A Project Report on

Optimization of Coagulant Blends for Dye Wastewater Colour Removal

Under the Supervision of Dr. Tarun. K. Bera Senior Chemist, NLC Nalco India Ltd, Pune

Undertaken by Ishita Kumar rd 3 Year, B.E Environmental Engineering Delhi Technological University, DTU Formerly known as Delhi College of Engineering, DCE

Abstract
Sedimentation aided with Coagulation and Flocculation was employed for the treatment of high concentration reactive dye wastewater. An organic polymer coagulant based on Cyanoguanidine and formaldehyde namely N-8123 was blended with inorganic coagulants such as PolyAluminium Chloride (133L), Ferric Chloride (FeCl3) , Ferrous Sulphate (FeSO4) etc. in order to carry out colourremoval study. The anionic flocculant N-9901 was used for the dye wastewater treatment. Optimization studies were conducted on synthetic dye wastewater prepared using 100ppm cotton blue dye as well as the real industrial wastewater from Huntsman Ltd and Merchem Ltd. However, the required dosage of FeCl3 and N-8123 blend was higher compared to 133L & N-8123 blend to achieve similar colour removal. The effect of pH on colour removal was also conducted using synthetic dye wastewater. The studies conducted on industrial wastewater sample from Huntsman Ltd. showed a colour removal performance of 92% using an optimized blend of FeSO4 and N-8123 and that for Merchem Ltd was found to be the ZnCl2 and N-8123 blend.

Keywords: Coagulation; Dye Wastewater; Dye; Polymer

Acknowledgement
I would like to offer my sincere gratitude to Hari Reddy for giving me an opportunity to work in a world-class organization. I also wish to thank Vaideeswaran Sivaswamy and Divagar Lakshmanan for their constant support and encouragement during the course of my internship programme. I owe thanks to Gaurav Garg and Bhumika Kadam for their help and advice which came across as a great help. I offer deep gratitude to my mentor Dr. Tarun.K. Bera for enhancing my knowledge and expertise in the field of wastewater. His consistent encouragement and feedback helped me to successfully complete my project. I also owe a great deal of my knowledge to Trishul Artham as he stood by me in the formative period of the internship. I also wish to thank all the colleagues in Nalco for being a great support system. The lab personnel and support staff were a great help while working in the lab. Last but not the least; I would like to thank my fellow interns for the wonderful time and a memorable experience.

Ishita Kumar 3 Year, B.E Environmental Engineering Delhi Technological University (DTU) (formerly) Delhi College of Engineering, DCE
rd

Certificate

This is to certify that the project entitled Optimization of Coagulation Blends on Dye Wastewater Colour Removal undertaken by Ishita Kumar, 3rd Year, B.E Environmental Engineering has been successfully completed in 8 weeks under the supervision of Dr. Tarun. K. Bera, Senior Chemist working at NLC Nalco Ltd, PUNE R&D, India.

Dr. Tarun. K. Bera Senior Chemist NLC, Nalco Ltd, Pune R&D, India

Contents 1. Introduction ................................................................................................................................ 7 1.1 Textile Industry Processes ..................................................................................................... 7 1.1.1 Yarn Formation ............................................................................................................... 7 1.1.2 Fabric Formation............................................................................................................. 7 1.1.3 Wet Processing ............................................................................................................... 8 1.1.4 Fabric Preparation .......................................................................................................... 8 1.2 Dyes: Definition and Types .................................................................................................. 11 1.2.1 Types of Synthetic Dyes ................................................................................................ 11 1.3 Textile Waste Streams......................................................................................................... 14 1.3.1 Wastewater .................................................................................................................. 14 1.3.2 Metal Toxicity ............................................................................................................... 18 1.3.3 Aquatic Toxicity ............................................................................................................ 18 1.3.4 Air Emissions ................................................................................................................. 18 1.3.5 Other Wastes ................................................................................................................ 19 2. Existing Nalco Program for Colour Removal ............................................................................. 20 3. Objective and Scope of the Project .......................................................................................... 21 4. Experimental Section ................................................................................................................ 22 4.1 Testing Procedure ............................................................................................................... 22 4.1.1 Jar Testing Method ....................................................................................................... 22 4.1.2 Measurement of True Colour ....................................................................................... 22 4.1.3 Turbidity Measurement ................................................................................................ 22 4.1.4 COD Measurement ....................................................................................................... 23 4.2Polymer Make-up Procedure ............................................................................................... 23 4.3Coagulant Make-Up Procedure ............................................................................................ 24 4.4 pH Measurement ................................................................................................................ 24 TDS Measurement ..................................................................................................................... 24 5. Results and Discussion .............................................................................................................. 25 5.1 Variation of Dye Concentration with Optimum Coagulant Dose........................................ 25 5.2 Dosage Optimization of N-8123 on 100 ppm Cotton Blue Dye. ......................................... 25
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5.3 Dosage Optimization of 133L Dose on 100 ppm Cotton Blue Dye Solution. ...................... 27 5.4 Dosage Optimization of N-8123 and 133L Blend ................................................................ 28 5.5 Optimization of FeCl3 Dose on 100 ppm Cotton Blue Dye .................................................. 30 5.6 Optimization of a blend of Ferric Chloride (FeCl3) and N-8123 on 100 ppm Cotton Blue Dye............................................................................................................................................. 32 5.7 Industrial Wastewater Testing ............................................................................................ 33 5.7.1 Industrial Sample 1 ....................................................................................................... 33 5.7.2. Industrial Sample 2 ...................................................................................................... 36 6.Conclusion .................................................................................................................................. 39 7.Future Directions ....................................................................................................................... 41 8.References ................................................................................................................................. 42

1. Introduction
The textile industry is comprised of a diverse, fragmented group of establishments that produce and or process textile-related products (fiber, yarn, fabric) for further processing into apparel, home furnishings, and industrial goods. Textile establishments receive and prepare fibers; transform fibers into yarn, thread, or webbing; convert the yarn into fabric or related products; and dye and finish these materials at various stages of production. The process of converting raw fibers into finished apparel and non-apparel textile products is complex; thus, most textile mills specialize. Little overlap occurs between hitting and weaving, or among production of manmade, cotton, and wool fabrics. The primary focus of this section is on weaving and knitting operations, with a brief mention of processes used to make carpets. In its broadest sense, the textile industry includes the production of yarn, fabric, and finished goods. This section focuses on the following four production stages, with a brief discussion of the fabrication of nonapparel goods:

1.1 Textile Industry Processes

1.1.1 Yarn Formation

Textile fibers are converted into yarn by grouping and twisting operations used to bind them together. Natural fibers, known as staple when harvested, include animal and plant fibers, such as cotton and wool. These fibers must go through a series of preparation steps before they can be spun into yarn, including opening, blending, carding, combing, and drafting.
1.1.2 Fabric Formation

The major methods for fabric manufacture are weaving and knitting. Weaving, or interlacing yarns, is the most common process used to create fabrics. Weaving mills classified as broad woven mills consume the largest portion of textile fiber and produce the raw textile material from which most textile products are made. Narrow woven, nonwovens, and rope are also produced primarily for use in industrial applications. Starch, the most common primary size component, accounts for roughly two-thirds of all size chemicals used in the U.S. (130 million pounds per year). Starch is used primarily on natural fibers and in a blend with synthetic sizes for coating natural and synthetic yarns. Polyvinyl alcohol (PVA), the leading synthetic size, accounts for much of the remaining size consumed in the U.S. (70 million pounds per year). PVA is increasing in use since it can be recycled, unlike starch. PVA is used with polyester cotton yarns and pure cotton yarns either in a pure form or in blends with natural and other synthetic sizes. Other synthetic sizes contain acrylic and acrylic copolymer components. Semisynthetic sizes, such as carboxymethyl cellulose (CMC) and modified starches are also used. Knitting is the second most frequently used method of fabric
7

construction. Manufacturers of knit fabrics also consume a sizeable amount of fibers. Knitted fabrics can be used for hosiery, underwear, sweaters, slacks, suits, coats, rugs, and other home furnishings.
1.1.3 Wet Processing

Woven and knit fabrics cannot be processed into apparel and other finished goods until the fabrics have passed through several water-intensive wet processing stages. Wet processing enhances the appearance, durability, and serviceability of fabrics by converting undyed and unfinished goods, known as gray or greige goods, into finished consumers goods. Also collectively known as finishing, wet processing has been broken down into four stages in this section for simplification: fabric preparation, dyeing, printing, and finishing. These stages involve treating gray goods with chemical baths and often require additional washing, rinsing, and drying steps. Note that some of these steps may be optional depending on the style of fabric being manufactured. In terms of waste generation and environmental impacts, wet processing is the most significant textile operation. Methods used vary greatly depending on end-products and applications, site specific manufacturing practices, and fiber type. Natural fibers typically require more processing steps than manmade fibers. For most wool products and some manmade and cotton products, the yarn is dyed before weaving; thus, the pattern is woven into the fabric. Processing methods may also differ based on the final properties desired, such as tensile strength, flexibility, uniformity, and luster (Snowden-Swan, 1995). Most manufactured textiles are shipped from textile mills to commission dyeing and finishing shops for wet processing, although some forms have integrated wet processing into their operations. A wide range of' equipment is used for textile dyeing and finishing (EPA, 1996). Much of the waste generated from the industry is produced during the wet processing stages. Relatively large volumes of wastewater are generated, containing a wide range of contaminants that must be treated prior to disposal. Significant quantities of energy are spent heating and cooling chemical baths and drying fabrics and yarns (Snowden-Swan, 1995).
1.1.4 Fabric Preparation

Most fabric that is dyed, printed, or finished must be first prepared, with the exception of denim and certain knit styles. Preparation, also known as pretreatment, consists of a series of various treatment and rinsing steps critical to obtaining good results in subsequent textile finishing processes. In preparation, the mill removes natural impurities or processing chemicals that interfere with dyeing, printing, and finishing. Typical preparation treatments include desizing, scouring, and bleaching. Singeing: If a fabric is to have a smooth finish, singeing is essential. Singeing is a dry process used on woven goods that removes fibers protruding from yarns or fabrics. These are burned off by passing the fibers over a flame or heated copperplates. Singeing improves the
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surface appearance of woven goods and reduces pilling. Pollutant outputs associated with singeing include relatively small amount of exhaust gases from the burners. Desizing: It is an important preparation step used to remove size materials applied prior to weaving. Manmade fibers are generally sized with water-soluble sizes that are easily removed by a hot-water wash or in the scouring process. Natural fibers such as cotton are most often sized with water-insoluble starches or mixtures of starch and other materials. Enzymes are used to break these starches into water-soluble sugars, which are then removed by washing before the cloth is scoured. Removing starches before scouring is necessary because they can react and cause color changes when exposed to sodium hydroxide in scouring. Scouring: It is a cleaning process that removes impurities from fibers, yarns, or cloth through washing. Alkaline solutions are typically used for scouring; however, in some cases solvent solutions may also be used. Scouring uses alkali, typically hydroxide, to break down natural oils and surfactants and to emulsify and suspend remaining impurities in the scouring bath. The specific scouring procedures, chemicals, temperature, and time vary with the type of fiber, yarn, and cloth construction. Impurities may include lubricants, dirt and other natural materials, water-soluble sizes, antistatic agents, and residual tints used for yarn identification. Typically, scouring wastes contribute a large portion of biological oxygen demand (BOD) loads from preparation processes (NC DEHNR, 1986). Bleaching: Bleaching is a chemical process that eliminates unwanted colored matter from fibers, yarns, or cloth. Bleaching decolorizes colored impurities that are not removed by scouring and prepares the cloth for further finishing processes such as dyeing or printing. Several different types of chemicals are used as bleaching agents, and selection depends on the type of fiber present in the yarn, cloth, or finished product and the subsequent finishing that the product will receive. The most common bleaching agents include hydrogen peroxide, sodium hypochlorite, sodium chlorite, and sulfur dioxide gas. Hydrogen peroxide is by far the most commonly used bleaching agent for cotton and cotton blends, accounting for over 90 percent of the bleach used in textile operations, and is typically used with caustic solutions. Bleaching contributes less than 5 percent of the total textile mill BOD load (NC DEHNR, 1986). Peroxide bleaching can be responsible for wastewater with high pH levels. Because peroxide bleaching typically produces wastewater with few contaminants, water conservation and chemical handling issues are the primary pollution concerns. Mercerizing: Mercerization is a continuous chemical process used for Mercerizing. Mercerization is a continuous chemical process used for cotton and cottod polyester goods to increase dye-ability, luster, and appearance. This causes the fiber to become more lustrous than the original fiber, increase in strength by as much as 20 percent, and increase its affinity for dyes. Mercerizing typically follows singeing and may either precede or follow
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bleaching (Corbman, 1975). During mercerizing, the fabric is passed through a cold 15 to 20 percent solution of caustic soda and then stretched out on a tender frame where hot-water sprays remove most of the caustic solution (Corbman, 1975). After treatment, the caustic is removed by several washes under tension. Remaining caustic may be neutralized with a cold acid treatment followed by several more rinses to remove the acid. Wastewater from mercerizing can contain substantial amounts of high pH alkali, accounting for about 20 percent of the weight of goods. Dyeing Operations: Dyeing operations are used at various stages of production to add color and intricacy to textiles and increase product value. Textiles are dyed using a wide range of dyestuffs, techniques, and equipment. Dyes used by the textile industry are largely synthetic; typically derived from coal tar and petroleum-based intermediates. Dyes are sold as powders, granules, pastes, and liquid dispersions, with concentrations of active ingredients ranging typically from 20 to 80 percent. Dyeing can be performed using continuous or batch processes. Batch Dyeing: In batch dyeing, a certain amount of textile substrate, usually 100 to 1,000 kilograms, is loaded into a dyeing machine and brought to equilibrium, or near equilibrium, with a solution containing the dye. Because the dyes have an affinity for the fibers, the dye molecules leave the dye solution and enter the fibers over a period of minutes to hours, depending on the type of dye and fabric used Continuous dyeing: In these processes typically consist of dye application, dye fixation with chemicals or heat, and washing. Dye fixation is a measure of the amount of the percentage of dye in a bath that will fix to the fibers of the textile material. Dye fixation on the fiber occurs much more rapidly in continuous dying than in hatch dyeing. Yarn Dyeing: Yarn dyeing is used to create interesting checks, stripes, and plaids with different colored yarns in the weaving process. In yarn dyeing, dyestuff penetrates the fibers in the core of the yarn. Some methods of yarn dyeing are stock, package, and skein dyeing. Stock dyeing: In this process dyes is done using perforated tubes. In package dyeing, spools of yarn are stacked on perforated rods in a rack and immersed in a tank where dye is then forced outward from the rods under pressure. The dye is then pressured back through the packages toward the center to wholly penetrate the entire yarn. Most carded and combed cotton used for knitted outerwear is package-dyed. Skein dyeing: In skein dyeing, yarn is loosely coiled on a reel and then dyed. The coils, or skeins, are hung over a rung and immersed in a dyebath (Corbman, 1975). Skein-dyed yarn is used for bulky acrylic and wool yarns. Typical capacity for package dyeing equipment is 1,210 pounds (550 kg) and for skein dyeing equipment is 220 pounds (100 kg).

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Piece Dyeing: Most dyed fabric is piece-dyed since this method gives the manufacturer maximum inventory flexibility to meet color demands as fashion changes. In terms of overall volume, the largest amount of dyeing is performed using beck and jig equipment. Beck dyeing: Beck dyeing is a versatile, continuous process used to dye long yards of fabric. About 1,980 pounds (900 kg) of fabric can be dyed on beck equipment at a time. The fabric is passed in rope form through the dyebath. The rope moves over a rail onto a reel which immerses it into the dye and then draws the fabric up and forward to the front of the machine. This process is repeated as long as necessary to dye the material uniformly to the desired color intensity. Jig Dyeing: Jig dyeing uses the same procedure of beck dyeing, however, the fabric is held on rollers at full width rather than in rope form as it is passed through the dye-bath (Corbman, 1975). This reduces fabric tendency to crack or crease. Jig dyeing equipment can handle 550 pounds (250 kg) of fabric. Jet dyeing: Fabric can be jet-dyed (at up to 1,100 pounds (500 kg)) by placing it in a heated tube or column where jets of dye solution are forced through it at high pressures. The dye is continually recirculated as the fabric is moved along the tube. Pad dyeing: Pad dyeing, like jig dyeing, dyes the fabric at full width. The fabric is passed through a trough containing dye and then between two heavy rollers which force the dye into the cloth and squeeze out the excess (Corbman, 1975).

1.2 Dyes: Definition and Types

A dye is 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 more than others. In contrast with a dye, a pigment generally is insoluble, and has no affinity for the substrate. Some dyes can be precipitated with an inert salt to produce a lake pigment, and based on the salt used they could be aluminum lake, calcium lake or barium lake pigments
1.2.1 Types of Synthetic Dyes

Acid dyes are water-soluble anionic dyes that are applied to fibers such as silk, wool, nylon and modified acrylic fibers using neutral to acid dye baths. Attachment to the fiber is attributed, at least partly, to salt formation between anionic groups in the dyes and cationic groups in the fiber. Acid dyes are not substantive to cellulosic fibers. Most synthetic food colors fall in this category.

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Basic dyes are water-soluble cationic dyes that are mainly applied to acrylic fibers, but find some use for wool and silk. Usually acetic acid is added to the dye-bath to help the uptake of the dye onto the fiber. Basic dyes are also used in the coloration of paper. Direct dyes or substantive dyeing is normally carried out in a neutral or slightly alkaline dye-bath, at or near boiling point, with the addition of either sodium chloride (NaCl) or sodium sulfate (Na2SO4). Direct dyes are used on cotton, paper, leather, wool, silk and nylon. They are also used as pH indicators and as biological stains. Mordant dyes require a mordant, which improves the fastness of the dye against water, light and perspiration. The choice of mordant is very important as different mordants can change the final color significantly. Most natural dyes are mordant dyes and there is therefore a large literature base describing dyeing techniques. The most important mordant dyes are the synthetic mordant dyes, or chrome dyes, used for wool; these comprise some 30% of dyes used for wool, and are especially useful for black and navy shades. The mordant, potassium dichromate, is applied as an after-treatment. It is important to note that many mordants, particularly those in the heavy metal category, can be hazardous to health and extreme care must be taken in using them. Vat dyes are essentially insoluble in water and incapable of dyeing fibers directly. However, reduction in alkaline liquor produces the water soluble alkali metal salt of the dye, which, in this leuco form, has an affinity for the textile fiber. Subsequent oxidation reforms the original insoluble dye. The color of denim is due to indigo, the original vat dye. Reactive dyes utilize a chromophore attached to a substituent that is capable of directly reacting with the fibre substrate. The covalent bonds that attach reactive dye to natural fibers make them among the most permanent of dyes. "Cold" reactive dyes, such as Procion MX, Cibacron F, and Drimarene K, are very easy to use because the dye can be applied at room temperature. Reactive dyes are by far the best choice for dyeing cotton and other cellulose fibers at home or in the art studio. Disperse dyes were originally developed for the dyeing of cellulose acetate, and are water insoluble. The dyes are finely ground in the presence of a dispersing agent and sold as a paste, or spray-dried and sold as a powder. Their main use is to dye polyester but they can also be used to dye nylon, cellulose triacetate, and acrylic fibers. In some cases, a dyeing temperature of 130 C is required, and a pressurized dyebath is used. The very fine particle size gives a large surface area that aids dissolution to allow uptake by the fiber. The dyeing rate can be significantly influenced by the choice of dispersing agent used during the grinding. Azoic dyeing is a technique in which an insoluble azo dye is produced directly onto or within the fibre. This is achieved by treating a fiber with both diazoic and coupling components. With suitable adjustment of dyebath conditions the two components react
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to produce the required insoluble azo dye. This technique of dyeing is unique, in that the final color is controlled by the choice of the diazoic and coupling components. This method of dyeing cotton is declining in importance due to the toxic nature of the chemicals used. Sulfur dyes are two parts "developed" dyes used to dye cotton with dark colors. The initial bath imparts a yellow or pale chartreuse color. This is after treated with a sulfur compound in place to produce the dark black we are familiar with in socks for instance. Sulfur Black 1 is the largest selling dye by volume. Food Dyes: One other class that describes the role of dyes, rather than their mode of use, is the food dye. Because food dyes are classed as food additives, they are manufactured to a higher standard than some industrial dyes. Food dyes can be direct, mordant and vat dyes, and their use is strictly controlled by legislation. Many are azo dyes, although anthraquinone and triphenylmethane compounds are used for colors such as green and blue. Some naturally-occurring dyes are also used. Table 1: Showing the pollutants associated with synthetic Dyes
S.No Dye Class Description 1. Acid Method of Application Water soluble, anionic Exhaust\Beck compounds \Continuous (Carpet) Water-Soluble, Exhaust\ applied in weakly Beck acidic dyebaths; bright dyes Water soluble, anionic Exhaust\ compounds, can be Beck applied directly to \Continuous cellulosics without mordants Not water soluble High Temperature Exhaust, Continuous Water-Soluble, Exhaust\ Anionic Compounds, Beck\ Largest Dye class Continuous Organic compounds Continuous containing Sulphur Fibers Applied to Wool, Nylon Typical Fixation% 80-93 Pollutants Associated with Dye Colour, Organic Acids, Unfixed Dyes N/A

2.

Basic

Acrylic, Some 97-98 Polyesters

3.

Direct

Cotton, 70-95 Rayon, Other Cellulosics

4.

Disperse

5.

Reactive

Polyester acetate, other synthetics Cotton, Other Cellulosics, Cotton, Cellulosics

80-92

60-90

Colour, salt, unfixed dyes, Cationic fixing agent, defoamers surfactants, leveling dispersing agents. Colour; organic acids; carriers; levelling agents;phosphates defoamers Colour, Salt, Unfixed Dye, Surfactant, Defoamers, Diluetants,
Colour, Alkali, Oxidising agents, Reducing agents, Unfixed Dye

Sulphur

60-70

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1.3 Textile Waste Streams

1.3.1 Wastewater

Wastewater is, by far, the largest waste stream for the textile industry. Large volume wastes include wash water from preparation and continuous dyeing, alkaline waste from preparation, and batch dye waste containing large amounts of salt, acid, or alkali. A primary source of biological oxygen demand (BOD) includes waste chemicals or batch dumps, starch sizing agents, knitting oils, and degradable surfactants. Wet processing operations, including preparation, dyeing, and finishing, generate the majority of textile wastewater. Desizing, or the process of removing size chemicals from te xtiles, is one of the industrys largest sources of wastewater pollutants. In this process, large quantities of size used in weaving processes are typically discarded. More than 90 percent of the size used by the U.S. textile industry, or 90,000 tons, is disposed of in the effluent stream. The remaining 10 percent is recycled (EPA, 1996). Desizing processes often contribute up to 50 percent of the BOD load in wastewater from wet processing (Snowden-Swan, 1995). Dyeing operations generate a large portion of the industrys total wastewater. The primary source of wastewater in dyeing operations is spent dyebath and wash water. Such wastewater typically contains by-products, residual dye, and auxiliary chemicals. Additional pollutants include cleaning solvents, such as oxalic acid. Of the 700,000 tons of dyes produced annually worldwide, about 10 to 15 percent of the dye is disposed of in effluent from dyeing operations (Snowden-Swan, 1995). However, dyes in wastewater may be chemically bound to fabric fibers (ATMI, 1997b). The average wastewater generation from a dyeing facility is estimated at between one and two million gallons per day. Dyeing and rinsing processes for disperse dyeing generate about 12 to 17 gallons of wastewater per pound of product. Refer Table#1 The effluent from the dyeing and finishing processes is characterized by strong color, high pH, high temperature, high COD, and low biodegradability. In recent years, reactive dyes have been most commonly used due to their advantages such as dyeing processing conditions and bright colors. Moreover, the use of reactive dyes is rapidly growing due to the increased use of cellulosic fibers. Generally reactive dyes contain functional groups such as azo, anthraquinone, phthalocyanine, formazin, and oxazine as chromophore. Among the reactive dyes, approximately 66%is unmetallized azo dye. The reactive site of the dyes reacts with functional group on fiber under influence of heat and alkali. One of the major factors determining the release of a dye into environment is its degree of fixation on the fiber. Reactive dye is hydrolyzed to some extent during application processes; some of reactive dyestuff is inactivated by a competing hydrolysis reaction. Consequently, the release of reactive dyes into dyebath effluent is exacerbated by their relatively low fixation
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(50e90%) to cellulosic fibers, compared with other dyes such as acid, basic, disperse and direct dye. Reactive dyes in dyeing wastewater have been identified as recalcitrant compounds since they contain high alkalinity, high concentration of organic materials and strong color in comparison with other dyes. Unless coloring materials are properly removed, dye wastewater significantly affects photosynthetic activity in aquatic life due to reduced light penetration. Refer Table 2 to know about the BOD Load associated with the textile processes. Table 2: Table showing BOD Load associated with textile processes Process Singeing Desizing Starch Starch, Mixed Size PVA or CMC Scouring Bleaching Peroxide Hypochlorite Mercerizing Pounds of BOD per 1000 Pounds of Production 0 67 20 0 40-50 3-4 8 15

Finishing processes typically generate wastewater containing natural and synthetic polymers and a range of other potentially toxic substances (Snowden-Swan, 1995). Pollution from peroxide bleaching normally is not a major concern. In most cases, scouring has removed impurities in the goods, so the only by-product of the peroxide reaction is water. The major pollution issues in the bleaching process are chemical handling, water conservation, and high pH. Hazardous waste generated by textile manufacturers results primarily from the use of solvents in cleaning knit goods (ATMI, 1997b). Solvents may be used in some scouring or equipment cleaning operations, however, more often scouring processes are aqueous-based and cleaning materials involve mineral spirits or other chemicals (ATMI, 1997b). Spent solvents may include tetrachloroethylene and trichloroethylene (NC DEHNR, P2 Pays, 1985). A few of the more common textile industry water pollutants and their sources are discussed below. In addition, Table 3 summarizes the typical pollutant releases associated with various textile manufacturing processes.

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Table 3: Table showing the pollution load associated with Textile Industry Process Air Emission Fiber Little or no air Preparation emission Yarn Spinning Slashing/ Sizing Weaving Wastewater Little or no wastewater generated Little or no air Little or no emission wastewater generated VOCs BOD; COD; metals; cleaning wastes; size Little or no air Little or no emission wastewater generated Little or no air Little or no emission wastewater generated Little or no air Little or no emission wastewater generated VOCS from BOD from waterGlycol Ethers soluble sizes; synthetic size; lubricants; Biocides; Antistatic Compounds VOCs from Disinfectant and Glycol Ether and Insecticide scouring residue; NaOH; solvents detergents; fats; oils; pectin; wax; knitting lubricants; spent solvents Little or no air Hydrogen emission Peroxide; Sodium Silicate Residual Waste Fiber waste; packaging waste and hard waste Packaging wastes; sized yarn; fiber waste; cleaning and processing wastes Fiber/ lint; yarn waste; packaging wastes; unused starch-based sizes Packaging wastes; yarn and fabric scraps; off-spec fabric; used oil Packaging wastes; yarn and fabric scraps; off-spec fabric Packaging wastes; yarn and fabric scraps; off-spec fabric Packaging wastes; yarn and fabric scraps; off-spec fabric

Knitting

Tufting

Desizing

Scouring

Little or no Residual Waste Generated

Bleaching

Little or no Residual Waste Generated

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or organic stabilizer; high pH Singeing Small amount of Little or no exhaust gases wastewater from burners generated Mercerizing Little or no air High pH; NaOH emission Heat Volatilization of Little or no setting spin finish wastewater agents generated Dyeing VOCs Metals; salt; surfactants; toxics; organic processing assisstants; cationic materials; colour; BOD; COD; acidity/ alkalinity Printing Solvents, Acetic Suspended Acid from Solids; Urea; drying, curing, Solvents; Colour; oven emissions, metals; heat; combustion BOD; foam gases and Particulate Matter Finishing VOCs, BOD; COD; Contaminants in Suspended purchased Solids; toxics; chemicals, gases Spent Solvents Particulate Matter

Little or no Residual Waste Generated Little or no Residual Waste Generated Little or no Residual Waste Generated Little or no Residual Waste Generated

Little or no Residual Waste Generated

Little or no Residual Waste Generated

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1.3.2 Metal Toxicity

Many textile mills have few or no metals in their effluent, but whenever metals are present, they may include metals such as copper, cadmium, chromium, nickel, and zinc. Sources of metals found in textile mill effluents may include fiber, incoming water, dyes, plumbing, and chemical impurities. Dyes may contain metals such as zinc, nickel, chromium, and cobalt (ATMI, 1997b). In some dyes, these metals are functional (i.e., they form an integral part of the dye molecule); however, in most dyes, metals are simply impurities generated during dye manufacture. For example, mercury or other metals may be used as catalysts in the manufacture of certain dyes and may be present as byproducts. Metals may be difficult to remove from wastewater (EPA, 1996).

1.3.3 Aquatic Toxicity

The aquatic toxicity of textile industry wastewater varies considerably among production facilities. Data are available that show that the wastewater of some facilities has fairly high aquatic toxicity, while others show little or no toxicity. The sources of aquatic toxicity can include salt, surfactants, ionic metals and their complexed metals therein, toxic organic chemicals, biocides, and toxic anions (EPA, 1996; ATMI, 1997b). Most textile dyes have low aquatic toxicity. On the other hand, surfactants and related compounds, such as detergents, emulsifiers, dispersants, are used in almost every textile process and can be an important contributor to effluent aquatic toxicity, BOD, and foaming (EPA, 1996).
1.3.4 Air Emissions

Although the textile industry is a relatively minor source of air pollutants compared with many other industries, the industry emits a wide variety of air pollutants, making sampling, analysis, treatment, and prevention more complex. Textile operations involve numerous sources of air emissions. Operations that represent the greatest concern are coating, finishing, and dyeing operations. Textile mills usually generate nitrogen and sulphur oxides from boilers and are often classified as major sources under the Clean Air Act (EPA, 1996). Other significant sources of air emissions in textile operations include resin finishing and drying operations, printing, dyeing, fabric preparation, and wastewater treatment plants (ATMI, 1997b). Hydrocarbons are emitted from drying ovens and, in particular, from mineral oil from hightemperature (200C) drying and curing.

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Carriers and solvents may be emitted during dyeing operations depending on the types of dyeing processes used and from wastewater treatment plant operations. Other potential pollutants can include solvent vapors containing toxic compounds such as acetaldehyde, chlorofluorocarbons, pdichlorobenzene, ethyl acetate, and others. Some process chemicals, such as methyl naphthalene or chlorotoluene, may exhaust into the fibers and are later emitted from dryers as VOCs (EPA, 1996). Textile manufacturing can produce oil and acid fumes, plasticizers, and other volatile chemicals. Acetic acid emissions may arise from storage tanks, especially from vents during filling. Carbonizing processes, used in wool yarn manufacture, may emit sulfuric acid fumes and decating, a finishing process applied to wool fabrics to set the nap and develop luster, produces formic acid fumes. In addition, cleaning and scouring chemicals were estimated at 10,500 metric tons in 1988 (EPA, 1996).
1.3.5 Other Wastes

The primary residual wastes generated from the textile industry are non-hazardous. These include fabric and yarn scrap, off-spec yarn and fabric, and packaging waste. Cutting room waste generates a high volume of fabric scrap that can be reduced by increasing fabric utilization efficiency in cutting and sewing. Typical efficiency for using fabric averages from 72 to 94 percent. As a result, fabrication waste from carpets amounts to about 2 percent of an annual 900 million square yards of production (a value of $100 million). Denim cutting waste accounts for approximately 16 percent of denim production, or 100 million pounds annually. Although, a large portion of cutting waste goes to landfill, some innovative programs being implemented to recycle this material. Some facilities collect cotton lint for resale. Cotton trash, leaves, and stems collected during the yarn formation have been sold to farmers as animal feed.

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2. Existing Nalco Program for Colour Removal

At present, Nalco has a specialized chemical N-8123 which is a polymer based on cyanoguanidine and formaldehyde. The chemical is very effective in removing colour. Besides, being an organic polymer it is bio-degradable and does not pose serious environmental hazards. Another added advantage is that the volume of sludge produced is much less. It, therefore, reduces the overall expenditure in sludge handling processes-dewatering, transportation and disposal. The problem concerning the current program is that the required dosage is very high for good colour removal. As high as 400-500 ppm of the coagulant is required to achieve effective colour removal. The industry prefers to purchase inorganic coagulants like alum, ferric chloride, ferrous sulphate etc. which are inexpensive and easily available. In order to cater to the real-world scenario Nalco looks forward to achieving an economical and sustainable program for colour removal.

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3. Objective and Scope of the Project

Indian Textile sector has grown by more than 5% in the last two fiscal years and is projected to grow at ~16% by 2012. This necessitates the need for proper infrastructure development to achieve the projected growth. One of the biggest challenges which already exists and is going to pose a challenge is the development of cost effective and sustainable treatment programs for the wastewater that comes out of textile processing (Desizing, Scouring, Bleaching, Mercerizing, Dyeing, and Washing). Over the last couple of years, Nalco has invested a tremendous amount of effort to develop new value added programs for textile wastewater treatment. The results of the studies have been very encouraging and are currently practiced in Nalco. However the market is in demand of more efficient and economical programs. This research work conducted at Nalco involved the study of the following: 1. Understand briefly about the different textile processes 2. Understand the contaminants and their concentration ranges in the textile wastewater 3. Perform background study on the existing treatment programs for the textile wastewater 4. Research for new possible treatment processes which could be efficient in treating the textile wastewater which could involve mechanical and/or chemical programs. 5. Evaluate the performance of these encouraging programs by running laboratory tests and comparing against the commonly used existing programs. Recent research has shown some promise on blended chemical programs which were tested by conducting experiments along with the new programs proposed from the research.

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4. Experimental Section
4.1 Testing Procedure
4.1.1 Jar Testing Method

Jar Tests were conducted to determine the optimum dosage of various chemicals added to carry out colour-removal using the process of Sedimentation Aided with Coagulation and Flocculation. One Jar was tested at a time using the following procedure. 1. First a 25O mL dye water solution was placed in a beaker. 2. The Jar was made to rotate at a speed of 250 R.P.M for duration of two minutes. This is known as the rapid mix. 3. To it freshly prepared Lime solution was added to raise the pH to the desired level. 4. Within few seconds of addition of Lime, freshly prepared solution of coagulant was added. 5. In the last thirty seconds of the rapid mix, flocculants was added to the beaker. 6. The Jar Tests is programmed to rotate at a speed of 75 R.P.M for one minute once the rapid mix is over. This is termed as slow mix. 7. On Completion of slow mix, the blades are removed and the flocs formed are made to settle down for five minutes.
4.1.2 Measurement of True Colour

1. On DR 2800 Spectrophotometer Press STORED PROGRAMS and press on the option Select By Number. 2. Select the number 120 for the measurement of True Colour. 3. Add 10 mL of Milli-Q water in the cuvette. Place it in the cuvette holder, close the light shield and press zero. 4. Once the display shows zero, recheck the value by pressing Read. 5. The water sample must be filtered through a 0.45 micro-meter syringe filter. 6. Place the filtered water sample in the cuvette and read the colour value in Pt.-Co units.
4.1.3 Turbidity Measurement

1. Turbidity is measured using HACH 2100 Qis Turbidimeter. 2. The instrument is first calibrated using standard solutions of known concentration prepared from formazin. 3. After calibration, the sample is placed is placed in cuvette and tightly capped. 4. It must be properly wiped out from the outer surface. 5. Shake vigorously and place the solution in turbidimeter. 6. Press READ and note down the reading of Turbidity.

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4.1.4 COD Measurement

1. Homogenize 100 mL of sample for 30 seconds in a blender. For samples containing large amounts of solids, increase the homogenization time. If the sample does not contain suspended solids, omit steps 1 and 2. 2. For the 20015,000 mg/L range or to improve accuracy and reproducibility of the other ranges, pour the homogenized sample into a 250-mL beaker and gently stir with a magnetic stir plate. 3. Turn on the DRB200 Reactor. Preheat to 150 C. 4. Remove the caps from two COD Digestion Reagent Vials. (Be sure to use vials for the appropriate range.) 5. Hold one vial at a 45-degree angle. Use a clean volumetric pipet to add 2.00 mL of sample to the vial. 6. Hold a second vial at a 45-degree angle. Use a clean volumetric pipet to add 2.00 mL of deionized water to the vial. 7. Use a Pipet to add 0.20 mL for the 20015,000 mg/L range. Cap the vials tightly. Rinse them with water and wipe with a clean paper towel. 8. Hold the vials by the cap over a sink. Invert gently several times to mix. Insert the vials in the preheated DRB200 Reactor. Close the protective lid. 9. The sample vials will become very hot during mixing. Heat the vials for two hours. 10. Turn the reactor off. Wait about 20 minutes for the vials to cool to 120 C or less. 11. Invert each vial several times while still warm. Place the vials into a rack and cool to room temperature. 12. Select the ultra-low range (DR 2800 only), low range, or high range test. Install the Light Shield in Cell Compartment #2. 13. Clean the outside of the vials with a damp towel followed by a dry one. 14. Insert the blank into the 16-mm cell holder. Press ZERO. The display will show: 0.0 mg/L COD. 15. Insert the sample vial into the 16-mm cell holder. 16. Press READ. Results are in mg/L COD. 17. If using High Range plus COD Digestion Reagent Vials, multiply the result by 10. For most accurate results with samples near 1500 or 15,000 mg/L COD, repeat the analysis with a diluted sample.

4.2Polymer Make-up Procedure

An anionic flocculant-9901 was prepared in 100 mL glass reactor using a mechanical stirrer. The solid crystals were thoroughly weighed and the final volume was made upto 100 mL. The aqueous solution was stirred for 30 minutes at 60-70 R.P.M.
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4.3Coagulant Make-Up Procedure

The Coagulant dose was calculated and weighed using a weighing balance. The weighed chemical was transferred to a volumetric flask and final volume was adjusted to 100 mL.

4.4 pH Measurement
pH is measured using an instrument called Myron L Company Ultrameter II. Each time before use it must be caliberated using pH standards of known pH. Three standards exist having pH 4, 7 and 10. The electrode must be properly rinsed in the solution.

TDS Measurement
Determination of TDS is done using Myron L Company Ultrameter II. Each time before use the instrument must be caliberated using a solution of known conductivity-0.1 N KCl having a conductivity of 12.88 S/cm. After calibration the electrode is thoroughly rinsed with the solution and the TDS is measured.

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5. Results and Discussion

5.1 Variation of Dye Concentration with Optimum Coagulant Dose.
Synthetic dye wastewater was prepared using Cotton Blue Dye. The Concentration of the dye used was varied from 15ppm, 50 ppm and 100 ppm. Jar Tests were conducted to determine the optimum coagulant Dose. N-8123 was used as the coagulant and the flocculant used was N9901. Refer# Figure 1.

500 8123 Dose (ppm) 400 300 200 100 0 0 20 40 60 80 Dye Concentration (ppm) 100 120 150 Optimum N-8123 Dose (ppm) 300 400

Figure 1: Graph showing variation of Coagulant Dose with Dye Concentration The result showed a linear variation of dye concentration with the optimum Coagulant Dose. With increase in dye concentration the dosage of coagulant dose needed for efficient colour removal was increased; Figure 1.

5.2 Dosage Optimization of N-8123 on 100 ppm Cotton Blue Dye.

Synthetic wastewater was prepared using 100 ppm Cotton Blue Dye. The dose of N-8123 was varied from 0 to 400 ppm and parameters such as pH, Turbidity, Colour and COD were

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determined. The optimum dose of lime and N-9901 was determined by conducting a series of bottle tests. The data obtained is shown in Table 4.

Table 4: Table showing optimum dose of N-8123 for 100ppm Dye Colour (Pt.Co.) 536 154 32 25 17 12

8123 (ppm) 0 300 325 350 375 400

pH 8.06 11.56 11.4 11.26 11.29 11.27

Turbidity(NTU) TDS (ppm) 2.88 58.1 4.2 3.17 3.01 2.97 98.97 297 342 361 382 400

COD (ppm) 115 76 64 37 18 16

In Table 4; 400ppm of N-8123 is required to lower down the colour value from 536 Pt.-Co units to 12 Pt.-Co units. The dose is quite high which makes it a very expensive option to be implemented.

600 525 450 375 300 225 150 75 0

536 Colour (Pt-Co)

True Colour (Pt.-Co)

154 32 25 17 12

300 325 350 375 400 N-8123 Dose (ppm)

Figure 2: Graph showing Optimum Dose of N-8123 v/s True Colour

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Picture 1: Photograph showing raw and treated dye solution using N-8123

5.3 Dosage Optimization of 133L Dose on 100 ppm Cotton Blue Dye Solution.

100 Colour (Pt.-Co) 95 90 85 80 75 200 83 77 250 300 350 133L Dose (ppm) 400 92 94 133L DOSE (ppm)

Figure 3: Plot showing Optimum 133L Dose for 100ppm Cotton Blue Dye

133L is an inorganic coagulant which is easily available in the market at low cost. While conducting Optimization Studies on 133L, it was observed that 133L worked at lower pH in comparison to N-8123. Lime dose was kept at 100 ppm and 3 ppm of flocculant was added. However, the colour removal performance of 133L was weaker as can be seen from the plot
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below. 133L could lower down the colour value to not less than 77 Pt.-Co. units; Refer Figure 2 and Figure 3. It can be inferred from the plot that the optimum dose of 133L is 250 ppm, Refer Figure 5. For Coagulant Dose lower than 200 ppm the solution was highly turbid and the colour removal performance was bad. One can also see that for dosage over 300 ppm the colour of the effluent is nearly constant. The table shown below shows the dosage of chemicals and effluent parameters-TDS, pH, Turbidity. Table 5: Table showing data collected on optimization of 133L Dose. LIME 9901 133L DOSE COLOUR TURBIDITY TDS pH DOSE DOSE (ppm) (Pt.-Co.) (NTU) (ppm) (ppm) (ppm) 0 0 0 532 2.56 100 8.04 100 100 3 HIGHLY TURBID 100 150 3 HIGHLY TURBID 100 200 3 83 4.73 300 9.96 100 250 3 77 1.14 200 8.68 100 300 3 92 0.94 300 8.93 100 350 3 94 1.16 400 9.84 The table shown above shows that the pH of the optimum system is 8.68 along with having TDS and Turbidity values as 200 ppm and 1.14 NTU respectively.

5.4 Dosage Optimization of N-8123 and 133L Blend.

In order to enhance the colour removal efficiency of N-8123 at lower dosage it was blended with 133L. The data obtained is shown. Table 6: Table showing data obtained by blending N8123 with 133L Lime (ppm) 0 100 100 100 100 N-8123 (ppm) 0 100 150 200 250 133L (ppm) 0 250 250 250 250 N-9901 (ppm) 0 3 3 3 3 Colour (Pt- Co) 525 58 59 61 22 Turbidity (NTU) 2.64 2.79 3.26 2.94 3.16 TDS (ppm) 100 300 300 300 300 COD (ppm) 144 47 36 35 37
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pH 8.21 9.42 9.5 9.42 9.36

In Table 6, it can be seen that the dosage of 133L is kept at 250 ppm. This is a result of another experiment wherein optimum dose of 133L was determined. The plot showing the variation of 133L Dose with Colour unit of the treated effluent is shown below:

Figure 4: Plot showing the optimum 133L Dose for blending with N-8123 It can be seen from the above plot that initially when the 133L dose is varied as 250ppm, 300ppm and 350ppm the colour value of the treated effluent is 59 Pt.-Co, 59 Pt.-Co and 58 Pt.Co respectively. As a result of which the most economical dose is chosen which 250ppm is. When the dose is increased to 400 ppm the colour value drops down to 38 Pt.-Co. The reason for choosing 250 ppm over 400 ppm is that it will increase the cost of handling, operation and maintenance of the plant. Moreover, 133L is used in combination with N-8123, therefore application of such high dosage of a single coagulant will not be economical. It can be inferred from Figure 5,that a blend of N-8123 with 133L lowered down the colour value from an initial value of 525 Pt.-Co to a final value of 58 Pt.-Co utilizing 100 ppm Lime, 100 ppm N-8123, 250 ppm 133L and 3 ppm Anionic-9901. This is a remarkable improvement as 250 ppm of 133L alone could not lower down colour value beyond 77 Pt.-Co (Refer Figure 4). The experiment conducted using N-8123 alone utilized 400 ppm of the chemical to lower down the colour value to 12 Pt.-Co units (Refer Figure 3). In order to compensate the high cost the idea of blend is considered feasible with respect to industry. The study of pH variation on the blend was also conducted; Refer Figure 5.

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Figure 5: Plot showing pH variation of the 133L and N-8123 Blend The pH was varied from 8.5 to 12 by varying the dose of Lime added. The minimum value of colour was obtained at 100 ppm of lime at a pH of 9.42 and was thus considered optimum. By varying the pH the final colour value lay in the range of 60 Pt.-Co to 85 Pt.-Co. No drastic changes were observed. This observation is highly useful with respect to a real world situation as it eliminates the constant monitoring of pH at all intervals. This will lower down the need for chemicals and plant personnel to maintain a certain pH. Below we can see the photograph the raw and treated effluent when N-8123 is used for colour removal.

5.5 Optimization of FeCl3 Dose on 100 ppm Cotton Blue Dye

Ferric Chloride is known to have good floc forming potential. Iron (Fe) undergoes a change in oxidation state from +3 to +2 i.e. ferric ion changes to ferrous ion and precipitates out. Since, it is inexpensive and easily available; it is widely used in Industry for carrying out coagulation and Flocculation. A lab study was conducted in order to optimize the dose of ferric chloride. The results are tabulated in Table 6.

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Table 7: Table showing Optimized FeCl3 Dose FeCl3 Lime Dose Dose(ppm) (ppm) 0 0 200 100 200 150 200 200 200 250 200 300 9901 Dose (ppm) 0 3 3 3 3 3 Colour (PtCo) 528 55 55 55 82 76 Turbidity TDS (NTU) (ppm) 2.04 4.98 2.55 3.50 1.94 2.01 100 1100 700 700 600 600

pH 8.01 11.39 11.20 11.30 10.98 10.73

Using the table above, one can conclude that a dose of 100 ppm, 150 ppm and 200 ppm lead to a final colour value of 55 Pt.-Co units. An increase in dosage beyond that showed no improvement. The plot of Ferric Chloride (FeCl3) v/s Colour value of the treated effluent is as follows:

Figure 6: Plot showing optimum Ferric Chloride Dose The colour removal performance of Ferric Chloride (FeCl3) was found to be better than 133L. The optimum dose was found to be 100 ppm of Ferric Chloride.

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5.6 Optimization of a blend of Ferric Chloride (FeCl3) and N-8123 on 100 ppm Cotton Blue Dye.
The results from the previous experiment (Refer to Figure 6) show that Ferric Chloride has a high colour removal potential. In order to exploit its potential it was blended with N-8123 in order to determine the best possible combination to carry out colour removal economically. Refer Table 8 for the data obtained in the experiment conducted above. Table 8: Table showing optimum Ferric Chloride Dose for Blending with N-8123 FeCl3 (ppm) 0 100 150 200 250 275 300 400 450 Colour (Pt- Co) 525 115 113 100 95 91 72 85 92 Turbidity (NTU) 3.07 3.86 1.87 3.34 1.13 1.66 1.28 1.21 2.56 TDS (ppm) 100 1000 1000 900 800 1000 800 900 800 pH 8.14 11.79 11.74 11.62 11.54 11.63 11.43 11.56 11.47

Initially the dose of N-8123 was kept constant at 100 ppm and the optimum FeCl 3 was determined. The Lime Dose was kept constant to 200 ppm and the dose of the flocculant was constant at 3 ppm. Using Table 8, one can conclude that 300 ppm of Ferric Chloride gave appreciably good results. Later the dose of FeCl3 was kept constant and the optimum concentration of N-8123 was determined. At 250 ppm of Lime, 300 ppm of FeCl 3 and 3 ppm of Anionic 9901, the optimum dose plot came as follows:

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Figure 7: Plot showing optimum Dose of N-8123 for blending with Ferric Chloride The graph shows that the optimum dose of N-8123 in combination with FeCl3 is 300 ppm. The final combination is as: 250 ppm Lime, 300 ppm FeCl3, 100 ppm N-8123 and 3 ppm Anionic 9901. In this case; the amount of chemicals used is much more than the previously used combination. The amount of chemicals used in the blend of 133L and N-8123 is: 100 ppm Lime, 100 ppm N-8123, 250 ppm 133L and 3 ppm Anionic 9901.

5.7 Industrial Wastewater Testing

5.7.1 Industrial Sample 1

Sample Description: Sample received from Huntsman Ltd. at Baroda, Gujarat. Background Huntsman Ltd. at Baroda is a textile manufacturing company. The effluent treatment plant is composed of both primary clarifier followed by a secondary one. The clarified water from secondary clarifier contains high level of color (~1000 Pt.-Co.). Currently, they are using activated carbon for the final color removal after secondary treatment. The clarified water is being discharged to the environment. The activated carbon process the very cost intensive. They wish to have a suitable program for the final color removal after secondary treatment. The current parameters are as follows:

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Currently Used Product Turbidity TDS Colour Flow Rate

Activated Charcoal 106 NTU ~7780 ppm 1000 Pt.-Co 600 m3/ day

Required Testing: Evaluation of suitable chemical program for the final color removal (<100 Pt.-Co.) after secondary treatment by conducting jar test. Refer 4.1. Testing Procedure: Sample was tested at the initial pH of ~6.06. The laboratory test procedure adopted here simulates very closely to the plant design. Recommended programs were tested using a procedure of 1.5 min fast mix after adding coagulant, 30 second fast mix after adding flocculant, 1 min slow mix and 5 min settling time. The supernatant was used to measure the pH, turbidity, TDS, and true color (after filtered through 0.45m). Optimum product dosage was determined from the true color vs. dosage of coagulant plot. Refer to Chapter 4. Results Obtained The pH for optimum color removal was found to be ~11. 60. It was achieved by dosing 800 ppm of Lime. The application of ~200 ppm of specialty Nalco product N-8123 and flocculants N9901, lead to lowering of color down to ~120 Pt.-Co.. The addition of ~300 ppm of FeSO4 along with 200 ppm of N-8123 was found to be the optimum dosage required for lowering the color below 100 Pt.-Co.. The data is shown below:

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Figure 8: Plot showing Colour Removal of Huntsman Ltd Sample

From the above graph one can conclude that 300ppm of FeSO4 gave a colour value less than 100 Pt.-Co units. Later the experiment was carried using N-8123 alone, in order to study the performance of N-8123 alone. The dose of 8123 was varied and the following plot was obtained:

Figure 9: Plot showing Colour Removal Performance of N-8123 alone.

Shown Below is a photograph of the Raw Samples and The treated Sample.
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Picture 2: Photograph of Huntsman Ltd. Sample

Recommended Program Option #1: 800 ppm Lime+ 200 ppm N-8123 + 300 ppm FeSO4 + 4 ppm N-9901 Option#2: 800 ppm Lime+ 200 ppm N-8123 + 200 ppm FeSO4 + 4 ppm N-9901 Industrial Sample 2
5.7.2. Industrial Sample 2

Sample Location: Merchem Limited, Gujarat Background Merchem Ltd. is a rubber specialty chemical manufacturing company. The effluent water is a mixture of mother liquor and washings from the process. The COD of the effluent is ~10,000ppm and there is a need for suitable COD removal program. The present ETP schematic is shown below. Presently they are sending the partially treated effluent (COD <1000ppm) to a central effluent treatment plant (CETP). The on-site laboratory test was conducted to see if the coagulation and flocculation can remove turbidity, COD and color. Several Jar-tests were conducted on the sample from Equalization Tank 2 (before Fenton). As we can see from the plot below that turbidity goes down to ~6 NTU with ~150 ppm dosage of N-8187 (coagulant) and 1 ppm of N 8173 (flocculant). However with their current program, the lowest turbidity achievable is ~45 NTU. So, sludge carryover is considerably minimized by using Nalcos program.

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List of Critical Topics Sludge carryover needs to be minimized. Stage wise COD reduction including the biological treatment needs to be improved. Alternative advanced oxidation process (AOP) to improve the biodegradability and reduce toxicity should be considered. Possibility of introducing continuous mode of operations needs to be explored (Presently neutralization/Fenton is being done in batch mode). Improved clarification system after coagulation stage. Alternative adsorption media other than carbon. Possibility of water reuses and recycles. Results Obtained The lab study conducted on Merchem Ltd, Gujarat Sample gave the following results: Table 9: Table showing data received by conducting Lab Study on Merchem Ltd Sample Lime Dose (ppm) 1500 1500 1500 1500 1500 1500 1500 ZnCl2 Dose (ppm) 2000 2500 3000 2500 2500 2500 0 8123 Dose (ppm) 500 500 500 1000 1500 0 1500 9901 Dose (ppm) 8 8 8 8 8 8 8

Colour Turbidity (Pt.-Co) (NTU) 124 102 83 81 88 124

TDS (ppm)

pH 10.33 9.64 9.15 9.56 9.31 9.39

6.15 49370 6.4 50190 10.03 51450 6.67 50610 8.44 50430 6.68 50620 HIGHLY TURBID

One can make the following conclusions: Very high dosage of Lime is required (~1500ppm) to maintain the optimum pH for colour removal. N-8123 alone could not lower down the colour value to less than 124 Pt.-Co units. ZnCl2 when applied alone produced an effluent having high colour and turbidity. The optimum combination is found to be 1500ppm Lime+2500ppm ZnCl2+1000ppm N8123+8ppm of Anionic 9901.
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The plot of percentage colour removal v/s the dosage of two coagulants used-ZnCl2 and a photograph of the treated effluent is shown below:

Figure 10: Plot showing % age Colour Removal

Treated Effluent Using Optimized Program-1500ppm Lime+2500 ZnCl2+1000ppm N-8123+ 8ppm N-9901 Colour Value of Treated Effluent=81 Pt.-Co

Sludge

Picture 3: Photograph of Merchem Ltd. Sample after Treatment The colour value of the Merchem Ltd. Sample came down from 492 Pt.-Co. units to 81 Pt.-Co units.

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6.Conclusion
The study conducted on Synthetic wastewater revealed that as the dye concentration is increased the amount of coagulant dose required increases linearly. The optimum dose of N8123 required for effective decolourization of 100 ppm Dye solution is 400ppm. Later, optimization studies were carried on inorganic coagulants such as 133L and Ferric Chloride. The results so obtained revealed that 250ppm of 133L could lower down the colour value to 59 Pt.Co units from an initial value of 525 Pt.-Co units. In order to enhance its colour removal efficiency it was blended with N-8123 and the optimized program was100 ppm Lime, 100 ppm N-8123, 250 ppm 133L and 3 ppm Anionic 9901. The colour of the treated effluent was 58, which is no improvement than 133L alone but the amount of chemicals in terms of Lime, 133L and N-8123 is much less. Also the turbidity of the effluent is improved. Another inorganic coagulant was blended with Nalco chemical in order to draw a comparison with the blending of 133L with N-8123. It was found that Ferric Chloride alone utilized 200ppm of Lime, 100 ppm of Ferric Chloride and 3 ppm of Anionic-9901 to lower down the colour value from 528 Pt.-Co units to 55 Pt.-Co units. When Ferric Chloride was blended with N-8123 it was seen that 250 ppm Lime, 300 ppm FeCl3, 250 ppm N-8123 and 3 ppm Anionic 9901 could lower down the colour value to 31 Pt.-Co units. pH variation Studies of both the optimized blends were also carried out and it was inferred that the pH of both the systems lied in the range of 8.5 to 10.5. Change in pH did not result in drastic results. This inference is favourable with respect to industry since sudden fluctuation in pH will not affect the colour removal performance of the system to a great extent. The laboratory studies were extended to the Industrial Wastewater Sample. Two Samples were Tested from Huntsman Ltd, Baroda and Secondly from Merchem Ltd, Gujarat. The Huntsman Ltd. Sample had an initial colour value of 1000 Pt.-Co units. It was tested for the blend of 133L and N-8123. It showed good results at very high dosage of 133L and 200 ppm of N-8123. It could remove colour upto a maximum limit of 126 Pt.-Co units. It was not accepted since the target colour of the effluent was less than 100 Pt.-Co units. Later, the combination of Ferric Chloride with N-8123 was tested. It could not bring down the colour value to lower than 230 Pt.-Co units. Thereafter, Ferrous Sulphate in combination with N-8123 was tested on the textile wastewater sample. It showed very good performance and the optimized combination was: 800ppm of Lime, 200ppm of N-8123, 300ppm of Ferrous Sulphate and 8ppm of Anionic 9901. The combination could bring down the colour value to 76 Pt.-Co units. The Second Sample tested was from Merchem Ltd, Gujarat. The optimized combination of N-8123 and 133L, N8123 and Ferric Chloride and N-8123 and Ferrous Sulphate failed to remove colour upto a great
39

extent. Therefore, a new combination of Nalco chemical based on Zinc Chloride was combined with N-8123 to bring down the colour value to 81 Pt.-Co units. The optimized combination was 1500ppm of Lime, 2500ppm of Zinc Chloride based Nalco Product, 1000ppm of N-8123 and 8ppm of 9901. Thus, one can infer that water coming from different sources has different chemistries and based on the specific water chemistry the chemicals can be blended to carry out effective colour removal.

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7.Future Directions
The overall aim of the project was to discover a new chemistry in the field of colour removal. The study conducted so far has employed the use of blends utilizing Nalco Chemicals and easily available Commercial chemicals to carry out colour-removal. The idea is to carry out wastewater treatment following a holistic approach. Colour Removal is not targeted at the expense of other impurities. Decolourization should be carried out alongwith overall wastewater treatment. In order to come up with a product that is cost-effective and sustainable, there is a need to study the water chemistry of wastewater coming from different sources. It is important to study the basic reaction mechanism responsible for colour removal. Based on the study of reaction mechanism, a new chemical can be developed that is environmental friendly and causes effective treatment at low dosage. The new chemical may follow an entire new mechanism based on the blends of Nalco Chemicals with inorganic chemicals. This can be postulated after thorough research work in this field.

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8.References
1. Karcher SA, Screening of commercial sorbents for the removal of reactive dyes. Pigments 2001;51:111e25. 2.Choi JH, Shin WS, Lee SH, Joo DJ, Lee JD, Choi SJ, et al. Applications of synthetic polyamine flocculants for dye wastewater treatment. Sep Sci Technol 2001;36(13):2945e58. 3.Papic S, Koprivanac N, Bo_zic AL. Removal of reactive dyes from wastewater using Fe(III) coagulants. J Soc Dyers Colour 2000;116(11):352e8. 4.Lee SH, Shin MC, Choi SJ, Shin JH, Park LS. Improvement of flocculation efficiency of water treatment by using polymer flocculants. Environ Technol 1998;19(4):431e6. 5. Profile of the Textile Industry, document number: EPA/310-R-97-009 6.Joo, et al., Decolorization of reactive dyes using inorganic coagulants and synthetic polymer, Dyes and Pigments, 2007, 73, 59-64. 7. Collins et al. United States Patent, vinylamine polymers and coagulants for removing colour from paper mill effluents, Patent Number 5,435,921 8. Selcuk, H., (2005). Decolonization and detoxification of textile waste water by ozonation and coagulation processes. J. Dye. Pig., 64, 217-222. 9. Kang, S., (2000). Decolonization of textile waste water by photo-fenton oxidation technology. J. Chemosphere, 41, 1287-1294. Dyes

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