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.

Sorption of Acid Dyes onto Silica Modified with Cetyltrimethylammonium Cations

The sorption behavior of acid dyes onto cetyltrimethylammonium bromide (CTAB)- modified silica as a function of pH in the aqueous medium was studied. Single- and multi-solute sorption equilibria of orange II(OR), phenol red (PR) and Eriochrome Black T (EBT) were studied at pH 3, unbuffered water pH and pH 11. Sorption behavior of EBT could not be conducted at pH 3 due to its aggregation in acidic medium. All the reaction conditions, experimental protocols and techniques remained the same throughout the sorption process. Sorption isotherms for single-solute system were fitted by the Langmuir model, while Langmuir competitive model (LCM) and the ideal adsorbed solution theory (IAST) coupled with Langmuir model (IAST/Langmuir) were used for the prediction of multisolute competitive sorption. Sorption affinities influenced by the factors like physical interactive forces between the molecules of CTA on silica and sorbate, structural limitations of the dyes based on their geometrical arrangement were investigated. Sorption affinity of OR was found to be higher than that of EBT and PR at all the pH values investigated. Magnitude of the sorption capacities was observed to be higher in acidic medium but lower in alkaline medium. Trends of the sorption affinities in multisolute system were similar to those in single-solute system but magnitude of the sorption capacities was significantly reduced due to the prevailing competition among the sorbates.

Application of Acid Dyestuffs with Different Molecule Structure in Combined Dyeing and Finishing of Cotton Fabric

Simultaneous dyeing and durable press finishing of cotton fabrics with acid dyes bearing the different molecule structure and durable press finishing agent (DP agent abbr.) based on modified DMDHEU were investigated by using the pad-dry-cure process. Some factors affecting the process, such as structure of acid dyes, DP agent, catalysts and curing temperature were discussed. The dyed and finished fabrics were evaluated with respect to color strength, fixation, crease recovery angle, breaking strength and fastness properties. The results indicate that structure of acid dyes has a striking effect on the color strength of dyed and finished cotton fabric. The color strength and dry crease recovery angle of dyed and finished cotton fabric increases, whereas breaking strength decreases with increasing concentration of DP agent. It is necessary for ammonium nitrate to serve as catalyst. It is found that relatively satisfactory properties of dyed and finished cotton fabric can be obtained with appropriate adjustment of treating conditions.

Sorption Behaviour of Acid Dyes by Soybean Protein/Poly(vinyl alcohol) Blend Fibre

The sorption behaviour of acid dyes by soybean protein/poly(vinyl alcohol) blend fibre was studied. The quantity of dye sorbed by the fibre increased markedly with the decrease in the pH of dyebath and reduced with the addition of neutral electrolyte when the pH was below 4.5. Acid dyes exhibited higher sorption rate constant and lower half dyeing time for the fibre than for spun silk and wool, which was related to the special morphological structure of the fibre. At pH 4, the sorption of disulphonated acid dyes with higher molecular weight followed the dual sorption mechanism of Langmuir plus Nernst-type partitioning well as they interacted with the fibre through electrostatic forces, hydrophobic forces and hydrogen bonds. It is considered that soybean protein and PVA components should be simultaneously dyed by disulphonated acid dyes with higher molecular weight.

Error Analysis of Adsorption Isotherm Models for Acid Dyes onto Bamboo Derived Activated Carbon

High surface area activated carbons were produced by thermal activation of waste bamboo scaffolding with phosphoric acid.Single component equilibrium dye adsorption was conducted on the carbons produced and compared with a commercially available carbon.Two acid dyes with different molecular sizes,namely Acid Yellow 117(AY117) and Acid Blue 25(AB25),were used to evaluate the adsorption capacity of the produced carbons.It was found that the dye with smaller molecular size,AB 25,was readily adsorbed onto the produced carbon,nearly three times higher than a commercially available carbon,while the larger size dye,AY117,showed little adsorption.The experimental data were analyzed using isotherm equations including Langmuir,Freundlich,Tempkin,Toth,Redlich-Peterson and Sips equations.The equilibrium data were then analyzed using five different non-linear error analysis methods.

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.

Properties of a novel acid dye 1-amino-4-[(6-nitro-2-benzothiazolyl)amino]-9,10-anthraquinone-2-sulfonic acid with anti-UV capability

A novel acid dye acid was synthesized by the condensation reaction between bromamine acid and 2-amino-6-nitrobenzothiazole and its anti-UV protection properties were evaluated.The results showed that silk dyed with this dye had very good ultraviolet radiation protection capability and excellent dyeing performance.The UV-absorption mechanism of this dye was also discussed.

Dyeing of Polypropylene Fibers with Vat Dyes

Polypropylene fibers have been extensively used in a variety of/products, including carpets and upholstery, due to their non-absorbency, good weather resistance, good resistance to macroorgamsms and so on. Because of their hydrophobic and highly crystalline nature, those well-established conventionai dyeing processes are difficult to apply to unmodified polypropylene. Colors of polypropylene fibers are primarily obtained by mass coloration which has the disadvantages of limited number of colors available and difficulties in inventory control due to the rapidly changing color needs of the market. In this paper, the use of vat dyes to dye polypropylene fabrics is investigated. Seventeen vat dyes were screened and factors influencing uptake of dyes by polypropylene fabrics were studied.

Kinetic analysis of experiment data for the formation of C.I.Acid Blue 9 leuco compound

A systematic study of the synthesis of C.I.Acid Blue 9 leuco compound in water is reported.The kinetic analysis of experimental data for the condensation reaction between 2-formylbenzenesulfonic acid sodium and N-ethyl-N-(3'-sulfonic acid benzyl) aniline obtained at four different temperatures ranging between 85 and 100°C is discussed.It is shown that the reaction followed second-order rate kinetics.The overall rate constant(k) increased with the increase of temperature.On the basis of the value of k,activation energy(E_a) of the reaction was evaluated.Importantly,it is found that reactant concentration has great effect on the formation of C.I.Acid Blue 9 leuco compound,implying that it is not enough to improve the conversion of N-ethyl-N-(3'-sulfonic acid benzyl) aniline by only prolonging reaction time in the late period of the reaction.

A Kinetic Spectrophotometric Method for the Determination of Iron (Ⅲ) in Water Samples

A new kinetic spectrophotometric method has been developed for the determination of iron （Ⅲ）. The method is based on the catalytic effect of iron （Ⅲ） on the oxidation of weak acid brilliant blue dye （RAWL） by KIO4 in acid medium. The advantages of the proposed method are that it is sensitive, accurate, rapid, inexpensive, can be operated under room temperature and has a large determination concentration range compared to other techniques. The obtained optimum conditions are： pH 3.15, RAWL （200 mgL^-1） 5.00mL, Potassium periodate solution （0.01 molL^-1） 0.30mL, phenanthroline （0.02 molL^-1） 1.00mL, reaction temperature 25℃ and reaction time 7 min. With this method iron could quantitively be determined in the range 0.00-0.02 mgL^-1, the detection limit being 4.10 × 10^10gmL^-1. The relative standard deviations （RSD） in five replicate determinations for 3 μgL^-1and 5 μgL^-1 iron （Ⅲ） are 3.1% and 1.9%, respectively. The method has been applied to the determination of iron （Ⅲ） in tap water samples and seawater samples （from the South China Sea）, the recovery rates being 98.0% and 100.5%, respectively.

Determination of Trace Copper (Ⅱ) in Water Samples by Kinetic-spectrophotometry

A new kinetic-spectrophotometric method is proposed for the determination of copper (Ⅱ). The method is based on the catalytic effect of copper (Ⅱ) on the oxidation of weak acid brilliant blue dye (RAWL) by hydrogen peroxide. The copper (Ⅱ) can be determined spectrophotometrically by measuring the decrease of absorbance of RAWL at λ = 626 nm using the fix-time method. The optimum reaction conditions are as follows: pH 7.20, buffer solution NaOH-KH2PO4, RAWL (200 mg L-1) 5.00 mL, H2O2 (30%) 0.50 mL, reaction temperature 80℃ and reaction time 20 min. The linear range of this method is between 0 μg L-1 and 12 μg L-1 and the limit of detection is 0.011 μg L-1, the relative standard deviation (RSD) in five replicate determinations for 2 and 8 μg L-1 copper (Ⅱ) are 3.2% and 2.3%, respectively. Twenty ions do not interfere in the determination of copper (Ⅱ). The method has been applied satisfactorily to the determination of copper (Ⅱ) in freshwater samples (tap water and Yellow River water from Lijin, Shandong, China) and seawater samples (from the South China Sea), the recovery rates are 98.0%, 102.5% and 96.0%, respectively.

Measurement of Trace Manganese(Ⅱ) by the Catalytic Kinetic Spectrophotometric Method

A new kinetic spectrophotometric method is developed for the measurement of manganese(Ⅱ) in water. The method is based on the catalytic effect of manganese(Ⅱ) with the oxidation of weak acid brilliant blue dye(RAWL) by KIO4 using the Nitrilo triacetic acid(NTA) as an activation reagent. The optimum conditions obtained are 40 mgL-1 RAWL,1×10-4molL-1 KIO4,2×10-4 molL-1 Nitrilo triacetic acid(NTA),pH = 5.8,the reaction time of 3.00 min and the temperature of 20.0 ℃. Under the optimum conditions,the proposed method allows the measurement of manganese(Ⅱ) in a range of 0-50.0 ng mL-1 and with a detection limit of down to 0.158 ng mL-1. The recovery efficiency in measuring the standard manganese(Ⅱ) solution is in a range of 98.5%-102%,and the RSD is in a range of 0.76%-1.25%. The new method has been successfully applied to the measurement of manganese(Ⅱ) in both fresh water and seawater samples with satisfying results. Moreover,few cations and anions interfere with the measurement of manganese(Ⅱ). Compared with other kinetic catalytic methods and instrumental methods,the proposed method shows fairly good selectivity and sensitivity,low cost,cheapness,low detection limit and rapidity. It can be applied on boats easily.

Study on the Determination of Trace Ni(II) by the Catalytic Kinetic Spectrophotometric Method

A new kinetic spectrophotometric method has been developed for the determination of trace Ni （Ⅱ in natural water. The method is based on the catalytic effect of Ni （Ⅱ） on the oxidation of weak acid brilliant blue dye （RAWL） by KIO4 in acid medium. The concentration of nickel （Ⅱ） can be determined spectrophotometrically by measuring the decrease of absorbance of RAWL at λ = 626 nm using the fix-time method. The influencing factors are investigated by the orthogonal experimental design. The obtained optimum analytical conditions are： pH = 2.00, CRAWL = 5.00×10^-5 mol·L^-1, c KlO4 = 2.00× 10^-5 mol·L^-1, the reaction time t= 10min and the temperature T = 25 ℃. Under the optimum conditions, the developed method allows the measurement of Ni （Ⅱ） in a range of 0 - 40.0ngmL1. The standard deviation of eleven independent measurements of blank reaction is S = 3.08× 10^-3 and the limit of detection is 2.20ng·mL^-1. The relative standard deviations （RSDs） in six replicate determinations of 5 ngmL-1 and 8 ngmL1 Ni （Ⅱ） are 2.87% and 1.11%, respectively. Moreover, the experiments show few cations and anions can interfere with the measurement of Ni （Ⅱ）. The recovery efficiencies of this method are in a range of 97.0%-102.5% in freshwater samples. But there is a decreasing effect, which is about 0.2 times the added Ni （Ⅱ） in seawater medium. After reasonable calibration this processing method is used for the determination of Ni （Ⅱ） in seawater samples successfully. The results show this developed method has high accuracy and precision, high sensitivity, large range of linearity and high speed. The method can, therefore, be employed at room temperature.

Synthesis and dyeing performance of a novel polycarboxylic acid azo dye

A novel reactive polycarboxylic acid dye was synthesized by the reaction of polymaleic anhydride（PMA） with 3-methyl-1-（4- sulfonylphenyl）-4-（4-aminophenylazo）-2-pyrazoline-5-one.The structure of the novel dye was characterized by FTIR,UV-vis and ^（13）C NMR spectra.The dyeing properties of dye on cotton were tested,and the novel dye possessed high fixation and good fastness.

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.