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.     

Modification of organo-zeolite surface for the removal of reactive azo dyes in fixed-bed reactors

Modification of zeolite (clinoptilolite) surface with a quaternary amine, hexadecyl trimethyl ammonium bromide (HTAB), to improve the removal efficiency of reactive azo dyes in a zeolite fixed bed was investigated. A series of adsorption tests were conducted to find out the uptake of three types of reactive dyes, i.e. CI Reactive Black 5, Red 239 and Yellow 176. Each run consisted of modifying zeolite with HTAB in the column followed by removal of color from the modified zeolite bed. The breakthrough curves for modification process were constructed under different conditions by plotting the normalized effluent concentration (C/C(0)) versus time or bed volumes (BV). Optimization studies show that 3g/l of HTAB dosage at a flowrate of 0.025l/min showed the best performance. Examination of the dye removal under the optimum modification conditions reveals that the black dye gives the highest breakthrough point among the three dyes tested. This is ascribed to the hydrophobic/hydrophilic match of the zeolite surface with the dye molecule, which depends upon the way zeolite is modified with HTAB. Calculations of the HTAB coverage on zeolite surface indicate that a bilayer formation is the most viable packing that enables maximum removal of the dye.     

Phosphorus reduction in a shallow hypereutrophic reservoir by in-lake dosage of ferrous iron

In Bautzen Reservoir (Germany), a technique of internally dosing iron compounds in combination with a local water column destratification was developed in order to control Microcystis blooms. In this paper, experimental results concerning the phosphorus (P) precipitation by iron application are reported. First, preliminary studies were conducted serving the choice of an appropriate precipitant. Subsequently, a whole-lake experiment was carried out. Fe2+ salts displayed a delayed oxidation and flocculation behaviour when injected into an ascending water jet. Nevertheless, the efficiency of soluble reactive phosphorus (SRP) elimination was equal to experiments with Fe3 + compounds both in laboratory and field experiments. During Fe2+ application, a large P-binding potential remained during the horizontal spreading of the treated water, since the proportion of the dissolved iron fraction near the dosage point was still high. Thus, measurements at a greater distance from the dosage point revealed higher amounts of P eliminated by Fe2+ than by Fe3+ dosage. Compared to the preceding year 1995, during the treatment periods in May-August 1996 and 1997 the SRP contents in the whole water body dropped by 72% and 54%, respectively, while the total phosphorus contents dropped by 45% at each period. We conclude that in-lake dosage of Fe2+ is an appropriate method to reduce the P loading of hypereutrophic reservoirs.     

Different binding mechanisms in biosorption of reactive dyes according to their reactivity

Various binding mechanisms for the uptake of reactive dyes by the protonated waste biomass of Corynebacterium glutamicum were investigated. As model reactive dyes, Reactive Blue 4 (RB 4), Reactive Orange 16 (RO 16) and Reactive Yellow 2 (RY 2) were used in this study. The solution pH strongly influenced the sorption capacity and the binding mechanisms of reactive dyes by C. glutamicum. At acidic pH, the electrostatic interaction was found to be a major binding mechanism. The maximum uptakes of RY 2, RO 16 and RB 4 at pH 2 were estimated to be 155.0+/-14.1, 156.6+/-6.7 and 184.9+/-16.4mg/g, respectively. Under alkaline conditions, the binding mechanisms were quite different according to the reactivity of reactive dyes. It was found that chemical bonding existed between the biomass surface and dye molecules under basic pH conditions.     

Degradation of reactive dyes in wastewater from the textile industry by ozone: Analysis of the products by accurate masses

The present work describes the use of ozone to degrade selected reactive dyes from the textile industry and the analysis of the resulting complex mixture by liquid chromatography/mass spectrometry (LC-MS). To allow certain identification of the substances detected in the wastewater, the original dyes were also investigated either separately or in a synthetic mixture of three dyes (trichromie). Since the reactive dyes are hydrolyzed during the dyeing process, procedures for the hydrolysis were worked out first for the individual dyes. The ozonated solutions were concentrated by solid-phase extraction, which separated very polar or ionic substances from moderately polar degradation products. The latter, which are the primary degradation products, were investigated by liquid chromatography/mass spectrometry with a tandem quadrupole time-of-flight mass analyzer. Accurate masses, which in most cases could be determined with a deviation of ≤5 ppm from the exact value, were also measured. In addition, a diode-array detector was placed before the mass analyzer to provide UV-vis spectra of the products in the same run. With retention times, mass spectra, accurate masses, UV-vis spectra and, of course, knowledge of the structures of the original dyes, plausible structures could be proposed for most of the components of the moderately polar fraction. These structures were confirmed by ¹H NMR in cases where it was practical to isolate the degradation products by preparative HPLC.     

Kinetic modeling of liquid-phase adsorption of reactive dyes and metal ions on chitosan

The rates of adsorption of three commercial reactive dyes and Cu(II) from water in the absence and presence of complexing agents using chitosan were measured at 30 degrees C. Three simplified kinetic models, i.e., pseudo-first-order, pseudo-second-order, and intraparticle diffusion, were tested to investigate the adsorption mechanisms. It was shown that the adsorption of reactive dyes and Cu(II) in the absence of complexing agents could be best described by the intraparticle diffusion model, whereas that of Cu(II) in the absence of complexing agents such as EDTA, citric acid, and tartaric acid by the pseudo-second-order equation. Kinetic parameters of the three models and the normalized standard deviations between the measured and predicted results were also calculated and discussed.     

Submerged microfiltration membrane coupled with alum coagulation/powdered activated carbon adsorption for complete decolorization of reactive dyes

Even the presence of very low concentrations of dyes (1mgL(-1)) in the effluent is highly visible and is considered aesthetically undesirable. It must be removed from wastewater completely. This study systematically evaluates the performance of adsorption (three kinds of powdered activated carbons), coagulation (AlCl3.6H2O) and membrane (submerged hollow fiber microfiltration) processes individually in treating two kinds of reactive dyes (Orange 16 and Black 5) and then using a hybrid process with combined coagulation-adsorption-membrane treatment system. Adsorption capacity and kinetics of Orange 16 were much higher and faster than those of Black 5. The dye removal efficiency by coagulation was highly dependent on dye concentration and solution pH. The hybrid process performance was far more superior that individual process in removing both kinds of dyes. It was evident that the combined coagulation-adsorption-membrane process has a great potential application for complete reactive dye removal, production of high-quality treated water and allows the reduction in the use of coagulant and adsorbent.     

Anion exchange resins for removal of reactive dyes from textile wastewaters

Sorption onto an easily regenerable sorbent in fixed bed filters would be an interesting option for removal of reactive dyes from textile wastewaters. A previous screening with model solutions (Dyes Pigm 51 (2001) 111) had shown two anion exchangers (strong basic S6328a and weak basic MP62, both Bayer) to exhibit good sorption characteristics for reactive dyes. The aim of this study was to evaluate these materials more closely. Thus filter breakthrough, the behavior with original wastewater samples, and the effect of inorganic wastewater parameters as well as regeneration were studied. Breakthrough curves for both materials are relatively unfavorable with a flat gradient, but throughput until breakthrough (100-800 bed volumes) should be sufficient for technical use. With both resins dye uptake is influenced little by competition of inorganic anions (sulfate, carbonate, phosphate) and they perform well in original wastewaters. However, the weak basic type is only efficient up to pH 8. Alkaline regeneration works well for MP62, for S6328a acid regeneration works for most dyes.     

Dye removal from textile dye wastewater using recycled alum sludge

The removal of dyes from textile dying wastewater by recycled alum sludge (RAS) generated by the coagulation process itself was studied and optimized. One hydrophobic and one hydrophilic dye were used as probes to examine the performance of this process. It was found that RAS is a good way of removing hydrophobic dye in wastewater, while simultaneously reducing the fresh alum dosage, of which one third of the fresh alum can be saved. The back-diffusion of residued dye from the recycling sludge is detected but is easily controlled as long as a small amount of fresh alum is added to the system. The use of RAS is not recommended for the removal of hydrophilic dyes, since the high solubility characteristics of such dyes can cause deterioration in the water quality during recycling.     

Enhanced catalytic levofloxacin degradation via persulfate activation over amorphous potassium ferricyanide@ZIF-67 nanocages

A facile method was used to synthesize amorphous potassium ferricyanide (PF)@ZIF-67 nanocages, a novel metal–organic framework derivative. The structure, composition and morphology of PF@ZIF-67 were analysed by scanning electron microscopy, transmission electron microscope, X-ray diffraction and X-ray photoelectron spectroscopy. The results show that PF@ZIF-67 nanoparticles were successfully prepared and its nanostructure has high crystallinity. The prepared materials were employed as heterogeneous persulfate catalysts for the degradation of levofloxacin (LEV). The effects of some key parameters including sodium persulfate (PS) dosage, PF@ZIF-67, initial solution pH and reaction time on LEV degradation were investigated. PF@ZIF-67 showed higher catalytic capacity for LEV degradation compared to ZIF-67, implying the iron-cobalt synergy in the material. Under the optimized conditions of 8.4-mM PS, 0.5 g/L PF@ZIF-67 at an initial solution pH of 7.2, 85.8% of LEV could be removed within 240 min. The quenching experiments suggest that sulfate radicals were the predominant reactive species.     

纳米TiO2-AC负载膜光催化降解偶氮染料

以钛酸四丁酯和活性炭为主要原料，采用溶胶-凝胶-浸渍法制备纳米TiO2-AC负载膜催化剂，并借助流化床反应器分别对两种典型的偶氮类染料橙黄C、活性艳红X-3B模拟废水进行了UV光降解、暗态吸附及光催化降解研究，探讨了pH值、外加氧化剂对光催化去除率的影响，同时对催化剂进行回收再生利用试验。结果表明：纳米TiO2-AC负载膜具有很好的光催化活性、吸附特性及可再生性，两种染料1h的光催化降解率最高分别可达99．71％和97．12％。反应过程中固、液、气三相能够有效分离，实现了反应与分离的一体化。     

Dechlorination of trichloroethylene by Ni/Fe nanoparticles immobilized in PEG/PVDF and PEG/nylon 66 membranes

The highly reactive bimetallic Fe/Ni nanoparticles immobilized in nylon 66 and PVDF membranes were synthesized and characterized for dechlorination of trichloroethylene (TCE) under anoxic conditions. Scanning electron microscopy (SEM) images and electron probe microanalysis (EPMA) elemental maps showed that the distribution of Fe in nylon 66 membrane was uniform and the intensity of Ni layer was higher than that in PVDF membrane. The particle sizes of bimetallic Fe/Ni in PVDF and nylon 66 membranes were 81 ± 12 and 55 ± 14 nm with the Ni layers of 12 ± 3 and 15 ± 2 nm, respectively. Low agglomeration of immobilized Fe/Ni nanoparticles in nylon 66 membrane was observed, presumably attributed to the more multifunctional chelating groups in membrane. A rapid hydrodechlorination of TCE with ethane as the main end product was observed by the immobilized Fe/Ni nanoparticles. The pseudo-first-order rate constants for TCE dechlorination were 6.44 ± 0.32 and 1.66 ± 0.08 h⁻¹ for nylon 66 and PVDF membranes, respectively. In addition, the efficiency and rate of TCE dechlorination increased upon increasing the mass loading of Ni, ranging between 2.5 and 20 wt%, and then decreased when further increased the Ni loading to 25 wt%. In addition, the stability and longevity of the immobilized Fe/Ni nanoparticles was evaluated by repeatedly injecting TCE into the solutions. A rapid and complete dechlorination of TCE by trace amounts of Fe/Ni nanoparticles was observed after 16 cycles of injection within 10 days, indicating that the immobilization of Fe/Ni nanoparticles in the hydrophilic nylon 66 membrane can retain the longevity and high reactivity of nanoparticles towards TCE dechlorination.     

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.     

Adsorption de colorants ioniques sur le dechet lainier de carbonisageAdsorption of ionic dyes on wool carbonizing waste

Wool carbonizing waste is not used although large amounts are available in the countries where wool is processed. Wool carbonizing waste is made up of two components: the plant particles can be considered as sulfo lignins; the short-size wool fibres have undergone chemical modifications. Owing to its physical structure and to the polar as well as apolar properties of its macromolecules, this waste is liable to adsorb ionic organic solutes. The adsorption of ionic dyes on wool carbonizing waste was therefore investigated so as to evaluate its possible use for the decolourization of dyeing effluents. The effect of the solution-substrate reaction time on the adsorption at various temperatures was studied first. Temperature had a marked effect on the adsorption of the acid dye (AB 80) (Fig. 1) whereas the basic dye (BR 22) (Fig. 2) was characterized by its faster diffusion within the wool carbonizing waste particles. These differences can be ascribed to the higher steric hindrance of the AB 80 molecules and to their possible aggregation. The L-type adsorption isotherms corroborated the temperature effect already mentioned as well as the high affinity of the wool carbonizing waste with acid (Fig. 3) and basic (Fig. 4) dyes. The shape of the adsorption isotherms suggests that the adsorption proceeds through ionic bonding; as the dye molecules are oriented flatwise on the surface of the waste, the dye-substrate hydrophobic interactions can be maximum. The amounts adsorbed were 0.744 mmol g^?1 (i.e. 52.5%) for AB 80 at pH 2 and 0.193 mmol g^?1 (i.e. 5.5%) for BR 22 at pH 4. Higher amounts of basic dyes might however be expected to be adsorbed since the adsorption maximum is reached at pH 9 in the case of BR 22 (Fig. 5), as a result of the increasingly electronegative charge of the substrate. The Langmuir and Freundlich equations (Table 1) were used to have a mathematical model for the operation of a waste water processing unit. As shown by the L-type adsorption isotherms, the wool carbonizing waste used is suitable for the processing of low concentration effluents, such as dyeing waste waters: the decolourization of synthetic solutions was therefore considred. The column processing of an AB 80 solution showed the effect of the reaction time on the efficiency of the material used (Table 2). Investigation of the processing of a BR 22 solution in a stirred reactor led to the determination of the optimum carbonizing waste concentration (Fig. 6). as well as of the optimum effluent-substrate reaction time and the number of reactors to be used (Fig. 7). Eventually, the adsorptive power of the wool carbonizing waste used was compared with that of various materials (Table 3): the uptake capacity of wool carbonizing waste is lower than or equal to that of other substrates in the case of basic dyes but it is 6–10-fold higher in the case of acid dyes.     

Adsorption de colorants ioniques sur le dechet lainier de carbonisage

Wool carbonizing waste is not used although large amounts are available in the countries where wool is processed. Wool carbonizing waste is made up of two components: the plant particles can be considered as sulfo lignins; the short-size wool fibres have undergone chemical modifications. Owing to its physical structure and to the polar as well as apolar properties of its macromolecules, this waste is liable to adsorb ionic organic solutes. The adsorption of ionic dyes on wool carbonizing waste was therefore investigated so as to evaluate its possible use for the decolourization of dyeing effluents. The effect of the solution-substrate reaction time on the adsorption at various temperatures was studied first. Temperature had a marked effect on the adsorption of the acid dye (AB 80) (Fig. 1) whereas the basic dye (BR 22) (Fig. 2) was characterized by its faster diffusion within the wool carbonizing waste particles. These differences can be ascribed to the higher steric hindrance of the AB 80 molecules and to their possible aggregation. The L-type adsorption isotherms corroborated the temperature effect already mentioned as well as the high affinity of the wool carbonizing waste with acid (Fig. 3) and basic (Fig. 4) dyes. The shape of the adsorption isotherms suggests that the adsorption proceeds through ionic bonding; as the dye molecules are oriented flatwise on the surface of the waste, the dye-substrate hydrophobic interactions can be maximum. The amounts adsorbed were 0.744 mmol g⁻¹ (i.e. 52.5%) for AB 80 at pH 2 and 0.193 mmol g⁻¹ (i.e. 5.5%) for BR 22 at pH 4. Higher amounts of basic dyes might however be expected to be adsorbed since the adsorption maximum is reached at pH 9 in the case of BR 22 (Fig. 5), as a result of the increasingly electronegative charge of the substrate. The Langmuir and Freundlich equations (Table 1) were used to have a mathematical model for the operation of a waste water processing unit. As shown by the L-type adsorption isotherms, the wool carbonizing waste used is suitable for the processing of low concentration effluents, such as dyeing waste waters: the decolourization of synthetic solutions was therefore considred. The column processing of an AB 80 solution showed the effect of the reaction time on the efficiency of the material used (Table 2). Investigation of the processing of a BR 22 solution in a stirred reactor led to the determination of the optimum carbonizing waste concentration (Fig. 6). as well as of the optimum effluent-substrate reaction time and the number of reactors to be used (Fig. 7). Eventually, the adsorptive power of the wool carbonizing waste used was compared with that of various materials (Table 3): the uptake capacity of wool carbonizing waste is lower than or equal to that of other substrates in the case of basic dyes but it is 6–10-fold higher in the case of acid dyes.     

Adsorption of anionic and cationic dyes on activated carbons with different surface chemistries

The influence of the surface chemical groups of an activated carbon on the removal of different classes of dyes is evaluated. Starting from the same material (NORIT GAC 1240 PLUS), the following treatments were carried out in order to produce a series of samples with different surface chemical properties but with no major differences in their textural properties: oxidation in the liquid phase with 6M HNO(3) and 10 M H(2)O(2) (acid materials) and heat treatment at 700 degrees C in H(2) or N(2) flow (basic materials). The specific micropores volume and mesopores surface area of the materials were obtained from N(2) adsorption equilibrium isotherms at 77K. The surface chemistry was characterised by temperature programmed desorption, by the determination of the point of zero charge (pH(pzc)) and by the evaluation of the acidity/basicity of the samples. Elemental and proximate analyses were also carried out. Equilibrium isotherms of selected dyes (an acid, a basic and a reactive dye) on the mentioned samples were obtained and the results discussed in relation to their surface chemistry. In general, the Langmuir model provided the best fit for the adsorption data. It is shown that the surface chemistry of the activated carbon plays a key role in dye adsorption performance. The basic sample obtained by thermal treatment under H(2) flow at 700 degrees C is the best material for the adsorption of all the tested dyes.     

The Simultaneous Bioremoval of Cr(III) and Dye by Immobilized <Emphasis Type="Italic">Phanerochaete Chrysosporium</Emphasis>

To attain better removal efficiency and higher toxic resistance, the alginate was used to immobilize Phanerochaete chrysosporium BKM-F-1767 in this study. And according to the characteristics of tannery wastewater, inhibitory effect of Cr(III) to the decolorization was investigated and adsorption kinetics of Cr(III) by the immobilized P. chrysosporium had been established. Furthermore, the Acid Violet 7 and Basic Fuchsin contributed as the experimental dyes in the paper, the removal studies were performed at an initial pH of 4.5. The combined effects of Cr and dyes on the simultaneous removal properties were determined in a batch system at different levels of Cr and dyes. Moreover, the dose-response relationship and a kinetic equation describing the simultaneous removal properties had been established. The results have proved that the immobilized P. chrysosporium has the ability to treat the tannery wastewater.     

Effect of OH and silanol groups in the removal of dyes from aqueous solution using diatomite

The removal of methylene blue, reactive black (C-NN), and reactive yellow (MI-2RN) from aqueous solution by calcined and raw diatomite at 980 degrees C was studied. These studies demonstrated the importance of the various functional groups on the mechanism of adsorption. The role of pore size distribution in the dye adsorption studies was also investigated. The adsorption isotherms were pH dependent. Henry and Freundlich adsorption isotherms were used to model the adsorption behavior and experimental results for all dyes used exhibited heterogeneous surface binding. The removal of the ionisable functional groups increased the pH(ZPC) value from 5.4 to 7.7, while FTIR, SEM and XRD analysis showed a remarkable decrease of the characteristic Si-OH peaks after calcinations at 980 degrees C. The removal of hydroxyl groups from the surface of diatomite lead to a decrease in the adsorption. It was evident from pH and infrared spectra results that mechanisms of methylene blue and reactive yellow adsorption differed from that of reactive black. Accordingly, adsorption on the external surface by n-pi interaction between the pi system of the RB and the electron lone pairs of the oxygen atoms of siloxane group and columbic attraction between the dye and the surface of calcined diatomite was proposed as a possible adsorption mechanism.     

Stability of commercial metal oxide nanoparticles in water

The fate of commercial nanoparticles in water is of significant interest to health and regulatory authorities. This research investigated the dispersion and stability of metal oxide nanoparticles in water as well as their removal by potable water treatment processes. Commercial nanoparticles were received as powder aggregates, and in water neither ultrasound nor chemical dispersants could break them up into primary nanoparticles. Lab-synthesized hematite was prepared as a primary nanoparticle (85 nm) suspension; upon drying and 1-month storage, however, hematite formed aggregates that could not be dispersed completely as primary nanoparticles in water. This observation may explain why it is difficult to disperse dry commercial nanoparticles. Except for silica, other nanoparticles rapidly aggregated in tap water due to electric double layer (EDL) compression. The stability of silica in tap water is related to its low Hamaker constant. For all these nanoparticles, at an alum dosage of 60 mg/L, coagulation followed by sedimentation could remove 20-60% of the total nanoparticle mass. Filtration using a 0.45 microm filter was required to remove more than 90% of the nanoparticle mass.     

混凝法去除水中TiO_2纳米颗粒

为了探讨混凝法去除水中纳米颗粒的可行性及最佳条件,研究了无机混凝剂(PAC、PFS、PAFC)和有机絮凝剂(CPAM、APAM、NPAM)对TiO_2纳米颗粒的去除效果,并考察了投加量、pH、沉淀时间、水力条件及有机无机复配对TiO_2纳米颗粒去除效率的影响。单独投加PAC、PFS和PAFC时,三者对应的最高去除率分别为92.51%、84.43%、95.66%。单独投加CPAM、APAM、NPAM时三者对应的去除率仅为61.72%、29.06%、55.37%。复配最佳混凝条件为:投加40mg/LPAC和3mg/LCPAM,pH值为9,G值143.5/s,沉淀时间15min,此时,TiO_2纳米颗粒去除率为99.6%。