also investigated. The experimental results show that the color removal efficiency of MgCl(2) is related to the type of dye and depends on the pH of the waste and the dosage of the coagulants used. Treatment of waste containing reactive dye or dispersed dye with MgCl(2) yielded an optimum color removal ratio when the pH of the solution was equal to or above 12.0. For both the reactive and dispersed dye waste, MgCl(2)/Ca(OH)(2) was shown to be superior to MgCl(2)/NaOH, Al(2)(SO(4))(3), PAC and FeSO(4)/Ca(OH)(2) for color removal. A magnesium hydroxide precipitate formed at pH values greater than 12.0, which provided a large adsorptive surface area and a positive electrostatic surface charge, enabling it to remove the dyes through charge neutralization and an adsorptive coagulating mechanism. So, the MgCl(2)/Ca(OH)(2) system is a viable alternative to some of the more conventional forms of chemical treatment, especially for treating actual textile waste with high natural pH.     

粉煤灰处理染料废水的研究

利用粉煤灰吸附性能较好、来源广泛及价格低廉等特点,对染料废水进行吸附试验研究。结果表明,粉煤灰的活化方式、粒度及用量对染料废水吸附性能有影响。160—200目30%硫酸活化粉煤灰吸附能力最强,且对染料废水的吸附过程符合Langmuir吸附等温曲线,最大吸附量为667mg/g。     

Implementation of sulfate adsorption in the SAFE model

An SO4(2-) adsorption submodel has been implemented in the dynamic soil chemistry model SAFE. The submodel calculates pH-dependent SO4(2-) and H+ adsorption to the soil, as well as the net surface charge development due to uneven adsorption of SO4(2-) and H+, using the empirical equations derived from an electrostatic model (Extended Constant Capacitance Model, ECCM) of SO4(2-) adsorption. The resulting new SAFE model was applied on a roof experiment plot in the Norway spruce [Picea abies (L.) H. Karst.] stand at Solling, Germany, where atmospheric S and N deposition was artificially reduced by the roof construction. The model performance was compared with the previous versions that used a pH-independent Freudlich model of SO4(2-) adsorption or assumed no SO4(2-) adsorption. With the ECCM-based SO4(2-) adsorption submodel, SAFE simulated soil solution SO4(2-) concentration and base saturation better, in comparison with measured data, than with the previous SO4(2-) adsorption formulations. Through the model application, also, need of additional improvement was suggested, such as calibration of mass transfer coefficients.     

Characterization and coagulation of a polyaluminum chloride (PAC) coagulant with high Al13 content

A polyaluminum chloride (PAC) coagulant was prepared from AlCl3 x 6H2O and Na2CO3. The Al13 species in PAC was separated and purified by the SO4(2-)/Ba2+ deposition-replacement method, and characterized by 27Al-NMR and XRD. From 27Al-NMR spectroscopy, it was found that PAC obtained after separation and purification contained more Al13 (PAC-Al13, for short) than original PAC before separation and purification. In XRD spectra, a strong Al13 signal appeared in the range of 2theta from 5 to 25 degrees. Jar tests were performed to test the coagulation efficiency of AlCl3, PAC and PAC-Al13 in treating synthetic or actual water samples. Compared with PAC and AlCl3, PAC-Al13 gives the best results for turbidity, humic acid and color removal, and achieves the highest charge-neutralizing ability. Under the study conditions, PAC-Al13 gave about 90% humic acid removal and almost 100% reactive blue dye removal when its dosages were 4.0 and 15 mg/L as Al, respectively. The Al13 species has a higher positive charge and is the most effective polymeric Al species in water and wastewater treatment.     

Mechanisms and chemistry of dye adsorption on manganese oxides-modified diatomite

The investigations into structural changes which occur during adsorbent modification and the adsorption mechanisms are essential for an effective design of adsorption systems. Manganese oxides were impregnated onto diatomite to form the type known as δ-birnessite. Initial investigations established the effectiveness of manganese oxides-modified diatomite (MOMD) to remove basic and reactive dyes from aqueous solution. The adsorption capacity of MOMD for methylene blue (MB), hydrolysed reactive black (RB) and hydrolysed reactive yellow (RY) was 320, 419, and 204 mg/g, respectively. Various analytical techniques were used to characterise the structure and the mechanisms of the dye adsorption process onto MOMD such as Fourier transform infrared (FTIR), X-ray diffraction (XRD) and atomic absorption spectrometry (A.A.). A small shift to higher values of the d-spacing of dye/MOMD was observed indicating that a small amount of the dye molecules were intercalated in the MOMD structure and other molecules were adsorbed on the external surface of MOMD. Two mechanisms of dye adsorption onto MOMD were proposed; intercalation of the dye in the octahedral layers and adsorption of the dye on the MOMD external surface. Moreover, the results demonstrated that the MOMD structure was changed upon insertion of MB and RY with an obvious decrease in the intensity of the second main peak of the MOMD X-ray pattern.     

Exploitation of Trichoderma harzianum mycelial waste for the removal of rhodamine 6G from aqueous solution

The harvested mycelial waste of Trichoderma harzianum was used as an adsorbent for the removal of rhodamine 6G and was studied in batch mode. The effects of agitation time and initial dye concentration, adsorbent dosage and pH were examined. The study revealed that the amount of dye adsorbed (mgg(-1)) increased with increase in agitation time and reached equilibrium after 120 min, for dye concentrations of 10-50 mg L(-1). The adsorbent dosage of 1.0 g/50 mL and pH of 8.0 were found to be optimum for maximum dye removal. The batch mode adsorption data followed both the Langmuir and Freundlich isotherms. The pseudo first- and second-order rate kinetics were applied to the adsorbent system. The adsorption kinetics of rhodamine 6G showed that the pseudo-second-order kinetic model provided the best correlation of the equilibrium data. The study implies that it is possible to develop a dye removal system by using T. harzianum biomass, which occurs as sludge in waste stream of fermentation industries.     

Adsorption of basic dye from aqueous solution onto fly ash

The fly ash treated by H₂SO₄ was used as a low-cost adsorbent for the removal of a typical dye, methylene blue, from aqueous solution. An increase in the specific surface area and dye-adsorption capacity was observed after the acid treatment. The adsorption isotherm and kinetics of the treated fly ash were studied. The experimental results were fitted using Langmuir and Freundlich isotherms. It shows that the Freundlich isotherm is better in describing the adsorption process. Two kinetic models, pseudo-first order and pseudo-second order, were employed to analyze the kinetic data. It was found that the pseudo-second-order model is the better choice to describe the adsorption behavior. The thermodynamic study reveals that the enthalpy (ΔH⁰) value is positive (5.63 kJ/mol), suggesting an endothermic nature of the adsorption.     

Solid phosphorus phase in aluminum- and iron-treated biosolids

Stabilization of phosphorus (P) in sewage sludge (biosolids) to reduce water-soluble P concentrations is essential for minimizing P loss from amended soils and maximizing the capacity of the soil to safely serve as an outlet for this waste material. The chemical form at which P is retained in biosolids stabilized by Al(2)(SO(4))(3) x 18H(2)O (alum) or FeSO(4) x 7H(2)O (FeSul) was investigated by scanning electron microscopy (SEM) equipped with energy-dispersive X-ray elemental spectrometry (EDXS) and by X-ray diffraction (XRD). Both treatments resulted in the formation of a Ca-P phase, probably brushite. Phosphorus was further retained in the alum-treated biosolids by precipitation of an Al-P phase with an Al/P molar ratio of about 1:1, while in the FeSul-treated biosolids, P was retained by both precipitation with Fe/P molar ratios of 1:1 or 1.5:1, and by adsorption onto newly formed Fe hydroxides exhibiting an Fe/P molar ratio of up to 11:1. All of these mechanisms efficiently reduced P solubility and are crucial in biosolids environmentally safe agronomic beneficial use for this waste product; however, each P phase formed may react differently in the amended soil, depending on soil properties. Thus, the proper P stabilization method would depend on the target soil.     

Adsorption of cadmium on carbonaceous adsorbents developed from used tire rubber

Carbonaceous adsorbents (CAs) are developed from used tire rubber (UTR) and tested as adsorbents of Cd(2+) in aqueous solution. In the preparation of the CAs, UTR was treated thermally at 400-900 °C for 2 h in N(2) and at 850 °C for 2 h in steam. Concentrated NaOH, HCl, H(2)SO(4), HNO(3) and H(2)O(2) solutions were also used. UTR and H900 (i.e. UTR pyrolyzed at 900 °C) were treated with O(3) at 25 °C for 1 h and with air at 250 °C for 1 and 24 h. CAs were characterized texturally by N(2) adsorption at -196 °C, mercury porosimetry, and density measurements. The surface groups were analyzed by FT-IR spectroscopy. Using the batch method, the adsorption process of Cd(2+) was studied mainly from the kinetic standpoint at various pH values of the adsorptive solution. Significant porosity developments are achieved only when UTR is heat-treated, in particular in steam. However, the variety and concentration of surface groups are low in CAs. This is so even for CAs prepared using oxidizing agents as strong as O(3) and H(2)O(2), which has been associated with a lack of available or accessible surface active sites for oxidation in UTR and H900, respectively. Thermal and thermal-chemical treatments are usually more effective than chemical treatments to increase the adsorption of Cd(2+) in aqueous solution. The adsorption process of Cd(2+) is first fast and then much slower. Adsorption-time data fit better to a pseudo-second order kinetic equation than to a pseudo-first order kinetic equation. The extent to which the adsorption process occurs is strongly dependent on the pH of the Cd(2+) solution, being larger at pH 4.6 or 7.0 according to the adsorbent.     

A comparative study on the properties,mechanisms and process designs for the adsorption of non-ionic or anionic dyes onto cationic-polymer/bentonite

The adsorption properties and mechanisms of a cationic-polymer/bentonite complex (EPI-DMA/bentonite), prepared from polyepicholorohydrin-dimethylamine and bentonite, for non-ionic dyes (Disperse Blue SBL and Vat Scarlet R) and anionic dyes (Reactive Violet K-3R and Acid Dark Blue 2G) were investigated in this study. The solution pH, presence of salt and surfactant can significantly affect the dye removal efficiency. The equilibrium data were analyzed using the Langmuir and Freundlich models. The Langmuir model is the most suitable to describe non-ionic dye adsorption, but for anionic dyes the Freundlich model is best. The kinetic data for the adsorption of different dyes were analyzed using pseudo first- and second-order equations, and the experimental data conformed to the pseudo second-order kinetic model better. The possibility of intraparticle diffusion was also examined by using the intraparticle diffusion equation. The single-stage batch adsorber design for the adsorption of both types of dyes onto EPI-DMA/bentonite was studied based on the Langmuir isotherm model for non-ionic dyes and the Freundlich isotherm model for anionic dyes. The results showed that the required amount of EPI-DMA/bentonite for 95% dye removal in 5 L dye solution with a concentration of 50 mg/L is 378.0 g for DB SBL, 126.5 g for VS R, 9.7 g for RV K-3R and 15.5 g for ADB 2G.     

Retention of gases by hexadecyltrimethylammonium-montmorillonite clays

Intercalated montmorillonite clays with different amounts of organic hexadecyltrimethylammonium (HDTMA) cations were studied to analyse their CO, CH(4), and SO(2) gas retentions. Equilibrium adsorption was measured by using a standard volumetric apparatus at 25 degrees C and 0.1 MPa. The solids were characterised by X-ray diffraction. The levels of adsorption of SO(2) by organo-montmorillonites (0.3595-1.6403 mmol/g) were higher than those of CO (up to 0.0202 mmol/g) and CH(4) (up to 0.0273 mmol/g) gases. HDTMA montmorillonites may be effective adsorbents for removing SO(2) and for its potential separation in the presence of CO and/or CH(4) molecules, which can be present in contaminated air.     

Matrix based fertilizers reduce nitrogen and phosphorus leaching in three soils

We compared the efficacy of matrix based fertilizers (MBFs) formulated to reduce NO3-, NH4+, and total phosphorus (TP) leaching, with Osmocoate 14-14-14, a conventional commercial slow release fertilizer (SRF) and an unamended control in three different soil textures in a greenhouse column study. The MBFs covered a range of inorganic N and P in compounds that are relatively loosely bound (MBF 1) to more moderately bound (MBF 2) and more tightly bound compounds (MBF 3) mixed with Al(SO4)3H2O and/or Fe2(SO4)3 and with high ionic exchange compounds starch, chitosan and lignin. When N and P are released, the chemicals containing these nutrients in the MBF bind N and P to a Al(SO4)3H2O and/or Fe2(SO4)3 starch-chitosan-lignin matrix. One milligram (8000 spores) of Glomus intradices was added to all formulations to enhance nutrient uptake. In all three soil textures the SRF leachate contained a higher amount of NH4+, NO3- and TP than leachate from all other fertilizers. In all three soils there were no consistent differences in the amount of NH4+, NO3- and TP in the MBF leachates compared to the control leachate. Plants growing in soils receiving SRF had greater shoot, root and total biomass than all MBFs regardless of Al(SO4)3H2O or Fe2(SO4)3 additions. Arbuscular mycorrhizal infection in plant roots did not consistently differ among plants growing in soil receiving SRF, MBFs and control treatments. Although the MBFs resulted in less plant growth in this experiment they may be applied to soils growing plants in areas that are at high risk for nutrient leaching to surface waters.     

常用氧化剂性能研究

用四种常用的氧化剂:高锰酸钾、漂白粉、NaClO和H2O2/Fe2+对大港油田港深11井酸化废水进行了处理。考察了氧化剂的投加量、氧化时间和pH值对酸化废水色度和COD去除率的影响。实验结果表明,在最佳条件下,H2O2/Fe2+对酸化废水的色度和COD的去除率最高;用高锰酸钾处理废水,其COD去除率较高,但脱色效果差;而漂白粉和NaClO的脱色率较高,但其氧化能力有限。建议油田用氧化法处理废水时应采用H2O2/Fe2+催化氧化体系。     

水处理用活性炭改性研究

利用锆和氯化十六烷基三甲铵共同改性活性炭,制备一种新型去除污水中硝酸盐和磷酸盐的水处理吸附剂,并考察吸附剂加量、反应温度、pH值、共存阴离子等影响因素对吸附效果的影响。结果表明:锆-氯化十六烷基三甲铵改性活性炭(Zr-CTAC-AC)吸附剂适用于硝酸盐和磷酸盐浓度在100mg/L以下的污水,随着Zr-CTAC-AC加量的增加,硝酸盐、磷酸盐去除率逐渐增加,单位吸附量逐渐下降,Zr-CTAC-AC加量为8g/L时,硝酸盐去除率为79%,Zr-CTAC-AC加量为4.0g/L时,磷酸盐去除率可达91%,但应在较低的pH值范围内使用;反应温度对Zr-CTAC-AC的吸附效果影响不大;共存Cl-、HCO3^-和SO4^2-可使硝酸盐的吸附率降低,但对磷酸盐吸附率影响较小;1mol/L NaCl溶液可使吸附到Zr-CTAC-AC表面的硝酸盐90.9%左右被解吸出来,1mol/L NaOH溶液可使吸附到Zr-CTAC-AC表面的磷酸盐78.4%左右被解吸出来。Zr-CTAC-AC能够有效去除污水中硝酸盐和磷酸盐,制备方法简单,且可循环利用,处理成本低。     

吸附-双催化氧化降解苯胺、硝基苯废水

苯胺、硝基苯废水利用吸附树脂吸附后,再利用过氧化氢作氧化剂,在亚铁离子和紫外光的双催化下氧化降解。通过对亚铁离子浓度、过氧化氢浓度等因素对光降解影响的考察,结果表明,在实验条件下,本氧化体系对苯胺、硝基苯废水有明显的降解效果,苯胺、硝基苯废水经该体系处理12h后,去除率最高分别达到99.7%和95.3%。     

Fenton试剂高级氧化法降解甲基橙模拟废水研究

甲基橙是一种较难降解的有机苯环偶氮染料之一,研究其降解性能对其他染料废水体系的降解研究具有普遍参考价值。通过研究Fenton试剂降解甲基橙过程中的H202浓度、Fe2＋浓度、反应时间和反应体系pH值对甲基橙降解的影响,确定其最佳降解工艺条件为：当甲基橙浓度为20mg／L、pH值为3、Fe2＋浓度为1．5mmol／L、H2O2为32mmol/L时,降解率达到最大值（98．95％）。     

Remediation of biodiesel wastewater by chemical- and electro-coagulation: a comparative study

The remediation of biodiesel wastewater was carried out using chemical and electrochemical techniques. Initially the fatty acid methyl esters (FAME or biodiesel) and free fatty acids (FFA) were chemically removed from the wastewater using three types of mineral acids, H(2)SO(4), HNO(3) and HCl, at different pH values within the range of 1.0-8.0. Optimally, approximately 24.3 ml/l of FAME/FFA were removed from the wastewater when using H(2)SO(4) to set a final pH of 2.5 for 7 min. All pollutant levels were markedly reduced during this step. That is, approximately 38.94%, 76.32% and 99.36% of COD, BOD5 and oil & grease were respectively removed. The acidic aqueous phase left after the removal of the FAME/FFA phase was then treated by chemical- and electro-coagulation processes. The results demonstrated that both investigated treatment processes were effective for treating wastewater from a biodiesel production plant. The chemical coagulation provided a lower operating cost (1.11 USD/m(3)) compared with the electro-coagulation process (1.78 USD/m(3)). However, the latter process provided a better quality of wastewater compared with the former process, with the exception of the BOD levels.     

磁性活性炭吸附苯酚的初步研究

本文研究了磁性活性炭对苯酚的吸附性能;探讨了Cd2＋对苯酚在磁性活性炭上吸附的影响。目的是对磁性活性炭进行研究,以及为在实际废水中吸附处理苯酚提供参考。结果表明,磁性活性炭对苯酚的吸附过程符合拟二级动力学模型,R2为0.9935;与Freundlich吸附模型相比,Langmuir吸附模型能更好地描述磁性活性炭对苯酚的吸附行为;在不影响去除率的情况下,Cd2＋的存在使苯酚吸附处理最佳浓度由30 mg/L增大至50 mg/L;同时,Cd2＋对磁性活性炭和活性炭吸附苯酚分别具有促进和抑制作用。针对苯酚的吸附去除率,当无Cd2＋时,磁性活性炭的比活性炭的低10.65%～20.2%;当有Cd2＋时,磁性活性炭的比活性炭的高0.3%～7.71%。     

电化学反应器吸附去除氟离子的研究

采用改性活性炭粉末对用纯净水加氟化钠配制而成的含氟水溶液进行动态电吸附去除实验.研究不同电压、电吸附时间,以及Cl-和SO2-4对氟离子去除的影响,并探讨吸附动力学和吸附方程.实验结果表明:活性炭对氟离子的吸附等温方程符合Freundlich方程,吸附动力学符合一级动力学方程;活性炭对氟离子去除与所施加的电位、吸附时间等因素有关,施加的电位越大,去除效果越好;随着吸附去除时间的延长,氟离子浓度下降趋缓;Cl-对氟离子去除影响很小,而SO2-4对氟离子去除有显著的不利影响.