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Wastewater Engineering: Advanced Wastewater Treatment Systems

Wastewater Engineering: Advanced Wastewater Treatment Systems © IJSR Publications

© IJSR Publications

Wastewater Engineering: Advanced Wastewater Treatment Systems

ISSN: 2322-4657 DOI 10.12983/1-2014-03-01 © IJSR Publications, Penang, Malaysia,

This work is subject to copyright. All rights are reserved by the Publisher, whether the whole or part of the material is concerned, specifically the rights of translation, reprinting, reuse of illustrations, recitation, broadcasting, reproduction on microfilms or in any other physical way, and transmission or information storage and retrieval, electronic adaptation, computer software, or by similar or dissimilar methodology now known or hereafter developed. Exempted from this legal reservation are brief excerpts in connection with reviews or scholarly analysis or material supplied specifically for the purpose of being entered and executed on a computer system, for exclusive use by the purchaser of the work. Duplication of this publication or parts thereof is permitted only under the provisions of the Copyright Law of the Publisher’s location, in its current version, and permission for use must always be obtained from IJSR Publications. Permissions for use may be obtained through RightsLink at the Copyright Clearance Center. Violations are liable to prosecution under the respective Copyright Law. The use of general descriptive names, registered names, trademarks, service marks, etc. in this publication does not imply, even in the absence of a specific statement, that such names are exempt from the relevant protective laws and regulations and therefore free for general use. While the advice and information in this book are believed to be true and accurate at the date of publication, neither the authors nor the editors nor the publisher can accept any legal responsibility for any errors or omissions that may be made. The publisher makes no warranty, express or implied, with respect to the material contained herein.

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ii

PREFACE

As the global population grows and many developing countries modernize, the importance of water supply and wastewater treatment becomes a much greater factor in the welfare of nations. Clearly, in today’s world the competition for water resources coupled with the unfortunate commingling of wastewater discharges with freshwater supplies creates additional pressure on treatment systems. Recently, researchers focus on wastewater treatment by difference methods with minimal cost and maximum efficiency. This volume of the Wastewater Engineering: Advanced Wastewater Treatment Systems is a selection of topics related to physical-chemical and biological processes with an emphasis on their industrial applications. It gives an overview of various aspects in wastewater treatments methods including topics such as biological, bioremediation, electrochemical, membrane and physical-chemical applications. Experts in the area of environmental sciences from diverse institutions worldwide have contributed to this book, which should prove to be useful to students, teachers, and researchers in the disciplines of wastewater engineering, chemical engineering, environmental engineering, and biotechnology. We gratefully acknowledge the cooperation and support of all the contributing authors.

Hamidi Abdul Aziz

Professor, School of Civil Engineering, Engineering Campus, Universiti Sains Malaysia, cehamidi@usm.my

Amin Mojiri

Research Assistant, School of Civil Engineering, Engineering Campus, Universiti Sains Malaysia, amin.mojiri@gmail.com

iii

TABLE OF CONTENTS

PREFACE

iii

TABLE OF CONTENTS

iv

CHAPTER

1:

INTRODUCTION

OF

PRELIMINARY

AND

SECONDARY

TREATMENTS

1

1.1

Introduction of preliminary and Secondary Treatments; Z. Amirossadat

2

CHAPTER

2:

WASTEWATER

TECHNOLOGIES

BY

TREATMENT

BY

PHYSICAL-CHEMICAL

05

2.1 Recent Development in Landfill Leachate Treatment Using Low Cost Adsorbent

Prepared From Waste Material; N. Azmi, J.K. Bashir, S. Sethupathi, C.A. Ng

06

2.2 Removal of Colour from Synthetic Dye Wastewater Using Adsorbent Prepared from

Psyllium Husk; I. Dahlana and S.M.O. Tayeh

15

2.3 COD and BOD Removal from Textile Wastewater Using Naturally Prepared

Adsorbents and Their Activation forms Using Sulphuric Acid; Patel and Vashi

2.4 Fenton

oxidation

for

the

Treatment

of

Liquid

Waste

with

High

31

COD

Anionic/Non-ionic Surfactants; M. Collivignarelli, S. Sorlini, A. Abbà, M. Sordi

41

and

2.5 Ultrasound Irradiation on the Treatment of Aromatic Compounds in Wastewater

W.L. Peng, G. Xinxin, M.J.K. Bashir

48

CHAPTER 3: WASTEWATER TREATMENT BY BIOLOGICAL METHODS

62

3.1 Wastewater Treatment by Biological Methods; A. Dadrasnia, N. Shahsavari and

C.U. Emenike

63

3.2 Biological Treatment of Recycled Paper Mill Wastewater Using Modified Anaerobic

Inclining-Baffled (MAIB) Bioreactor; H.M. Zwaina and I. Dahlan

71

3.3 Augmentation of Biological Nitrogen Removal via Optimization of Support Media

Size and Aeration Strategy in Moving Bed Sequencing Batch Reactor; J.Wei Lim, M.J.K.

Bashir, S.L. Ng, S. Sethupathi, L.P. Wong

iv

87

CHAPTER 4: ELECTROCHEMICAL METHODS

96

4.1 Electrochemical

Oxidation

Process

Contribution

in

Remediating

Wastewaters; M.J. K. Bashir, J.W. Lim, S.Q. Aziz, S.S.A. Amr

Complicated

97

CHAPTER

5:

WASTEWATER

TREATMENT

BY

BIOREMEDIATION

TECHNOLOGIES

107

5.1 Wastewater Treatment by Bioremediation Methods; A.N. Amenaghawon and K.O.

Obahiagbon

108

5.2 Supplementation of Novel Solid Carbon Source Prepared from Dried Attached-

Growth Biomass for Bioremediation of Wastewater Containing Nitrogen; J.W. Lim,

M.J.K. Bashir, C.A. Ng, X.

125

CHAPTER 6: WASTEWATER TREATMENT BY MEMBRANE TECHNIQUES . 136

6.1 Supported Liquid Membrane in wastewater Treatment; T.T. Teng, A. Talebi, and G.

Muthuraman

137

6.2 Role of Emulsion Liquid Membrane (ELM) in Separation Processes; T.T. Teng, M.

Soniya, G. Muthuraman and A. Talebi

149

6.3 Bulk Liquid Membrane and its Applications in Wastewater Treatment; T.T. Teng, S.

Elumalai, G. Muthuraman and A. Talebi

158

6.4 Challenges in Fabricating Suitable Membrane for Water Treatment Application;

L.Y. Wong, C.A. Ng, MJ.K. Bashir, T.L. Chew

171

6.5 Removal of Copper from Aqueous Solution by Using Thermo-responsive Polymer

Hydrogel as Copper Chelator via Polymer-enhanced Ultrafiltration (PEUF); J.J. Chen,

A.L. Ahmad and B.S. Ooi

CHAPTER

7:

WASTEWATER

TREATMENT

BY

183

PHYTOREMEDIATION

TECHNOLOGIES

193

7.1

Wastewater Treatment by Phytoremediation Methods; H. Farraji

194

CHAPTER 8: LANDFILL LECHATE TREATMENT TECHNIQUES

207

8.1 Municipal Landfill Leachate Treatment Techniques: An Overview; S.Q. Aziz, H.A.

Aziz, M.J.K. Bashir, A. Mojiri

v

208

CHAPTER 9: APPLICATION OF OPTIMIZATION IN TREATMENT

225

9.1 Application of Optimization in Wastewater Treatment; Y.L. Lim, Y.C. Ho, A.F.M.

Alkarkhi

vi

226

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Wastewater Engineering: Advanced Wastewater Treatment Systems

Chapter 1: Introduction of preliminary and Secondary Treatments

1

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online at http://www.ijsrpub.com/books ©2014 IJSRPUB Introduction of preliminary and Secondary Treatment Zahra

Introduction of preliminary and Secondary Treatment

Zahra Amirossadat

Isfahan (Khorasgan) Branch, Islamic Azad University, Isfahan, Iran

Abstract. Recently, the amounts of wastewater are sharply increasing and the kinds of pollutants are also varied as the world wide industry is being developed incessantly. With respect to both the quantity and composition, the textile processing wastewater is recorded as the most polluted source among all industrial sectors. This chapter explained the preliminary and secondary treatment of wastewater.

Keywords: Preliminary treatment, Secondary treatment, Wastewater

1. INTRODUCTION

Recently, the amounts of wastewater are sharply increasing and the kinds of pollutants are also varied as the world wide industry is being developed incessantly. With respect to both the quantity and composition, the textile processing wastewater is recorded as the most polluted source among all industrial sectors (Chang et al., 2009). At wastewater treatment plants, wastewater is treated before it is allowed to be returned to the environment, lakes, or streams. Discharge criteria required the installation of facilities that performed what is now called primary treatment of wastewater. This involved using screens and sedimentation tanks to remove most of the materials in the wastewater that float or settle. As subsequent discharge criteria were tightened, secondary treatment became necessary. Secondary treatment is accomplished by bringing together waste, bacteria and oxygen in trickling filters or the activated sludge process. Bacteria are used to consume the organic parts of the wastewater. Facilities and their designers are now considering and installing tertiary treatment facilities to comply with the latest regulatory and permit parameters. These advanced treatment processes go beyond conventional secondary treatment and include the removal of recalcitrant organic compounds, as well as excess nutrients such as nitrogen and phosphorus (Coppen, 2004). Conventional wastewater treatment consists of a combination of physical, chemical, and biological processes and operations to remove solids, organic matter and, sometimes, nutrients from wastewater. General terms used to describe different degrees of treatment, in order of increasing treatment level, are preliminary, primary, secondary, and tertiary and/or advanced wastewater treatment. In some countries, disinfection to remove pathogens sometimes follows the last treatment step.

2. Primary treatment

The objective of primary treatment is the removal of settleable organic and inorganic solids by sedimentation, and the removal of materials that will float (scum) by skimming. Approximately 25 to 50% of the incoming biochemical oxygen demand (BOD 5 ), 50 to 70% of the total suspended solids (SS), and 65% of the oil and grease are removed during primary treatment. Some organic nitrogen, organic phosphorus, and heavy metals associated with solids are also removed during primary sedimentation but colloidal and dissolved constituents are not affected. The effluent from primary sedimentation units is referred to as primary effluent. In many industrialized countries, primary treatment is the minimum level of reapplication treatment required for wastewater irrigation. It may be considered sufficient treatment if the wastewater is used to irrigate crops that are not consumed by humans or to irrigate orchards, vineyards, and some processed food crops. However, to prevent potential nuisance conditions in storage or flow-equalizing reservoirs, some form of secondary treatment is normally required in these countries, even in the case of non-food crop irrigation. It may be possible to use at least a portion of primary effluent for irrigation if off-line storage is provided. Primary sedimentation tanks or clarifiers may be round or rectangular basins, typically 3 to 5 m deep, with hydraulic retention time between 2 and 3 hours. Settled solids (primary sludge) are normally removed from the bottom of tanks by sludge rakes that scrape the sludge to a central well from which it is pumped to sludge processing units. Scum is swept across the tank surface by water jets or mechanical means from which it is also pumped to sludge processing units.

Primary treatment involves:

2

Amirossadat Advanced Wastewater Treatment

1. Screening- to remove large objects, such as

stones or sticks that could plug lines or block tank

inlets.

2. Grit chamber- slows down the flow to allow grit

to fall out

3. Sedimentation tank (settling tank or clarifier)-

settleable solids settle out and are pumped away,

while oils float to the top and are skimmed off

2. Secondary treatment

Secondary wastewater treatment is the second stage of wastewater treatment that takes place after the primary treatment process. The process consists of removing or reducing contaminants or growths that are left in the wastewater from the primary treatment process. Usually biological treatment is used to treat wastewater in this step because it is the most effective type of treatment on bacteria, or contaminant, growth. Secondary treatment processes can remove up to 90 percent of the organic matter in wastewater by using biological treatment processes. The two most common conventional methods used to achieve secondary treatment are attached growth processes and

processes

suspended growth

water_treatment/secondary-treatment). Secondary treatment typically utilizes biological

treatment processes, in which microorganisms convert nonsettleable solids to settleable solids. Sedimentation typically follows, allowing the settleable solids to settle out. Three options include:

1. Activated Sludge- The most common option

uses microorganisms in the treatment process to break down organic material with aeration and agitation, then allows solids to settle out. Bacteria-containing

“activated sludge” is continually recirculated back to the aeration basin to increase the rate of organic decomposition.

2. Trickling Filters- These are beds of coarse

media (often stones or plastic) 3-10 ft. deep. Wastewater is sprayed into the air (aeration), then allowed to trickle through the media. Microorganisms

attached to and growing on the media, break down organic material in the wastewater. Trickling filters drain at the bottom; the wastewater is collected and then undergoes sedimentation.

3. Lagoons- These are slow, cheap, and relatively

inefficient, but can be used for various types of wastewater. They rely on the interaction of sunlight, algae, microorganisms, and oxygen (sometimes aerated). After primary and secondary treatment, municipal

wastewater is usually disinfected using chlorine (or other disinfecting compounds, or occasionally ozone

3

or ultraviolet light). An increasing number of wastewater facilities also employ tertiary treatment, often using advanced treatment methods. Tertiary treatment may include processes to remove nutrients such as nitrogen and phosphorus, and carbon adsorption to remove chemicals. These processes can be physical, biological, or chemical. Settled solids (sludge) from primary treatment and secondary treatment settling tanks are given further treatment and undergo several options for disposal

The objective of secondary treatment is the further treatment of the effluent from primary treatment to remove the residual organics and suspended solids. In most cases, secondary treatment follows primary treatment and involves the removal of biodegradable dissolved and colloidal organic matter using aerobic biological treatment processes. Aerobic biological treatment (see Box) is performed in the presence of oxygen by aerobic microorganisms (principally bacteria) that metabolize the organic matter in the wastewater, thereby producing more microorganisms and inorganic end-products (principally CO2, NH3, and H2O). Several aerobic biological processes are used for secondary treatment differing primarily in the manner in which oxygen is supplied to the microorganisms and in the rate at which organisms metabolize the organic matter. High-rate biological processes are characterized by relatively small reactor volumes and high concentrations of microorganisms compared with low rate processes. Consequently, the growth rate of new organisms is much greater in high-rate systems because of the well-controlled environment. The microorganisms must be separated from the treated wastewater by sedimentation to produce clarified secondary effluent. The sedimentation tanks used in secondary treatment, often referred to as secondary clarifiers, operate in the same basic manner as the primary clarifiers described previously. The biological solids removed during secondary sedimentation, called secondary or biological sludge, are normally combined with primary sludge for sludge processing. Common high-rate processes include the activated sludge processes, trickling filters or biofilters, oxidation ditches, and rotating biological contactors (RBC). A combination of two of these processes in series (e.g., biofilter followed by activated sludge) is sometimes used to treat municipal wastewater containing a high concentration of organic material from industrial sources.

(a) Activated Sludge

In the activated sludge process, the dispersed-growth reactor is an aeration tank or basin containing a

Wastewater Engineering: Advanced Wastewater Treatment Systems Chapter 1: Introduction of preliminary and Secondary Treatments

suspension of the wastewater and microorganisms, the mixed liquor. The contents of the aeration tank are mixed vigorously by aeration devices which also supply oxygen to the biological suspension. Aeration devices commonly used include submerged diffusers

that release compressed air and mechanical surface aerators that introduce air by agitating the liquid surface. Hydraulic retention time in the aeration tanks usually ranges from 3 to 8 hours but can be higher with high BOD 5 wastewaters. Following the aeration step, the microorganisms are separated from the liquid

by sedimentation and the clarified liquid is secondary

effluent. A portion of the biological sludge is recycled

to the aeration basin to maintain a high mixed-liquor

suspended solids (MLSS) level. The remainder is removed from the process and sent to sludge processing to maintain a relatively constant concentration of microorganisms in the system. Several variations of the basic activated sludge process, such as extended aeration and oxidation ditches, are in common use, but the principles are similar.

(b) Trickling Filters

A trickling filter or biofilter consists of a basin or

tower filled with support media such as stones, plastic

shapes, or wooden slats. Wastewater is applied intermittently, or sometimes continuously, over the media. Microorganisms become attached to the media and form a biological layer or fixed film. Organic matter in the wastewater diffuses into the film, where it is metabolized. Oxygen is normally supplied to the film by the natural flow of air either up or down through the media, depending on the relative temperatures of the wastewater and ambient air. Forced air can also be supplied by blowers but this is rarely necessary. The thickness of the biofilm

4

increases as new organisms grow. Periodically, portions of the film 'slough off the media. The sloughed material is separated from the liquid in a secondary clarifier and discharged to sludge processing. Clarified liquid from the secondary clarifier is the secondary effluent and a portion is often recycled to the biofilter to improve hydraulic distribution of the wastewater over the filter.

(c) Rotating Biological Contactors

Rotating biological contactors (RBCs) are fixed-film reactors similar to biofilters in that organisms are attached to support media. In the case of the RBC, the support media are slowly rotating discs that are partially submerged in flowing wastewater in the reactor. Oxygen is supplied to the attached biofilm from the air when the film is out of the water and from the liquid when submerged, since oxygen is transferred to the wastewater by surface turbulence created by the discs' rotation. Sloughed pieces of biofilm are removed in the same manner described for biofilters

REFERENCES

Chang W, Tran H, Park D, Zhang R, Ahn D (2009). Ammonium nitrogen removal characteristics of zeolite media in a Biological Aerated Filter (BAF) for the treatment of textile wastewater. Journal of Industrial and Engineering Chemistry, 15: 524-528. Cppen J (2004) Advanced Wastewater Treatment Systems. Courses ENG4111 and 4112 Research Project, University of Southern Queensland, Faculty of Engineering and Surveyin.

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Chapter 2: Wastewater Treatment by Physical- Chemical Technologies

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online at http://www.ijsrpub.com/books ©2014 IJSRPUB Recent Development in Landfill Leachate Treatment Using Low

Recent Development in Landfill Leachate Treatment Using Low Cost Adsorbent Prepared From Waste Material

Nurshazwani Binti Azmi, Mohammed J.K. Bashir*, Sumathi Sethupathi, Choon-Aun Ng

Department of Environmental Engineering, Faculty of Engineering and Green Technology (FEGT), University Tunku Abdul Rahman, 31900 Kampar, Perak, Malaysia *Corresponding Author: jkbashir@utar.edu.my; Tel: 605-4688888 ext: 4559; Fax: 605-4667449

Abstract. Landfill leachate has become the subject of recent research interest as it is a strongly polluted wastewater. The produced leachate is one of the most important drawbacks of municipal solid waste disposal (MSW) in sanitary landfill. Adsorption by activated carbon (AC) appears to have considerable potential in landfill leachate treatment due to the simplicity design, superior removal of organic compound and less land area required. However, the high demand for AC is a major problem due to limited carbon based substances such as coal, wood and lignite. Therefore, waste material seems to be a good option as an alternatives source of AC. Consequently, this paper focuses on effectiveness of using AC in landfill leachate treatment and highlighted the recent development treating landfill leachate using adsorbent prepared from waste material.

Keywords: Landfill Leachate, Treatment, Adsorbent

1. INTRODUCTION

As the exponential population and social civilization growth, together with the developments of industries and technologies, rapid generation of MSW has becomes a global environmental problem (Saeed et al., 2009). There are many options available for MSW disposal such as sanitary landfill, open dump, incineration, composting, grinding, hog feeding, milling, and anaerobic digestion (Aziz et al., 2010). Sanitary landfill is the most common MSW disposal method due to such advantages as the simple disposal procedure, low cost, and landscape-restoring effect on holes from mineral workings (Bashir et al., 2010). However, the production of highly contaminated leachate is a major drawback of this method (Aziz et al., 2010). Landfill leachate is defined as any contaminated liquid effluent percolating through deposited waste and emitted within a landfill or dump site through external sources (Taulis, 2005). In a more precise definition, it is a soluble organic and mineral compound formed when water infiltrates into the refuse layers, which extracts a series of contaminants and instigates a complex interplay between the hydrological and biogeochemical reactions that acts as a mass transfer mechanisms for producing of moisture content sufficiently high to start the liquid flow (Aziz et al., 2004). As shown in Figure 1, leachate generation induced by the gravity force, precipitation, irrigation, surface runoff, rainfall, snowmelt, recirculation, liquid waste co-disposal, refuse decomposition, groundwater intrusion and initial moisture content present within the landfills (Achankeng, 2004). As the consequences, leachate may contain high concentration of organic matter (biodegradable and non-biodegradable), ammonia nitrogen, heavy metals, chlorinated organic and

6

inorganic salts (Renou et al., 2008). Without an appropriate treatment, landfill leachate could be a potential source of surface and groundwater contamination, as it could seep into soils and subsoil, causing severe pollutions to receiving water body (Oman and Junestedt, 2008). Typically, leachate characteristics and compositions depends on various factors such as waste composition, age of landfill, site hydrogeology, specific climate conditions, moisture routing through the landfill, and the landfill design and operation (Ghafari et al., 2010). Age of landfill site is one of the main variables that affect the leachate characteristics (Bashir et al., 2012), where the concentration of leachates parameters changes with the age of the leachate. Young acidogenic landfill leachate commonly characterized by high biochemical oxygen demands(BOD) and chemical oxygen demands(COD) , high concentration of ammonium nitrogen followed by low pH value as low as pH 4 (Wu et al., 2001). The degradation of biological matter by microorganism lead to generation of Volatile Fatty Acid(VFA) that lead to low ph value and high BOD/COD ratio. On the contrary, aged landfill (i.e. >10 years old) produces mature (stabilized) leachate that contains bio-refractory compounds such as humic acid (HA) and fulvic acids (FA), with BOD 5 /COD ratio less than 0.1 (Alvariz-Vazqurez et al., 2004) as illustrated in Table 1. Biological treatment of landfill leachates have been shown to be very effective in removing organic matter in early stages (Berruetta and Castrillon, 1992) with high BOD/COD ratio. As the BOD/COD ratio decrease with the passage of time (Rodriguez et al., 2000), the biodegradable organic content of leachate reduced where biological treatment no longer effective due to the presence of refractory organic matter and physico-chemical processes may become

Azmi et al. Recent Development in Landfill Leachate Treatment Using Low Cost Adsorbent Prepared From Waste Material

one of the appropriate options for stabilized landfill leachate. Various physico-chemical process have been practiced for old landfill leachate treatments such as adsorption (Halim et al., 2012), ion-exchange (Bashir et al., 2012), Fenton reaction (Mohajeri et al., 2011), coagulation/flocculation (Ghafari et al., 2010), electrochemical oxidation process (Marco et al., 2013) ozonation (Salem et al., 2013), and air stripping (Bloor and Banks, 2005). Among all process, adsorption technology is one of the most applicable and simple methods. Adsorption is defined as a mass transfer process by which a substance is transferred from liquid or gas phases to the solid surface of adsorbent and form attachment via physical or chemical interactions. The material providing the solid surface is called the adsorbent and material removed from the liquid phase is called as adsorbate. AC demonstrated significant adsorption efficiency in gas and liquid phases due to its high micropore volume, large specific surface area,

favorable pore size distribution, thermal stability, and capability for rapid adsorption and low acid/base reactivity (Li et al., 2009). The unique adsorptive properties of AC, makes it as one of the best filtration media in the world. However, high manufacturing cost and expensive carbonaceous material for producing high quality AC (Mohan and Pittman, 2006) lead to limitation of this application for landfill leachate treatment especially in developing countries. Thus, the use of non-conventional material such as agriculture waste and industrial by-product that are locally available can be chemically modified and utilized as a low carbon adsorbent (Babel and Kurniawan, 2003). Several studies have been conducted by using AC for various types of waste water. Consequently, the present work reviews and evaluates the recent published works focuses on landfill leachate treatment using adsorbent prepared from the waste materials.

leachate treatment using adsorbent prepared from the waste materials. Fig. 1 : Leachate Formation (Agamuthu, 2001)

Fig. 1: Leachate Formation (Agamuthu, 2001)

7

Wastewater Engineering: Advanced Wastewater Treatment Systems Chapter 2: Wastewater Treatment by Physical-Chemical Technologies

Table 1: Classification of landfill leachate (Alvarez-Vazquez et al., 2004)

Parameters

Young

Intermediate

Stabilized

Age (years)

<5

5-10

>10

pH

<6-5

6-5-7-5

>7.5

COD (mg L -1 )

>10 000

4000-10 000

<4000

BOD 5 /COD TOC/COD NH-N Heavy metal (mg L -1 )

0.5-1

0.1-0.5

<0.1

<0.3

0.3-0.5

>0.5

<400

NA

>400

Low to

Low

Low

 

medium

Organic compound

80%

5-30%

HA+FA

VFA

VFA+ HA+ FA

Biodegradability

Important

Medium

Low

Kjeldahl Nitrogen (g L -1 )

0.1-0.2

NA

NA

2. PREPARATION OF ACTIVATED CARBON

In general, the process for manufacturing of AC involves two steps, carbonization of the raw material followed by the activation of the carbonized product. The activation process can be carried out in two ways, either by physical activation (PhA) or chemical activation (Cha). Pretreatment of the raw material normally conducted before carbonization process. Few preliminary stages involves such as crushing, milling and sieving for appropriate particle size are important for subsequent handling of the raw material (Alslaibi et al., 2013). During carbonization, the raw material will undergo thermal decomposition in inert atmosphere through gasification by Nitrogen gas. Carbonization process can be carried out using tubular furnaces, reactors, muffle furnace and more recently in a glass reactor placed in a modified microwave oven (Foo and Hameed, 2011). This process known as pyrolysis where the non-carbon elements such hydrogen, nitrogen and oxygen will be released leaving a rigid carbon skeleton with a rudimentary pore structure. Based on previous studies, pyrolysis of lignocellulosic material such as olive stones, coconut shells or olive shells will remove most of non-carbon elements in the form of char, tar (oil) and gas where the proportion depends on the parameter during pyrolysis such as temperature of pyrolysis, nitrogen flow rate and heating rate. According to Mohammed et al., (2010), flash pyrolysis will give high liquid production, while slow heating rate recommended for high yields of the char residue. Physical activation is normally made by carbonization followed by activation in partial or

8

control gasification at high temperature (Rodriguez- Reiniso and Molina-Sabio, 1992). Activation completed through gasification using oxidizing agent (Table 2) or mixture of it at temperature ranging from 700-1100 o C to develop the porosity (micropores and mesopores) of the carbonized material (Rodrigues- Reinoso and Molina-Sabio, 1992). CO 2 can develop narrow micropores, while steam will widen the initial micropores. Accordingly, CO 2 produced larger volume and narrower micropores (Mohamed et al., 2010) while steam created a larger volume of mesopores and micropores. Meanwhile in ch(A), carbonization and activation can be run simultaneously, where the raw material will be impregnated with chemical agent (Table 2) followed by conventional heating at moderate temperature between 400-800 o C (Demiral and Gunduzoglu, 2010). The chemical agent acts as deactivating agent where it inhibits formation of tar and develops AC porosity via dehydration and degradation. The pore distribution and surface area is determined by the impregnation ratio between the mass of precursor and the chemical agent chosen. The resulting AC produced is then washed with distilled water or mild acid in order to remove residual chemicals from the material. Nowadays, chemical activation is widely applied for the activation because of its lower activation temperature and higher product yield compared with the physical one (Guo and Rockstraw, 2007). Based on the literature reviewed, it was found that alkaline hydroxides (KOH and NaOH) (Lillo-Rodenas et al., 2007) can be used to prepare the activated carbon, which gave high specific surface area in the range of 23183500 m 2 /g (Tseng, 2006).

Azmi et al. Recent Development in Landfill Leachate Treatment Using Low Cost Adsorbent Prepared From Waste Material

Table 2: Common activating agent for different activation method in preparation of AC (Alslaibi et al., 2013)

method in preparation of AC (Alslaibi et al., 2013) Some additional studies combine the physical activation

Some additional studies combine the physical activation with chemical activation where it is known as physicochemical activation. In general, physicochemical activation is performed by changing the activation atmosphere of the chemical activation by a gasification atmosphere (steam, CO 2 ) at higher temperatures or the chemical activation is carried out directly under the presence of a gasifying agent. The combination of both types of carbon activation makes ACs with textural and chemical properties which are different from those obtained by any of the activations alone. For example, steam reduces the occurrence of heteroatoms into the carbon structures. Also, the combination of oxidizing reagents in the liquid phase (nitric or sulfuric acids) with gasification agents improves the development of porosity on the final carbons. In addition, continued development of activated carbon lead to the new application of microwave heating in preparing activated carbons. Recently, the usage of microwave heating as an alternative to conventional heating in ch(A) receives considerable attention in many research works. Microwave synthesis is an alternative technique that overcomes the problems of conventional fast firing because microwave synthesis is a non-contact technique where the heat is transferred to the product via electromagnetic waves, and large amounts of heat can be transferred to the interior of the material, minimizing the effects of differential synthesis (Jones et al., 2002). This leads to uniform heating, rapid temperature rise and saving energy (Zhang et al., 2011). In addition, the short period of treatment time, reduced extra processing cost by reduction in energy consumption (Xin-Hui et al., 2011) and gas consumption within the process (Foo and Hameed,

2009). Besides, previous study illustrate relatively higher surface areas developed during AC preparation by microwave heating compared to conventional heating for the same precursor (Alsalibi et al., 2013). Since carbonaceous materials are a good microwave absorber, microwave assisted thermal process turned to interesting alternative approach in preparation of AC. The experimental apparatus used in ch(A) by microwave heating in the laboratory scale is shown in Figure 2.

3. PERFORMANCE OF AC

Performance of AC is largely depends on two parameters e.g. the surface area and the pore structure (Figueiredo et al., 1999). The larger surface area will contribute to higher adsorption capacity. Although a microporous AC is generally desired for adsorption purposes, the presence of mesopores is also valuable for the adsorption of large molecules or where a faster adsorption rate is required (Huang et al., 2011). Meanwhile, the macropores have larger pore volume and act as access pores that provide a passageway to the particles. The pore volume limits the size of particles that can be access while the surface area limits the amount of material that can be adsorbed. According to the International Union of Pure and Applied Chemistry (IUPAC), porosity within the adsorbent has been categorized according to width. The largest macropores (access pores) generally have width between 50nm-100nm, the mesopores (transport pores), between 2-50nm wide and the smallest pores, micropores (high adsorption properties) have width < 2nm. Figure 3 shows the three types of AC pore structure: micropores,mesopores and macropores.

9

Wastewater Engineering: Advanced Wastewater Treatment Systems Chapter 2: Wastewater Treatment by Physical-Chemical Technologies

2: Wastewater Treatment by Physical-Chemical Technologies Fig. 2: A schematic diagram of the experimental apparatus

Fig. 2: A schematic diagram of the experimental apparatus used in activation process (Deng et al., 2009)

4. RECENT DEVELOPMENTS IN LANDFILL LEACHATE TREATMENT VIA ADSORBENTS FROM WASTE MATERIALS

In the recent years, adsorption technology has been applied in landfill leachate treatment by using low cost adsorbents prepared from waste materials, particularly agricultural waste, as precursors for AC production. As adsorption by AC offer number of advantages such as not getting affected by toxic compound, superior removal of organic contaminants (Weber, 1978), high degree of porosity and very well developed surface area (Sevilla et al., 2011), it has turned to a powerful standard technique for removing toxic and non-biodegrable metal ion (Foo and Hameed, 2011). The effectiveness of adsorption process by physical and chemical activation method is presented in Table 3. Study conducted by Foo et al., (2013a) showed good removal of NH 3 -N and orthophosphate by 79.63% and 85.06% via adsorption, where adsorptive removal increased as adsorbent dosage increased from 0.5g/200ml to 5.0g/200ml. The experimental data revealed the feasibility of sugarcane bagasse as developed adsorbent for leachate treatment with micropore volume 0.515cm 3 /g and micropore surface area 659.25 mg/cm 2 . In another study conducted by Foo et al., (2013b), the potential of the

10

banana front as the precursor in AC production was attempted. The experimental data showed that, with increasing of adsorbent dosage, from 0.5g/200ml to 3.5g/200ml and from 0.5g/200ml to 4.0mg/200ml at 30 o C, the adsorptive removal of Boron and Iron increased. The greatest adsorptive removal of boron and total Iron is by 97.45% and 95.14% with maximum monolayer adsorption capacity at 11.09 and 26.15 mg/g. Meanwhile, tamarind fruit seed derived granular activated carbon showed higher adsorptive removal of colour (91.22%) while COD (79.93%). The optimum adsorbent dosage in this experiment is 6.0g/200ml at temperature 30 o C. The adsorption of COD and color onto TSAC was best described by the Langmuir isotherm model, with a monolayer adsorption capacity of 64.93 mg/g and 168.57 PtCo/g, respectively. The results indicated that the tamarind fruit seed derived granular activated carbon adsorption process was sufficient for removing these targeted contaminants, to reach to the industrial discharge limit of COD (500 mg/L) permitted by the World Health Organization (WHO).Kamarudin et al., (2012) presented the physical activation of durian peels for AC preparation, with 41.98% and 39.86% removal of color and COD with optimum activation temperature at 800 o C, activation time 2.1H and CO 2 flow rate 68.68 mg/L. In another study conducted by Ching et al., (2011), impregnated coffee ground with

Azmi et al. Recent Development in Landfill Leachate Treatment Using Low Cost Adsorbent Prepared From Waste Material

H 2 SO 4 by chemical activation via microwave heating, they found that the optimum impregnation ratio was 0.5 and 2.5 with a 10g AC dosage at pH 8.1, with removal of iron by 77% and PO 4 -P by 84%. In the case of rice husk, Kalderis et al., (2008) observed that

the micropore volume of Rice Husk Activated Carbon produced was 0.42cm 3 /g with chemical activation by ZnCl 2 via microwave heating. The percentage removal of COD was by 60% and colour by 70% with optimum AC dosage at 30g/L.

by 60% and colour by 70% with optimum AC dosage at 30g/L. Fig. 3: Diagram of

Fig. 3: Diagram of Activated Carbon (Source: Sushrut Chemicals, 2013)

Table 3: Application of adsorbent prepared from various waste materials in treating landfill leachate

Chemicals, 2013) Table 3 : Application of adsorbent prepared from various waste materials in treating landfill

11

Wastewater Engineering: Advanced Wastewater Treatment Systems Chapter 2: Wastewater Treatment by Physical-Chemical Technologies

Based on the previous experimental works, waste material especially agriculture waste has high potential to be converted to AC and then utilized in treating hazardous landfill leachate. The percentage of COD, colour, and heavy metals such as Iron, orthophosphate and Boron reduced and meet the requirement set by the officially authorized prior discharge to the surface water. However, only small numbers of research works conducted for landfill leachate treatment by using waste material as adsorbent. Thus, more studies should be conducted to understand the process of low-cost landfill leachate treatment through adsorption process by AC.

landfill. Together with simplicity design, less land area required, alongside with the recycling of waste material as a low- cost precursor reduces the numbers of MSW and resolves the landfill leachate problem. However, full cooperation between communities, private sectors, local government and states are required in order to apply this valuable technology towards sustainable environment.

ACKNOWLEDGEMENTS

The authors are grateful for the financial support provided by the Universiti Tunku Abdul Rahman

 

(UTAR)

through

grant

No:

5.

OPPORTUNITIES AND CHALLENGES

IPSR/RMC/UTARRF/2012-C2/M03

and

Recently, many research works have been done to highlight the potential use of waste material as a precursor for landfill leachate treatment. Higher availability with lower cost makes waste material such as agriculture waste and industrial waste as an alternative choice of precursor. Furthermore, with favorable characteristic as an adsorbent (high porosity and large surface area), waste materials are comparable with the typical precursor (coal, wood, lignite). Although the precursor selection depends on their availability, cost and purity, but the manufacturing process and the application of the product are also important considerations (Yavuz et al., 2010). In addition, low social acceptability and lack of economical affordability, especially in the management of the treatment such as treatment facilities, chemical, labor, energy consumption, transportation, collection and maintenance are among the main key drivers deciding its flexibility, reliability and suitable manner. Thus, corrective and transparent policies, mandates and standards which governing the collection, transportation, disposal prevention, recycling, reuse, monitoring, designing and supervision of solid waste management should to be pointed out and well- planned. Besides, the sound of professional in order to creates environmental awareness for public participation, adequate financial provisions, engineering and operating standards, responsibilities sharing, product stewardship, staff capacities upgrading formal procedures redressing, regular opinion survey, site rehabilitation and aftercare maintenance need to be properly assigned and counteracted (Bernache, 2003).

6. CONCLUSION

Landfill leachate treatment by adsorption process using AC has a potential to be practice in sanitary

IPSR/RMC/UTARRF/2013-C2/T02.

12

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precursor/alkaline hydroxide J. Anal. Appl. Pyrol, 80: 166174 Li W, Peng J, Zhang L, Yang K, Xia H, Zhang S, Guo SH (2009). Preparation of activated carbon from coconut shell chars in pilot-scale

microwave heating equipment at 60 Kw. Waste Management, 29:756760. Marco P, Carlos A, Martinez-Huitle (2013). Role of electrode materials for the anodic oxidation of a real landfill leachate-Comparison between Ti- Ru-Sn ternary oxide,PbO 2 and Boron doped diamond anode.Chemosphere, 90(4): 1455-

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Review & Opportunity. J Hazard Mater, 150:

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Rodriguez IJ, Castrillon PL, Maranon ME., Sastre AH (2000). Biomethanisation of municipal solid waste in a pilot plant. Water Res., 4(2):447-54. Rodríguez-Reinoso F, Molina-Sabio, M. (1992). Activated carbons from lignocellulosic materials by chemical and/or physical

activation: an overview. Carbon, 30(7): 1111-

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Saeed MO, Hassan MN, Mujeebu MA (2009). Developement of municipal solid waste generation and recyclable components rate of Kuala Lumpur : Perspective study. Waste Mangement, 9: 2209. Abu Amr S.S, Aziz HA, Adlan MN Bashir MJK (2013). Pretreatment of stabilize leachate using ozone/persulfate oxidation. Chem. Eng. Journsl, 221: 492-499 Sevilla M, Fuertes AB, Mokaya R (2011). Preparation and hydrogen storage capacity of highly porous activated carbon materials derived from polythiophene. Int. J. Hydrog. Energy, 36:

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Taulis M (2005). Metal contaminants in leachate from sanitary landfills', Metal Contaminants in New Zealand: Sources, Treatments, and Effects on Ecology and Human Health, pp. 119-38. Tseng RL (2006). Mesopore control of high surface area NaOH-activated carbon. J. Coll.Sci.Imp.U.Tok, 303:494-502 Wu JJ, Wu CC, Ma HW, Chang CC, Masten SJ (2001). Treatment of landfill leachate by ozone- based advanced oxidation process. In:

Proceeding of the 15 th IOA world congress,

London,UK: 339-34. Xin-hui D, Srinivasakannan C, Jin-hui P, Li-bo Z, Zheng-yong Z (2011). Comparison of activated carbon prepared from Jatropha hull by conventional heating and microwave heating. Biomass Bio-energy, 35:39203926. Yavuz R, Akyildiz H, Karatepe N, C Etinkaya E (2010). Influence of preparation conditions on porous structures of olive stone activated by H3PO4. Fuel Process Technol., 91:8087. Zhang G, Zhang L, Deng Hand Sun P (2011). Preparation and characterization of sodium carboxymethyl cellulose from cotton stalk using microwave heating. J. Chem. Technol. Biotechnol, 86:584589.

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Wastewater Engineering: Advanced Wastewater Treatment Systems Available online at http://www.ijsrpub.com/books ©2014 IJSRPUB

online at http://www.ijsrpub.com/books ©2014 IJSRPUB Removal of Colour from Synthetic Dye Wastewater Using

Removal of Colour from Synthetic Dye Wastewater Using Adsorbent Prepared from Psyllium Husk

Irvan Dahlan 1* , Somaia M.O. Tayeh 2

1 School of Chemical Engineering, Universiti Sains Malaysia, Engineering Campus, Seri Ampangan, 14300 Nibong Tebal, Pulau Pinang, Malaysia.

2 School of Civil Engineering, Universiti Sains Malaysia, Engineering Campus, Seri Ampangan, 14300 Nibong Tebal, Pulau Pinang, Malaysia. *Corresponding Author: chirvan@eng.usm.my

Abstract. Color removal from textile effluents has been given much attention in the last few years by the adsorption process using low cost adsorbents. In this study, four different adsorbents were prepared from psyllium husk (i.e. PH/CFO-Al, PH/CFO-Ac, QPH and NPH) for removal of direct blue dye (DB71) from synthetic wastewater. From the preliminary study, PH/CFO-Ac adsorbent gave the highest color removal efficiency. PH/CFO-Ac adsorbent was prepared from psyllium husk and CoFe 2 O 4 by a facile refluxing route in acidic solution. PH/CFO-Ac adsorbent was selected to be used for further batch studies to examine the effect of various experimental parameters, i.e. contact time, adsorbent amount, shaking rate, initial dye concentration, pH and temperature. The best conditions for dye removal using PH/CFO-Ac adsorbent were obtained at pH 9.0, temperature of 30 ° C, shaking rate of 150 rpm and contact time of 2 hours. The adsorption kinetics was found to follow pseudo- second-order kinetic model. The experimental data fitted well with the Langmuir model with a monolayer adsorption capacity of 188.7mg/g. It was also found that prepared and spent PH/CFO-Ac adsorbents have a homogenous particle size distribution. In addition, the surface morphology of the spent PH/CFO-Ac adsorbents had more compact structures with small granular particles attached on the surface.

Keywords: Colour removal, Synthetic Dye Wastewater, Psyllium Husk

1. INTRODUCTION

Due to the increase in the world population and development of industrial applications, environmental pollution problem became very important, especially wastewater pollution problem. Communities produce both liquid and solid wastes. The liquid waste, i.e. wastewater, is essentially the water supply of the community after it has been used in a variety of applications. Wastewater handling, disposal & treatment are serious worldwide problem. Many industrial and agricultural activities use water in an excessive way. However, it is now well known that the fresh water resources are limited and fragile, so they must be protected. Discharge of sanitary wastewater, industrial effluent and agricultural field’s runoff can be the main source of freshwater pollution. This causes many diseases for human, and it is known that 70-80% of illness in developing countries is related to water contamination, particularly for children and women (WHO/UNICEF, 2000). Textile industries consume large volumes of water and chemicals for wet processing of textiles. The chemical reagents used are very diverse in chemical composition, ranging from inorganic compound to polymers and organic compound (Correia et al., 1994). The color is an evident indicator of water pollution by the dyes. Industrial dye effluents are visible even at concentrations lower than 1 mg/l. Moreover, some dyes and their degradation products are carcinogenic (Ahn et al., 1999). Also, some dyes

15

are harmful to aquatic life in rivers where they are discharged. Since, dye can reduce light penetration into the water thereby decreasing the efficiency of photosynthesis in aquatic plants and hence having adverse impact on their growth (Che Ani, 2004). Textile wastewater is generally high in both color and organic content. Effluents discharged from dyeing industries are highly colored and they can be toxic to aquatic life in receiving waters (Lee et al., 1999, Kadirvelu et al., 2003). Color removal from textile effluents has been given much attention in the last few years, not only because of its potential toxicity, but mainly due to its visibility problems (Morais et al., 1999). The total dye consumption of the textile industry worldwide is in excess of 10 7 kg/year, and an estimated 90% of this ends up on fabrics. Consequently, 1000 tonnes/year or more of dyes are discharged into waste streams by the textile industry worldwide (Ahmad et al., 2007). Development of the appropriate techniques for treatment of dye wastewater is important for the protection of natural water. To eliminate dyes from aqueous colored effluents and reduce their ecological consequences, several biological and chemical techniques have been proposed: anaerobic/aerobic degradation (Ahmed et al., 2007), coagulation/flocculation (Papić et al., 2000) and also oxidative/reductive chemical and photochemical processes (Lucas and Peres, 2006). Due to relatively high operating costs and low removal efficiencies using the above-mentioned processes, textile, pulp and

Dahlan and Tayeh Removal of Colour from Synthetic Dye Wastewater Using Adsorbent Prepared from Psyllium Husk

paper industries seldom apply these to treat their effluents. Among several chemical and physical methods, the adsorption has been found to be superior to other techniques in water reuse methodology because of its capability for adsorbing a broad range of different types of adsorbates efficiently, and simplicity of design. Many researchers researched for cheaper substitutes, which are relatively inexpensive, and are at the same time endowed with reasonable adsorptive capacity. These studies include the use of coal, fly ash, activated clay, palm-fruit bunch, Bagasse pith, cellulose-based waste, peat, bentonite, slag and fly ash, rice husk, activated sludge, etc (Ahmad et al.,

2007).

Psyllium husk has not been investigated as adsorbent for color removal from dye solutions. This research studied the adsorption for color removal from synthetic dye wastewater using an adsorbent prepared from an inexpensive and readily available material,

i.e. psyllium husk. Also, the study aims to achieve the following measureable objectives:

1- To prepare and characterize adsorbent from

psyllium husk using quaternized and magnetic

methods.

2- To investigate the ability of the best psyllium

husk adsorbent for removal of color from synthetic

dye under various operating conditions (initial dye concentration, amount of sorbent, shaking rate, contact time, pH, and temperature). 3- To determine the kinetic behavior and isotherms for the adsorption process of color onto psyllium husk adsorbent.

2. MATERIALS AND METHODS

2.1. Materials

The raw psyllium husk (Fig. 1) was obtained directly from a store in Parit Buntar, Penang, and used in the preparation of the adsorbent for this study. Direct blue dye (DB71) was provided by Sigma Aldrich, Co., and used without further purification. The dye was used as the adsorbate in the batch experimental study. The chemicals used in this study are Na 2 CO 3 and Ferric nitrate [Fe(NO 3 ) 3 ·9H 2 O] which is provided by Bendosen Laboratory Chemicals, whereas NaOH, H 2 SO 4 and Cobalt nitrate [Co(NO 3 ) 2 ·6H 2 O] are provided by Qrëc, Bright Chem. Sdn Bhd. In addition,

N-(3-chloro-2-hydroxy-propyl)-trimethylammonium

chloride was provided by Aldrich Chemistry. All chemicals were used without any purification process.

All chemicals were used without any purification process. Fig. 1: Raw psyllium husk (PH). 2.2. Preparation

Fig. 1: Raw psyllium husk (PH).

2.2. Preparation of Adsorbent

2.2.1. Preparation of raw psyllium husk

The raw psyllium husk was dried in the oven at 100 o C for 24 hours, and then ground by using domestic blender to pass through a 1mm-sieve (Laboratory Test Sieve). The husk obtained was kept in a closed plastic and labeled as raw psyllium husk (RPH).

2.2.2. Preparation of Quaternized Adsorbent

About 20g of the raw psyllium husk was treated with 250 ml of 1% w/v Na 2 CO 3 solution (Fig. 2a). The mixture was shaken for 45 min at room temperature

16

(Fig. 2b). It was subsequently rinsed several times with distilled water (Fig. 2c) and dried at 60°C (Fig. 2d). The husk obtained was labeled as natural psyllium husk (NPH). A portion of NPH was quaternized according to the method reported by Low and Lee (1997). The natural psyllium husk (10g) in 12.5 ml of 5 M NaOH solution was left at room temperature for 30 min (Fig. 2e). At the end of incubation period 10 ml of 4 M N - (3-chloro-2- hydroxy-propyl) - trimethylammonium chloride was added to the mixture (Fig. 2f). It was thoroughly left in the oven at 60-70°C for 4 hours (Fig. 2g) with intermittent stirring. The reaction mixture was then rinsed several times with water and finally with

Wastewater Engineering: Advanced Wastewater Treatment Systems Chapter 2: Wastewater Treatment by Physical-Chemical Technologies

distilled water (Fig. 2h). The product after drying was labeled as quaternized psyllium husk (QPH).

2.2.3.

adsorbent (PH/CFO)

Preparation

of

psyllium

husk/CoFe 2 O 4

Psyllium husk/CoFe 2 O 4 adsorbent was synthesized by a facile refluxing route in alkaline solution as reported by Ai et al., (2010) with some modifications. In a typical procedure, 8g of raw psyllium husk was added into a 150mL alkaline solution containing 3.4g NaOH, and stirred at room temperature for 30 minutes (Fig. 3a) to get the psyllium husk suspension. The suspension was then maintained at 100°C to keep

boiling state (Fig. 3b). A 50mL metal nitrate aqueous solution was prepared by dissolving Fe(NO 3 ) 3 ·9H2O (5.4944 g) and Co(NO 3 ) 2 ·6H2O (1.9790 g) in distilled water (Fig. 3c). The solution was poured as quickly as possible into the above boiling suspension (Fig. 3d). The mixture solution was then refluxed at 100°C for 2 h (Fig. 3e). By a simple magnetic procedure, the resulting product was separated from water, dried at 80°C for 12 h (Fig. 3f), and the product was labeled as PH/CFO-Al. This preparation method was repeated twice, the second time was by replacing the 150 mL alkaline solution NaOH by 150ml acidic solution H 2 SO 4 (2N ) to obtain PH/CFO-Ac.

Table 1: Summary of batch studies

 

Preliminary Batch study

 

Main Batch study

Using four types of adsorbent prepared from psyllium husk, to select the best adsorbent with the highest efficiency to be used in the main study, the effect of two parameters were studied:

Main experiments for synthetic wastewater

a.

Effect of contact time using 1hr, 2hr, 3hr, 4hr and 5hr

b.

Effect of adsorbent amount using 0.1g, 0.3g, 0.6g, 1g

and 1.5g

 

Effect of shaking rate using 100rpm, 150rpm, 200rpm, 250rpm and 350rpm.

c.

Effect of adsorbent amount (using 1g and 3g adsorbent)

a-

d.

Effect of initial dye concentration using 15, 30, 60,

 

100 and 200mg/L

b-

Effect of initial dye concentration (using

e. Effect of pH using pH 3, 4.5, 6, 7.5, 9 and10.5

5mg/ L, 15mg/L)

f. Effect of temperature using 30, 40, 50 and 60 o C

2.4. Isotherm and Kinetic studies

For the isotherm and kinetic studies, one batch experiment was conducted using 1000ml of synthetic wastewater with initial dye concentration of 200mg/L and pH 9. About 1.0g of adsorbent was added to the sample, it was agitated at the agitation rate of 150 rpm. Samples were taken at different time intervals (0 60 min), and the final concentration of the dye was measured at each time t. At time t = 0 and equilibrium, the dye concentration was measured and the amount of adsorption at equilibrium, q e (mg/g) was calculated using Equation

at equilibrium, q e (mg/g) was calculated using Equation where C o and C e (mg/L)

where C o and C e (mg/L) are the liquid-phase concentrations of sample at initial and equilibrium, respectively. W (g) is the mass of sorbent used and V (L) is the volume of the solution. The removal efficiency of dye can be calculated from Equation 2

removal efficiency of dye can be calculated from Equation 2 where C t is the dye

where C t is the dye concentration at time t. Adsorption isotherm is fundamentally essential to explain how solutes interact with sorbents, and is critical in optimizing the use of sorbents. In the present study, the equilibrium isotherms were

analyzed using the Langmuir and Freundlich, isotherms. The linear form of Langmuir isotherm is given in Equation 3 (Keleşoğlu, 2007) and Freundlich isotherm is given in Equation 4 (Schwarzenbach et al., 2003),

is given in Equation 4 (Schwarzenbach et al., 2003), where the constant Q o signifies the
is given in Equation 4 (Schwarzenbach et al., 2003), where the constant Q o signifies the

where the constant Q o signifies the adsorption capacity (mg/g) and b is related with the energy of the adsorption (L/mg), K F and n are Freundlich constants. To investigate the adsorption mechanism, pseudo- first-order and pseudo-second-order kinetic models were tested to find the best fitted model for the experimental data. The pseudo-first-order equation is given by Equation 5.

The pseudo- first -order equation is given by Equation 5. where k 1 is the pseudo-

where k 1 is the pseudo-first-order rate constant (min 1 ), q e and q t are the amounts of dye adsorbed (mg/g ) at equilibrium and at time t (min). The pseudo-second-order model can be expressed in Equation 6 (Ho and McKay, 1998):

17

Dahlan and Tayeh Removal of Colour from Synthetic Dye Wastewater Using Adsorbent Prepared from Psyllium Husk

Dye Wastewater Using Adsorbent Prepared from Psyllium Husk where k 2 (g mg − 1 min

where k 2 (g mg 1 min 1 ) is the rate constant of the pseudo-second-order adsorption.

2.5. Analysis and Characterization

The initial concentration of dye (direct blue 71 dye solution) and samples after sorption treatment were measured using DR 2800 spectrophotometer according to the Platinum Cobalt Standard Method (Adopted from Standard Methods for the Examination of Water and wastewater and NCASI, Technical Bulletin No. 253, Dec. 1971). All the concentrations of sample analysis were conducted in triplicate to increase the precision of the results, and only the average value was reported throughout this analysis. Selected magnetic sorbents, before and after the adsorption process, were characterized using Mastersizer 2000 in order to study the particle size distribution for the adsorbent. To obtain the surface morphologies of the selected adsorbent, before and after the adsorption process, the scanning electron microscopy (SEM) examinations were performed with 5 kV of accelerating voltage using Leo Supra 35VP- 24-58 microscope.

3. RESULTS AND DISCUSSIONS

3.1. Preliminary Batch Study

As described before, four types of adsorbents were prepared to select the best adsorbent for the main batch experimental studies. Figure 4(a) shows the results for the adsorbent selection based on dye concentration, and Figure 4(b) shows the results for the adsorbent selection based on adsorbent amount. It was noticed from Figure 4(a) that the PH/CFO-Ac which is the magnetic adsorbent prepared from psyllium husk treated with acidic solution (H 2 SO 4 ) has the best removal efficiency with 79% color removal from the 5mg/L initial DB71 dye concentration, and 88% color removal from the 15mg/L initial dye

concentration, while the other kinds of adsorbent (PH/CFO-Al, QPH and NPH), gave negative efficiency due to the color of dye became more darker. It was noticed also from Figure 4 (b) that the PH/CFO-Ac, has the best removal efficiency, with 88.6%% color removal when 1g adsorbent was used and 73% color removal when 3g adsorbent was used, while the other three kinds of adsorbent gave negative efficiency due to the color of dye became more darker. Based on the results of the preliminary study, PH/CFO-Ac was selected to be used for the main study.

3.2. Batch Experiments for Synthetic Wastewater

3.2.1. Effect of contact time

One of the most important parameters affecting the adsorption process is the contact time. It is supposed that the color removal efficiency will increase by the increasing of the contact time, until reaching a time at which no significant amount of dye is removed; this time is called the equilibrium time. Figure 5 shows the effect of contact time on the adsorption of DB71 using PH/CFO-Ac adsorbent It was shown in Figure 5 that the removal efficiency of PH/CFO-Ac increased rapidly from 90.8% to 94.03 % when the contact time was increased from 1 to 2 hours. After that, no significant increase was noticed in the removal efficiency with increasing the contact time. This is probably due to larger surface area of the PH/CFO-Ac adsorbent being available at the beginning of the adsorption process, so the adsorption rate was fast. As the surface adsorption sites become exhausted, the uptake rate is controlled by the rate at which the adsorbate is transported from the exterior to the interior sites of the adsorbent particles (Ai et al., 2010, Kumar et al.,

2010).

18

Wastewater Engineering: Advanced Wastewater Treatment Systems Chapter 2: Wastewater Treatment by Physical-Chemical Technologies

Systems Chapter 2: Wastewater Treatment by Physical-Chemical Technologies Fig. 2: Preparation of quaternized adsorbent 19

Fig. 2: Preparation of quaternized adsorbent

19

Dahlan and Tayeh Removal of Colour from Synthetic Dye Wastewater Using Adsorbent Prepared from Psyllium Husk

Dye Wastewater Using Adsorbent Prepared from Psyllium Husk Fig. 3: Preparation of psyllium husk/CoFe 2 O

Fig. 3: Preparation of psyllium husk/CoFe 2 O 4 adsorbent (PH/CFO)

20

Wastewater Engineering: Advanced Wastewater Treatment Systems Chapter 2: Wastewater Treatment by Physical-Chemical Technologies

2: Wastewater Treatment by Physical-Chemical Technologies Fig. 4: (a) Adorbent selection based on dye concentration,

Fig. 4: (a) Adorbent selection based on dye concentration, and (b) adsorbent selection based on adsorbent amount.

and (b) adsorbent selection based on adsorbent amount. Fig. 5: Effect of contact time on the

Fig. 5: Effect of contact time on the adsorption of DB71 from synthetic wastewater

3.2.2. Effect of adsorbent amount

Figure 6 shows the plot of amount of PH/CFO-Ac adsorbent against percentage removal efficiency of DB71. It was observed that the removal efficiency is varied with varying amount of adsorbent and it decreased with increasing the amount of adsorbent.

21

The removal efficiency decreased from 94.78% to 81.1% for an increase in adsorbent amount from 0.1g/100ml to 1.5g/100ml. The decrease in removal efficiency with increasing adsorbent amount may be due to the concentration gradient between solute concentration in the solution and the solute concentration in the surface of the adsorbent. Thus

Dahlan and Tayeh Removal of Colour from Synthetic Dye Wastewater Using Adsorbent Prepared from Psyllium Husk

with increasing adsorbent amount, the amount of dye adsorbed onto unit weight of adsorbent gets reduced, thus causing a decrease in adsorption capacity and

removal efficiency with increasing adsorbent amount (Vadivelan and Kumar, 2005).

increasing adsorbent amount (Vadivelan and Kumar, 2005). Fig. 6: Effect of adsorbent amount on the adsorption

Fig. 6: Effect of adsorbent amount on the adsorption of DB71 from synthetic wastewater

3.2.3. Effect of shaking rate

Figure 7 shows the effect of shaking rate on the adsorption of DB71. The removal efficiency of DB71 was 98.74% at low shaking rate (100 rpm) and rose to 99.36% as the shaking rate was increased to 150 rpm. This effect can be attributed to the decrease in

boundary layer thickness around the adsorbent particles being a result of increasing the degree of mixing (Gupta et al., 2011). The removal efficiency decreased again when the shaking rate was increased to 350 rpm. This might be due to higher boundary layer resistance to mass transfer in the bulk (Dahlan and Razali, 2011).

to mass transfer in the bulk (Dahlan and Razali, 2011). Fig. 7: Effect of shaking rate

Fig. 7: Effect of shaking rate on the adsorption of DB71 from synthetic wastewater

3.2.4. Effect of initial dye concentration

The effect of initial dye concentration in the range of 15 to 200 mg/l on adsorption was investigated and the results are shown in Figure 8. It is evident from figure that the percentage dye removal increased with the

22

increasing in initial concentration of dye. The increase in initial dye concentration enhances the reaction between dye and PH/CFO-Ac. The percentage dye removal was found to be 95.11% for 15 mg/l of initial concentration, and it increased to 99.54% when the initial dye concentration was increased to 200mg/l.

Wastewater Engineering: Advanced Wastewater Treatment Systems Chapter 2: Wastewater Treatment by Physical-Chemical Technologies

2: Wastewater Treatment by Physical-Chemical Technologies Fig. 8: Effect of initial dye concentration on the

Fig. 8: Effect of initial dye concentration on the adsorption of DB71 from synthetic wastewater

3.2.5. Effect of pH

The pH of the solution plays an important role in the whole adsorption process. To determine the optimum pH for the adsorption of DB71 using PH/CFO-Ac, the effect of solution pH was investigated in the range of 310.5 and the results are shown in Figure 9. The removal efficiency of DB71 at pH less than 7 is relatively lower than at pH more than 7. It increased

up from 87.8% to 91.5% when pH was increased from 3 to 9. Solution pH may affect both aqueous chemistry and surface binding-sites of the adsorbent. The decrease of adsorption at pH less than 7 can be explained by the fact that at this acidic pH, H + may compete with dye ions for the adsorption sites of adsorbent, thereby inhibiting the adsorption of dye (Hameed and El-Khaiary, 2008).

the adsorption of dye (Hameed and El-Khaiary, 2008). Fig. 9: Effect of pH on the adsorption

Fig. 9: Effect of pH on the adsorption of DB71 from synthetic wastewater

3.2.6. Effect of temperature

The effect of temperature on the adsorption process was investigated by carrying out the adsorption experiments using PROTECH Shaker Incubator with different degrees of temperature ranging from 30 -

60 o C. Figure 10 shows that the highest removal

efficiency (92.04%) was obtained at temperature

30 o C, and decreased slowly until temperature 50 o C,

after that it decreased rapidly to 76.36% when the

23

temperature was increased to 60 o C. Similar results were obtained by various authors for the adsorption of dyes on various adsorbents (Ho and McKay, 1998; Chern and Wu, 2001; Chiou and Li, 2002; Hamdaoui, 2006). This can be explained by the exothermic spontaneity of the adsorption process and by the weakening of bonds between dye molecules and active sites of adsorbents at high temperatures (Amin,

2009).

Dahlan and Tayeh Removal of Colour from Synthetic Dye Wastewater Using Adsorbent Prepared from Psyllium Husk

Dye Wastewater Using Adsorbent Prepared from Psyllium Husk Fig. 10: Effect of temperature on the adsorption

Fig. 10: Effect of temperature on the adsorption of DB71 from synthetic wastewater

3.3. Adsorption kinetics

Figure 11 shows that the adsorption capacity of PH/CFO-Ac increased rapidly in the initial stages of the experiment and it reached equilibrium at 40 minutes although the data were measured for 2 hours. The results indicate that, at the beginning the dye ions were adsorbed by the exterior surface of PH/CFO-Ac, so the adsorption rate was fast. When the adsorptions of the exterior surface reached saturation, the dye

exerted onto the pores and was adsorbed by the interior surface of the adsorbent. The time profile of dye uptake is a single, smooth and continuous curve leading to saturation, suggesting also the possible monolayer coverage of dye on the surface of the PH/CFO-Ac A similar phenomenon was observed from previous study for the adsorption of direct blue 71 dye on palm ash adsorbent and the equilibrium time was 1 hour (Sengil, 2003).

and the equilibrium time was 1 hour (Sengil, 2003). Fig. 11: The variation of adsorption capacity

Fig. 11: The variation of adsorption capacity of DB71 onto PH/CFO-Ac with adsorption time, 1L solution, 1g adsorbent, 200mg/L dye concentrations, pH 9, at 30 ◦C

To investigate the adsorption kinetic of DB71 on the surface of PH/CFO-Ac, pseudo-first-order and pseudo-second-order kinetic models were tested. The plots of pseudo-first-order and pseudo-second-order kinetic models are shown in Figure 12 and Figure 13, respectively. Kinetic constants obtained by linear regression for the two models are listed in Table 2.

The correlation coefficient for the pseudo-first-order model is relatively good (R 2 = 0.85), however, the calculated q e (q e , cal ) obtained from this equation does not give reasonable value (Table 2), which is much lower compared with q e obtained from the experimental data (q e,exp ).

24

Wastewater Engineering: Advanced Wastewater Treatment Systems Chapter 2: Wastewater Treatment by Physical-Chemical Technologies

Y= -0.013X + 0.545 R 2 = 0.85
Y= -0.013X + 0.545
R 2 = 0.85

Fig.12: Pseudo-first-order kinetic plot for adsorption of DB71 onto PH/CFO-Ac (C 0 = 200mg/L, pH 9)

Y = 0.00509 X + 0.00083 R 2 = 0.997
Y = 0.00509 X + 0.00083
R 2 = 0.997

Fig. 13: Pseudo-second-order kinetic plot for adsorption of DB71 onto PH/CFO-Ac (C 0 = 200mg/L, pH 9)

Table 2: Kinetic parameters for adsorption of DB71 onto PH/CFO-Ac

q e,exp

(mg g

-1 )

Pseudo-first-order

Pseudo-second-order

K 1 (min -1 )

q e,cal

(mg g

-1 )

R 2

K 2 (g mg -1 min -1 )

q e,cal

(mg g

-1 )

R

2

196.48

0.032

3.0

0.85

0.031

196

0.997

This result suggests that the adsorption process does not follow the pseudo-first-order kinetic model, which is similar to the result reported for adsorption of direct blue 71 onto palm ash adsorbent (Ahmad et al., 2007). In many cases the pseudo-first-order equation of Lagergren does not fit well to the whole range of contact time and is generally applicable over the initial stage of the adsorption processes (Ho and McKay, 1999, Hameed and Hakimi, 2008). For the pseudo-second-order kinetic model, the R 2 value is

0.997 and the (q e,cal =196mg/g) agrees very well with the (q e,exp =196.48mg/g) value, which indicates that the adsorption of DB71 onto PH/CFO-Ac follows a pseudo-second-order kinetic model.

3.4. Adsorption isotherm

The adsorption isotherm is the most important information which indicates how the adsorbate molecules distribute between the liquid phase and the

25

Dahlan and Tayeh Removal of Colour from Synthetic Dye Wastewater Using Adsorbent Prepared from Psyllium Husk

solid phase when the adsorption process reaches an equilibrium state. To optimize the design of an adsorption system for the adsorption of adsorbates, it is important to establish the most appropriate correlation for the equilibrium curves. In this study, the equilibrium isotherms were examined using the Langmuir and Freundlich isotherms. In the linear form of Langmuir isotherm, a plot of C e /q e versus C e (Fig. 14) yields a straight line with slope 1/Q 0 and intercepts 1/Q 0 b. The essential

characteristics of the Langmuir isotherm can be expressed in terms of dimensionless constant separation factor R L given by (Mahmoodi et al., 2011)

separation factor R L given by (Mahmoodi et al., 2011) (7) where b is the Langmuir

(7)

where b is the Langmuir constant and C o is the highest initial dye concentration (mg/L). According to the value of RL the isotherm shape may be interpreted as shown in Table 3.

the isotherm shape may be interpreted as shown in Table 3. Fig. 14: Linearized Langmuir isotherm

Fig. 14: Linearized Langmuir isotherm

Table 3: Adsorption Types based on R L value (Mahmoodi et al., 2011)

Value of R L

Type of adsorption

R L > 1.0 R L = 1.0 0 < R L < 1.0 R L = 0

Unfavourable

Linear

Favourable

Irreversible

The value of R L calculated (0.00066) was in the

that the

adsorption is favorable at operation conditions

range between 0 and 1 which indicate

studied. Table 4 summarizes Langmuir constants and computed maximum adsorption capacity Q 0 of DB71 onto the PH/CFO-Ac.

Table 4: Langmuir and Freundlich isotherm model constants and correlation coefficients for adsorption of DB71 onto PH/CFO-Ac

Langmuir

isotherm

b (L/mg)

Q o (mg/g)

R L

R 2

7.57

188.7

0.00066

0.997

Freundlich isotherm

K F

203

Q o (mg/g)

n

177.7

40

R 2

0.991

In addition, the Freundlich isotherm is an empirical equation based on a heterogeneous surface. A plot of ln q e versus ln C e (Fig. 15) enables the constant K F and exponent n to be determined. K F can be defined as adsorption of distribution coefficient and represents the quantity of dye adsorbed onto adsorbent for an equilibrium concentration. The slope 1/n is a measure

of adsorption intensity or surface heterogeneity. These values together with the correlation coefficient are presented in Table 3.3. Based on the values of correlation coefficients (R 2 ) and Q o shown in Table 3.3, the adsorption isotherm with PH/CFO-Ac can be described by Langmuir equation. The Langmuir equation yields a better fit of the experimental data than Freundlich equation.

26

Wastewater Engineering: Advanced Wastewater Treatment Systems Chapter 2: Wastewater Treatment by Physical-Chemical Technologies

2: Wastewater Treatment by Physical-Chemical Technologies Fig. 15: Linearized Freundlich isotherm 3.5. adsorbent

Fig. 15: Linearized Freundlich isotherm

3.5.

adsorbent

Characterization

of

magnetic

PH/CFO-Ac

3.5.1. Particle Size Distribution analysis

Figure 16 shows the particle size distribution of prepared adsorbent, spent adsorbent with high removal efficiency and spent adsorbent with low removal efficiency, respectively. The maximum volume percentage corresponds to the particle size of approximately 1000µm, 900µm and 600µm for prepared adsorbent, spent adsorbent with low removal and spent adsorbent with high removal, respectively. The average volume of the particle size distribution range of spent PH/CFO-Ac adsorbents is higher than the prepared PH/CFO-Ac adsorbent, which means that

higher particle size distributions range are formed after DB71 adsorption onto PH/CFO-Ac adsorbent. It was also found that the specific surface area of the prepared adsorbent was much higher (0.034 m 2 /g) than that of the spent adsorbent with low removal and spent adsorbent with high removal (0.0158 and 0.0112 m 2 /g, respectively). The lower specific surface area of spent PH/CFO-Ac adsorbents could be due to the agglomerating of smaller particles (which is most probably the dye particles that cover the surface of the adsorbent) during the adsorption process. It was also shown from the figure that prepared and spent PH/CFO-Ac adsorbents have a unimodal particle size distribution, which indicates a homogeneous particle size for the prepared and the spent adsorbents.

27

Dahlan and Tayeh Removal of Colour from Synthetic Dye Wastewater Using Adsorbent Prepared from Psyllium Husk

Dye Wastewater Using Adsorbent Prepared from Psyllium Husk Fig. 16: Particle size distribution of prepared PH/CFO-Ac

Fig. 16: Particle size distribution of prepared PH/CFO-Ac adsorbent, spent adsorbent with high removal efficiency, and spent adsorbent with low removal efficiency.

3.6.2. Surface morphology analysis (SEM)

The morphology of the raw psyllium husk, prepared and spent PH/CFO-Ac adsorbent is shown in Figure 17. Surface analysis indicated that the surface morphology of the raw psyllium husk (Figure 17a) consists of lumps of uneven shapes particles. After the preparation of PH/CFO-Ac adsorbent, it can be observed from Figure 17b that the prepared adsorbent consists of irregular rough particles that were unevenly scattered together which might be due to the CoFe 2 O 4 particles deposited on the surface of raw psyllium husk. After the adsorption of DB71, the surface of the PH/CFO-Ac adsorbents was found to have more compact structures with small granular particles attached on the surface (Figure 17c) which is most probably the dye particles that covered the external surface of PH/CFO-Ac adsorbents.

28

4. CONCLUSIONS

This study showed that PH/CFO-Ac adsorbent was successfully synthesized by a facile one-step refluxing route could be used as an effective adsorbent for the removal of direct blue dye (DB71) from synthetic wastewater. All experimental parameters such as contact time, adsorbent amount, shaking rate, initial dye concentration, pH and temperature affected the adsorption of dye from synthetic wastewater. The equilibrium of adsorption of dye onto PH/CFO-Ac adsorbent was suitably described by the Langmuir models. The process of adsorption was relatively rapid and was best described by the pseudo-second-order kinetic model. The results obtained in this study shows that PH/CFO-Ac adsorbent could be used as an effective adsorbent for the removal of direct blue dye from synthetic wastewater and this has never been reported in the literature.

Wastewater Engineering: Advanced Wastewater Treatment Systems Chapter 2: Wastewater Treatment by Physical-Chemical Technologies

2: Wastewater Treatment by Physical-Chemical Technologies Fig. 17: SEM micrographs of (a) raw psyllium husk, (b)

Fig. 17: SEM micrographs of (a) raw psyllium husk, (b) prepared PH/CFO-Ac adsorbent and (c) spent PH/CFO-Ac adsorbent

ACKNOWLEDGMENT

The authors wish to acknowledge the financial support from the Universiti Sains Malaysia (Short Term Grant A/C. 60310014 and Incentive Grant).

REFERENCES

Ahmad A, Hameed B, Aziz N (2007). Adsorption of direct dye on palm ash: Kinetic and equilibrium modeling. Journal of Hazardous Materials, 141:

70-76.

Ahn DH, Chang WS, Yoon TI (1999). Dyestuff wastewater treatment using chemical oxidation, physical adsorption and fixed bed biofilm process. Process Biochemistry, 34: 429-439. Ai L, Huang H, Chen Z, Wei X, Jiang J (2010). Activated carbon/CoFe2O4 composites: Facile

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synthesis, magnetic performance and their potential application for the removal of malachite green from water. Chemical Engineering Journal, 156: 243-249. Amin NK (2009). Removal of direct blue-106 dye from aqueous solution using new activated carbons developed from pomegranate peel:

Adsorption equilibrium and kinetics. Journal of Hazardous Materials, 165: 52-62. Che Ani Y (2004). Adsorption Studies Of Dyes Using Clay-based And Activated Carbon Adsorbents. MscThesis.Universiti Sains Malaysia, Penang. Chern, JM, Wu CY (2001). Desorption of dye from activated carbon beds: effects of temperature, pH, and alcohol. water research, 35: 4159-4165. Chiou MS, Li HY (2002). Equilibrium and kinetic modeling of adsorption of reactive dye on

Dahlan and Tayeh Removal of Colour from Synthetic Dye Wastewater Using Adsorbent Prepared from Psyllium Husk

cross-linked chitosan beads. Journal of Hazardous Materials, 93: 233-248. Correia VM, Stephenson T, Judd SJ (1994).

Characterisation of textile wastewatersa review. Environmental Technology, 15: 917-

929.

Dahlan I, Razali MHM (2011). Waste-Derived Siliceous Materials as a Novel Sorbent for Removal of Ni 2+ from Aqueous Solutions. Water, Air, & Soil Pollution, 1-7. Gupta V, Agarwa S, Saleh TA (2011). Chromium removal combining the magnetic properties of iron oxide with adsorption properties of carbon nanotubes. Water Research, 45: 2207-2212. Hamdaoui O (2006). Batch study of liquid-phase adsorption of methylene blue using cedar sawdust and crushed brick. Journal of Hazardous Materials, 135: 264-273. Hameed B, El-Khaiary M (2008). Malachite green adsorption by rattan sawdust: Isotherm, kinetic and mechanism modeling. Journal of Hazardous Materials, 159: 574-579. Hameed B, Hakimi H (2008). Utilization of durian (Durio zibethinus Murray) peel as low cost sorbent for the removal of acid dye from aqueous solutions. Biochemical Engineering Journal, 39: 338-343. Ho Y, Mckay G (1998). Sorption of dye from aqueous solution by peat. Chemical Engineering Journal,

70: 115-124. Ho Y, Mckay G (1999). The sorption of lead (II) ions on peat. Water Research, 33: 578-584. Kadirvelu K, Kavipriya M, Karthika C, Radhika M, Vennilamani N, Pattabhi S (2003). Utilization of various agricultural wastes for activated carbon preparation and application for the removal of dyes and metal ions from aqueous solutions. Bioresource Technology, 87: 129-

132.

Kelesoglu S (2007). Comparative Adsorption Studies of Heavy Metal Ions on Chitin and Chitosan Biopolymers.Msc Thesis. İzmir Institute of Technology, İzmir.

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Kumar PS, Gayathri R, Arunkumar RP (2010). Adsorption of Fe (III) ions from aqueous

solution by Bengal Gram Husk powder:

equilibrium isotherms and kinetic approach. Electronic Journal of Environmental, Agricultural and Food Chemistry, 9: 1047-

1058.

Lee C, Low K, Gan P (1999). Removal of some organic dyes by acid-treated spent bleaching earth. Environmental Technology, 20: 99-104. Low KS, Lee CK (1997). Quaternized rice husk as sorbent for reactive dyes. Bioresource

Technology, 61: 121-125. Lucas MS, Peres JA (2006). Decolorization of the azo dye Reactive Black 5 by Fenton and photo- Fenton oxidation. Dyes and Pigments, 71: 236-

244.

Mahmoodi NM, Hayati B, Arami M, Lan C (2011). Adsorption of textile dyes on Pine Cone from colored wastewater: Kinetic, equilibrium and

thermodynamic studies. Desalination, 268: 117-

125.

Morais L, Freitas O, Goncalves E, Vasconcelos L, Gonzalez BC (1999). Reactive dyes removal

from wastewaters by adsorption on eucalyptus bark: variables that define the process. Water Research, 33: 979-988.

Papic S, Koprivanac N, Bozic AL (2000). Removal of reactive dyes from wastewater using Fe (III) coagulant. Coloration Technology, 116: 352-

358.

Schwarzenbach RP, Gschwend PM, Imboden DM, Wiley J (2003). Environmental organic chemistry, Wiley Online Library. Sengil IA (2003). Adsorption of reactive dyes on calcined alunite from aqueous solutions. Journal of Hazardous Materials, 98: 211-224. Vadivelan V, Kumar KV (2005). Equilibrium, kinetics, mechanism, and process design for the sorption of methylene blue onto rice husk. Journal of Colloid and Interface Science, 286:

90-100.

WHO/UNICEF (2000). Global Water Supply and Sanitation Assessment Report 2000. WHO, Geneva.

Wastewater Engineering: Advanced Wastewater Treatment Systems Available online at http://www.ijsrpub.com/books ©2014 IJSRPUB

online at http://www.ijsrpub.com/books ©2014 IJSRPUB COD and BOD Removal from Textile Wastewater Using Naturally

COD and BOD Removal from Textile Wastewater Using Naturally Prepared Adsorbents and Their Activation Forms Using Sulphuric Acid

Himanshu Patel*, R.T. Vashi

Department of Chemistry, Navyug Science College, Rander Road, Surat 395009, Gujarat, INDIA *Corresponding Author: hjpatel123@yahoo.co.in

Abstract. Comparative adsorption studies of naturally prepared adsorbents (Neem leaf powder, Gauva leaf powder and Tamarind seed powder) and their activation forms using sulphuric acid were conducted for removal COD and BOD from textile wastewater. Process parameters like adsorbent dose, conduct duration, temperature and pH were examined in this study. The adsorption data were analyzed using Freundlich, Langmuir, Dubinin-Raduskevich, Flory-Huggins, Redlich-Peterson, Sips, Toth and Khan model to understand adsorption mechanism. Activated Neem leaf powder was most suitable than investigated adsorbents. The maximum adsorption capacities were found to be 87.58, 85.65 and 81.25 mg/g for NLPs, GLPs and TSPs respectively for COD and 84.51, 81.45 and 75.54 mg/g for NLPs, GLPs and TSPs respectively for BOD.

Keywords: Textile wastewater, Naturally prepared adsorbents and their activated form, Process Parameters, Adsorption equilibrium isotherms

1. INTRODUCTION

Increasing public pressure and administrative concern to arrest further deterioration of the environment may result in more stringent standards. The objective of wastewater treatment has expanded considerably from simple nuisance control to include public health, environmental, aesthetic and ecological considerations. The day is not far off when industries will have to acquire a nonpolluting or zero polluting status to meet future environmental regulations. The problem is more severe for the textile industry because of its dynamic nature. Constantly changing process lines result in diverse and complex wastes that are ever changing in constitution and color (Venkata Mohan et al., 1999). The textile industry is very chemical-intensive; wastewater from textile- processing contains huge residues from different textile dyeing and finishing operations. Of particular concern are dyestuffs, which are often major sources of heavy metals, salt, adsorbable organic halogens and color in dyehouse effluent, sizing agents, which have high BOD and COD levels; and anionic/non-ionic surfactants, most of which are still of poorly biodegradable nature (Alaton et al., 2006). There are many methods for the removal of contaminations from wastewater, such as membrane process, ion exchange, biological degradation and adsorption using various kinds of adsorbent. Adsorption process is proven to be an effective process for the removal of various pollutants from its aqueous solutions because adsorption process can remove pollutant in wide range of concentrations (Budyanto et al., 2008). The adsorption process has not been used extensively in wastewater treatment, but demands for a better quality of treated wastewater effluent, including toxicity reduction, have led to an intensive examination and use of the process of

31

adsorption. The relative advantages of adsorption over other conventional advanced treatment methods are:

(1) it can remove both organic as well as inorganic constituents even at very low concentrations, (2) it is relatively easy and safe to operate, (3) both batch and continuous equipment can be used, (4) no sludge formation, and (5) the adsorbent can be regenerated and used again. Moreover the process is economical because it requires low capital cost and there are abundant low-cost materials available which can be used as adsorbents (Mohanty, et al., 2006). Low cost adsorbents especially made from natural sources like plant root, leaf, seed, peel, etc are being investigated. Ulmus leaves and their ash, rubber (Hevea brasiliensis) seed shell, Platanus orientalis leaves, Rich husk, Sunflower stalks and Neem leaf powder have been used for wastewater treatment and adsorption has emerged as a cost-effective and efficient alternative for the removal of hazardous contaminations including dyes from low strength wastewaters. Also, some acids were also utilized for activation of adsorbents (Patel and Vashi, 2011). Previously we had utilized activated neem leaf powder (Patel and Vashi, 2012), activated guava leaf powder (Patel and Vashi, 2011) and tamarind seed powder (Patel and Vashi, 2010) for removal of dyes from its aqueous solution and provided outstanding results. There are very few research literatures available for removal of COD and BOD from real wastewater as per author’s best knowledge. Present investigation involved the preparation of naturally prepared adsorbents (and its activation form) and treatment of textile wastewater using these adsorbents for removal of COD and BOD. Effect of adsorbent dose, contact duration, temperature and pH were studied. Freundlich, Langmuir, Dubinin-Raduskevich, Flory-Huggins, Redlich-Peterson, Sips, Toth and Khan models were tested for their applicability.

Patel and Vashi COD and BOD Removal from Textile Wastewater Using Naturally Prepared Adsorbents and Their Activation Forms Using Sulphuric Acid

2. METHODS AND MATERIALS

2.1. Adsorbent

The Neem (scientific name: Azadirachta indica) belongs to the meliaceae family and is native to Indian sub-continent. The Guava (Psidium Guajava; Family:

Myrtaceae) tree are easily available in Indian region. The mature leaves of plant (Neem and Guava) used in the present investigation are collected from the available trees near Navyug Science College, Gujarat. The mature leaves of plant washed thrice with water to remove dust and water soluble impurities and were dried until the leaves become crisp. The dried leaves were crushed and powdered and further washed with distilled water till the washings were free from color and turbidity. Then this powder was dried in an oven at 60 ± 2 °C and placed in desiccator for the adsorption studies, thus natural adsorbent prepared. The Tamarind (Tamarindus indica), a family of Fabaceae, has used for preparation of medicines for internal and external applications and as condiment in many dishes. Tamarind fruit seed, collected from nearby Navyug Science College, Gujarat, a waste product of tamarind pulp, are washed, dried and pulverized. This powder was washed with distilled water till the washings were free from color and

turbidity and thereafter, dried in the oven at 60 ºC. For activation of adsorbent, each adsorbent was stirred with excess amount of 0.1 N sulphuric acid. Thereafter, it washed with de-ionized water to remove untreated acid dried in an oven at 60 ± 2 °C.

2.2. Experimental Details

The textile wastewater samples were withdrawn from Pandesara, GIDC, Gujarat, India. Combine wastewater samples were collected bimonthly for three times in sampling bottles and placed in ice box to preserve the characteristics of wastewater and were analyzed as per standard method (APHA, 1992). For removal of COD and BOD, batch experiments of textile wastewater were carried out as per table 1. Briefly, each adsorbent i.e. NLP and a-NLP (NLPs), GLP and a-GLP (GLPs) and TSP and a-TSP (a-TSP) was added to wastewater samples and the mixture was stirred at 400 rpm. Each adsorbent was kept in contact till equilibrium state was attained. The required pH of system was maintained by using 0.1 N HCl or 0.1 N NaOH during experiment. All chemicals used were of analytical reagent grade and purchased from Qualigens, India. The important physico-chemical characteristics i.e. COD and BOD were determined before and after treatment using standard methods.

Table 1: Experimental Details for treatment of wastewater using adsorbents

Effect of System

Adsorption Dose (g/l)

Temperature (K)

Contact Duration (min)

pH

Effect of adsorption dose

1, 2, 4, 6, 8, 10, 12, 14, 16, 18 and 20

300

180

7

Effect of contact duration

5.0

300

30, 60, 90, 120, 150, 180, 210 and 240

7

Effect of temperature

5.0

298, 303, 308, 313, 318, 323 and 328

180

7

Effect of pH

5.0

300

180

3, 5, 7, 9 and 11

2.3. Batch adsorption model

The equilibrium sorption isotherm is fundamentally important in the design of sorption systems. Equilibrium studies in sorption give the capacity of the sorbent. It is described by sorption isotherm characterized by certain constants whose values express the surface properties and affinity of the sorbent. (samsun clone). Different equilibrium models were available to predict the sorption behavior. The most commonly available models are Freundlich, Langmuir, Dubinin-Raduskevich, Flory-Huggins, Redlich-Peterson, Sips, Toth and Khan models.

2.3.1. Freundlich Isotherm

The Freundlich expression is an empirical equation based on sorption on a heterogeneous surface and

32

effectively on multilayer and is expressed by the following equation.

q e = K F C e 1/n or log q e = log K F + 1/n log C e Where, q e and C e is the amount of adsorbed adsorbate per unit weight of adsorbent and unadsorbed adsorbate concentration in solution at equilibrium, respectively and K F (L/mg) and n are Freundlich constant characteristics of the system, which are determined from the log q e vs. log C e . If the value of exponent n was greater than 1 (n >1) then the adsorption represent favorable adsorption

2.3.2. Langmuir Isotherm

This monolayer adsorption isotherm is very useful for predicting adsorption capacities and also interpreting into mass transfer relationship. The isotherm can be written as follows:

Wastewater Engineering: Advanced Wastewater Treatment Systems Chapter 2: Wastewater Treatment by Physical-Chemical Technologies

q e

=

k L C e / (1 + a L C e ) or (C e /q e ) = (1/ K L ) + (a L /K L )

C e The constant K L (L/g) is the Langmuir equilibrium constant and the K L /a L gives the theoretical monolayer saturation capacity, Q max (mg/g). These Langmuir parameters were obtained from the linear correlations between the values of C e /q e and C e . Generally, the Langmuir equation, applies to the cases of adsorption on completely homogeneous surfaces where interactions between adsorbed molecules are negligible (Ozacar and Sengil, 2005).

2.3.3. Dubinin-Raduskevich Isotherm

This isotherm can be used to describe adsorption on both homogenous and heterogeneous surfaces. The DubininRadushkevich equation has the following form:

q e = q m e -βε2 or In q e = In q m - βε 2 Where q m (mg/g) is the DubininRadushkevich

monolayer capacity a constant related to sorption energy, and ε is the Polanyi potential which is related

to the equilibrium concentration as follows:

ε = RT In (1 + 1/C e )

Where R is the gas constant (8.314 J/mol K) and T

is the absolute temperature. The constant β gives the

mean free energy, E, of adsorption per molecule of the adsorbate when it is transferred to the surface of the solid from infinity in the solution and can be computed using the relationship.

E = 1/ (2β) ½

The magnitude of E is useful for estimating the mechanism of the adsorption reaction. In the case of E

< 8 kJ/mol, physical forces may affect the adsorption.

If E is in the range of 816 kJ/mol, adsorption is governed by ion exchange mechanism, while for the values of E > 16 kJ/mol, adsorption may be dominated by particle diffusion.

2.3.4. Flory-Huggins Isotherm

The Flory-Huggins model accounts for the degree of surface coverage characteristics of adsorbate on the adsorbent and the linear form of the Flory-Huggins equation is expressed as:

ln (q/C e ) = ln(K FH ) + a FH ln(1- q e ) Where q is the surface coverage of the adsorbent by adsorbate. K FH (mg/g) and a FH are the Flory- Huggins constants. These constants can be obtained from the plot of log (q/C e ) versus log (I-q e ) Furthermore the equilibrium constant K FH , obtained from the Flory-Huggins isotherm model is used to compute the Gibbs free energy for the adsorption process. The Gibbs free energy is related to equilibrium constant as follows:

33

ΔG 0 = - RT/ In K FH Where R is universal gas constant 8.314 J/K/mol, T is absolute temperature (K) and K FH is equilibrium constant from Flory-Huggins isotherm equation (Israel et al., 2010).

2.3.5. Redlich-Peterson Isotherm

The Redlich-Peterson isotherm model is widely used as a compromise between the Langmuir and Freundlich systems, since it combines elements from both the Langmuir and Freundlich equations, where the mechanism of adsorption is a hybrid one and does not follow ideal monolayer adsorption. The Redlich- Peterson isotherm has a linear dependence on concentration in the numerator and an exponential function in the denominator. It approaches the Freundlich model at high concentration and is in accordance with the low concentration limit of the Langmuir equation. It can be applied either in homogenous or heterogeneous systems due to the high versatility of the equation. This model incorporates three parameters into an empirical isotherm. It can be described as follows,

ln[(K RP C e /q e ) – 1] = β RP ln(C e ) + ln(a RP ) Where, q e (mg/g), is the solid-phase adsorbate concentration at equilibrium, C e (mg/l) is the liquid- phase adsorbate concentration at equilibrium, K RP (1/mg) and a RP (L β mg β ), are the Redlich-Peterson isotherm constants and β RP is an exponent, which lies between 1 and 0. If ‘β RP ’ is equal to one, the equation modifies to Langmuir model, and if ‘β RP ’ is equal to zero then the equation changes to Henry’s law equation (Quintelas et al., 2008).

2.3.6. Sip Isotherm

Sips isotherm is a combined form of Langmuir and Freundlich expressions deduced for predicting the heterogeneous adsorption systems and circumventing the limitation of the rising adsorbate concentration associated with Freundlich isotherm model. At low adsorbate concentrations, it reduces to Freundlich isotherm; while at high concentrations, it predicts a monolayer adsorption capacity characteristic of the Langmuir isotherm. As a general rule, the equation parameters are governed mainly by the operating conditions such as the alteration of pH, temperature and concentration. The linear form of Sip isotherm model is represented as

β s ln(C e ) = - ln(K s /q e ) + ln(a s ) Where K s is the total number of binding sites (mg/g), as the median association constant (L/mg) and 1/n is the heterogeneity factor. If the value for β s is

Patel and Vashi COD and BOD Removal from Textile Wastewater Using Naturally Prepared Adsorbents and Their Activation Forms Using Sulphuric Acid

less than one, it indicates that it is heterogeneous adsorbents, while values closer to or even one indicates that the adsorbent has relatively more homogeneous binding sites.

2.3.7. Toth Isotherm

Toth isotherm model, is another empirical equation developed to improve Langmuir isotherm fittings (experimental data), and useful in describing heterogeneous adsorption systems, which satisfying both low and high-end boundary of the concentration. Its correlation presupposes an asymmetrical quasi- Gaussian energy distribution, with most of its sites has adsorption energy lower than the peak (maximum) or means value

q e = (q m b T C e ) / [1 + (b T C e ) 1/nT ] nT Where, q m (mg/g) is the Khan adsorption capacity, and b T (1/mg) is the Toth model constant and n T the Toth model exponent (Foo and Hameed, 2010).

3. RESULTS AND DISCUSSION

3.1. Characterization of Textile Wastewater

It was reported that water requirement vary from 61 to 646 liters per kg of cloth processed with an average value of 235 liters per kg. These values correspond to 12 - 130 liter per meter of cloth with an average value of 47 liters per kg. The pH of the investigated textile mill effluent ranges from 9.24 to 7.64 having average value of 8.2. The color of the wastewater is brownish yellow having color unit 291.3 Hazen. The average value of COD, BOD, Total Dissolved Solid (TDS), Hardness, Alkalinity, Fluoride, Chloride and Sulphate were 1556.2, 924.1, 6845.3, 1086.7, 670.7, 874.3, 475.3 and 877.1 ppm respectively. Also, average

value of Electrical Conductivity and Sulphate were found to be 7417.0 µs/cm. High value of contaminations are presented due to usage of chemicals such as starches, dextrin, gums, glucose, waxes, pectin, alcohol, fatty acids, acetic acid, soap, detergents, sodium hydroxide, carbonates, sulfides, sulfites, chlorides, dyes, pigments, carboxymethyl cellulose, gelatin, peroxides, silicones, flourcarbons, resins, etc. in wet processes of textile mill. Same types of contaminations were found, while investigating textile wastewater (Fanchiang et al., 2006, Pathe et al., 2005, Martins et al., 2006).

3.2. Effect of Adsorbent Dose

Figure 1, 2 and 3 shows the effect of different doses (Ceq vs. Adsorbent dose) of naturally prepared adsorbents i.e. NLPs, GLPs and TSPs respectively maintaining temperature of 300 K, contact duration of 180 and pH 7. It can be seen that there is a large reduction in the COD content when NLPs was used, from an initial value of 1625.8 ppm to zero and 110.2 ppm at a dosage of 20 g/L of a-NLP and NLP respectively. BOD had an initial value of 1002.4 to 11.2 and 51.5 ppm by 20 g/L of a-NLP and NLP respectively. It can be also seen that there is a large reduction in the COD content when GLPs is used, from an initial value of 1625.8 to 258.4 and 411.2 ppm at a dosage of 20 g/L of a-GLP and GLP respectively. BOD had an initial value of 1002.4 to 201.2 and 212.2 ppm when 20 g/L of a-GLP and GLP was used respectively. It can be seen that there is a large reduction in the COD content using TSPs, from an initial value of 1625.8 to 411.2 and 312.2 ppm at a dosage of 20 g/L of TSP and a-TSP respectively. BOD had an initial value of 1002.4 to 280.5 and 251.2 ppm by 20 g/L of TSP and a-TSP respectively.

280.5 and 251.2 ppm by 20 g/L of TSP and a-TSP respectively. Fig. 1: Effect of

Fig. 1: Effect of adsorbent dose for percentage COD and BOD removal using NLPs

34

Wastewater Engineering: Advanced Wastewater Treatment Systems Chapter 2: Wastewater Treatment by Physical-Chemical Technologies

2: Wastewater Treatment by Physical-Chemical Technologies Fig. 2: Effect of adsorbent dose for percentage COD and

Fig. 2: Effect of adsorbent dose for percentage COD and BOD removal using GLPs

adsorbent dose for percentage COD and BOD removal using GLPs Fig. 3: Effect of adsorbent dose

Fig. 3: Effect of adsorbent dose for percentage COD and BOD removal using TSPs

From all the adsorbents, a-NLP was found to be more effective than all investigated adsorbents for removal of COD and BOD. Also, it was easily appeared that value of Ceq was continuously decreasing with increasing adsorbent dose upto 18.0 g/L. The increase in adsorption with increase in adsorbent may be attributed due to the reason of increased adsorbent surface and availability of more adsorption sites. The reason behind the phenomenon may be speculated to be due to the interference between binding sites at higher concentrations in solution with respect to available binding sites. Then after straight line indicated the equilibrium was attained at dose of 18.0 g/l for all adsorbents investigated. It can explain that further increase in the dose of adsorbent did not affect the uptake capacity because of the unavailability of adsorbate sites due to saturation (Li et al., 2008).

3.3. Effect of Contact Duration

Table 2 reveals effect of different contact durations (30 to 240 minutes) on the COD, BOD and color removal using 5.0 g/L dosage of NLPs, GLPs and

35

TSPs at constant temperature (300 K), pH (7) and agitator speed (400 rpm). Percentage removal of COD

was found to be 30.3 to 63.6, 19.6 to 63.4 and 9.5 to

41.5 using a-NLP, a-GLP and a-TSP respectively.

Also, percentage removal of COD was found to be 20.1 to 57.2, 11.2 to 47.5 and 13.4 to 56.2 using NLP,

GLP and TSP respectively. Percentage removal of BOD was found to be 26.1 to 57.4, 14.6 to 49.7 and

5.2 to 32.1 using a-NLP, a-GLP and a-TSP

respectively. Also, percentage removal of BOD was found to be 15.2 to 46.2, 9.2 to 42.1 and 10.1 to 40.1 using NLP, GLP and TSP respectively. These removals were found at contact duration of 30 to 240 min respectively. In adsorption process, a knowledge regarding the contact time required to achieve the equilibrium is highly important. Table 2 clearly indicates a rapid increase in the amount of adsorption with increase in time initially, gradually leading to equilibrium. Although at higher contact time, the rate of adsorption decreased and a saturation stage was attained due to the accumulation of the adsorption sites. This decline is due to decrease in total adsorbent surface area and increased diffusion pathway. It can also elucidate that

Patel and Vashi COD and BOD Removal from Textile Wastewater Using Naturally Prepared Adsorbents and Their Activation Forms Using Sulphuric Acid

mechanism of solute transfer to the solid includes diffusion through the fluid film around the adsorbent particle and diffusion through the pores to the internal adsorption sites. Initially the concentration gradient between the film and the solid surface is large, and hence the transfer of solute onto the solid surface is

faster. That is why it takes lesser time to attain percentage removal of COD and BOD. As time increases, intraparticle diffusion becomes predominant. Hence solute takes more time to transfer from solid surface to internal adsorption sites through the pores (Hameed et al., 2008, Gulipalli et al., 2011).

Table 2: Effect of contact duration for percentage COD and BOD removal using naturally prepared adsorbents

Contact Duration (min)

Adsorbent

% Removal

30

60

90

120

150

180

210

240

a-NLP

COD

30.3

39.9

50.4

54.1

57.2

60.1

63.6

63.6

BOD

26.1

31.2

39.0

49.5

53.6

55.7

57.4

57.4

COD

20.1

30.2

41.2

45.2

51.0

55.2

57.2

57.2

NLP

BOD

15.2

20.5

28.5

40.5

44.2

45.5

46.2

46.2

a-GLP

COD

19.6

32.3

44.3

48.9

56.5

58.5

63.4

63.4

BOD

14.6

28.6

34.5

40.1

45.1

48.1

49.7

49.7

COD

11.2

20.2

30.2

35.5

41.2

45.5

47.4

47.4

GLP

BOD

9.2

15.4

20.4

30.2

34.5

40.1

42.1

42.1

a-TSP

COD

9.5

14.5

19.5

28.9

33.3

39.5

41.5

41.5

BOD

5.2

10.2

16.5

20.5

27.5

30.2

32.1

32.1

TSP

COD

13.4

20.9

30.5

39.7

50.4

53.1

56.2

56.2

BOD

10.1

18.8

24.7

31.2

36.7

38.0

40.1

40.1

3.4. Effect of Temperature

temperature may produce a swelling effect within the

2007).

The effect of variation in temperature i.e. 298, 303, 308, 313, 318, 323 and 328 K on the adsorption by a-

internal structure of adsorbents (NLPs, GLPs and TSPs), enabling to penetrate further (Malkoc et al.,

NLP, a-GLP and TSP at constant contact duration, with respect to COD, BOD and color of wastewater is depicted in Table 3. It can be seen that the increase in temperature leads to linear decrease in percent removal in three cases. Also, straight line after temperature of 323 K indicating equilibrium accomplished at temperature of 323 K. The values of percent removal of COD were seen to increase from 39.1 to 75.6 % by a-NLP, 20.15 to 65.6 by NLP whereas from 30.3 to 72.3 % by a-GLP, 20.1 to 61.2

3.5. Effect of pH

The effect of pH (3 to 11) is represented in Table 4 using NLPs, GLPs and TSPs (dose: 5.0 g/L) for removal of COD, BOD and color from textile wastewater at constant contact duration of 180 min, temperature of 300 K and agitator speed of 400 rpm. The percentage removal was increasing, as pH of system increases. The highest percentage removal of

1999).

%

using GLP and from 15.2 to 47.7 % by a-TSP and

COD was found to be 64.8, 55.5, 57.4, 47.5, 50.2 and

also, 24.3 and 63.0 % by TSP at temperature of 298 to 328 K respectively. The values of percent removal of

56.5 by a-NLP, NLP, a-GLP, GLP, a-TSP and TSP respectively at pH 11. The highest percentage removal

BOD were seen to increase from 34.7 to 63.2 % by a- NLP, 20.25 to 55.5 by NLP whereas from 29.0 to 68.0

of BOD was found to be 60.0, 54.2, 48.7, 40.2, 41.2 and 44.7 by a-NLP, NLP, a-GLP, GLP, a-TSP and

%

by a-GLP, 18.2 to 60.0 % using GLP and from 7.2

TSP respectively at pH 11. Though, the factor pH is

to 47.7 % by a-TSP and also, 18.7 and 58.1 % by TSP at temperature of 298 to 328 K respectively. The adsorption capacity increases with the increasing temperature, indicating that the adsorption is an endothermic process. This may be a result of an increase in the mobility of chemicals (contributing COD and BOD) with increasing temperature. An increasing number of molecules may also acquire sufficient energy to undergo an interaction with active sites at the surface. Furthermore, the increasing

an important parameter in adsorption studies, but due to presence of various elements in dyeing mill wastewater such as starches, dextrin, gums, glucose, waxes, pectin, alcohol, fatty acids, acetic acid, soap, detergents, sodium hydroxide, carbonates, sulfides, sulfites, chlorides, dyes, pigments, carboxymethyl cellulose, gelatin, peroxides, silicones, flourcarbons, resins; the moderate removal of COD, BOD and color was found with change of factor, pH (O’Neill et al.,

36

Wastewater Engineering: Advanced Wastewater Treatment Systems Chapter 2: Wastewater Treatment by Physical-Chemical Technologies

Table 3: Effect of temperature for percentage COD and BOD removal using naturally prepared adsorbents

Adsorbent

Temperature (K)

 

% Removal

298

303

308

313

318

328

328

a-NLP

COD

39.1

48.6

56.0

62.2

70.1

75.6

76.0

BOD

34.7

41.4

48.0

52.6

60.1

63.0

63.2

COD

20.1

32.2

45.5

50.5

61.2

65.6

65.6

NLP

BOD

20.2

32.2

35.6

42.5

51.2

55.5

55.5

a-GLP

COD

30.3

39.1

54.6

62.2

68.3

72.3

73.0

BOD

29.0

35.0

45.4

52.1

61.6

67.6

68.0

COD

20.0

28.5

44.2

52.1

57.2

61.2

61.2

GLP

BOD

18.2

25.5

34.4

41.1

54.2

60.0

60.0

COD

15.2

20.2

26.5

37.3

44.5

47.5

47.5

a-TSP

BOD

7.8

12.5

25.5

35.8

43.6

47.7

47.7

TSP

COD

24.3

37.9

44.9

52.2

56.5

62.5

63.0

BOD

18.7

25.9

38.6

45.9

51.6

58.1

58.1

Table 4: Effect of temperature for percentage COD and BOD removal using naturally prepared adsorbents

pH

Adsorbent

% Removal

3

5

7

9

11

a-NLP

COD

14.8

23.6

39.0

56.5

64.8

BOD

9.7

17.6

32.1

50.1

60.0

COD

10.0

15.5

27.4

45.5

55.5

NLP

BOD

5.2

10.5

20.5

41.4

54.2

a-GLP

COD

7.5

14.8

26.5

42.1

57.4

BOD

3.2

10.2

20.2

34.7

48.7

COD

5.5

10.2

15.5

30.2

47.5

GLP

BOD

1.2

5.5

11.1

25.5

40.2

COD

4.5

12.5

24.5

41.5

50.2

a-TSP

BOD

3.5

15.2

20.5

31.5

41.4

COD

8.0

24.2

34.8

50.4

56.5

TSP

BOD

5.7

21.7

31.7

40.0

44.7

3.6. Adsorption Model

adsorbent then other investigated adsorbents.

Table 5 described Freundlich and Langmuir parameters for COD and BOD removal using naturally prepared adsorbents i.e. NLPs, GLPs and

Activation of Neem Leaf Powder and Guava Leaf Powder using sulphuric acid were found more proficient than regular NLP and GLP. Regular Tamarind Seed Powder (TSP) was found to be more

TSPs. Freundlich adsorption capacity, K F was found to be 79.39 and 41.64 L/mg using a-NLP and 45.12 and 40.25 L/mg using NLP for COD and BOD respectively. Freundlich adsorption capacity was found to be 28.69 and 12.13 L/mg using a-GLP and

efficient than activated TSP using sulphuric acid. This shows that H 2 SO 4 is effective in creating well- developed pores on the surface of NLP and GLP with large surface area and porous structure. But in the case of TSP, there was no change in surface of TSP while

20.45

and 15.18 L/mg using GLP for COD and BOD

activation using sulphuric acid. Further, value of

respectively. Freundlich adsorption capacity was

exponent n was greater than 1 (n > 1), so, the

found to be 20.45 and 15.18 L/mg using a-TSP and

adsorption represents favorable adsorption.

23.07

and 11.71 L/mg using TSP for COD and BOD

DubininRadushkevich and FloryHuggins

respectively. Langmuir adsorption capacity, Q max for

parameters for COD and BOD removal using

COD and BOD was obtained 87.58 and 84.51 mg/g respectively using a-NLP and 80.45 and 79.58 mg/g

naturally prepared adsorbents were depicted in Table 6. Maximum DubininRadushkevich monolayer

respectively using NLP. Langmuir adsorption capacity for COD and BOD was obtained 85.65 and 81.45 mg/g respectively using a-GLP and 82.41 and 78.57 mg/g respectively using GLP. Langmuir adsorption capacity for COD and BOD was obtained 75.14 and

capacity, q m was found to be 18.45, 15.27 and 10.65 mg/g for NLPs, GLPs and TSPs respectively for COD and 13.27, 12.17 and 8.54 mg/g for NLPs, GLPs and TSPs respectively for BOD. All these value are close to that obtained from the Langmuir isotherm model.

70.45

mg/g respectively using a-TSP and 81.25 and

The calculate energy was found to be in the range of

75.54

mg/g respectively using TSP. Freundlich and

1.2412 - 0.5258 KJ/mol, which confirm physical

Langmuir adsorption capacities indicate the good sorbing capacity of the naturally prepared adsorbents. Also, it shows that a-NLP is more preferable

adsorption reaction. Physisorption processes have adsorption energies less than 8 KJ/mol and the energy in the range of 1.2412 - 0.5258 KJ/mol for removal of

37

Patel and Vashi COD and BOD Removal from Textile Wastewater Using Naturally Prepared Adsorbents and Their Activation Forms Using Sulphuric Acid

COD and BOD using naturally prepared adsorbents indicates that the sorption process is physisorption and the positive value of energy (E), of sorption indicates that the sorption process is endothermic and that higher solution temperature will favor the sorption process. The FloryHuggins adsorption capacity, k FM was calculated and found to be 0.0555, 0.0450 and

0.0252 mg/g for NLPs, GLPs and TSPs respectively

for COD and 0.0452, 0.0402 and 0.0301 mg/g for

NLPs, GLPs and TSPs respectively for BOD. The

ΔG 0 for this study was computed in the range of -

9.1909 to -13.8271 kJ/mol. The negative value of ΔG 0

indicates that the sorption process is spontaneous in nature.

Table 5: Freundlich and Langmuir parameters for COD and BOD removal using naturally prepared adsorbents

Adsorbent

Removal

Freundlich Parameters

Langmuir Parameters

K F (L/mg)

n

Q max (mg/g)

K L (L/mg)

a-NLP

NLP

a-GLP

GLP

a-TSP

TSP

COD

79.39

0.1377

87.58

0.049

BOD

41.64

0.2262

84.51

0.037

COD

45.12

0.1379

80.45

0.045

BOD

40.25

0.1919

79.58

0.012

COD

28.69

0.4065

85.65

0.12

BOD

12.13

0.1447

81.45

0.14

COD

20.45

0.3175

82.41

0.21

BOD

15.18

0.2809

78.57

0.54

COD

17.4

0.2353

75.14

0.14

BOD

7.45

0.1212

70.45

0.024

COD

23.07

0.1570

81.25

0.17

BOD

11.71

0.1350

75.54

0.016

Table 6: DubininRadushkevich and Flory-Huggins parameters for COD and BOD removal using naturally prepared adsorbents

Adsorbent

Particular

Dubinin-Radushkevich Parameters

Flory-Huggins Parameters

q m (mg/g)

Β (mmol 2 /J 2 )

E (kJ/mol)

n FH

k FH (mg/g)

ΔG 0 (kJ/mol)

a-NLP

NLP

a-GLP

GLP

a-TSP

TSP

COD

18.45

4.613

1.2412

-0.699

0.0552

-6.9707

BOD

13.27

10.332

0.9574

-0.657

0.0452

-7.2395

COD

15.21

15.485

0.8747

-0.547

0.0212

-6.1091

BOD

8.27

22.258

0.8547

-0.512

0.0392

-6.7909

COD

15.27

0.3547

0.8258

-0.431

0.0450

-10.2111

BOD

12.17

0.3948

0.6847

-0.379

0.0402

-11.2551

COD

12.41

0.5158

0.5258

-0.3954

0.0166

-9.1909

BOD

7.55

0.7414

0.6868

-0.354

0.0305

-10.7929

COD

8.65

0.3470

0.7265

-0.407

0.0185

-9.4405

BOD

5.87

0.5081

0.8584

-0.317

0.0205

-12.6157

COD

10.65

0.6587

0.7457

-0.375

0.0252

-10.2332

BOD

8.54

0.8714

0.6585

-0.298

0.0301

-13.8271

Table 7 depicted Redlish-Peterson and Sips parameters for COD and BOD removal using naturally prepared adsorbents, in which an exponent of Redlish-Peterson, β RP not far from 1, indicate that the Langmuir isotherm best-fits the isotherm data for removal of COD and BOD using naturally prepared adsorbents. The Sips adsorption capacity, q m was calculated and found to be 19.7, 17.9 and 15.5 mg/g for NLPs, GLPs and TSPs respectively for COD and 18.5, 17.9 and 10.0 mg/g for NLPs, GLPs and TSPs respectively for BOD. Similar to the RedlichPeterson model constants, the same trends were observed for the Sips model constants. The exponent, n values were close to unity. This means that sorption data obtained in this study is more suited to Langmuir form than Freundlich.

Table 8 described the Toth and Khan Isotherm parameters for COD and BOD removal using naturally prepared adsorbents. Maximum Toth adsorption capacity, q m was found to be 14.25, 10.47 and 6.58 mg/g for NLPs, GLPs and TSPs respectively for COD and 7.87, 5.84 and 4.58 mg/g for NLPs, GLPs and TSPs respectively for BOD. Further, It is obvious that for Toth model exponent, n T = 1, this isotherm reduces to the Langmuir sorption isotherm equation. Maximum Khan adsorption capacity, q m was found to be 17.34, 11.44 and 11.14 mg/g for NLPs, GLPs and TSPs respectively for COD and 15.82, 10.78 and 10.47 mg/g for NLPs, GLPs and TSPs respectively for BOD.

38

Wastewater Engineering: Advanced Wastewater Treatment Systems Chapter 2: Wastewater Treatment by Physical-Chemical Technologies

Table 7: Redlish-Peterson and Sips parameters for COD and BOD removal using naturally prepared adsorbents

Redlish-Peterson Parameters

Sips Parameters

Adsorbent

Particular

KRP

 

(1/mg)

aRP (Lβmg–β)

βRP

qm (mg/g)

Ks (L/mg)

n

a-NLP

COD

2.40

0.234

0.874

19.7

1030.2

0.734

BOD

3.18

7.489

0.907

18.5

9217.4

0.847

NLP

COD

1.25

45.12

0.915

14.4

9845.5

0.745

BOD

1.02

0.245

0.995

10.8

5545.5

0.824

a-GLP

COD

1.23

61.67

0.940

17.9

8462.5

0.885

BOD

0.31

0.032

1.007

15.2

1251.4

0.755

GLP

COD

0.915

75.45

0.954

10.5

4578.5

0.705

BOD

0.29

0.025

0.54

7.4

1020.2

0.821

a-TSP

COD

0.83

149.8

0.991

12.1

1656.5

0.927

BOD

0.24

0.004

0.96

7.2

768.5

0.835

COD

0.71

158.5

0.542

15.5

754.5

0.812

TSP

BOD

0.12

0.0011

0.547

10.0

625.5

0.714

Table 8: Toth and Khan parameters for COD and BOD removal using naturally prepared adsorbents

Adsorbent

Particular

 

Toth Isotherm

Khan Isotherm

q m (mg/g)

b T (1/mg)

n T

q m (mg/g)

b K (L/mg)

a K

a-NLP

NLP

a-GLP

GLP

a-TSP

TSP

COD

14.25

0.025

0.854

17.34

0.245

0.057

BOD

7.87

0.058

0.754

15.82

0.547

0.047

COD

11.24

0.047