POLLUTION CONTROL IN DYE INDUSTRY

Introduction A dye can generally be described as a colored substance that has an affinity to the substrate to which it is being applied. The dye is generally applied in an aqueous solution, and may require a mordant to improve the fastness of the dye on the fiber Both dyes and pigments appear to be colored because they absorb some wavelengths of light preferentially. In contrast with a dye, a pigment generally is insoluble, and has no affinity for the substrate.

Electronic excitation energies

Examples of chromophores are –N=N-. 1. -C=N.     σ → σ* π → π* n → σ* n → π* aromatic π → aromatic π* Chromophore: it is a functional groups which are unsaturated and they cause a compound to become coloured. 2. Transitions involving σ. -C=C-. π.and -C=O. 3. and n electrons Transitions involving charge-transfer electrons Transitions involving d and f electrons .

— NR2. —SH are common examples for auxochrome. —OH. —NH2. The effect of the auxochrome is due to its ability to extend the conjugation of a chromophore by the sharing of non-bonding electrons. nitro (-NO2).Auxochrome  Auxochromes are groups that does not impart color to the compound but increase the color of the compound. alkyl (-R). —NHR. —OR. Functional groups such as hydroxyl (–OH). amino ( -NH2).     Bathochromic Effect Hypsochromic shift Hyperchromic Effect Hypochromic Effect .

Pictorial representation of bathochromic shift and hypsochromic shift in the absoption spectra Typical data on some chromophre .

They owe their name to the presence of aromatic amino (basic) groups.CLASSIFICATION OF DYES  Acid Dyes These are generally applied to textile fibers from dye baths containing acid. Basic dyes Basic dyes were developed to dye negatively charged acrylic fibers. and in this case a cationic amino group is present. Most have one or two sodium sulfonate (–SO3Na) groups which are water soluble and capable of bonding with fibers having cationic sites. . they have excellent brightness and color strength. especially when monoazo and anthraquinone structures are used. their lightfastness is often Low. forming ionic bonds. They give a wide range of bright colors on textiles. Generally.

giving rise to the term direct-cotton dyes. They are also used as pH indicators and as biological stains. wool. silk and nylon.  Direct dyes are anionic colorants that have affinity for cellulosic fibers. Direct dyes are used on cotton. leather. Direct dyes Direct Dyes or substantive dyeing is normally carried out in a neutral or slightly alkaline dyebath. at or near boiling point. paper. . with the addition of either sodium chloride (NaCl) or sodium sulfate (Na2SO4). They were the first dyes with the ability to dye cotton in the absence of a mordanting agent.

brown. With suitable adjustment of dyebath conditions the two components react to produce the required insoluble azo dyes. olive. While yellow. These are mainly give dull shades. sulfur dyes are most important for their ability to deliver washfast black shades on cotton Examples of (a) sulfur yellow and (b) red dye structures Sulfur Dyes Azo Dyes: It is a technique in which an insoluble azoic dye is produced directly onto or within the fibre. This technique of dyeing is unique. red. Sulfur dyes are waterinsoluble dyes that are applied to cotton. in that the final color is controlled by the . and blue colors can be produced. This is achieved by treating a fibre with both diazoic and coupling components.

most vat dyes display high wash fastness Representative Anthraquinone vat dye structures (a) Vat Red 13. As would be anticipated.  Vat dyes have mainly anthraquinone (82%) or indigoid/thioindigoid (9%) structures. and (e) Vat Green 1. (d) Vat Blue 4. (c) Vat Orange 2.Vat Dyes:  Water insoluble and fast dyes applied along with strong reducing agents (sodium hydro sulfite) and alkali to make the dye soluble. with the former having better fastness properties  Vat dyes are easier to reoxidize than sulfur dyes and the oxygen in air is often the agent used. (b) Vat Black 27.  The cloth is then exposed to air for oxidation. .  The excess alkali remaining on the cloth is neutralized by scouring.

metals and unreacted raw materials) in dye application processes produce wastewaters that poses unacceptable environmental risks.. high levels of electrolytes.g. In the case of textile dyeing operations. the concerns raised can arise from incomplete dye bath exhaustion and the presence of dyeing auxiliaries and metal ions that are toxic to aquatic life. toxic substances (e. .DYESTUFF INDUSTRY TREATMENT The presence of residual color.

Sources of effluent  Dyeing and printing  industries  Textile industries  Paper and ink manufacturing industries  Cosmetics  Pharmaceuticals  Food .

The mineral materials. Dyes increases BOD of effluent thereby affecting aquatic life Toxic to fish & microbial organisms The discharge of heavy metals into aquatic ecosystemsIncrease in alkalinity of water The turbidity and colour along with oil and scum create an unsighty appearance.Properties of effluent          Impart colour to water bodies even if present in small quantity Reduces light penetration and photosynthesis Carcinogenic or mutagenic Azo dyes are more toxic as they affect microbes thereby affecting biological degradation treatment. . mostlysodium salts increase salinity of the water.

These effluents are usually hot. nitrites. It contains dyes. acids (acetic acid). mordants. Removal of Sulfides by treatment with chlorine or hypochlorites Spent vat dyes are strongly alkaline and have fairly high permanganate value . highly coloured with a high pH and sulfide content Care must be taken while neutralising these liquors as acid may liberate hydrogen sulfide gas. chromium salts. alkalis.Volume of effluent       The volume of effluent generated in dyeing is comparatively more. sodium chloride and soaps.

and dosage must be taken into consideration for optimum removal of dyes from wastewater  The most commonly used method of dye removal by adsorption.  Factors such as the choice of activated carbon. pH. temperature. contact time. It can be Effective for adsorbing cationic.Effluent Treatment Methods Physical Methods Adsorption  Activated carbon adsorption has been widely studied as a waste treatment method for the removal of different classes of dyes from wastewater. mordant and acid dyes and reactive dyes  Performance depends on the type of carbon used and the characteristics of the wastewater. .

Equalization Regulation of flow rate. also maintains pH levels of the system. Neutralization .

molecular. or macroparticulate in nature. 98—99. which may be ionic. colloidal.Adsorptive Bubble Separation Surface-active material. is selectively adsorbed at the surface of bubbles rising through the liquid.8% of Direct Blue1 was removed from wastewater .

Chemical methods   Fenton’s reagent (Fe2/H2O2) has been used commercially to oxidize and decolorize effluents containing a number of azo.). . anthraquinone. Two of the final degradation products are phthalic acid and carbon dioxide. Titanium Dioxide (TiO2)  The cationic dye Rhodamine B. Basic Violet 10 and the anthraquinone mordant dye Alizarine Red (Mordant Red 3) can be decomposed by Ti02 in the presence of visible light. Degradation occurs via the interaction of dye with hydroxyl radicals (OH. Dyes removed in these studies include reactive azo and anthraquinone dyes. and reactive dyes.

Borohydride Reduction  Sodium borohydride is one of the strongest water soluble reducing agent commercially available SO2 is produced when borohydride is used in combination with bisulfite catalysis in the pH rang e of 5 – 8 which readily reduces azo dyes The utility of this process involving a variety of azo dyes. and 0—200 mg cationic flocculant. direct.9% for metalized direct and phthalocyanine dyes This method was extended to industrial wastewater containing either a mixture of azo disperse dyes or azo reactive black dyes. giving percent colour reduction of 83-99% for acid. 12—25 mg/L NaBH4. reducing color by 93 – 99%     . and reactive dyes and 74-99. These solutions were treated with a mixture of 400—500 mg/L Na2S2O5.

Acid Yellow 17 (14). and Vat Golden Yellow .Structures of dyes removed using biological treatments: Acid Blue 113 (13). Direct Red 16 (15). Disperse Blue 73 (16).

and manganese peroxidases have proved effective in cleaving aromatic rings Structures of dyes used in borohydride reduction studies: (1) direct Red 254. (6) reactive red 120 . (2) direct yellow 4. enzymes such as laccases.Bioaugmentation and Bioremediation These methods are currently used by the textile and dyestuff industries to decolorize waste water using enzymes. lignin peroxidases. (3) acid red 1. (5) reactive red 24. (4) acid red 361. In this regard.

and leather industries is associated with the manufacture and use of metallized azo dyes that are complexed with chromium or cobalt to obtain desirable fastness properties various chemical. Fe-complexed dyes as environmentally friendly alternatives to widely used Cr and Co complexed acid dyes . and biological methods. such treatments can be expensive and may result in sludges that must be disposed by incineration or land filling In view of an emphasis on pollution prevention instead of waste treatment. physical.Metal Complexed Dyes     One of the most serious environmental problems in the dye. the merits of substituting iron (Fe) for chromium (Cr) and cobalt (Co) in a group of commercially important acid dyes. textile.

Application of an electrical potential between the two electrodes causes a migration of cations and anions towards respective electrodes Because of the alternate spacing of cation and anion permeable membranes. cells of concentrated and dilute salts are formed .Electrodialysis    The ionic components (heavy metals) are separated through the use of semi-permeable ion-selective membranes.

are slowly growing one. their loss shall reduce the efficiency of the treatment system and nutrient removal In the MBR.Membrane Bioreactor in Textile Waste Water Treatment       Utilization of membrane filtration results in the retention of active microorganisms. especially nitrifiers. The overall efficiency of BOD (Biological Oxygen Demand) and COD (Chemical Oxygen Demand) removal is improved . extra cellular enzymes generated by these micro-organisms for degradation of the organics present in the effluent Some micro-organisms. these organisms are retained and a better treatment is achieved In addition retention of active enzymes secreted by mico organisms taking part in the metabolization of organics present in the textile waste water is an important aspect of MBR technology Maintenance of higher concentration of these enzymes shall result in rapid and better degradation of complex organic molecules present in the textile waste water.

i) anoxic. the anoxic zone shall have very low levels of dissolved oxygen brought back by the recirculating effluent. which is then digested by the aerobic bacterial population persisting in the aerobic zone.. MBR is normally designed to incorporate two zones viz. The bacteria growing under anoxic condition has the capability to break down recalcitrant macromolecules. aerobic. In this way. and membrane compartments with re-circulation from the membrane zone to the anoxic zone. ii) aerobic Some bacteria can use oxygen as an electron acceptor when it is available. anoxic biological degradation is an important step if we consider MBR treatment for textile waste water     . Thus. and in the absence of oxygen the same bacteria can switch the respiration mode to utilize nitrate/nitrite as electron acceptors (facultative bacteria) and these can be used in both in anoxic as well as in aerobic conditions As MBR configuration involves anoxic. a significant portion of the dye stuff and other organics could be broken down and oxidized.

and any oscillations in effluent parameters are dampened The dampening effect shall be linear for all parameters having linear relationship with concentration viz.. and therefore outflow. BOD. TDS (Total Dissolved Solids Recirculation pattern inside MBR compartments This stabilized output water quality is due to the prevalence of a steady-state condition inside the MBR compartments due to the maintenance of high microbial activity . with a recirculation from membrane compartment to anaerobic being 3X When ever the feed quality changes. its characteristics are dampened by this re-circulation as the feed waste water gets diluted by the re-circulating fluid. anaerobic to aerobic and.If X is the inflow. COD. aerobic to membrane flow is 4X.

. are retained in MBR. High molecular weight organic compounds. their residence time is prolonged and the possibility of biodegradation is improved. and microbiological organisms along with suspended material present an excellent output from these systems whereby the biofouling and chemical scaling of the reverse osmosis system could be drastically minimized. Thus.Advantages of MBR     Membrane Bioreactors have proven to be quite effective in removing both organic and inorganic contaminants as well as biological entities from waste water. inorganic. The removal of organic. which are not readily biodegradable in conventional systems. It also minimizes use of cleaning chemicals in the secondary treatment.

S. John Wiley & Sons. Coimbatore. New Delhi. 2003 . Publication 4. Encyclopedia of chemical technology.ecpconsulting. Y.wikipedia. S. 3. India.org 2. Wiley Interscience. India.Eshwaramoorthi.com/doc/12949482/Dyestuff-IndustryTreatment. R.. Sharma. www. K. Elements of organic spectroscopy. Dhanapal and D.scribd.S. 9th Volume.Chauhan. Chand & Company LTD. Environment With People's Involvement & Co-ordination in India. www. 5th Edition.in 5. Kirk – Othmer.REFERENCES       1. Inc. http://www.

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