mr. piseth. som_advanced research _major assignment

7/30/2019 Mr. Piseth. Som_Advanced Research _Major Assignment

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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. Bioligical Method .......................................................................................... 11

2.3.2. Physical Method ............................................................................................ 13

2.3.3. Chemical Method .......................................................................................... 15

2.4. Advanced Oxidation Processes (AOPs) .............................................................................. 16

2 5 C i l F P 17


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Abbreviation

AOPs : Advanced Oxidation Processes

BOD : Biological Oxygen Demand

COD : Chemical Oxygen Demand

EOP : Electrochemical Oxidation Potential

EPA : Environment Protection Agency

F/M : Food to Microorganism

mg/l : milligram per liter

Pt-Co : Platinum Cobalt

SS : Suspended Solid

TDS : Total Dissolved Solid

Vol : Volt

WOP : Wet Air Oxidation Process


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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 additiveare 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

b f bi h i l d d (BOD) h i l d d


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non-biodegradable organic matter. The removal of colour and COD from textile

industry and dyestuff manufacturing industry wastewaters represents a majorenvironmental 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 wastewatertreatment 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

h d i d i h h d d id i hi h h h i


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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 extendedsurface area, microporous structure, high adsorption capacity and high degree of

reactivity. However, commercially available activated carbons are very expensive

(Malik, 2003 ).

I l d d h i l d


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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

Thi h d i li i d h f ll i di i


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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.


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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


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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 Likelysources 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 highpH 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 Santoset al., 2007 ;Shanshask et al,. 2011 ).

2.2. Textile Wastewater Characteristics and Environmental Impact

l h h ffl h d ff l h h


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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 fromdyeing 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 ValuespH

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)

C l ( C )

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

0 2 00


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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 manywater 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 groundwater 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 suchas hydrogen sulfides may be produced. This will consequently upset the biological

activity in the receiving stream.

2.3. Treatment of Textile Wastewater


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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 wasteis 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 (aerobictreatment) 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) (


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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

ph ysical, chemical, and physicochemical operations (Rai, 2005; Banat et al., 1997 ).

Physical and chemical treatment techniques are effective for color removal but usemore 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 alternativetechnologies, 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 ).


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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 thistechnology 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 eitheralone or combined with biological treatment, in order to remove suspended solids

and organic matter as well as providing high color removal in textile industry

was tewater ( Meri et al, 2004 ). Many coagulants are widely used in the

conventional wastewater treatment processes such as aluminum, ferrous sulphate,


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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 )


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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


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Table 3: Advanced Oxidation Processes

H2O2/UV/ Fe 2+ (photo assisted Fenton)H2O2 /Fe 2+ (Fenton)H2O2/UV(also applicable in the gas phase)Ozone/ H 2O2 Ozone /UV/ H 2O2 Ozone/TiO 2/Electron beam irradiation

Ozone/TiO 2 / H 2O2 Ozone + electron-beam irradiationOzone/ultrasonicsH2O2/UV

Source: Shanshask et al,. 2011; Adel et al, 2004; and www. H 2O2 .com

2.5. Conventional Fenton Process

The Fenton process produces radical intermediate compounds by the reaction

of H2O2 and Fe 2+ . 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


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2003; and www. H 2O2 .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 (CO 2, water and inorganic salts). Fento ns

reagents are H 2O2 and ferrous ions. They generate hydroxyl radicals following the

chain reaction schematized as follow:

Fe 2+ + H2 O2 Fe3+ + OH + OH (chain initiation) (1)

OH + Fe 2+ OH + Fe 3+ (chain termination) (2)

As shown in Equation (1) and (2) , the ferrous iron (Fe 2+) starts the reaction and

catalyses the decomposition of H 2 O2 in hydroxyl radicals (B. Bianco et al., 2011;Mathew A. Tarr, 2003 ). However, the newly formed ferric ions (Fe 3+) may decompose

hydrogen peroxide in water and oxygen (forming ferrous ions and radicals):

Fe 3+ + H2 O2 FeOOH2+ + H+ (3)2+ 2 +


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The reaction mechanism has been summarized as follow:

Fe 2+ + H2O2 Fe 3+ + OH + OH (6)RH + OH R + H2O (7)

R + Fe 3+ product + Fe 2+ (8)

Fe 2+ + OH Fe 3+ + OH (9)

Fe 3+ + H2O2 Fe 2+ + H+ + HO2 (10)

Inhibitions to the Fenton process have also been investigated in recent studies.

Anions like H 2PO4, Cl-, NO3 and ClO -4 was found to inhibit the Fenton reaction;

therefore, reducing its efficiency. Among the anions, H 3PO4 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


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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 8.4 8.7, 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 Value

pHCOD (mg/L)BOD (mg/L)Color (absorbance at 287

8.4 8.76,500 27, 0008,500-10,000

2.1


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Sample(Textile wastewater)

pH adjustment to 4

standing flasks. Experimental conditions were varied as following. First, the initial pH,

reaction time, and Fe 2+ dose were kept constant while the H 2O2 dose was varied.

Second, the initial pH, reaction time, and H 2O2 dose were kept constant while the Fe 2+

dose was varied. Third, the reaction time, H 2O2 dose, and Fe 2+ dose were kept

constant while the initial pH was varied. Fourth, the initial pH, H 2O2 dose and Fe 2+

dose were kept constant while the reaction time was varied. Finally, all other

conditions were kept constant while either Fe 2+ dose or H 2O2 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 Fe 2+ was given in either one or

five doses and H 2O2 was given in either one or three doses (Adapted from Hyunhee

Lee Method (2008).


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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 H 2O2 concentrations

are measured by using a H 2O2 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 Removal Eff. % =COD in COD (out)

COD in100

Color Removal Eff. % =Abs in Abs (out)

Abs in100

Where

COD (in) : Initial COD concentration (mg/l)

COD (out) : COD concentration after treatment (mg/l)

Color (in) : Initial Color value


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References

Adel A. K., Azni I., Katayon S., Chuah, T. G., (2004). Treatment of Textile Wastewaterby Advanced Oxidation Processes- A review

Anouzla A., Abrouki Y., Souabi S., Safi M., Rhbal H., (2009). Color and CODremoval of disperse dye solution by a novel coagulant: Application of statisticaldesign for the optimization and regression analysis, Journal of Hazardous Materials166, 1302 1306.

APHA,(1989). Standard Methods for the Examination of Water and Wastewater.20 th Edition. American Public Health Association, American Water Work Association,Water Environment Federation, Washington, D.C.

Banat .M.,Nigam P.,Singh D.,Marchant R, (1997).Mcrobal decolorzaton of textle-dyecontanng effluents: A revew, Bioresource Technology 58, 217 -227.

Birgl A., Solmaz S.K.A., (2007). Investigation of COD and color Removal in textileindustry by using advanced oxidation and chemical treatment, Ekoloji 62, 72-80.

Ciardelli G., Capanelli G., Bottino A.,(2001). Ozone treatment of textile wastewatersfor reuse, Water Science and Technology Vol 44 No 5 pp 61 67, IWA Publishing.


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Giusy. L, (2012). Green Technologies for Wastewater Treatment: Energy Recoveryand Emerging Compounds Removal, Springer Dordrect heidlberg, New York London.

Gogate P.R., Pandit A.B.(2004) A review of Imperative Technologies for WastewaterTreatment I:Oxidation Technologies at Ambient Conditions. Advances in Environm-ental Research. 8, 501 551.

Hyunhee L., Makoto S., (2008). Removal of COD and color from livestock wastewaterby the Fenton method, Journal of Hazardous Materials, 153, 1314 1319

Laccasse K. and Baumann W., (2004) Textile Chemicals- Environmental Data andFacts, Springer-Verlag, Dortmund, Germany.

Lu M.C., Chang Y.F., Chen I.M., Huang Y.Y.(2005) Effect of Chloride Ions on theOxidation of Aniline by Fenton s Reagent. J. Envi. Management, Vol. 75, 177-182.

Mantzavinos D., Psillakis, E., (2004). Review enhancement of biodegradability of industrial wastewaters by chemical oxidation pre-treatment, Journal of ChemicalTechnology and Biotechnology, 79, 431-454.

Matthew A. Tarr, (2003). Fenton and Modified Fenton: Methods for pollutiondegradation, University of New Orleans, New Orleans, Louisiana, U.S.A.

Meri S., Seluk H., Belgiorno V., (2005). Acute toxicity removal in textile finishing


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Rai H.S.,(2005). Removal of dyes from the effluent of textile and dyestuff manufacturing industry: A review of emerging techniques with reference to

biological treatment, Critical Reviews in Environmental Science and Technology, 35:3, 219 - 238.

Robinson T., McMullan G., Marchant R., Nigam P., (2001). Remediation of dyes intextile effluent: A critical review on current treatment technologies with a proposedalternative, Bioresource Technology 77, 247-255.

Sajiki J., Yonekubo J. (2004) Inhibition of Seawater on bisphenol A (BPA) Degradationby Fenton Reagents.Environment International.30, 145 150.

Sevimli M.F., Sarkaya H.Z.,(2002). Ozone treatment of textileeffluents and dyes:Effect of applied ozone dose, pH and dye concentration, Journal of ChemicalTechnology and Biotechnology 77, 842-850.

Shahsank. S. K., et al. (2011). Advanced Oxidation Processes for Treatment of Textile

and Dye Wastewater:A Review, 2011 2nd International Conference on EnvironmentalScience and Development IPCBEE vol.4 (2011) IACSIT Press, Singapore.

Shaw C.B., Carliell C.M., Wheatley A.D., (2002).Anaerobic/aerobic treatment of colored textile effluents using sequencing batch reactors, Water Research 36, 1993 2001.


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Appendix 1: Research Action Plan

Activities2013 2014

Dec Jan Feb Mar May Apr Jun Jul Aug Sep Oct Nov Dec Jan Feb Mar Apr May

Topic Selection

Literature Review

Proposal Preparation

Proposal Defense

Proposal Revision

Sample collection

Laboratory Testing

Data Analysis

Thesis Reports

Thesis submission

and RevisionFinal Thesis Report

Final Thesis Defense

Publication

mr. piseth. som_advanced research _major assignment

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