BURAPHA UNIVERISTY Faculty of Engineering

Term Assignment in Advanced Researh Method Proposed Topic REMOVAL OF COD AND COLOUR FROM TEXTILE WASTEWATER BY ADVANCED OXIDATION PROCESS USING FENTON PROCESS

Submitted to : Pro. Wirogana Submitted by: Mr. Piseth Som

Academic Year: 2012

Table of Content
Chapter I Introduction ........................................................................................................... 3 1.1. Background ....................................................................................................................................... 3 1.2. Problem Statement ........................................................................................................................ 4 1.3. Objective of the Study ................................................................................................................... 6 1.4. Scope of Study .................................................................................................................................. 6 1.5. Singneficant of Study ..................................................................................................................... 7 Chapter II Literature Review ................................................................................................ 8 2.1. Wastewater from textile industry ............................................................................................ 8 2.2. Textile Wastewater Characteristics and Environmental Impact ................................. 9 2.3. Treatment of Textile Wastewater ......................................................................................... 11 2.3.1. 2.3.2. 2.3.3. Bioligical Method .......................................................................................... 11 Physical Method ............................................................................................ 13 Chemical Method .......................................................................................... 15

2.4. Advanced Oxidation Processes (AOPs) .............................................................................. 16 2.5. Conventional Fenton Process ................................................................................................. 17 Chapter III Research Methodology............................................................................................. 20 3.1. Textile Wastewater ..................................................................................................................... 20 3.2. Material and Fentons Reagent .............................................................................................. 20 3.3. Experimental Procedures ......................................................................................................... 20 3.4. Laboratory Analytical Method ................................................................................................ 22 3.5. Statistical Analysis Method ...................................................................................................... 22 References ................................................................................................................................................. 23 Appendix.........................................................................................................................................................27

Abbreviation AOPs BOD COD EOP EPA F/M mg/l Pt-Co SS TDS Vol WOP : Advanced Oxidation Processes : Biological Oxygen Demand : Chemical Oxygen Demand : Electrochemical Oxidation Potential : Environment Protection Agency : Food to Microorganism : milligram per liter : Platinum Cobalt : Suspended Solid : Total Dissolved Solid : Volt : Wet Air Oxidation Process

Chapter I Introduction
1.1. Background Textile industry is one of the most complicated industries among manufacturing industry . The main sources of wastewater normally come from cleaning water, pretreatment, dyeing and finishing process water non-contact cooling water and others. The amount of wastewater varies widely depending on the type of process operated at the mill, and various toxic chemicals such as complexing agents, sizing, wetting, softening, anti-felting and finishing agents, wetting agents, biocides, carriers, halogeneted benzene, surfactants, phenols, pesticides dyes and many other additive are used in wet processing, which are mainly called washing scouring, bleaching, mercerizing, dyeing, finishing (EPA, 2004; Adel et al, 2004). It was also provided that composite textile wastewater is characterized mainly by measurements of biochemical oxygen demand (BOD), chemical oxygen demand (COD), suspended solids (SS) and dissolved solids (DS). Textile wastewater includes a large variety of dyes and chemicals additions that make the environmental challenge for textile industry not only as liquid waste but also in its chemical composition (Adel et al, 2004 (Cited from Venceslau et al., 1994 ). Main pollution in textile wastewater came from dyeing and finishing processes. These processes require the input of a wide range of chemicals and dyestuffs, which generally are organic compounds of complex structure. Because all of them are not contained in the final product, became waste and caused disposal problems. The combination of textile processes and products make the wastewater from textile plant contains many type of pollutants. These pollutants contributes to high suspended solids (SS), chemical oxygen demand (COD), biochemical oxygen demand (BOD), heat, color, acidity, basicity and other soluble substances. COD values of composite wastewater are extremely high compare to other paremeter. In most cases, BOD/COD reatio of the composite textile wastewater is primarily high which can represent the fact that wastewater contains large amount of
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non-biodegradable organic matter. The removal of colour and COD from textile industry and dyestuff manufacturing industry wastewaters represents a major environmental concern as reported that out of 87 dyestuff only 47% are biodegradable. (shanshask et al,. 2011; Adel et al, 2004).

1.2. Problem Statement The application of conventional textile wastewater treatment processes become challenged to environmental engineers with restrictive effluent quality by water authorities and national standard for effluent. Conventional treatment such as biological treatment discharges will no longer be tolerated as 53% of 87 colours are identified as non-biodegradable. Therefore, the use of convitional textile wastewater treatment processses become drastically challenged to fresh water bodies and environment. The conventional treatment such as biological treatment discharges will no longer to tolerated as 53% of 87 colours are indentified as non-biodegradable and toxic to the microorganisms. These dyes can be treated if conventional treatment methods are incorporated with the advanced oxidation process which have their potential application for breaking the complex structure of the dye and make it more amenable to bio-degradation (shanshask et al,. 2011; Adel et al, 2004). Therefore, Advanced Oxidation Process (AOPs) have recieved considerable atttention and hold great promise to provide alterative for better treatment and protection of environment because it is possible to degrade organic compounds and colours from textile wastewater. Also, it was supported by Giusy Lofrano(2012) that AOPs are being employed to treat biologically inert, hazardous, toxic, and other problematic pollutants found in air, water, and wastewater. Amoung the variety of AOPs available, Fenton and Photo-fenton (Fe2+/H202/UV) treatment system have gain its practical use than other due to their superior reation rate and effeciency, technical feasibility and attractive process economic. At present, several methods have been developed to treat textile wastewater but they cannot be used individually because this wastewater has high salinity, color and non biodegradable organics. In coagulation process, large amount of sludge is
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created which may become a pollutant itself and increase the treatment cost. Oxidation process such as ozonation effectively decolorizes almost all dyes except disperse dyes but does not remove COD effectively (Ahn et al., 1999). Adsorption is an effective method of lowering the concentration of dissolved dyes in the effluent resulting in color removal. Other means of dye removal such as chemical oxidation, coagulation and reverse osmosis are generally not feasible due to economic considerations (Tsai et al., 2001). The adsorption process is one of the most efficient methods to remove dyes from effluent. The process of adsorption has an edge over the other methods due to it sludge free clean operation and complete removal of dyes even from dilute solution (Malik, 2003). Activated carbon is the most widely used adsorbent because of its extended surface area, microporous structure, high adsorption capacity and high degree of reactivity. However, commercially available activated carbons are very expensive (Malik, 2003). It was also documented taht conventional process used to treat wastewater from textile industry includes chemical precipitation with alum or ferrous sulphate which suffers from drawbacks such as generation of a large volume of sludge leading to the disposal problem, the contamination of chemical substances in the treated wastewater, etc. Moreover these processes are inefficient in completely oxidizing dyestuffs and organic compounds of complex structure (Shanshask et al,. 2011). Therefore, Advanced Oxidation Process (AOPs) have recieved considerable atttention and hold great promise to provide alterative for better treatment and protection of environment because it is possible to degrade organic compounds and colours from textile wastewater. Also, it was supported by Giusy Lofrano(2012) that AOPs are being employed to treat biologically inert, hazardous, toxic, and other problematic pollutants found in air, water, and wastewater. Amoung the variety of AOPs available, Fenton and Photo-fenton (Fe2+/H202/UV) treatment system have gain its practical use than other due to their superior reation rate and effeciency, technical feasibility and attractive process economic (Giusy Lofrano, 2012).

1.3. Objective of the Study The overal objective of this study is to apply Fenton Method in Advance Oxidation Process (AOPs) for COD and colour reduction in a selected textile industrial wastewater, which will minimize the treatment cost. The specific objectives are : To determine the treatment performance of Fenton in removing the Coulor and COD To find optimal conditions for removal of COD and color of dying textile wastewater To investigate the effect of the H202 dosage, Fe2+ dosage, H2O2/ Fe2+ molar ratio, initial pH, reaction time and dosage method on Fenton Oxidation process

1.4. Scope of Study This research study is limited to the following condition: Focus only the removal effeciecy of COD and color parameters Kenetic Study will not be conducted in this study Due to the limitation of the equibment, only conventional Fenton Oxidation will be applied in this studies. Operational other parameters such as temperature and mixing time is mentioned in this study

1.5. Singneficant of Study Price competition, demand in high quality products, new and innovative products that are highly durable put further pressure to the industry as they have to use more dosage of chemicals and continually change to new chemicals to suit the market demand. However, the national regualation and law have put the restriction on the effluent standard which industries have to be complied. This will finally result in the complication in the wastewater that is being discharged. Thus there is a need for continues study and research on the waste water treatment to find new methods of treatment in order to sustain the industry. The overall motivation for the present study is to explore the possibility of using Fenton processes in the treatment of highly colored wastewater from a dying textile producing plant and, eventually, to evaluate the best treatment technology for this specific industrial sector. Better water and wastewater management is of great importance to textile industry. The results of this study should contribute to the evaluation of the best method of treatment of dying textile wastes and eventual water reuse.

Chapter II Literature Review

2.1. Wastewater from textile industry There are several different steps in the production of textiles and these processes generate highly contaminated liquid streams. The quantity and composition of these wastewaters depend on many different factors, including the processed fabric and the type of process. Type of machinery, chemicals applied and other characteristics of the processes also determine the amount and composition of the generated wastewater. The main sources of wastewater normally come from cleaning water, pretreatment, dyeing and finishing process water non-contact cooling water and others. The amount of wastewater varies widely depending on the type of process operated at the mill, and various toxic chemicals such as complexing agents, sizing, wetting, softening, anti-felting and finishing agents, wetting agents, biocides, carriers, halogeneted benzene, surfactants, phenols, pesticides dyes and many other additive are used in wet processing, which are mainly called washing scouring, bleaching, mercerizing, dyeing, finishing (Adel et al, 2004). It was also provided by Shanshask et al,. (2011) that the textile wastewater is characterized by high content of dyestuff, salts, high COD derived from additives, suspended solid(SS) and fluctuating pH. The textile industry uses approximately 21-377 m3 of water per ton of textile produced and thus generates large quantities of wastewater from different steps of dyeing and finishing process. In the textile sector, although processes should be considered separately, treatment of each process may not be considered individually. Combined selected streams can lead to a better treatable wastewater. A stream could be separated from the rest to facilitate the recovery of water or chemicals, or to prevent dilution of a compound difficult to remove(Adel et al, 2004). Some processes in a textile mill hardly generate wastewater, such as yarn manufacture, weaving (some machines use water), and singeing (just some lightly polluted cooling water). The amount of wastewater produced in a process like sizing is small, but very concentrated. On the other hand, processes like scouring, bleaching
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and dyeing generate large amounts of wastewater, varying much in composition (Metcalf and Eddy, 1991). According to EPA, (2004), it was documented that Likely sources of textile process wastewater include wet processes such as scouring, dyeing, finishing, printing and coating of textile products. Dyeing processes are one of the largest sources of wastewater. The primary source of wastewater from dyeing operations is spent dyebath and washwater. Finishing processes generally produce wastewater containing natural and synthetic polymers. Chemical handling and high pH are the primary pollution concerns associated with the bleaching process. Although effluent characteristics differ greatly even within the same process, some general values for major processes in a textile mill. Mixed textile wastewater generally contains high levels of COD and color, and usually has a high pH (Dos Santos et al., 2007 ;Shanshask et al,. 2011).

2.2. Textile Wastewater Characteristics and Environmental Impact Although effluent characteristics differ greatly even within the same process, some general values for major processes in a textile mill. Mixed textile wastewater generally contains high levels of COD and color, and usually has a high pH (Dos Santos et al., 2007 ;Shanshask et al,. 2011). Strong colour is another important component of the textile wastewater which is very difficult to deal with and colour is noticed in the wastewater effluent and the presence of small concentrations of dyes in water is highly visible, and may affect their transparency and aesthetics (EPA, 2004). The non-biodegradability of textile wastewater is due to the high content of dyestuffs, surfactants and other additives, which are generally organic compounds of complex structure (Gharbani et al., 2008). Textile mill effluents are known to have extremes pollutants contributes to high suspended solids (SS), chemical oxygen demand (COD), biochemical oxygen demand (BOD), heat, color, acidity, basicity and other soluble substances(table 1). As presented in Table 1 below, COD values of composite wastewater are extremely high compare to other paremeter. In most cases, BOD/COD reatio of the composite textile
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wastewater is around 0.26 that implies that wastewater contains large amount of non-biodegradable organic matter. Main pollution in textile wastewater came from dyeing and finishing processes. These processes require the input of a wide range of chemicals and dyestuffs, which generally are organic compounds of complex structure (shanshask et al,. 2011; Adel et al, 2004). Table 1 : typical charateristics of textile wastewater
Parameters pH Temperature (0 C) Biochemical Oxygen Demand (mg/L) Chemical Oxygen Demand (mg/L) Total Suspended Solids (mg/L) Total Dissolved Solids (mg/L) Chloride (mg/L) Total Alkalinity (mg/l) Sodium (mg/l) Total Kjeldahl Nitrogen (mg/L) Colour (Pt-Co) Values 6.0 10.0 35-45 100 4,000 150 10,000 100 5,000 1,800 -6,000 1,000 6,000 500 800 610 2,175 70 80 50-2500

Source: Sheng and Chi, 1993; Txitzi et al., 1994; Azbar et al., 2004 (cited in nshask et al,. 2011; Adel et al, 2004). Dye wastewater from textile mills is a serious pollution problem because it is high in both colour and organic content. A dye is a colored substance that can be applied in solution or dispersion to a substrate in textile manufacturing, thus giving a color appearance to textile materials. Discharging of dyes into water resources even in a small amount can affect the aquatic life and food web. One of the main problem regarding textile waste-waters is the colored effluent. The colored effluent contains visible pollutants. The primary concern about effluent color is not only its toxicity but also its undesirable aesthetic impact on receiving waters. Non-biodegradable nature of most of the dyes reducing aquatic diversity by blocking the passage of sunlight through the water represents serious problems to the environment. In some cases, dyes in lowconcentration are harmful to aquatic life. Since many dyes have adverse effect on human beings, the removal of color from the effluent or process has appeared of importance for ensuring healthy environment. Hence, it is imperative
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that a suitable treatment method should be applied. The colour of the effluent discharges into receiving waters affects the aquatic flora and fauna and causes many water borne diseases. Some of dyes are carcinogen and others after transformation or degradation yield compound such as aromatic amines, which may carcinogen or otherwise toxic. In addition, dyes accumulate in sediments at many sites, especially at location of wastewater discharge, which has an impact on the ecological balance in the aquatic system. These pollutants because of leaching from soil also affect ground water system (EPA, 2004). EPA,(2004) also raised that the discharge of organic pollutant either BOD or COD to the receiving stream can lead to the depletion of dissolved oxygen and thus creates anaerobic condition. Under anaerobic condition foul smelling compound such as hydrogen sulfides may be produced. This will consequently upset the biological activity in the receiving stream.

2.3. Treatment of Textile Wastewater Common treatment methods for textile wastewaters are: biological treatment, physical treatment and chemical treatment. These treatment methods and their efficiencies are reviewed in following sections.

2.3.1.

Bioligical Method

There are many types of biological treatment methods. Among them include trickling filters, activated sludge process, anaerobic process, oxidation ponding etc. To date the commonest treatment of textile wastewater has been based on mainly on aerobic biological process, consisting mainly conventional and extended activated sludge system. The trickling filters simulate stream flow by spraying wastewater over a broken, medium such as stone or plastic. The medium serves as a base for biological growth, which attacks the organic matter of wastewater, and uses it as food. In activated sludge process, the wastewater flows into a tank after primary settling. The microorganism in activated sludge is suspended in the wastewater as
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aggregates. The sludge and wastewater is kept in suspension by compressed air, which also supplies the oxygen, necessary for biological activities. The aerated waste is continuously withdrawn and settled and a portion of the sludge is returned to the influent (Metcalf and Eddy, 1991). Biological treatment can be applied to textile wastewaters as aerobic, anaerobic and combined aerobic-anaerobic. In most cases, activated sludge systems (aerobic treatment) are applied. In all activated sludge systems, easily biodegradable compounds are mineralized whereas heavily biodegradable compounds need certain conditions, such as low food-to-mass-ratios (F/M) (<0.15 kg BOD5/kg MLSS.d), adaptation (which is there if the concerned compounds are discharged very regularly) and temperature higher than 15oC (normally the case for textile wastewater) (Lacasse and Baumann, 2004). Ineffectiveness of aerobic biological treatment in reducing color caused by heavily biodegradable organics causes aesthetic problems in the receiving waters and encourages researchers to investigate alternatives. Dyes themselves are generally resistant to oxidative biodegradation, and a difficulty occurs in acclimation the organisms to this substrate. Acclimation presents a problem with textile wastewater due to constant product changes and batch dyeing operations (Reife and Freeman, 1996). Depending on the dyeing process; many chemicals like metals, salts, surfactants, organic processing assistants, sulphide and formaldehyde may be added to improve dye adsorption onto the fibers (Dos Santos, 2007). These chemicals are mainly in toxic nature and decrease the efficiency of biological treatment in color removal regarding textile wastewater. The treatment and safe disposal of hazardous organic waste material in an environmentally acceptable manner and at a reasonable cost is a topic of great universal importance. There is little doubt that biological processes will continue to be employed as a baseline treatment process for most organic wastewaters, since they seem to fulfill the above two requirements. However, biological processes do not
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always give satisfactory results, especially applied to the treatment of industrial wastewaters, because many organic substances produced by the chemical and related industries are inhibitory, toxic or resistant to biological treatment. Due to insufficiency of biological treatment in the removal of the dyes from textile and dyestuff manufacturing, this process requires the involvement of other physical, chemical, and physicochemical operations (Rai, 2005; Banat et al., 1997). Physical and chemical treatment techniques are effective for color removal but use more energy and chemicals than biological processes. They also concentrate the pollution into solid or liquid side streams requiring additional treatment or disposal (Shaw et al., 2001). Therefore, the tendency in recent years is towards using alternative technologies, especially advanced oxidation processes for the removal of color caused by hardly biodegradable organics (Baban et al., 2003; Sevimli and Sarkaya, 2002; Birgl and Solmaz, 2007).

2.3.2.

Physical Method

The common physical treatment methods used for the treatment of colored textile effluents include membrane filtration, ion exchange, adsorption with activated carbon, irradiation and coagulation and flocculation (Doble and Kumar, 2005; Metcalf and Eddy, 1991) Membrane based separation processes have gradually become an alternative method in the treatment of textile wastewaters. Application of membrane processes allows reuse of water besides high removal efficiencies. Ultrafiltration has been successfully applied for recycling high molecular weight and insoluble dyes (e.g. indigo, disperse), auxiliary chemicals (polyvinyl alcohol) and water. However, ultrafiltration does not remove low molecular weight and soluble dyes (acid, reactive, basic, etc.), but efficient color removal has been achieved by nanofiltration and reverse osmosis (Fersi et al., 2005).

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Related to ion exchange, Mock and Hamodua (1998) reported that an ion exchange system would decolorize a dilute mixture of a colored wastewater sample. However, because the colorant was irreversibly adsorbed onto the resin and regeneration was not possible this technology does not seem effective. They claimed that, further testing with ion exchange-macroreticular polymer systems might have been successful but initial cost estimates, requirement for off-site resin regeneration, and secondary waste disposal requirements resulted in removal of this technology from consideration for color destruction. Robinson et al. (2001) also documented that ion exchange can not be used for the treatment of dye-containing effluents mainly due to cost disadvantage and its ineffectiveness in disperse dyes. The coagulation and flocculation process is a versatile method used either alone or combined with biological treatment, in order to remove suspended solids and organic matter as well as providing high color removal in textile industry wastewater (Meri et al, 2004). Many coagulants are widely used in the conventional wastewater treatment processes such as aluminum, ferrous sulphate, sulphate and ferric chloride (Anouzla, 2009). The adsorption is one of the effective methods and the main adsorbent used in dye removal is activated carbon. Activated carbon has been generally used to remove composite reactive dye from dyeing unit effluent. The main disadvantage of activated carbon adsorption method is its high regeneration cost (Demirba, 2009). Moreover, the color of wastewater from todays new dyes is much more difficult to treat by physical techniques such as adsorption and chemical coagulation to achieve complete decolorization, especially for highly soluble dyes (Ouz and Keskinler, 2008). On the other hand, methods such as coagulation/flocculation and activated carbon adsorption can only transfer the contaminants from one phase to another leaving the problem of color in dyehouse effluent essentially unsolved. Therefore, much attention has been paid to the development of water treatment techniques that lead to complete destruction of the dye molecules (Solmaz et al., 2006).

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2.3.3.

Chemical Method

Chemical method includes coagulation or flocculation and oxidation. The main advantage of the conventional coagulation and flocculation is removal of the waste stream due to the removal of dye molecules from the dyebath effluent and not due to partial decomposition of dyes which can lead to an even more potentially harmful and toxic aromatic compound (Metcalf and Eddy, 1991). It was also documented that in treatment of textile wastewaters, chemical treatment methods are known to be much more effective than others in breaking down the straight, unsaturated bonds in the dye molecules (Ciardelli et al., 2001). Chemical oxidation uses strong oxidizing agents such as hydrogen peroxides, chlorine and others to force degradation of resistant organic pollutant. Chemical oxidation is the most commonly used method of decolourization by chemical owing to its simplicity and the main oxidizing agent is hydrogen peroxide (Metcalf and Eddy, 2003) Chemical oxidation typically involves the use of an oxidizing agent such as ozone(O3), hydrogen peroxide(H2O2), Fentons reagent, permanganate (MnO4) etc. to change the chemical composition of a compound or a group of compounds, e.g. dyes (Metcalf and Eddy, 2003). Fenton oxidation operates at acidic pH in the presence of H2O2 and excess ferrous ions yielding hydroxyl radicals which oxidize organic matter. Fentons reagent is effective in reducing COD, color and toxicity of textile wastewaters, but has the disadvantage shifting problems from water into the solid phase. Therefore a further removal mechanism is required for the Fenton sludge (Meri et al., 2004; Eckenfelder et al., 1994). Recently, a growing interest is observed in combined methods of chemical oxidation by means of H2O2 and O3 as well as O3 and UV radiation, and of the three agents simultaneously (Perkowski et al., 1999). Advanced technologies based on chemical oxidation seem to be viable options for decontaminating a biologically recalcitrant wastewater. Such oxidation technologies are broadly classified as follows:

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(i) advanced oxidation processes (AOPs) including wastewater remediation based on ozone, hydrogen peroxide, hydrogen peroxide/ferrous iron catalyst (the so called Fentons reagent), UV irradiation, photocatalysis and electrochemical oxidation; (ii) wet air oxidation processes (WAO) (Mantzavinos and Psillakis, 2004).

2.4. Advanced Oxidation Processes (AOPs) Advanced Oxidation Processes( AOPs) represents the newest development in H202 technology, and have been defined as a process that generate highly reactive oxygen radicals. The goal of any AOPs design is to generate and use hydroxyl free radical (HO-) as strong oxidant to destroy compound that can not be oxidized by conventional oxidant. Table 2 shows the relative oxidation potentials of several chemical oxidizers. Advanced oxidation processes are characterized by production of OH- radicals and selectivity of attack which is a useful attribute for an oxidant.The application of AOP is also enhanced by the fact that they offer different possible ways for OH- radicals. A list of the different possibilities offered by AOP is given in Table 3. Generation of HO- is commonly accelerated by combining O3 , H2O2 , TiO2 , UV radiation, electron-beam irradiation and ultrasound (shanshask et al,. 2011; Adel et al, 2004). Table 2: Oxidizing potential for conventional oxidizing agents
Oxidizing agent Fluorine Hydroxyl radical Oxygen (atomic) Ozone Hydrogen peroxide Hypochlorite Chlorine Chlorine dioxide Oxygen (molecular) Electrochemical oxidation potential (EOP), V 3.06 2.80 2.42 2.08 1.78 1.49 1.36 1.27 1.23 2.25 2.05 1.78 1.52 1.30 1.10 1.00 0.93 0.90 EOP relative to chorine

Source: (Shanshask et al,. 2011; Adel et al, 2004; Metcalf and Eddy, 2003; and www. H2O2 .com)

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Table 3: Advanced Oxidation Processes

H2O2/UV/ Fe2+ (photo assisted Fenton) H2O2 /Fe2+ (Fenton) H2O2/UV(also applicable in the gas phase) Ozone/ H2O2 Ozone /UV/ H2O2 Ozone/TiO2/Electronbeam irradiation Ozone/TiO2 / H2O2 Ozone + electron-beam irradiation Ozone/ultrasonics H2O2/UV

Source: Shanshask et al,. 2011; Adel et al, 2004; and www. H2O2 .com 2.5. Conventional Fenton Process The Fenton process produces radical intermediate compounds by the reaction of H2O2 and Fe2+. The Fenton process has been applied in wastewater treatment processes and is known to be very effective in the removal of many hazardous organic pollutants (Mathew A. Tarr, 2003). Radical intermediate compounds produced from the Fenton process is composed mostly of hydroxyl radicals. Hydroxyl radicals exhibit faster rates of oxidation reactions as compared to those using conventional oxidants like hydrogen peroxide or permanganate (Gogate, 2002).

The conventional Fenton process was first discovered and used by H. J. H. Fenton in 1894 when he observed that the rate of oxidation of tartaric acid increased dramatically when dilute hydrogen peroxide was added with the solution containing dissolved Fe2+ ions. Fentons chemistry is a reaction between hydrogen peroxide (H2O2) and Fe2+ ions forming hydroxyl radicals, which is the main oxidizing agent. However the hydroxyl radical mechanism of the Fentons reaction was only identified 40 years after its discovery (Mathew A. Tarr, 2003). Hydroxyl radicals (OH) are short-lived reactive oxygen species with a high oxidation potential that can rapidly destroy many biorefractory contaminants (Watts, 2005). It is one of the most reactive chemical species; second only to elemental fluorine in its relative oxidation power as listed in Table 2 above (Metcalf and Eddy,

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2003; and www. H2O2 .com). It was raised by B. Bianco et al., (2011) that the oxidation using Fentons reagents (Fentons process) causes the dissociation of the oxidant and the formation of reactive hydroxyl radicals that destroy organic pollutants to harmless com-pounds (CO2, water and inorganic salts). Fentons reagents are H2O2 and ferrous ions. They generate hydroxyl radicals following the chain reaction schematized as follow: Fe2+ + H2 O2 Fe3+ + OH + OH OH + Fe2+ OH + Fe3+ (chain initiation) (1) (2)

(chain termination)

As shown in Equation (1) and (2), the ferrous iron (Fe2+) starts the reaction and catalyses the decomposition of H2 O2 in hydroxyl radicals (B. Bianco et al., 2011; Mathew A. Tarr, 2003). However, the newly formed ferric ions (Fe3+) may decompose hydrogen peroxide in water and oxygen (forming ferrous ions and radicals): Fe3+ + H2 O2 Fe OOH2+ + H+ Fe OOH2+ HO2 + Fe2 + (3) (4)

The above reactions are referred as Fenton-like reaction. The organics (RH) are oxidized by hydroxyl radicals proton-abstraction ending with the production of organics radicals (R). These last products are highly reactive and can be further oxidized: (5) RH + OH H2 O + R + further oxidation It was also supported in AOPs applicationn that Fentons reagent treatment system have gain its practical use than other due to their superior reation rate and effeciency, technical feasibility and attractive process economic. The oxidation mechanism in the Fenton process involves the reactive hydroxyl radical generated under acidic conditions by the catalytic decomposition of hydrogen peroxide, which reacts unselectively with organic substances (RH), which are based on carbon chains or rings and also contain hydrogen, oxygen, nitrogen, or other elements (Giusy Lofrano, 2012).

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The reaction mechanism has been summarized as follow: Fe2+ + H2O2 Fe3+ + OH + OH RH + OH R + H2O R + Fe3+ product + Fe2+ Fe2+ + OH Fe3+ + OH Fe3+ + H2O2 Fe2+ + H+ + HO2 (6) (7) (8) (9) (10)

Inhibitions to the Fenton process have also been investigated in recent studies. Anions like H2PO4, Cl-, NO3 and ClO-4 was found to inhibit the Fenton reaction; therefore, reducing its efficiency. Among the anions, H3PO4 was found to inhibit the reaction the most since the phosphate ions will produce a complex reaction with ferrous and ferric ions (Lu 1997). The inhibition of low concentration chloride ions was found to be controlled by extending the reaction time. However inhibition is significant if the ratio of chloride to ferrous ions is greater than 200. Likewise, inhibition by chloride ions was controlled by increasing the initial pH near to 5 and increasing the amount of ferrous ions (Lu 2005; Sajiki 2004). Presence of chloride ions in the Fenton process also produces chloroorganic compounds as byproducts (Gaca 2005). The effect of temperature on the rate of reaction of the Fenton process was also studied and was found to increase as the solution temperature was increased. However, the effect of temperature was only obvious at temperatures lower than 200C. In addition to this application of temperatures greater than 400C, the treatment efficiency declines due to decomposition of H2O2 into oxygen and water. Application of the Fenton process has been normally conducted at temperatures of 20 to 400C (Watts, 2005). The optimal pH range for the application of the Fenton process was also determined to be at pH 3 and pH 6. Application of the Fenton process at high pH values will result into inhibition of the Fenton reaction since the Fe2+ ions will form colloidal Fe3+ ions. Likewise, application of the Fenton process at very low pH values would result into the decomposition of H2O2 into oxygen and water by iron without forming hydroxyl radicals (Neyens, 2003)
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Chapter III Research Methodology

3.1. Textile Wastewater Textile wastewater used was supplied by textile industry in Rayong Province, Thailand. Raw textile wastewater is containing high content of COD, pH, and Color which resulting from Dying and Finishing processes. Table 4 shows characteristics of the livestock wastewater. The main characteristics of this textile wastewater are that the pH was in the range of 8.48.7, the chemical oxygen demand (COD) was 5,000 5,700 mg/L. The maximum color absorbance at 287 nm was 2.1 and the color was dark grey. Table 4: Characteristics of textile wastewater from Rayong Textile Industry.
Parameters pH COD (mg/L) Value 8.4 8.7

BOD (mg/L) Color (absorbance at 287 nm ) (*Based on Secondary data) 3.2. Material and Fentons Reagent

6,500 27, 000 8,500-10,000 2.1

H2O2 (34.5% v/v) and FeSO4 7H2O will be used during experiments. H2SO and NaOH also used for pH adjustment. 3.3. Experimental Procedures The Fenton method was applied in 200 mL flasks containing 100 mL samples of textile wastewater. All procedures were carried out at room temperature (2225 0C) and at atmospheric pressure. First, the initial pH of the sample was adjusted to the desired pH value at 4 using 0.2N and 2N H2SO4. Then, a H2O2 solution (34.5%, v/v) and FeSO47H2O powder were added to the flask and the mixture was vigorously stirred to dissolve the powder FeSO47H2O for 1min. The flask was then allowed to stand without stirring for 30 min. After that, the pH was neutralized to 78 (average 7.5) using 1N and 10N NaOH, and the precipitation was allowed to occur for 1h in

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standing flasks. Experimental conditions were varied as following. First, the initial pH, reaction time, and Fe2+ dose were kept constant while the H2O2 dose was varied. Second, the initial pH, reaction time, and H2O2 dose were kept constant while the Fe2+ dose was varied. Third, the reaction time, H2O2 dose, and Fe2+ dose were kept constant while the initial pH was varied. Fourth, the initial pH, H2O2 dose and Fe2+ dose were kept constant while the reaction time was varied. Finally, all other conditions were kept constant while either Fe2+ dose or H2O2 dose was given in several aliquots. The experimental procedures are shown in Fig. 1, where the initial pH was set at 4, the reaction time at 30 min, and the Fe2+ was given in either one or five doses and H2O2 was given in either one or three doses (Adapted from Hyunhee Lee Method (2008).
Sample (Textile wastewater) pH adjustment to 4

Total dosage of Fe2+ and

division dosage of 1/3 H2O2
10 min

Total dosage of H2O2 and division dosage of 1/5 Fe2+

6 min

Total dosage of H2O2

pH adjustment to 4

pH adjustment to 4

Total dosage of Fe2+

30 min

Repeat once

Division dosage of 1/3 H2O2

10 min

Repeat 3 times

Division dosage of 1/5 Fe2+

6 min

Neutralization to 7-8

Precipitation
1h

Analysis of supernatant

Figure.1. Experimental procedures in this study including a single H2O2 dosage and three division H2O2 dosages and a single Fe2+ dosage and five division Fe2+dosages (initial pH 4, reaction time = 30 min)
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3.4. Laboratory Analytical Method COD was measured by a closed reflux titrimetric method according to standard methods. The pH values will be measured with a pH meter. The H2O2 concentrations are measured by using a H2O2 sensor. Color intensities of samples are measured in Space Unit (SU) by a spectrophotometer in consistent with Standard Method. COD and color removal efficiency are principally determined as following:
COD in COD (out) 100 COD in Abs in Abs (out) 100 Abs in

COD Removal Eff. % =

Color Removal Eff. %

Where COD (in) COD (out) Color (in) Color (out) : Initial COD concentration (mg/l) : COD concentration after treatment (mg/l) : Initial Color value : Color effluent after treatment

3.5. Statistical Analysis Method Statistical analyses used for calculating significant differences are the PairedSamples T-test and Single Sample T-test using SPSS version 16.0 of SPSS. Significant differences were concluded when the significance level value obtained was less than 0.05 using 95% level of confidence. Likewise the Single Sample T-test was used when the significant difference between two parameters or indexes was determined at the same experimental conditions. In addition, Microsoft Excel 2007 is also used for simple calculation of COD and Color Removal Efficiency and Graphical representation when a set of data obtained from SPSS data will have been revealed.

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Appendix 1: Research Action Plan

Activities Topic Selection Literature Review Proposal Preparation Proposal Defense Proposal Revision Sample collection Laboratory Testing Data Analysis Thesis Reports Thesis submission and Revision Final Thesis Report Final Thesis Defense Publication 2013 Dec Jan Feb Mar May Apr Jun Jul Aug Sep Oct Nov Dec Jan Feb 2014 Mar Apr May

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