Chitosan and chemically modified chitosan beads for acid dyes sorption

The capabilities of chitosan and chitosan-EGDE （ethylene glycol diglycidyl ether） beads for removing Acid Red 37 （AR 37） and Acid Blue 25 （AB 25） from aqueous solution were examined. Chitosan beads were cross-linked with EGDE to enhance its chemical resistance and mechanical strength. Experiments were performed as a function ofpH, agitation period and concentration of AR 37 and AB 25. It was shown that the adsorption capacities of chitosan for both acid dyes were comparatively higher than those of chitosan- EGDE. This is mainly because cross-linking using EGDE reduces the major adsorption sites -NH3＋ on chitosan. Langmuir isotherm model showed the best conformity compared to Freundlich and BET. The kinetic experimental data agreed very well to the pseudo second-order kinetic model. The desorption study revealed that after three cycles of adsorption and desorption by NaOH and HCl, both adsorbents retained their promising adsorption abilities. FT-IR analysis proved that the adsorption of acid dyes onto chitosan-based adsorbents was a physical adsorption. Results also showed that chitosan and chitosan-EGDE beads were favourable adsorbers and could be employed as low-cost alternatives for the removal of acid dyes in wastewater treatment.

Synthesis of Novel Acid Dyes with Coumarin Moiety and Their Utilization for Dyeing Wool and Silk Fabrics

This article describes the synthesis of some novel coumarin compounds to use as acid dyes by using compounds 1 - 4 as starting materials, which were prepared by interaction of 2-hydroxybenzaldehyde with ethyl 3-oxobutanoate, diethylmalonate, 4-nitrobenzenediazonium chloride and 4-sulfobenzenediazonium chloride, respectively. Compound 1 reacted with bromine and 2-cyanoacetohydrazide to give phenacyl bromide derivative 5 and 2-cyanoacetohydrazone derivative 6, respectively. Coupling of compound 6 with equimolar amount of 2-sulfo-4-((4-sulfophenyl) diazenyl)benzenediazonium chloride gave coumarin acid dye 8. Phenacyl bromide derivative 5 re-acted with potassium cyanide in refluxing ethanol to produce compound 7, which on coupling with equimolar amount of 8-hydroxy-6-sulfonaphthalene-2-diazonium chloride and 8-hydroxy-3,6-disulfonaphthalene-1-diazonium chloride gave coumarin acid dyes 9 and 10, respectively. Interaction of compound 2 with 2-amino-5-((4-sulfophenyl)diazenyl)benzenesulfonic acid, benzene-1,4-diamine and 3,3’-dimethoxy-[1,1’-biphenyl]-4,4’-diamine in refluxing ethanol afforded compounds 11, 12 and 14, respectively. Diazonium sulphate of compounds 12 and 14 coupling with 4-amino-5-hydroxynaphthalene-2,7-disulfonic acid gave compounds 13 and 15, respectively. Cyclocondensation of compound 3 with ethyl 3-oxobutanoate, diethyl malonate and malononitrile afforded derivatives of 3-acetyl-2H-chromen-2-one 16, ethyl 2-oxo-2H-chromene-3-carboxylate 17 and 2-imino-2H-chromene-3-carbonitrile 18, respectively. Reaction of sodium benzenesulfonate derivative 4 with ethyl 3-oxobutanoate and hydrazine hydrate gave compounds 19 and 20, respectively. The structures of the newly synthesized compounds were confirmed by elemental analysis, UV/ VIS, IR, 1H NMR and Ms spectral data. The suitability of the prepared dyestuffs for dyeing of wool and silk fabrics has been investigated. The dyed fabric shows good light fastness, very good rubbing, perspiration, washing and excellent sublimation fastness. These dyes have been color shade from blue to violet with very good depth and levelness on fabrics. The dye bath exhaustion and fixation on fabric has been found to be very good.

CI Acid Orange 52 Dye Removal Using Natural and Formulated Clay-Lime Materials: Isotherm, Kinetic and Thermodynamic Studies

The main objective of the study is to improve the removal efficiency of Ourlago-kaolin (Kao), sodium montmorillonite (Na-MMT), and two formulated clay-lime (F13 and F23) towards CI Acid Orange 52 dye (AO52). F13 and F23 were obtained by chemical stabilization through thermal treatment at 300°C. Fourier Transform Infrared spectra showed different surface functional groups on the clay materials, X-ray diffraction patterns revealed the raw materials contain many crystalline phases, scanning electron microscopy micrographs showed the variation of the layered structures of different clay materials, energy dispersive X-Ray analysis micrographs revealed compositional information and thermogravimetric-differential scanning calorimetry curves indicated the higher weight loss of 11.26% and 11.38% were observed for F13 and F23 respectively. BET surface area analyzed gave 133.0071 m2•g−1 for F13 and 132.34803 m2•g−1 for F23. The optimum pH value was 2.0 for Kao and Na-MMT. The adsorption experiments indicated that F13 and F23 have the maximum uptake abilities of 7.8740 and 3.1645 mg•g−1, respectively, compared to Kao (0.8761 mg•g−1) and Na-MMT (2.6178 mg•g−1). The pseudo-second-order model well described the adsorption kinetic model of AO52 dye onto the overall samples;Langmuir and Freundlich’s isotherms appropriately described the uptake mechanism. The positive values of ∆G° and negative value ∆H° indicated that the adsorption process was spontaneous and endothermic for Na-MMT, and non-spontaneous and exothermic for Kao, F13, and F23 because of their positive values of ∆G° and negative value of ∆H°. The modified clays have higher adsorption capacities and better life cycles compared hence opening new avenues for efficient wastewater treatment.

[Azo-Hyd] Tautomerism and Structure of Selected Metal Complex Dyes AM1 and ZINDO/1 Methods

Quantum-chemical calculation methods have been used to examine an influence of tautomeric equilibrium [Azo Hydrazo] on a structure of 1:2 chromium metal complex dyes called Gryfalan Navy Blue RL (CI 15 707, Acid Blue 193) and Gryfalan Black RL (Acid Black 194). Chromatographic analysis indicates that synthesis yields a mixture of several dyes with different shades. Studies conducted to date have suggested that such dye complexes can constitute Drew-Pfitzner or Pfeiffer-Schetty structural isomers [1]. It is a know fact, that o-hydroxy-azo dyes exist in equilibrium of tautomeric azo and hydrazone forms. We decided to examine, whether color properties of examined metal-complex dyes can be influenced also by an azo-hydrazone equilibrium and what kind of influence on it has sulphonic groups present in molecules. Calculation and optimization of the geometrical structure were performed using the AM1 methods for monoazoo-hydroxy-azo dyesand ZINDO/1 for 1:2 chromium metal complex dyes. It was stated that monoazo dyes can create complexes in both forms: azo and hydrazone, because energy differences between each form of the metal complex dye are so small, that the monoazo dye can, in practice, create complexes in both the azo and the hydrazone form, with energy differences not exceeding about 4 - 11 kcal/mol. It is calculated that spatial structure changes with an angle of about 90° between two molecules of the dye, and angles of 10° - 20° between the naphthalene moieties. Similar electron density on the hydroxyl and ketone groups suggests that the mixture contains a dominant share of the azo form. The presence of an ionised sulphonic group was also found to affect on the tautomer equilibrium.

Study on Decoloration of Acidic Scarlet GR by Pyrolusite Oxidation under an Acid Condition

Decoloration of acidic scarlet GR by pyrolusite is studied in this paper. The effects of pH in solution, dosage and granularity of pyrolusite, reaction temperature, and vibration speed on decoloration efficiency are discussed. According to experiment results, the decoloration efficiency may exceed 95% for 40 mg/L GR solution by pyrolusite, pH is most important among all factors which impact the decoloration of acidic scarlet GR. Dosage and granularity of pyrolusite, reaction temperature, and vibration speed have a little benitfit on decoloration. The high decoloration efficiency and low removal efficiency of COD as well as FT-IR spectra of products between pyrolusite and acidic scarlet GR indicate that acidic scarlet GR undergoes the redox reaction on the interface of mineral and its chromophore is oxidated and decolored, but it is not removed thoroughly by oxidation.

A Facile Method for Dye and Heavy Metal Elimination by p H Sensitive Acid Activated Montmorillonite/Polyethersulfone Nanocomposite Membrane

Modified clay/polyethersulfone（PES） mixed matrix membranes（MMMs） were prepared by acid activated montmorillonite（AA-MMT） with different concentrations and used to eliminate dyes and remove heavy metals from aqueous solution. The morphology and physiochemical properties of prepared clay nanoparticles and MMMs were characterized using X-ray diffraction（XRD）, Fourier transform infrared（FTIR） spectroscopy, scanning electron microscopy（SEM）, enegy dispersive X-ray（EDX） spectroscopy, Brunauer-Emmett-Teller（BET） analysis, atomic force microscopy（AFM）, contact angle measurement and fouling studies. The filtration study showed that removal of dyes and heavy metals was strongly dependent on p H so that dyes with positive and negative charges showed different separation efficiency in acidic and alkaline conditions. The modified membranes possessed better heavy metal removal in acidic and alkaline p Hs. When the rejection of heavy metals was measured in an alkaline environment, it was observed that the rejection had a great increase compared to the neutral values for Zn^（2＋） and Ni^（2＋） ions, while rejection of Cu^（2＋） and Cd^（2＋） did not undergo significant changes. So it can be concluded that modified membranes show good selectivity for elimination of Zn^（2＋） and Ni^（2＋） ions with respect to other cations.

Insights into properties of activated carbons prepared from different raw precursors by pyrophosphoric acid activation

Low-cost activated carbons（ACs） were prepared from four kinds of solid wastes：petroleum coke,Enteromorpha prolifera,lignin from papermaking black liquid and hair,by pyrophosphoric acid（H_4P_2O_7） activation.Thermo-gravimetric analysis of the pyrolysis of H_4P_2O_7-precursor mixtures implied that H_4P_2O_7 had different influences on the pyrolysis behavior of the four raw materials.N_2 adsorption/desorption isotherms,scanning electron microscopy,Fourier transform infrared spectroscopy and adsorption capacities for dyes were used to characterize the prepared activated carbons.AC derived from E.prolifera exhibited the highest surface area（1094 m^2/g） and maximum monolayer adsorption capacity for malachite green（1250 mg/g）.Kinetic studies showed that the experimental data were in agreement with the pseudo-second-order model.The adsorption isotherms were well described by the Langmuir isotherm model,indicating the adsorption of dye onto the ACs proceeded by monolayers.

Synthesis of an electron-rich aniline-containing dye and its dyeing behaviors on silk through a three-component Mannich-type reaction

Under the guidance of the finding that the tyrosine residues in proteins could undergo three-component Mannich-type reactions with formaldehyde and electron-rich aniline-containing compounds,which forms covalent bonding connections between the protein of interest and the aniline with high levels of selectivity under relatively mild conditions,an orange aromatic primary amine-containing acid dye AMODB was designed and readily synthesized.The molecular structure was characterized by FTIR,^1H NMR,mass spectrometry and elemental analysis.The synthesized dye and a similar control dye（C.I.Acid Yellow 11） without primary amine groups were applied to dye silk fabric by three dyeing processes：Mannich-type dyeing（with and without the addition of formaldehyde） and acidic dyeing.Their washing and rubbing fastness properties with different dyeing methods were examined and compared.It was found that the dyed silk fabric with AMODB by the Mannich-type dyeing showed higher color depth,better anti-stripping ability to DMF and better washing fastness than those of the dyed silk fabric with C.I.Acid Yellow 11 by acidic dyeing due to the covalent bond formation between the dye chromophore of AMODB and silk fiber.In addition,mild Mannich dyeing conditions suitable for silk（AMODB at 3%owf,75：1 liquor-to-goods ratio,dyebath pH 5.5,30℃,10 h） were provided.

A novel approach for Apocynum venetum/cotton blended fabrics modification by cationic polymer nanoparticles

Apocynum venetum/cotton blended fabrics have been subjected to treat with cationic polymer nanoparticles followed by dyeing with Acid Red B,and then studied for their dyeing performance and morphology.The investigation on the effect of modification factors on the blended fabrics indicated that the 0.5 g/L nanoparticles concentration,60 min treating time,60 ℃ treating temperature and pH 6-8 are the optimum modification process to improve the dyeability of acid dye.In addition,the SEM images show that nanoparticles can be adsorbed on the surface of modified A.venetum or cotton fibers,and the two different fibers could have the same adsorption ability to Acid Red B.

Electrochemical decolorization of dye wastewater by surface-activated boron-doped nanocrystalline diamond electrode

Complex organics contained in dye wastewater are difficult to degrade and often require electrochemical advanced oxidation processes（EAOPs） to treat it. Surface activation of the electrode used in such treatment is an important factor determining the success of the process.The performance of boron-doped nanocrystalline diamond（BD-NCD） film electrode for decolorization of Acid Yellow（AY-36） azo dye with respect to the surface activation by electrochemical polarization was studied. Anodic polarization found to be more suitable as electrode pretreatment compared to cathodic one. After anodic polarization, the originally H-terminated surface of BD-NCD was changed into O-terminated, making it more hydrophilic.Due to the oxidation of surface functional groups and some portion of sp2 carbon in the BD-NCD film during anodic polarization, the electrode was successfully being activated showing lower background current, wider potential window and considerably less surface activity compared to the non-polarized one. Consequently, electrooxidation（EO） capability of the anodically-polarized BD-NCD to degrade AY-36 dye was significantly enhanced, capable of nearly total decolorization and chemical oxygen demand（COD） removal even after several times of re-using. The BD-NCD film electrode favored acidic condition for the dye degradation; and the presence of chloride ion in the solution was found to be more advantageous than sulfate active species.

Fast Degradation of Green Pollutants Through Nanonets and Nanofibers of the Al-Doped Zinc Oxide

In this study, series of nanolayered structures of Zn–Al LDHs were prepared by urea hydrolysis. Nanofibers and nanonets of the Al-doped ZnO were formed via the decomposition of the nanolayers under high pressure and temperature. Nanospheres were also prepared for comparison. The different morphologies of the prepared nanomaterials were confirmed by several techniques. An improvement for the optical properties of the doped zinc oxides was observed through narrowing of their band gap energies because of transforming the nanolayers to nanonets and nanofibers. The photocatalytic activities of the prepared nanomaterials were studied through photocatalytic degradation of the pollutants of acid green dyes. Complete decolorization and mineralization of green dyes happened in the presence of the nanolayers and nanospheres within 4–6 h,while the nanonets and the nanofibers achieved the complete decolorization and degradation of the dyes at shorter time 1.3 h. These results could be explained though the kinetic study of the photocatalytic degradation of dyes. It was concluded that the nanonets and the nanofibers were very effective for the photocatalytic degradation of pollutants.

Enhanced anaerobic fermentation with azo dye as electron acceptor: Simultaneous acceleration of organics decomposition and azo decolorization

Accumulation of hydrogen during anaerobic processes usually results in low decomposition of volatile organic acids（VFAs）. On the other hand, hydrogen is a good electron donor for dye reduction, which would help the acetogenic conversion in keeping low hydrogen concentration. The main objective of the study was to accelerate VFA composition through using azo dye as electron acceptor. The results indicated that the azo dye serving as an electron acceptor could avoid H2 accumulation and accelerate anaerobic digestion of VFAs. After adding the azo dye, propionate decreased from 2400.0 to 689.5 mg/L and acetate production increased from 180.0 to 519.5 mg/L. It meant that the conversion of propionate into acetate was enhanced. Fluorescence in situ hybridization analysis showed that the abundance of propionate-utilizing acetogens with the presence of azo dye was greater than that in a reference without azo dye. The experiments via using glucose as the substrate further demonstrated that the VFA decomposition and the chemical oxygen demand（COD） removal increased by 319.7 mg/L and 23.3% respectively after adding the azo dye. Therefore, adding moderate azo dye might be a way to recover anaerobic system from deterioration due to the accumulation of H2 or VFAs.