Hybrid Treatment Systems for Dye Wastewater

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Hybrid Treatment Systems for DyeWastewaterFaisal Ibney Hai a , Kazuo Yamamoto b & Kensuke Fukushi ba Department of Urban Engineering , University of Tokyo , Tokyo,Japanb Environmental Science Center , University of Tokyo , Tokyo, JapanPublished online: 14 May 2007.

To cite this article: Faisal Ibney Hai , Kazuo Yamamoto & Kensuke Fukushi (2007) Hybrid TreatmentSystems for Dye Wastewater, Critical Reviews in Environmental Science and Technology, 37:4,315-377, DOI: 10.1080/10643380601174723

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Critical Reviews in Environmental Science and Technology, 37:315–377, 2007Copyright © Taylor & Francis Group, LLCISSN: 1064-3389 print / 1547-6537 onlineDOI: 10.1080/10643380601174723

Hybrid Treatment Systems for Dye Wastewater

FAISAL IBNEY HAIDepartment of Urban Engineering, University of Tokyo, Tokyo, Japan

KAZUO YAMAMOTO and KENSUKE FUKUSHIEnvironmental Science Center, University of Tokyo, Tokyo, Japan

Virtually all the known physicochemical and biological techniques

have been explored for treatment of extremely recalcitrant dye

wastewater; none, however, has emerged as a panacea. A single

universally applicable end-of-pipe solution appears to be unrealis-

tic, and combination of appropriate techniques is deemed imper-

ative to devise technically and economically feasible options. An

in-depth evaluation of wide range of potential hybrid technologies

delineated in literature along with plausible analyses of available

cost information has been furnished. In addition to underscoring

the indispensability of hybrid technologies, this article also endorses

the inclusion of energy and water reuse plan within the treatment

scheme, and accordingly proposes a conceptual hybrid dye wastew-

ater treatment system.

KEY WORDS: dye wastewater, decolorization, energy and waterreuse, hybrid treatment systems

1. INTRODUCTION

Large amounts of dyes are annually produced and applied in many differentindustries, including the textile, cosmetic, paper, leather, pharmaceutical, andfood industries.136 There are more than 100,000 commercially available dyeswith an estimated annual production of over 7 × 105 tons,179 15% of which islost during the dyeing process.70 The textile industry accounts for two-thirdsof the total dyestuff market136 and consumes large volumes of water and other

Address correspondence to Faisal Ibney Hai, Department of Urban Engineering, Univer-sity of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo, 113-8656, Japan. E-mail: faisal [email protected]

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316 F. I. Hai et al.

refractory chemicals for wet processing of textiles.210 The chemical reagentsused are very diverse in chemical composition, ranging from inorganic andlow-molecular-weight organic compounds to polymers.

The presence of even trace concentrations of dyes in effluent is highlyvisible and undesirable.79 The release of colored wastewater in the ecosystemis a remarkable source of esthetic pollution, eutrophication, and perturbationsin aquatic life.70 Dye effluent usually contains chemicals, including dye itself,that are toxic, carcinogenic, mutagenic, or teratogenic to various microbiolog-ical and fish species.50 Concern arises, as many dyes are made from knowncarcinogens such as benzidine and other aromatic compounds.179Also azoand nitro compounds have been reported to be reduced in sediments ofaquatic bodies, consequently yielding potentially carcinogenic amines thatspread in the ecosystem.211 The presence of dyes or their degradation prod-ucts in water can also cause human health disorders such as nausea, hem-orrhage, and ulceration of skin and mucous membranes,195 and can causesevere damage to the kidney, reproductive system, liver, brain, and centralnervous system.94 These concerns have led to new and/or stricter regulationsconcerning colored wastewater discharges, compelling the dye manufactur-ers and users to adopt “cleaner technology” approaches, for instance, devel-opment of new lines of ecologically safe dyeing auxiliaries and improvementof exhaustion of dyes on to fiber.79,180,210

Concomitant with the in-house multidimensional pollution minimizationefforts, a number of emerging material recovery/reuse and end-of-pipe de-colorization technologies are being proposed and tested at different stagesof commercialization. However, due to their synthetic origin and complexstructure deriving from the use of different chromophoric groups, dyes areextremely recalcitrant.179 Along with the recalcitrant nature of dye wastewa-ter, the frequent daily variability of characteristics of such wastewater adds tothe difficulty of treatment.77 Accordingly, despite the fact that virtually all theknown physicochemical and biological techniques have been explored fordecolorization,79 none has emerged as a panacea. Cost-competitive biologicaloptions are rather ineffective, while physicochemical processes are restrictedin scale of operation and pollution profile of the effluent. Table 1 lists theadvantages and disadvantages of different individual techniques. It appearsthat a single, universally applicable end-of-pipe solution is unrealistic, andcombination of different techniques is required to devise a technically andeconomically feasible option. In light of this researchers have put forward awide range of hybrid decolorization techniques. Figure 1 depicts a simplifiedrepresentation of the proposed combinations.

Although still mostly in laboratory stage of development, of late, a wealthof studies have been reported on implementation of advanced oxidation pro-cesses (AOPs) and their combinations for dye wastewater treatment. Manystudies have focused on different combinations of physicochemical treat-ments, which often have been employed by industries in simple, standalone

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TAB

LE1

.A

dva

nta

ges

and

Shortco

min

gsofIn

div

idual

Dye

Was

tew

ater

Tre

atm

entTe

chniq

ues

Pro

cess

Adva

nta

ges

Dis

adva

nta

ges

Sele

cted

refe

rence

s

Bio

logi

cal

Cost

-com

pet

itive

optio

n.D

irec

t,dis

per

se,an

dbas

icdye

shav

ehig

hle

velofad

sorp

tion

on

toac

tivat

edsl

udge

.

Dye

sar

ege

ner

ally

toxi

can

dve

ryre

sist

antto

bio

deg

radat

ion.A

cid

and

reac

tive

dye

sar

ehig

hly

wat

er-s

olu

ble

and

hav

epoor

adso

rptio

non

tosl

udge

.

160

Coag

ula

tion

Eco

nom

ical

lyfe

asib

le;sa

tisfa

ctory

rem

ova

lof

dis

per

se,su

lfur,

and

vatdye

s.Rem

ova

lis

pH

dep

enden

t;pro

duce

sla

rge

quan

tity

of

sludge

.M

aynotre

move

hig

hly

solu

ble

dye

s;unsa

tisfa

ctory

resu

ltw

ithaz

o,re

activ

e,ac

idan

dbas

icdye

s.

61,7

9,17

9

Act

ivat

edC

adso

rptio

nG

ood

rem

ova

lofw

ide

variet

yofdye

s,nam

ely,

azo,

reac

tive

and

acid

dye

s;es

pec

ially

suita

ble

for

bas

icdye

.

Rem

ova

lis

pH

dep

enden

t;unsa

tisfa

ctory

resu

ltfo

rdis

per

se,su

lfur,

and

vatdye

s.Reg

ener

atio

nis

expen

sive

and

invo

lves

adso

rben

tlo

ss;nec

essi

tate

sco

stly

dis

posa

l.

61,7

9,17

9

Ion

exch

ange

Adso

rben

tca

nbe

rege

ner

ated

with

outlo

ss,dye

reco

very

conce

ptu

ally

poss

ible

.Io

nex

chan

gere

sins

are

dye

-spec

ific;

rege

ner

atio

nis

expen

sive

;la

rge-

scal

edye

reco

very

cost

-pro

hib

itive

.17

9,19

6

Mem

bra

ne

filtr

atio

nA

ppro

priat

em

embra

ne

may

rem

ove

allty

pes

ofdye

san

dth

us

real

ize

reusa

ble

wat

erfr

om

dye

-bat

hef

fluen

t.

Conce

ntrat

edsl

udge

pro

duct

ion

and

cost

lym

embra

ne

repla

cem

entim

ped

ew

ides

pre

aduse

.36

Chem

ical

oxi

dat

ion

Initi

ates

and

acce

lera

tes

azo-b

ond

clea

vage

.Ther

modyn

amic

and

kinet

iclim

itatio

ns

along

with

seco

ndar

ypollu

tion

are

asso

ciat

edw

ithdiffe

rent

oxi

dan

ts.N

otap

plic

able

for

dis

per

sedye

s.N

eglig

ible

min

eral

izat

ion

poss

ible

,re

leas

eofar

om

atic

amin

esan

dad

diti

onal

conta

min

atio

nw

ithch

lorine

(in

case

of

NaO

Cl)

issu

spec

ted.

179,

196

Adva

nce

doxi

dat

ion

pro

cess

es,A

OPs

Gen

erat

ea

larg

enum

ber

ofhig

hly

reac

tive

free

radic

als

and

by

far

surp

ass

the

conve

ntio

nal

oxi

dan

tsin

dec

olo

riza

tion.

AO

Ps

inge

ner

alm

aypro

duce

further

undes

irab

leto

xic

by

pro

duct

san

dco

mple

tem

iner

aliz

atio

nm

aynotbe

poss

ible

.Pre

sence

sofra

dic

alsc

aven

gers

reduce

effici

ency

ofth

epro

cess

esso

me

ofw

hic

har

epH

dep

enden

t.Cost

-pro

hib

itive

atth

eir

pre

sentst

age

of

dev

elopm

ent.

(Con

tin

ued

on

nex

tpa

ge)

317

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TAB

LE1

.A

dva

nta

ges

and

Shortco

min

gsO

fIn

div

idual

Dye

Was

tew

ater

Tre

atm

entTe

chniq

ues

(Con

tin

ued

)

Pro

cess

Adva

nta

ges

Dis

adva

nta

ges

Sele

cted

refe

rence

s

UV

/O3

Applie

din

gase

ous

stat

e,no

alte

ratio

nofvo

lum

e.G

ood

rem

ova

lofal

most

allty

pes

ofdye

s;es

pec

ially

suita

ble

for

reac

tive

dye

s.In

volv

esno

sludge

form

atio

n,nec

essi

tate

ssh

ort

reac

tion

times

.

Rem

ova

lis

pH

dep

enden

t(n

eutral

tosl

ightly

alka

line)

;poor

rem

ova

lofdis

per

sedye

s.Pro

ble

mat

ichan

dlin

g,im

pose

additi

onal

load

ing

ofw

ater

with

ozo

ne.

Neg

ligib

leor

no

CO

Dre

mova

l.H

igh

cost

of

gener

atio

nco

uple

dw

ithve

rysh

ort

hal

f-lif

ean

dga

s-liq

uid

mas

stran

sfer

limita

tion;su

ffer

sfr

om

UV

lightpen

etra

tion

limita

tion.In

crea

sed

leve

loftu

rbid

ityin

effluen

ts.

61,7

3,79

,90

,140

,17

9

UV

/H2O

2In

volv

esno

sludge

form

atio

n,nec

essi

tate

ssh

ort

reac

tion

times

and

reduct

ion

ofCO

Dto

som

eex

tentm

aybe

poss

ible

.

Notap

plic

able

for

alldye

types

,re

quires

separ

atio

nof

susp

ended

solid

and

suffer

sfr

om

UV

lightpen

etra

tion

limita

tion.Lo

wer

pH

required

tonulli

fyef

fect

of

radic

alsc

aven

gers

.

73,1

40

Fento

nre

agen

tEffec

tive

dec

olo

riza

tion

ofboth

solu

ble

and

inso

luble

dye

s;ap

plic

able

even

with

hig

hsu

spen

ded

solid

conce

ntrat

ion.Si

mple

equip

men

tan

dea

syim

ple

men

tatio

n.Red

uct

ion

ofCO

D(e

xcep

tw

ithre

activ

edye

s)poss

ible

.

Effec

tive

with

innar

row

pH

range

of<

3.5;

and

invo

lves

sludge

gener

atio

n.Com

par

ativ

ely

longe

rre

actio

ntim

ere

quired

79,14

0,17

9,20

3

Photc

atal

ysis

No

sludge

pro

duct

ion,co

nsi

der

able

reduct

ion

of

CO

D,pote

ntia

lofso

lar

lightutil

izat

ion.

Ligh

tpen

etra

tion

limita

tion,fo

ulin

gofca

taly

sts,

and

pro

ble

moffine

cata

lyst

separ

atio

nfr

om

the

trea

ted

liquid

(slu

rry

reac

tors

)

105

Ele

ctro

chem

ical

Effec

tive

dec

olo

riza

tion

ofso

luble

/inso

luble

dye

s;re

duct

ion

ofCO

Dposs

ible

.N

otaf

fect

edby

pre

sence

ofsa

ltin

was

tew

ater

.

Sludge

pro

duct

ion

and

seco

ndar

ypollu

tion

(fro

mch

lorinat

edorg

anic

s,hea

vym

etal

s)ar

eas

soci

ated

with

elec

troco

agula

tion

and

indirec

toxi

dat

ion,re

spec

tivel

y.D

irec

tan

odic

oxi

dat

ion

requires

further

dev

elopm

ent

for

indust

rial

acce

pta

nce

.H

igh

cost

ofel

ectric

ityis

anim

ped

imen

t.Effi

cien

cydep

ends

on

dye

nat

ure

.

40,1

79

Sonoly

sis

Additi

on

ofch

emic

alad

diti

ves

notre

quired

and

hen

cedoes

notpro

duce

exce

sssl

udge

.Req

uires

alo

tofdis

solv

edga

s(O

2);

com

ple

tedec

olo

ratio

nan

dm

iner

aliz

atio

nby

sonifi

catio

nal

one

are

notec

onom

ical

atpre

sentle

velofre

acto

rdev

elopm

ent.

2,11

Ioniz

ing

radia

tion

No

sludge

pro

duct

ion;ef

fect

ive

oxi

dat

ion

atla

bsc

ale.

Req

uires

alo

tofdis

solv

edO

2;co

mple

tedec

olo

ratio

nan

dm

iner

aliz

atio

nby

stan

dal

one

applic

atio

nnot

poss

ible

.Ener

gyef

fici

entsc

ale-

up

yetto

be

achie

ved.

179

Wet

air

oxi

dat

ion,

WA

OW

ell-es

tablis

hed

tech

nolo

gyes

pec

ially

suita

ble

for

effluen

tto

odilu

tefo

rin

ciner

atio

nan

dto

oto

xic

and/o

rco

nce

ntrat

edfo

rbio

logi

caltrea

tmen

t.

Com

ple

tem

iner

aliz

atio

nnotac

hie

ved,as

low

erm

ole

cula

rw

eigh

tco

mpounds

are

notam

enab

leto

WA

O.H

igh

capita

lan

doper

atin

gco

sts

are

asso

ciat

edw

ithel

evat

edpre

ssure

and

tem

per

ature

emplo

yed.

10,1

1

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Hybrid Treatment Systems for Dye Wastewater 319

FIGURE 1. Simplified representation of broad spectrum of combinations proposed in theliterature.

manner. Combinations of conventional physicochemical techniques with theAOPs have also appeared as attractive options. The biological systems, inaddition to varieties of combinations among themselves, have also been ex-plored in fusion with virtually all sorts of physicochemical and advancedoxidation processes.

This article offers a comprehensive review of the potential hybrid tech-nologies delineated in literature for treatment of dye wastewater in generaland textile wastewater in particular. Analogous to the aforementioned trends,the combinations have been outlined under three broad categories: com-bination among AOPs, combination of physicochemical treatments amongthemselves and those with the AOPs, and, with paramount importance, thecombination of biological systems with conventional physicochemical pro-cesses and AOPs (Figure 1). Before elaborating on the combinations, the ba-sic principles and limitations of relevant individual techniques are discussedbriefly. Based on the array of potential hybrid technologies and the avail-able cost information, a conceptual on-site textile dye wastewater treatmentsystem integrated with energy and water recovery/reuse has been proposed.

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2. COMBINATION AMONG AOPs

While advanced oxidation processes (AOPs) have been studied extensivelyboth for recalcitrant wastewater in general and dye wastewater in particu-lar, their commercialization has yet not been realized because of prevailingbarriers.72,73 These processes are cost prohibitive and complex at the presentlevel of their development.163 Additional impediment exists in treatment ofdye wastewater with relatively higher concentration of dyes, as AOPs areonly effective for wastewater with very low concentrations of organic dyes.Thus, significant dilution is necessary as a facility requirement. The pres-ence of dye additives/impurities such as synthetic precursors, by-products,salts, and dispersing agents in commercial dye bath recipe causes furtherreduction in process efficiency.11,149,152 Although the usual small-scale labo-ratory investigations reveal encouraging results, such studies are insufficientto cast light on practical feasibility of AOPs. For example, in photochemi-cal/photocatalytic decoloration, most of the investigations involve reactorsranging from as small as few tens of milliliters (e.g., 40 ml38) to several hun-dreds of milliliters (e.g., 250 ml146) or at best few liters (e.g., 4 L64), whichare inadequate to explicitly address the light penetration issue, the inherentdrawback of this technology. Only a handful of pilot plant explorations withless than persuasive192,193 or moderate187results have been documented. Re-ports on full-scale application of sole AOP treatment of dye bath effluentsare apparently lacking.

Nevertheless, such processes generate a large number of highly reactivefree radicals and by far surpass the conventional oxidants in decolorization.The conventional oxidants have more significant thermodynamic and kineticlimitations.46 For the AOPs, the basic reaction mechanism is the generation offree radicals and subsequent attack by these on the pollutant organic species.Hence it is strongly believed that their combination will result in more freeradicals, thereby increasing the rates of reactions.72,73 Moreover, some of thedrawbacks of the individual AOPs may be eliminated by the characteristicsof other AOPs. The cost/energy efficiency, however, will be dependent onthe operating conditions and the type of the effluent. Table 2 furnishes aquasi-exhaustive list of typical examples of studies on combinations amongAOPs for dye wastewater treatment. Information on type of associated dyeshas been included wherever available.

2.1. Different Photochemical Processes

The photo-activated chemical reactions are characterized by a free radi-cal mechanism initiated by the interaction of photons of a proper energylevel with the chemical species present in the solution. Generation of rad-icals through ultraviolet (UV) radiation by the homogenous photochemical

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TAB

LE2

.Typ

ical

Exa

mple

sofCom

bin

atio

ns

Am

ong

AO

Ps

for

Dye

Was

tew

ater

Tre

atm

ent

Tech

nolo

gyD

ye/w

aste

wat

erD

etai

lsRef

eren

ce(y

ear)

UV

/O3

2-nap

hth

alen

esulfonat

e[A

zoD

yein

term

edia

te]

Min

eral

izat

ion

of2-

NS

via

ozo

nat

ion

(40

mg/

L)is

rem

arka

bly

enhan

ced

by

UV

radia

tion

(60.

35W

/m2,25

4nm

),trip

ling

the

rate

.N

otm

uch

diffe

rence

in2-

NS

dec

om

posi

tion.

39(2

002)

UV

/O3,U

V/H

2O

2A

cid

N=N

-re

d1/

bla

ck1/

red14

/red

18/o

range

10/y

ello

w17

/yel

low

23;

Direc

tN=N

yello

w4

Dec

olo

ratio

n(2

0m

g/L

dye

):10

0%in

10m

inby

O3(6

L/m

inO

2)

with

/with

outU

V;80

%in

25m

inby

H2O

2–U

V.N

eglig

ible

enhan

cem

entofozo

nat

ion

by

UV

(low

pow

er)

due

toab

sorp

tion

of

most

UV

by

dye

.D

ilutio

nofsa

mple

and/o

roptim

um

reac

tor

des

ign

reco

mm

ended

.

192

(199

5)

UV

/H2O

2H

ispam

inB

lack

CA

[Direc

tN=N

Bla

ck22

]U

V(1

25W

)-H

2O

2(5

65.8

mg/

L,16

.6m

M):

Com

ple

tedec

olo

ratio

n(3

5m

in)

&82

%TO

Cre

mova

l(6

0m

in)

for

40m

g/L

dye

atnat

ura

lpH

(7.5

),al

though

subse

quen

tto

xici

tyte

stre

com

men

ded

.

46(2

002)

UV

/H2O

2A

cid

dye

[ora

nge

8N=N

/blu

e74

C=C

,M

ethyl

ora

nge

N=N

]Rem

ova

lby

Only

UV

(15

W,25

3.7

nm

,in

ciden

tphoto

nflux

=6.

1×

10−6

Ein

stei

ns−1

,4.

54≤

pH

≤5.

5)an

donly

H2O

2in

abse

nce

ofU

Vw

asneg

ligib

le.Com

bin

ed:D

ecolo

riza

tion

rate

rise

sby

incr

easi

ng

the

initi

aldosa

geofH

2O

2up

toa

criti

calva

lue

([H

2O

2]/

[dye

]=

50–7

0)bey

ond

whic

hit

isin

hib

ited.

4(2

003)

UV

/H2O

2Rea

ctiv

e-re

d12

0N=N

/bla

ck5N

=N

/yel

low

84N

=NU

V(1

5W

)/H

2O

2(o

ptim

um

dose

24.5

mm

ol/

l):15

min

:[D

ecolo

riza

tion

>65

%,CO

Dre

mova

l=

40–7

0%],

60m

in:[D

ecolo

riza

tion

>99

%];

Deg

radat

ion

by

pro

duct

sunobje

ctio

nab

le.

152

(200

2)

UV

/H2O

2an

dso

lar/

H2O

2

Chlo

rotria

zine

Rea

ctiv

eN=N

Ora

nge

4D

yere

mova

l(0

.5m

mol/

L),15

0m

in,pH

3:U

V(6

4W,36

5nm

)-H

2O

2(1

0m

mol)

=88

.68%

dec

olo

riza

tion

,59

.85%

deg

radat

ion.

Sunlig

ht–

H2O

2=

80.1

5%dec

olo

riza

tion,50

.91%

deg

radat

ion.D

yeau

xilia

ries

like

Na 2

CO

3,N

aOH

seriousl

yre

tard

dec

olo

ratio

nra

tew

hile

NaC

ldoes

not.

149

(200

4)

O3

follo

wed

by

UV

/H2O

2

Was

tew

ater

from

cotton

&poly

este

rfiber

dye

ing

text

ilem

illU

nder

nat

ura

lpH

(10.

66)

5m

inpre

ozo

nat

ion

(293

mg/

L),re

movi

ng

hig

hU

V-a

bso

rbin

gco

mponen

ts(6

0%re

duct

ion

inU

V25

4),

acce

lera

ted

subse

quen

t55

min

H2O

2(5

0m

mol/

L)-U

V(2

5W

)trea

tmen

t,en

han

cing

itsCO

D&

TO

Cre

mova

lef

fici

ency

by

afa

ctor

of13

&4,

resp

ectiv

ely;

the

com

bin

edtrea

tmen

tyi

eldin

g25

%CO

D,50

%TO

C&

com

ple

teco

lor

rem

ova

l(I

niti

alCO

D=

1476

mg/

L;TO

C=

336

mg/

L).

8(2

001)

UV

/H2O

2/O

3W

aste

wat

erco

nta

inin

gdis

per

sedye

stuff

&pig

men

ts99

%CO

D(I

niti

ally

930

mg/

L)an

d96

%co

lor

rem

ova

lin

90m

in[p

H=

3;H

2O

2=

200

mg/

L;O

3=

2g/

h;15

Wla

mp,25

4nm

].O

ver

90%

rem

ova

lby

UV

/O3

with

less

cost

due

tono

requirem

entofpH

adju

stm

entan

dH

2O

2.

12(2

004)

(Con

tin

ued

on

nex

tpa

ge)

321

Dow

nloa

ded

by [

Kan

sas

Stat

e U

nive

rsity

Lib

rari

es]

at 0

5:45

01

Dec

embe

r 20

13

TAB

LE2

.Typ

ical

Exa

mple

sofCom

bin

atio

ns

Am

ong

AO

Ps

for

Dye

Was

tew

ater

Tre

atm

ent

(Con

tin

ued

)

Tech

nolo

gyD

ye/w

aste

wat

erD

etai

lsRef

eren

ce(y

ear)

Fe+2

/O3

Sim

ula

ted

dis

per

sedye

bat

h(

CI

dis

per

se-vi

ole

t93

1,blu

e29

1;tw

om

ore

azo

dye

san

dco

mpounds)

95%

colo

r(D

yes

=0.

5g/

L),48

%CO

D(initi

ally

=37

84m

g/L)

rem

ova

lan

d10

times

impro

vem

entin

BO

D5/C

OD

ratio

atnat

ura

lac

idic

pH

of

dye

bat

h(

3.6

mM

Fe+2

;[F

e+2]:

[O3]=

1:14

;Fe

SO4.7

H2O

=10

00m

g/L)

.N

eglig

ible

TO

Cre

mova

lis

due

tolo

wO

3dose

of14

g/L.

9(2

001)

UV

/Fen

ton

Dis

per

seN

=Nre

d35

485

%co

lor

rem

ova

l(D

ye=

100

mg/

L)&

90%

CO

Dre

mova

lw

ithin

10m

inw

ith24

.5m

molH

2O

2/L

and

1.22

5m

molFe

SO4/L

atpH

=3,

resu

lting

effluen

thav

ing

only

7.29

%in

hib

ition

inbio

lum

ines

cence

test

.Pre

sence

ofdis

per

sing

agen

tre

duce

sre

mova

lef

fici

ency

.

153

(200

3)

UV

/Fen

ton

Rea

ctiv

eN

=Nbrilli

antre

dX

-3B

Stab

ledec

olo

ratio

n(D

ye=

7.7

×10

−5M

)w

ithin

20m

inw

ith[H

2O

2]=

18x

10−4

M,[F

e+2]or

[Fe+3

]=

1.1

×10

−4M

,75

WU

V(λ

<32

0nm

)la

mp.U

seofFe

+2is

pre

fera

ble

toFe

+3bec

ause

offa

ster

reac

tion

rate

with

H2O

2an

dev

olu

tion

ofH

O.in

stea

dofH

O2.

226

(200

1)

Sola

r/Fe

nto

nO

range

II(A

cid

N=N

ora

nge

7)D

ecolo

ratio

nofhig

hly

conce

ntrat

ed(2

.9m

M≡

0.8

g/L)

dye

inle

ssth

an2

han

d95

%m

iner

aliz

atio

nw

ithin

8h

by

aso

lar

sim

ula

tor

(90

mW

cm−2

)an

dal

soby

nat

ura

lsu

nlig

ht(8

0m

Wcm

−2)

with

0.92

mM

Fe+3

and

10m

MH

2O

2/h

r[p

H=

2].

20(1

996)

Sola

r/Fe

nto

nM

onore

activ

eN=N

Pro

cion

red

H-E

7B,

Het

ero-b

irea

ctiv

eN=N

Red

cibac

ron

FN-R

,St

andar

dtric

hro

mat

icm

ixtu

re

Sunlig

ht,

supply

ing

hig

her

num

ber

ofphoto

ns

(3–4

x10

−3W

cm−2

)th

anth

elo

wpow

erar

tifici

also

urc

e(3

50nm

,6

W,1.

3x

10−4

Wcm

−2),

resu

lted

infa

ster

com

ple

tedec

olo

ratio

n(1

5–30

min

)an

dco

mple

te(o

rnea

r)TO

Cre

mova

l(2

0–60

min

)fo

rdye

conce

ntrat

ion

of10

0m

g/L

with

10m

g/L

Fe+2

and

100–

250

mg/

LH

2O

2[p

H=

3].

207

(200

4)

Cu(I

I)/g

luar

icac

id/H

2O

2

Direc

tChic

ago

sky

blu

eN=N

,M

ethyl

ora

nge

N=N

,Rea

ctiv

eN=N

bla

ck5;

Poly

AQ

B-4

11,Rea

ctiv

eAQ

blu

e2,

RB

BR

AQ,A

crid

in(B

asic

)AQ

ora

nge

;A

zure

blu

eTH,Cry

stal

viole

tTPM

Ove

r90

%dec

olo

riza

tion

of10

0ppm

dye

with

in24

h(7

0–80

%w

ithin

firs

t6

h)

with

10m

MCuSO

4,20

0m

MH

2O

2an

dlo

wdose

ofgl

uca

ric

acid

(15

mM

).In

sensi

tive

topH

,unlik

eFe

nto

nre

actio

n.

212

(200

4)

UV

/O3/T

iO2

Text

ileef

fluen

tco

nta

inin

gRea

ctiv

eN=N

dye

Rem

ova

ls(6

0m

in)-

Photo

cata

lysi

s(0

.1g/

Lan

atas

eTiO

2,12

5W

,fluen

cyra

te31

.1J

m2

s−1,pH

=11

):Colo

r=

90%

,TO

C=

50%

;O

zonat

ion

(pH

=11

,14

mg/

L):Colo

r=

60%

,TO

C=

neg

ligib

le;Com

bin

ed:

Colo

r=

100%

,TO

C>

60%

,To

xici

ty=

50%

146

(200

0)

UV

/H2O

2/T

iO2

Eosi

nY

XN

Enhan

ced

dec

olo

ratio

n(1

00%

for

50m

g/L

dye

)&

min

eral

izat

ion

(95%

)in

1h

(19

Wla

mp,1g

/LTiO

2,10

0m

g/L

H2O

2,pH

=5.

4)al

ong

with

85%

reduct

ion

into

xici

ty.

173

(200

3)

322

Dow

nloa

ded

by [

Kan

sas

Stat

e U

nive

rsity

Lib

rari

es]

at 0

5:45

01

Dec

embe

r 20

13

Sola

r/H

2O

2/p

oly

mer

icm

etal

loporp

hyr

ins

Acr

idin

(Bas

ic)A

Qora

nge

%[D

ecolo

ratio

n,D

egra

dat

ion]:

Hg

lam

p(4

50W

,8

h)

Cat

alys

is(3

mg/

35m

l)w

ithH

2O

2(0

.4g/

L)=

[87,

92];

with

outH

2O

2=

[77,

86].

Sola

rlig

ht(

3h)

Cat

alys

isw

ithoutH

2O

2=

[77,

90].

Dye

=13

.3m

g/L,

hig

hpH

favo

rable

.

38(2

002)

Puls

edst

ream

erco

rona

dis

char

ge(e

lect

rica

l)/H

2O

2

Rhodam

ine

BXN

(Bas

ic),

Aci

dN

=NM

ethyl

ora

nge

,D

irec

tN=N

Chic

ago

sky

blu

e

Puls

edhig

hvo

ltage

(20

kV,25

Hz)

elec

tric

aldis

char

gein

wat

er,

yiel

din

gphoto

dis

soci

atio

nofad

ded

H2O

2(8

.8×

10−4

mol/

L),sh

ow

eden

han

ced

dec

olo

ratio

nra

te(1

00%

for

10m

g/L

dye

in60

min

)as

com

par

edto

indiv

idual

pro

cess

-per

orm

ance

s.

200

(200

2)

Photo

elec

troch

emic

alM

ethyl

ene

blu

eTH

Chem

ical

syner

gism

ofphoto

chem

ical

&el

ectroch

emic

alpro

cess

esyi

elded

enhan

ced

dec

olo

ratio

n(9

5%),

CO

Dre

mova

l(8

7%)

&TO

Cre

mova

l(8

1%)

in30

min

[Dye

=1

mm

ol/

L;50

0W

lam

p,6.

64m

Wcm

−2;1

gTiO

2/2

00m

l;30

VD

C;N

atura

lpH

(6.6

)].

6(2

002)

Mic

row

ave

(MW

)/Photo

cata

lysi

sRhodam

ine

BXN

(Bas

ic)

Inco

ntras

tto

neg

ligib

lere

mova

lby

MW

(300

W),

or

less

rem

ova

lby

photo

cata

lysi

s(7

5W,0.

3mW

cm−2

;30

mg

TiO

2/3

0m

l)al

one,

com

bin

edpro

cess

achie

ved

97%

dec

olo

ratio

n(D

ye=

0.05

mM

)an

d73

%TO

Cre

mova

lw

ithin

3h

atpH

=5.

5.

84(2

002)

Photo

elec

troca

taly

sis

Rea

ctiv

eN=N

brilli

antora

nge

K-R

Dec

olo

ratio

nan

dTO

Cre

mova

lofdye

(0.5

mM

)in

0.5

mm

oll−1

NaC

lso

lutio

nw

ithin

60m

in(N

atura

lpH

):i)

Adso

rptio

non

pac

ked

mat

eria

l:9%

,–

;ii)

Photo

cata

lysi

s[T

iO2

(anta

se=

70%

)-co

ated

quar

tzsa

nd,50

0W

hig

h-p

ress

ure

mer

cury

lam

p]:

70%

,20

%;iii

)Ele

ctro

-oxi

dat

ion

[30.

0V

DC

cell

volta

ge,re

actio

nflow

rate

=19

0m

lm

in−1

,0.

05M

Pa

airfl

ow

]:77

%,7%

;iv

)Photo

elec

troca

taly

sis:

96%

,38

%.O

bvi

ous

enhan

cem

entef

fect

(unlik

ephoto

cata

lysi

s)ofsa

ltin

solu

tion.

238

(200

3)

UV

/ele

ctro

-Fen

ton

Rea

ctiv

eN=N

Red

120

TO

Cre

mova

l[1

80m

in]:

30%

;D

ecolo

ratio

n[3

0m

in]:

75–8

5%fo

r60

-100

mg/

Lco

nce

ntrat

ion;Lo

wef

fici

ency

due

tora

dic

alsc

aven

ging

by

the

grap

hite

cath

ode.

Det

oxi

fica

tion

[90

min

]:Sa

fely

dis

posa

ble

.

116

(200

4)

Gam

ma

irra

dia

tion/H

2O

2

Rea

ctiv

eTC

blu

e15

(Chro

zoltu

rquose

blu

eG

),Rea

ctiv

eN=N

bla

ck5

(Chro

zolbla

ck5)

H2O

2,yi

eldin

g.O

Hby

reac

ting

with

hyd

rate

del

ectron

form

edin

radio

lysi

sofw

ater

,ac

hie

ved

enhan

ced

dec

olo

ratio

n(1

00%

,50

ppm

dye

)an

dCO

Dre

mova

l(7

6–80

%)

with

1an

d15

kGy

dose

sfo

rRB

5an

dRB

15,re

spec

tivel

y,dec

olo

ratio

n(%

)bei

ng

the

hig

hes

tat

the

low

estdose

rate

(0.1

4kG

y/h).

194

(200

2)

(Con

tin

ued

on

nex

tpa

ge)

323

Dow

nloa

ded

by [

Kan

sas

Stat

e U

nive

rsity

Lib

rari

es]

at 0

5:45

01

Dec

embe

r 20

13

TAB

LE2

.Typ

ical

Exa

mple

sofCom

bin

atio

ns

Am

ong

AO

Ps

for

Dye

Was

tew

ater

Tre

atm

ent

(Con

tin

ued

)

Tech

nolo

gyD

ye/w

aste

wat

erD

etai

lsRef

eren

ce(y

ear)

Sonoly

sis/

MnO

2A

cid

N=N

red

BSo

nic

atio

n(5

0kH

z,15

0W

)en

han

ced

oxi

dat

ion

pro

per

tyofM

nO

2

(1g/

L)by

impro

ving

mas

stran

sfer

,re

mova

lofpas

siva

ting

oute

roxi

de

laye

r&

pro

duct

ion

ofH

2O

2,ev

entu

ally

real

izin

g94

.93%

dec

olo

riza

tion

(arg

on

atm

osp

her

e)an

d48

.12

%TO

Cre

mova

l(o

xyge

nat

mosp

her

e)[in

itial

pH

=3,

240

min

].

68(2

003)

Sonoly

sis

/Fen

ton

reac

tion

Aci

dN

=NM

ethyl

ora

nge

Additi

on

ofFe

SO4

([Fe

+2]=

0.1–

0.5

mM

)re

sulte

din

Fento

n’s

reac

tion

with

H2O

2ev

olv

ing

from

sim

ulta

neo

us

sonifi

catio

n(5

00kH

z,50

W)

and

achie

ved

3-fo

ldin

crea

sein

dec

olo

ratio

n(1

5m

in,10

μM

dye

)an

dTO

Cre

mova

l(5

0%,20

min

)as

com

par

edto

sonifi

catio

nonly

.

93(2

000)

Sonoly

sis/

O3

C.I

Rea

ctiv

eN=N

bla

ck5

(RB

B)

Com

bin

edso

noly

sis

(520

kHz)

and

ozo

nat

ion

(irr

adia

tion

inte

nsi

ty,O

3

inputan

dvo

lum

ew

ere

1.63

Wcm

−2;50

Lh/1

;an

d60

0m

l)sh

ow

edsy

ner

gist

icef

fect

,doublin

gth

edec

olo

riza

tion

(100

%,15

min

)an

dm

iner

aliz

atio

n(7

6%,1

h)

rate

.

90(2

001)

Sonoly

sis/

O3

Aci

dN

=NM

ethyl

ora

nge

Com

bin

edso

noly

sis

(500

kHz,

50W

)an

dozo

nat

ion

(50V

)sh

ow

edsy

ner

gist

icef

fect

(dea

den

dbyp

roduct

sofone

pro

cess

bei

ng

deg

raded

by

the

oth

er)

yiel

din

gin

stan

tdec

olo

ratio

n(1

0μ

Mdye

)an

d80

%m

iner

aliz

atio

n(3

h)

asco

mpar

edto

20-3

0%by

stan

d-a

lone

applic

atio

n.

53(2

000)

Sonoly

sis/

UV

/O3

C.I

Aci

dN

=Nora

nge

7Enhan

ced

O3

(40

g/m

3)

diffu

sion

by

mec

han

ical

effe

cts

ofultr

asound

(520

kHz,

600

W)

&th

ephoto

lysi

s(1

08W

)ofultr

asound-g

ener

ated

H2O

2to

pro

duce

.O

Hle

dto

com

ple

tedec

olo

ratio

n(D

ye=

57μ

M),

40%

TO

Cre

mova

l&

anim

pro

vem

entofB

OD

5/T

OC

from

zero

to0.

45w

ithin

60m

in(initi

alpH

=5.

5).

206

(200

4)

Sonoly

sis

/H2O

2Vin

ylsu

lfone

reac

tive

dye

s[C

.IRea

ctiv

e-Yel

low

15N

=N,Red

22N

=N,

Blu

e28

,B

lue

220,

Bla

ck5N

=N;

Rem

azoldar

kbla

ckN

150%

]

Com

bin

edso

noly

sis

(20

kHz)

and

H2O

2(3

.49

mol/

L)sh

ow

edsy

ner

gist

icef

fect

,doublin

gth

edec

olo

riza

tion

(90–

99%

dep

endin

gon

dye

,4

h)

rate

.

216

(200

3)

324

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Sonoly

sis/

UV

/H2O

2Cupro

phen

yle

yello

wRLC

=CSo

nic

atio

n(3

20kH

z)dra

mat

ical

lyen

han

ced

oxi

dat

ion

effici

ency

of

UV

(6at

11W

)+

H2O

2(0

.1m

l/L)

syst

em(p

H=

11)

by

impro

ving

oxy

gen

upta

ke&

tran

sfer

,th

eco

mbin

edpro

cess

achie

ving

94%

dye

(0.1

g/L)

rem

ova

lin

60m

info

llow

ing

pse

udo

firs

t-ord

erki

net

ics.

63(1

999)

Sonoly

sis

/UV

/TiO

2N

aphth

olblu

ebac

kN=N

Sim

ulta

neo

us

or

sequen

tialso

noly

sis

(640

kHz,

240

W)

and

photo

cata

lysi

s(1

g/L

TiO

2)

show

edad

diti

veef

fect

on

dec

olo

ratio

n(1

00%

in20

0m

in;50

μM

dye

)w

hile

,in

term

sofm

iner

aliz

atio

n,

sim

ulta

neo

us

applic

atio

n(5

0%,4

h;80

%,12

h),

due

tom

ass

tran

sfer

impro

vem

entofre

acta

nts

&pro

duct

sto

and

from

TiO

2su

rfac

e,per

form

edbet

ter

than

sequen

tialap

plic

atio

n(<

20%

,h;50

%,1

h).

198

(200

0)

Sonoly

sis/

UV

/TiO

2A

cid

N=N

-re

d1,

Ora

nge

8Si

multa

neo

us

sonoly

sis

(20

kHz,

15W

)an

dphoto

cata

lysi

s(0

.1g/

LTiO

2)

show

edsy

ner

gist

icef

fect

on

dec

olo

ratio

n/d

egra

dat

ion

(2.5

×10

−5M

dye

)due

topro

motin

gde-

aggr

egat

ion

ofTiO

2,des

orp

tion

ofre

acta

nts

&pro

duct

sfr

om

TiO

2su

rfac

e&

mai

nly

by

scis

sion

ofpro

duce

dH

2O

2,

ther

eby,

incr

easi

ng

oxi

diz

ing

spec

ies

inaq

ueo

us

phas

e.

148

(200

3)

Sonoly

sis

UV

/H2O

2C.I

reac

tiveN

=Nre

d12

0So

nifi

catio

n(3

20kH

z)si

gnifi

cantly

enhan

ced

the

dec

olo

ratio

n(D

ye=

0.1

g/L)

effici

ency

ofU

V/H

2O

2.H

igher

flow

rate

(insu

ffici

ent

irra

dia

tion)

nec

essi

tate

dhig

her

dosi

ng

rate

ofH

2O

2.

64(2

001)

Sonoel

ctro

lysi

sA

cid

N=N

sandola

nYel

low

Ele

ctro

-oxi

dat

ion

ofdye

(50

mg/

L)in

salin

eso

lutio

n(0

.01

mol/

LN

aCl)

invo

lvin

gin

situ

gener

atio

nofhyp

och

lorite

ion

was

enhan

ced

usi

ng

ultr

asound

(20

kHz,

22W

)w

hen

carr

ied

outin

ase

mis

eale

dce

ll,w

hic

hm

inim

ized

the

effe

cts

ofultr

asonic

deg

assi

ng.

135

(200

0)

Note

.D

iffe

rentdye

chro

mophore

s:N

=N:Azo

,AQ

:Anth

raquin

one,

TPM

:Triphen

ylm

ethan

edye

,TH:Thia

zine;

XN:Xan

then

e;C=C

:Stil

ben

edye

;TC:Phth

alocy

anin

e.

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degradation of oxidizing compounds like hydrogen peroxide,4 ozone,39 orFenton’s reagent152 has been frequently reported to be superior to solelyUV radiation or sole utilization of such oxidants. Highly UV absorbing dyewastewater may inhibit process efficiency by limiting penetration of UVradiation, necessitating use of high-intensity UV lamps192 and/or a specif-ically designed reactor.119 One example of an appropriate reactor is a re-actor that generates internal liquor flow currents bringing all liquor com-ponents into close proximity to the UV source. Conversely, a thin-channelcoiled reactor may also be used.187 Arslan et al.8 proposed pre-ozonationto remove high UV-absorbing components, and thereby to accelerate subse-quent H2O2–UV treatment by increasing UV penetration. Simultaneous useof UV/H2O2/O3 has also been reported to yield enhanced reaction kinetics.12

However, this entailed additional cost as compared to UV/H2O2 or UV/O3,and hence such use is recommended to be weighed against degree of re-moval required and associated cost. As activators of oxidants like O3or H2O2,a handful of studies have put forward other alternatives to UV, namely,reduced transition metals,9 gamma irradiation,80,194 humic substances,82

etc.An alternative way to obtain free radicals is the photocatalytic mecha-

nism occurring at the surface of semiconductors, that is, heterogeneous pho-tocatalysis. Various chalcogenides (oxides such as TiO2, ZnO, ZrO2, CeO2,etc. or sulfides such as CdS, ZnS, etc.) have been used as photocatalysts so farin different studies. However, titanium dioxide (TiO2) in the anatase form isthe most commonly used photocatalyst, as it has reasonable photoactivity.143

Moreover, it also furnishes the advantages of being insoluble, comparativelyinexpensive, and nontoxic, together with having resistance to photocorrosionand biological immunity.6 The photocatalytic process can be carried out bysimply using slurry of the fine catalyst particles dispersed in the liquid phasein a reactor or by using supported/immobilized catalysts. Limitations of slurryreactors are low irradiation efficiency due to the opacity of the slurry, foulingof the surface of the radiation source due to the decomposition of the catalystparticles, and the requirement that the ultrafine catalyst to be separated fromthe treated liquid. On the other hand, drawbacks of supported photocatal-ysis are scouring of films comprising immobilized powders of catalyst andreduced catalyst area to volume ratio. Recently fluidized bed reactors havebeen reported to take advantages of better use of light, ease of temperaturecontrol, and good contact between target compound and photocatalysts overslurry reactors or fixed bed reactors.

Besides sole photocatalysis, reports on utilization of photocatalysis inpresence of O146

3 or H2O2,200 exhibiting enhanced decoloration and miner-alization, are also available. Considering the total mineralization of the com-pounds, the photocatalytic ozonation (UV/O3/TiO2) may show much lowerspecific energy consumption than the conventional photocatalysis (UV/TiO2)and ozonation (UV/H2O2/O3).106

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Fenton reagent (a mixture of H2O2 and Fe2+) and its modificationssuch as the thermal Fenton process201 or the photo-Fenton reaction usingFe(II)/Fe(III) oxalate ion, H2O2, and UV light have received great attentionas means for decolorization of synthetic dyes.190,202 In the case of the photo-Fenton technique, H2O2 is utilized more rapidly by three simultaneous reac-tions, namely, direct Fenton action, photoreduction of Fe(III) ions to Fe(II),and H2O2 photolysis. Thus this process produces more hydroxyl radicals incomparison to the conventional Fenton method or to photolysis.20,73 Certainreports suggest that in case of similar removal performance, Fenton’s processmay be preferred to related advanced oxidation alternatives (e.g., UV/H2O2)in view of lower energy consumption, lower H2O2 consumption, lowersludge disposal cost (as compared to higher reagent cost), higher flexibility,and lower maintenance requirement.24 However, Fenton reagent necessitatesuse of a large amount of acidic and alkaline chemicals (ideal pH about 2.5).Compared to Fenton’s reagent, the β-FeOOH-catalyzed H2O2 oxidation pro-cess takes advantage of its applicability over a wider pH range between 4to 8, and moreover no sludge is produced.107 In order to take advantage ofthe oxidizing power of Fenton’s reagent yet eliminate the separation of ironsalts from the solution, the use of an “H2O2/iron powder” system has beenrecommended. Such process may yield better dye removal than “H2O2/Fe+2”due to the chemisorption on iron powder in addition to the usual Fenton-type reaction.203 Fenton-type reactions based on other transition metals (e.g.,copper), although less explored to date, have also been reported to be in-sensitive to pH and effective for degradation of synthetic dyes.211,212

Among the AOPs, the photo-Fenton reaction207 and the TiO2-mediatedheterogeneous photocatalytic treatment38processes are capable of absorbingnear-UV spectral region to initiate radical reactions. Their application wouldpractically eliminate major operating costs when solar radiation is employedinstead of artificial UV light. The ferrioxalate solution that has long beenbeing used as chemical actinometer may be used in photo-Fenton process toderive further benefit by replacing UV with solar radiation.7 Recently, severalattempts have been made to increase the photocatalytic efficiency of TiO2;these include noble metal deposition, ion doping, addition of inorganic co-adsorbent, coupling of catalysts, use of nanoporous films, and so on. Apartfrom that, new catalysts, such as polymeric metalloporphyrins, have beenreported to be easily excited by violet or visible light, whereas availableutilization of solar energy by commonly used TiO2 is only about 3%.38

2.2. Photochemical/Electrochemical

In electrochemical treatments, oxidation is achieved by means of elec-trodes where a determined difference of potential is applied. On thisprinciple, several different processes have been developed as cathodicand anodic processes: direct and indirect electrochemical oxidation,

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electrocoagulation, electrodialysis, electromembrane processes, and electro-chemical ion exchange.40 Occasionally, combination of electrochemical tech-nology and photocatalysis has been adopted to yield some unique advan-tages. For instance, chemical synergism of photocatalysis and electrochemicalprocesses may yield enhanced decoloration and chemical oxygen demand(COD) removal,6 and added advantage may be derived from existence of saltin solution, which originally is detrimental for sole photocatalysis.238 Con-versely, the electro-Fenton process requires no addition of chemical otherthan a catalytic quantity of Fe+2, since H2O2 is produced in situ, therebyavoiding transport of this hazardous oxidant.76,154 In the pulsed high-voltageelectric discharge process, addition of oxidants such as H2O2 yields highlyreactive free radical species through photodissociation of H2O2 and therebyenhances the whole process.200

2.3. Sonolysis and other AOPs

Acoustic cavitation due to ultrasound vibration within a liquid generates localsites of high temperature and pressure for a short period of time, which givesrise to H2O sonolysis with production of radical species and direct or indirect(via free radicals) destruction of solute. However, stand-alone application ofsonolysis hardly results in complete mineralization of pollutant streams con-taining complex mixtures of organic and inorganic compounds.73 In viewof the substantial amount of energy employed in generating free radicals viaacoustic cavitation bubbles, efforts have been made to improve its efficiency.It has frequently been explored in association with other AOPs. For exam-ple, combined use of sono-photochemical process can prevent severe masstransfer limitation and reduced efficiency of photocatalyst owing to adsorp-tion of contaminants at the surface. On the other hand, such combinationcan alleviate the limitations of separate application of sonolysis.148,198 A sim-ilar advantage has been reported in case of concurrent sonolysis and MnO2

oxidation.68 Sonification has also been reported to bring about dramatic en-hancement in oxidation efficiency of UV/H2O2 by improving oxygen uptakeand transfer.63,64,216 Combined application of sonolysis and O3/UV facilitatesO3 diffusion and photolysis of ultrasound-generated H2O2.53,90,206 Such acombination hence yields large number of free radicals. Addition of FeSO4

in solution may result in Fenton reaction with H2O2 evolved from simultane-ous sonification and may achieve improved decoloration and TOC removalas compared to sonification only.93 Simultaneous sonolysis has also beenreported to enhance electro-oxidation of dye.135

3. COMBINATION: AOPs AND OTHERPHYSICOCHEMICAL PROCESSES

Many studies have focused on different combinations among physicochem-ical systems for treatment of textile and dye wastewaters. Combinations of

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conventional physicochemical techniques with the AOPs have as well ap-peared as an attractive option. Table 3 encapsulates information derived frombroad spectrum of typical studies dealing with such combinations.

3.1. Coagulation-Based Combinations

Coagulation/flocculation/precipitation processes have been used intensivelyfor decolorizing wastewater. For the pretreatment of raw wastewater beforedischarging to publicly owned treatment plants, these processes may be sat-isfactory with respect to COD reduction and partial decolorization. Theirstand-alone application in treating textile/dye waste is, however, relativelyineffective;79,101,163 for example, only 50% removal was achieved using eitheralum or ferrous sulfate for an azo reactive yellow dye.79 In the coagulationprocess, it is difficult to remove highly water-soluble dyes, and, even moreimportant, the process produces a large quantity of sludge.179

Nevertheless, researchers are persistent in their pursuit of minimizingthe limitations of this technology. For instance, polyaluminum ferric chlo-ride (PAFC), a new type of composite coagulant, was reported to have theadvantages of high stability and good coagulating effect for hydrophobic aswell as hydrophilic dyes. Its decoloration capacity surpassed that of polyalu-minum chloride and polyferric sulfate.66 On the other hand, to avoid massivesludge disposal problem, different novel approaches, such as coagulation oflow-volume segregated dye bath (rather than that of a colossal amount ofmixed wastewater),74 alum sludge recycling,41 coagulant recovery from tex-tile chemical sludge,122 reuse of textile sludge in building materials,16 andprocesses like vermicomposting of textile mill sludge67 and coagulation fol-lowed by activated carbon adsorption163 have been proposed. Coagulationfollowed by adsorption was reported to produce effluent of reuse standard,apart from cutting down the coagulant consumption by 50%, hence loweringthe volume of sludge formed, in comparison to coagulation only.163

Coagulation in combination with advanced oxidation processes, eitherin sequential or in concurrent manner, has been reported for dye wastewater.For example, simultaneous application of coagulation and Fenton oxidationhas revealed improved performance over their stand-alone applications.101

One of the limitations of the Fenton oxidation process is that large amountsof small, hard-to-settle flocs are consistently observed during the process.Chemical coagulation following Fenton treatment has been found to re-duce floc settling time, enhance decoloration, and reduce soluble iron ineffluent.131 Conversely, the photo-Fenton process subsequent to coagulationwas reported to complete decoloration and yield better COD removal, withthe added advantage of reducing load on the advanced oxidation process,thereby reducing chemical usage.18 Investigation on sequential use of co-agulation and ozonation revealed the superiority of the scheme involvingozonation preceded by coagulation over the reversed scheme.209 Multistage

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TAB

LE3

.Typ

ical

Exa

mple

sofCom

bin

atio

ns

Bet

wee

nConve

ntio

nal

Phys

icoch

emic

alPro

cess

esan

dA

OPs

Tech

nolo

gyD

ye/w

aste

wat

erD

etai

lsRef

eren

ce(y

ear)

Fento

n/c

hem

ical

coag

ula

tion

C.I

direc

tN=N

blu

e20

2,C.I

reac

tiveN

=Nbla

ck5;

PVA

81–8

6%CO

D(I

niti

ally

>10

00m

g/L)

rem

ova

l&

dec

olo

ratio

n(D

ye=

200

mg/

L)in

2h

with

[H2O

2]/

[FeS

O4]=

1000

/400

atpH

=3,

while

subse

quen

tco

agula

tion

atpH

=7–

10w

ith10

0m

g/L

PAC

&2m

g/L

poly

mer

reduce

dfloc

settlin

gtim

e,en

han

ced

dec

olo

ratio

nan

dre

duce

dso

luble

Fein

effluen

t.

131

(199

7)

Fento

n+

chem

ical

coag

ula

tion

Dis

per

se-B

lueN

=N10

6,Yel

low

AQ

54;Rea

ctiv

e-B

lueA

Q49

,Yel

low

N=N

84

Coag

ula

tion

(pH

=5–

7):Rem

ova

lper

molFe

+3[C

OD

,D

YE]:

Dis

per

se(0

.74–

0.93

mM

FeCl 3

)=

[460

.2–4

77g,

525.

7–67

2.7]

;Rea

ctiv

e(1

.85–

2.78

mM

FeCl 3

)=

[37.

4–86

.5g,

109.

5–19

2.7

g].Fe

nto

n(p

H=

3;30

min

;[F

e+2]:

[H2O

2]=

1:0.

2–1:

0.37

):Rem

ova

lper

molFe

+2[C

OD

,D

YE]:

Dis

per

se=

[14–

80g,

3.7–

20.8

g];Rea

ctiv

e=

[114

.2–1

99.6

g,11

8.9–

489.

2g].

Com

bin

ed:B

oth

dye

s,90

%CO

D&

99%

dye

rem

ova

l.

101

(200

4)

O3/c

oag

ula

tion

Azo

dye

man

ufa

cturing

was

tew

ater

(subje

cted

toch

lorinat

ion)

Rem

ova

l:A

fter

Ozo

nat

ion

[70

min

;56

mg

O3

/min

;1.

6L/

min

;pH

=10

.3]CO

D=

25%

,Colo

r=

43%

..A

fter

subse

quen

tCa(

OH

) 2co

agula

tion

[787

mg/

L,pH

=12

]CO

D=

50%

,TO

C=

42%

,Colo

r=

62%

.;ef

fect

ive

rem

ova

lofch

loro

org

anic

saf

ter

two

stag

es.

186

(199

8)

Coag

ula

tion/O

3Te

xtile

was

tew

ater

Coag

ula

tion

[Al 2

(SO

4) 3

,60

ppm

;poly

elec

troly

te0.

6ppm

]re

sulte

din

65–7

5%&

20%

reduct

ion

ofCO

D&

abso

rban

ce(initi

alCO

D=

890

mg/

L),w

hile

subse

quen

tozo

nat

ion

(3m

g/m

in,10

–15

min

)ga

vea

further

90%

&20

–25%

reduct

ion

ofre

sidual

colo

r&

CO

D.O

zonat

ion

pre

ceded

by

coag

ula

tion

gave

wors

ere

sult.

209

(199

4)

Multi

stag

e(c

oag

ula

tion/O

3)

Dye

man

ufa

cturing

was

tew

ater

Singl

est

age

coag

ula

tion

(2.5

%,v/

v,Fe

Cl 2

;35

mg/

Lpoly

mer

;pH

=8.

5)fo

llow

edby

ozo

nat

ion

(pH

=11

;90

min

)ac

hie

ved

[19%

CO

D,88

%co

lor]

and

[67%

CO

D,99

.3%

colo

r]re

mova

l,re

spec

tivel

y(initi

alCO

D=

7700

mg/

L;Colo

r=

6700

0A

DM

I).Thre

etim

esre

pet

ition

ofth

ese

quen

cew

hile

keep

ing

tota

lozo

nat

ion

time

sam

e(3

at30

min

)ac

hie

ved

>90

%CO

D&

99.9

9%co

lor

rem

ova

l,th

esu

per

iority

of

multi

stag

etrea

tmen

tbei

ng

less

convi

nci

ng

for

was

tew

ater

with

sim

ple

rco

mposi

tion.

86(1

998)

330

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Coag

ula

tion/U

V-

Fento

nIn

tegr

ated

pla

ntco

nta

inin

gva

riet

yofpro

cess

esra

ngi

ng

from

des

izin

gto

dye

ing

and

ulti

mat

efinis

hin

g

UV

(20

W)/

TiO

2(1

g/L)

/H2O

2(1

0m

M)/

Fe+2

(1

mM

)trea

tmen

t(p

H=

4)fo

llow

ing

coag

ula

tion

trea

tmen

tac

hie

ved

com

ple

tedec

olo

ratio

n(3

0m

in)

&a

max

imal

48%

(ove

rth

atac

hie

ved

by

coag

ula

tion)

CO

Dre

mova

l(1

h),

the

CO

Dofra

w,co

agula

ted,an

doxi

diz

edsa

mple

bei

ng

1063

,55

6,&

269

mg/

L,re

spec

tivel

y.

18(2

003)

Coag

ula

tion/c

arbon

adso

rptio

nC.I

reac

tiveN

=Nre

d45

,C.I

reac

tiveN

=Ngr

een

8Rem

ova

l(D

ye=

1g/L

):A

fter

AlC

l 3·6H

2O

coag

ula

tion

[0.8

g/L;

pH

=3.

5]:RR

45[Colo

r98

.8%

,TO

C98

.1%

,CO

D93

.4%

];RG

8[C

olo

r99

%,

TO

C96

.9%

,CO

D83

.8%

].A

fter

carb

on

adso

rptio

n[0

.24

&0.

84g/

L;2

hr]:RR

45[C

olo

r99

.9%

,TO

C99

.7%

,CO

D95

.7%

];RG

8[Colo

r99

.9%

,TO

C99

.2%

,CO

D91

.3%

].H

alfth

eco

agula

ntco

nsu

mptio

nan

dlo

wer

volu

me

ofsl

udge

form

atio

nin

com

par

ison

todye

rem

ova

lby

coag

ula

tion

only

.

163

(200

4)

Photo

cata

lysi

s/ad

sorp

tion

(pow

der

edac

tivat

edca

rbon,PA

C)

Hum

icac

id(n

atura

lco

loring

mat

ter)

3–4

hirra

dia

tion

induce

ddec

reas

ein

UV

280,

UV

254,

TO

Can

dCO

Dan

dsi

multa

neo

us

impro

vem

entofbio

deg

radab

ility

with

no

sign

ifica

nt

dec

reas

ein

adso

rptiv

ityofsu

bse

quen

tPA

C.

22(1

996)

Solv

entex

trac

tion

(&dye

reco

very

)/Fe

nto

nre

agen

t

1-D

iazo

-2-n

aphth

ol-4-

sulfonic

acid

(aci

ddye

inte

rmed

iate

)

82%

Ext

ract

ion

usi

ng

solv

ent(t

rial

kyla

min

eN

235)

and

subse

quen

tdye

reco

very

by

strippin

gle

dto

95%

dec

olo

ratio

nofth

eorigi

nal

effluen

t.Su

bse

quen

tra

ffinat

etrea

tmen

t(a

fter

lime

neu

tral

izat

ion)

by

Fento

nre

agen

tac

hie

ved

achro

mat

icef

fluen

tw

ithCO

D<

100

mg/

L.

87(2

004)

O3/i

on

exch

ange

Cu-c

om

ple

xD

irec

tN=N

Blu

e80

Concu

rren

tdec

olo

ratio

n&

met

alre

leas

eby

0.2

mg

O3/m

gdye

and

subse

quen

tm

etal

rem

ova

lby

stro

ng

acid

catio

n-e

xchan

gere

sin

atpH

=2

achie

ved

Cu

conce

ntrat

ion

bel

ow

det

ecta

ble

limits

inth

eef

fluen

t.

97(1

996)

Adso

rptio

n(fl

uid

ized

GA

C)

+O3

Aci

dblu

e9,

Mord

antN

=N

bla

ck11

,Rea

ctiv

eAQ

blu

e19

,Rea

ctiv

eN=N

ora

nge

16

Influen

t:pH

=5.

1–9.

2,CO

D=

250–

1800

mg/

1,SS

=45

–320

mg/

,tu

rbid

ity(N

TU

)=

50–2

10.Com

bin

edozo

nat

ion

and

GA

Cad

sorp

tion

(4L

O3/m

inper

100

gmG

AC)

offer

sm

utu

alen

han

cem

entnam

ely

rege

ner

atio

nofG

AC

&ca

taly

sis

ofO

3.

132

(200

0)

(Con

tin

ued

on

nex

tpa

ge)

331

Dow

nloa

ded

by [

Kan

sas

Stat

e U

nive

rsity

Lib

rari

es]

at 0

5:45

01

Dec

embe

r 20

13

TAB

LE3

.Typ

ical

Exa

mple

sofCom

bin

atio

ns

Bet

wee

nConve

ntio

nal

Phys

icoch

emic

alPro

cess

esan

dA

OPs

(Con

tin

ued

)

Tech

nolo

gyD

ye/w

aste

wat

erD

etai

lsRef

eren

ce(y

ear)

Adso

rptio

n(G

AC)

+UV

/H2O

2

Rea

ctiv

eEve

rzolB

lack

–GSP

Sim

ulta

neo

us

adso

rptio

n(8

g/L)

&U

V–

H2O

2oxi

dat

ion

(0.0

09M

)ac

hie

ved

syner

gist

icdec

olo

ratio

n&

TO

Cre

mova

l(c

om

ple

te&

50%

,30

min

)fo

rth

eorigi

nal

lypoorly

adso

rbab

ledye

(36

ppm

)co

ncu

rren

tw

ithco

stsa

ving

due

tore

use

ofad

sorb

ent.

91(2

002)

Adso

rptio

n(β

-Fe

OO

H)/

oxi

dat

ive

(H2O

2)

rege

ner

atio

n

C.I.Rea

ctiv

eN=N

Red

198

Adso

rptio

nonto

gran

ula

ted

β-F

eOO

H(1

70m

g/g)

and

itsre

pea

ted

reuse

(6cy

cles

)fo

llow

ing

rege

ner

atio

nby

cata

lytic

oxi

dat

ion

usi

ng

H2O

2(7

mg

dye

/mg;

6h

at24

.5m

l/m

in);

sele

ctiv

ead

sorp

tion/o

xidat

ion,lo

wer

oxi

dan

tdose

and

no

conve

ntio

nal

conce

ntrat

etrea

tmen

t.Si

multa

neo

us

trea

tmen

tre

com

men

ded

for

hig

hsa

lt-co

nta

inin

gw

aste

wat

er.

107

(200

2)

Ion-e

xchan

ger

(quar

tern

ized

amm

oniu

mce

llulo

se)

/chem

ical

reduct

ion

(bis

ulfi

te-m

edia

ted

boro

hyd

ride)

Ora

nge

II(A

cid

N=N

Ora

nge

7),Rea

ctiv

eN=N

red

180

Anio

nex

chan

ger

bound

383

mg/

gofO

range

II&

272

mg/

gofre

activ

edye

while

subse

quen

tK

BH

4/N

aHSO

3(2

mM

/10

mM

)re

duct

ion

of

dye

(1m

Mso

lutio

n)

follo

wed

by

salt

or

bas

eex

trac

tion

resu

lted

inal

most

com

ple

tere

gener

atio

nofth

eco

stly

ion

exch

ange

r,es

tablis

hin

ga

feas

ible

pro

cess

couplin

gtw

ote

chnolo

gies

with

limite

dpote

ntia

lal

one.

117

(199

7)

Adso

rptio

n(P

AC)/

wet

air

oxi

dat

ion

(WA

O)

Chem

ictiv

eB

rill.

Blu

eR

(Rea

ctiv

eAQ);

Cib

acorn

Turq

uois

eB

lue

G(R

eact

iveT

C)

Effi

cien

ttrea

tmen

toflo

wer

conce

ntrat

ions

ofunhyd

roliz

edre

activ

edye

sby

firs

tad

sorb

ing

on

PAC,an

dsu

bse

quen

tly,re

gener

atin

g(>

98%

afte

rco

nse

cutiv

e4

cycl

esw

ithonly

8%to

talw

eigh

tlo

ss)

spen

tPA

Cby

WA

O(1

50–2

50◦ C

,O

2par

tialpre

ssure

0.69

–1.3

8M

pa)

,an

dre

cycl

ing

the

rege

ner

ated

carb

on.

191

(200

2)

Adso

rptio

n(C

uFe

2O

4)/

cata

lytic

com

bust

ion

Aci

dN

=NRed

BD

ye,pre

conce

ntrat

edon

adso

rben

t/ca

taly

stCuFe

2O

4(>

95%

rem

ova

lfr

om

100

mg/

L;pH

<5.

5,dose

=0.

1g/

50m

l),af

ter

mag

net

icso

lid/l

iquid

separ

atio

n,w

assu

bje

ctto

com

ple

teco

mbust

ion

atre

lativ

ely

low

tem

p(3

00◦ C

)w

ithoutev

olu

tion

ofhar

mfu

lpro

duct

s;an

din

the

pro

cess

,CuFe

2O

4w

asre

gener

ated

allo

win

gef

fici

entre

use

ove

rex

tended

cycl

es.

223

(200

4)

332

Dow

nloa

ded

by [

Kan

sas

Stat

e U

nive

rsity

Lib

rari

es]

at 0

5:45

01

Dec

embe

r 20

13

Adso

rptio

n(f

erro

us

modifi

edG

AC)

+m

icro

wav

e(M

W)

induce

dO

xidat

ion

Arg

azolB

lue

BF-

BR

150%

(bifunct

ional

N=N

reac

tive

dye

)

98.3

%dec

olo

ratio

nan

d96

.8%

CO

Dre

mova

lw

asac

hie

ved

when

dye

solu

tion

(50

ml,

300

mg/

L)co

nta

inin

gfe

rrous

modifi

edG

AC

(2g)

was

subje

ctto

MW

irra

dia

tion

(5m

in,50

0W,24

50M

Hz)

,th

ere

mova

lm

echan

ism

invo

lvin

gG

AC

adso

rptio

n&

subse

quen

tco

mbust

ion

(induce

dby

MW

)on

itssu

rfac

e.N

eglig

ible

strippin

gofFe

+2fr

om

GA

Csu

rfac

eunder

reuse

for

man

ytim

es.

166

(200

4)

Adso

rptio

n(G

AC)/

mic

row

ave

(MW

)re

gener

atio

n

C.I

Aci

dN

=NO

range

7D

ye(5

00m

g/L)

-ex

hau

sted

GA

Cco

uld

be

succ

essf

ully

rege

ner

ated

by

mic

row

ave

irra

dia

tion

(245

0M

Hz,

850

W,5

min

)fo

rre

pea

ted

cycl

esin

volv

ing

low

GA

Clo

ss(6

.5%

,4

cycl

es)

and

adso

rptio

nra

teev

enhig

her

than

that

ofvi

rgin

GA

Cdue

topore

-siz

edis

trib

utio

n&

surf

ace

chem

istry

modifi

catio

n.

176

(200

4)

Sonic

atio

n/F

e0

reduct

ion

C.I

Aci

dN

=NO

range

7Puls

edso

nic

atio

n(2

0kH

z,25

0W

),by

impro

ving

mas

stran

sfer

&al

soin

crea

sing

activ

esi

tes

on

Fe-s

urf

ace,

dra

mat

ical

lyen

han

ced

dye

(50

mg/

L)dec

olo

ratio

nef

fici

ency

ofm

ildre

duci

ng

agen

tFe

0(1

g/L,

pH

=3)

,th

eco

mbin

edpro

cess

achie

ving

91%

dye

rem

ova

lin

30m

info

llow

ing

1stord

erki

net

ics.

237

(200

5)

Mem

bra

ne

bas

edozo

nat

or

Blu

e19

reac

tive

dye

;U

ntrea

ted

exhau

sted

dye

-bat

h

Thin

coat

ing

ofTiO

2&

γ-A

l 2O

3on

cera

mic

mem

bra

ne

(ZrO

2,α-A

l 2O

3)

elim

inat

eddef

ects

&hen

ceal

low

edoper

atio

nat

hig

hga

spre

ssure

with

subst

antia

lozo

ne

tran

sfer

impro

vem

ent,

even

tual

lyyi

eldin

g10

0%&

62%

dec

olo

ratio

nofpure

dye

(0.0

72m

mol/

L)&

untrea

ted

dye

bat

h,re

spec

tivel

y,in

2h

45(2

003)

Photo

cata

lytic

mem

bra

ne

reac

tor

Congo

red

N=N

,Pat

ent

blu

eN=N

The

contin

uous

photo

cata

lytic

mem

bra

ne

(NF;

30–7

0L/

m2h)

reac

tor

with

susp

ended

TiO

2(1

g/L)

&im

mer

sed

UV

lam

p(1

25W

)outp

erfo

rmed

itsco

unte

rpar

tw

ithTiO

2en

trap

ped

on

mem

bra

ne

and

irra

dia

ted

with

exte

rnal

lam

p(5

00W

),ac

hie

ving

alm

ost

com

ple

tephoto

deg

radat

ion

ofdye

s(5

00m

g/L)

with

hig

her

rate

.

145

(200

4)

(Con

tin

ued

on

nex

tpa

ge)

333

Dow

nloa

ded

by [

Kan

sas

Stat

e U

nive

rsity

Lib

rari

es]

at 0

5:45

01

Dec

embe

r 20

13

TAB

LE3

.Typ

ical

Exa

mple

sofCom

bin

atio

ns

Bet

wee

nConve

ntio

nal

Phys

icoch

emic

alPro

cess

esan

dA

OPs

(Con

tin

ued

)

Tech

nolo

gyD

ye/w

aste

wat

erD

etai

lsRef

eren

ce(y

ear)

Mem

bra

ne/

wet

air

oxi

dat

ion,W

AO

Dis

per

seN

=Nblu

eCI

79N

Fm

embra

ne

achie

ved

>99

%co

lor

and

97%

CO

Dre

ject

ion

ofdye

com

pound

while

the

hom

oge

neo

us

copper

sulfat

eca

taly

zed

WA

O(1

60◦ –

225◦ C

,O

2par

tialpre

ssure

0.69

–1.3

8M

pa)

reduce

d90

%CO

Dfr

om

conce

ntrat

e(1

20m

in).

55(2

000)

Mem

bra

ne/

wet

air

oxi

dat

ion,W

AO

Dye

ing

was

tew

ater

conta

inin

gRea

ctiv

eblu

e,In

dig

o,Su

lfur

bla

ck&

oth

erpro

cess

chem

ical

s

Rep

laci

ng

O2

with

stro

nge

roxi

dan

tH

2O

2(5

0%ofst

oic

hio

met

ric

amount)

&ad

din

gCu-A

Cca

taly

st(2

g/L)

,80

%TO

C&

90%

colo

rw

asre

move

dfr

om

mem

bra

ne

conce

ntrat

eby

WO

under

mild

conditi

on

(110

◦ C,T

ota

lP

=50

kPa)

in30

min

118

(199

8)

Mem

bra

ne/

sonic

atio

n/

WA

ORea

ctiv

eTC

Turq

uois

eblu

eCI2

5N

Fm

embra

ne

(1.5

Mpa;

flux

=0.

084

m/h

)re

move

d90

.3%

CO

D&

98.7

%co

lor

from

pu

red

ye

solu

tion

(CO

D=

1500

mg/

L),w

hile

WO

(190

◦ C,O

2pre

ssure

=0.

69M

pa;

pH

=7)

reduce

d90

%CO

Dfr

om

dilu

ted

(CO

D=

500–

700

mg/

L)co

nce

ntrat

e(1

20m

in).

Sonic

atio

n(1

50/3

50W

,av

g./p

eak;

40kH

z;30

min

)w

ases

sentia

lto

mak

em

embra

ne

rete

nta

tefr

om

act

ua

lw

ast

ewa

ter

tobe

amen

able

tosu

bse

quen

tW

O.

54(1

999)

Mem

bra

ne/

O3

Rea

ctiv

e(R

emaz

olblu

eB

B,

Intrac

orn

gold

enye

llow

VS-

GA

,Rem

azolre

dRB

)&

salt

NF

mem

bra

ne

(9.4

1L/m

in;Re

=83

8)ge

ner

ated

reusa

ble

per

mea

te(8

5%oforigi

nal

volu

me)

with

>99

%ofco

lor

&Cu,an

donly

15%

ofsa

ltre

mova

lw

hile

subse

quen

tozo

nat

ion

(7.7

3m

g/L.

min

,pH

=11

)re

move

dco

lor

from

the

conce

ntrat

efo

llow

ing

1stord

erki

net

ics,

the

rate

dec

reas

ing

with

incr

easi

ng

initi

aldye

colo

r.

222

(199

8)

UV-F

ento

n/c

oag

ula

tion

/mem

bra

ne

Rea

ctiv

eN=N

(Pro

cion

Red

HE7B

)Com

ple

teco

lor

rem

ova

l(D

ye=

50m

g/L)

and

79%

TO

Cre

mova

lw

ithin

20m

inby

photo

-Fen

ton

(pH

=3;

[H2O

2]/

[Fe+2

]=

20:1

;4

at15

WU

Vla

mp).

How

ever

9tim

esin

crea

sein

dis

solv

edso

lids

war

rants

subse

quen

tco

agula

tion/m

embra

ne

syst

emfo

rre

use

indye

/rin

sepro

cess

.

88(1

999)

334

Dow

nloa

ded

by [

Kan

sas

Stat

e U

nive

rsity

Lib

rari

es]

at 0

5:45

01

Dec

embe

r 20

13

Phys

icoch

emic

al/

mem

bra

ne

(UF/

NF)

Synth

etic

text

ilem

anufa

cturing

was

tew

ater

Raw

wat

er:Conduct

ivity

(mS/

cm)

2.06

;S.

S.(m

g/L)

82.6

;CO

D(m

g/L)

1640

;Turb

idity

(NTU

)15

.65;

Inord

erto

reuse

the

wat

erin

rinse

pro

cess

es,it

isnec

essa

rya

neg

ligib

leCO

Dan

da

conduct

ivity

low

erth

an1

mS/

cm.Phys

icoch

emic

al(p

H=

8.5,

CD

K−F

ER20

=20

0m

g/L,

Cnal

co,fl

occ

ula

nt=

1m

g/L)

:50

%CO

Dre

mova

l;N

Fm

embra

ne

(flow

rate

=40

0L/

h,TM

P=

1M

Pa)

:10

0%CO

Dre

mova

l,85

%co

nduct

ivity

rete

ntio

n.[R

eusa

ble

]

25(2

002)

Phys

icoch

emic

al/

mem

bra

ne

(N

F)Te

xtile

was

tew

ater

Raw

wat

er:Conduct

ivity

(mS/

cm)

4.53

;CO

D(m

g/L)

1630

.Phys

icoch

emic

al(p

H=

12,Fe

+2=

700

mg/

L):72

.5%

CO

Dre

mova

l;N

Fm

embra

ne

(flow

rate

=20

0L/

h,TM

P=

20bar

,flux

=8–

10L/

m2h):

CO

D<

100

mg/

L;Conduct

ivity

<1

mS/

cm

26(2

003)

Cla

riflocc

ula

tion/

ozo

na-

tion/m

embra

ne

(UF)

Was

tew

ater

from

carb

oniz

ing

pro

cess

,fr

om

dye

ing

and

fulli

ng

49%

turb

idity

&71

%co

lor

rem

ova

lby

clar

iflocc

ula

tion

&ozo

nat

ion,

resp

ectiv

ely,

and

hig

htu

rbid

ity(2

7%)

&TSS

(30%

)re

mova

lby

the

subse

quen

tU

Fm

embra

ne

contrib

ute

dto

achie

vem

entoffinal

66%

CO

Dan

d93

%co

lor

rem

ova

l,m

akin

gre

use

,af

ter

50%

dilu

tion

with

wel

lw

ater

,poss

ible

.

139

(200

2)

Act

ivat

edC/m

embra

ne

(NF/

RO

)Rea

ctiv

edye

for

cotton

Hotw

ater

reuse

inrinsi

ng

afte

rre

clam

atio

nby

mem

bra

ne

(deg

radat

ion

offiltr

atio

nre

man

ence

inan

aero

bic

dig

este

rs);

and

reuse

ofdye

bat

hw

ater

and

salts

afte

rad

sorp

tion

ofdye

stuff

and

CO

Don

activ

ated

carb

on.

219

(199

6)

Mem

bra

ne

(UF)

/adso

rptio

n(a

ctiv

ated

carb

on

cloth

,A

CC)

Aci

dN

=NO

range

II,A

cid

N=N

Brilli

antYel

low

(colo

r)&

Ben

tonite

(turb

idity

)

Both

pro

cess

are

com

ple

men

tary

inth

atco

mpounds

too

larg

eto

be

adso

rbed

onto

ACC

are

succ

essf

ully

reta

ined

by

the

mem

bra

ne

(>98

%tu

rbid

ity&

15–4

0%dye

rem

ova

l),w

hile

low

-mole

cula

r-w

eigh

torg

anic

sar

ew

ellad

sorb

edby

the

ACC

(38–

180

mg/

g,dye

-spec

ific)

.Rep

laci

ng

UF

with

NF,

or

UF

mem

bra

ne

wra

pped

up

ina

ple

ated

ACC

reco

mm

ended

toav

oid

early

bre

akth

rough

ofA

CC.

168

(200

0)

Note

.D

iffe

rentdye

chro

mophore

s:N

=N: A

zo,

AQ

:Anth

raquin

one,

TC:Phth

alocy

anin

e.

335

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application of coagulation followed by ozonation was proved to be superiorto their single-pass sequential application (total ozonation time the same).86

The advantage of the multistage application was more convincing in the caseof wastewater with more recalcitrant composition.

3.2. Adsorption-Based Combinations

Adsorption techniques, specially the excellent adsorption properties ofcarbon-based supports, have been utilized for the decolorization of dyesin the industrial effluents.60 Activated carbon, either in powder or granularform, is the most widely used adsorbent for this purpose because of its ex-tended surface area, microporous structure, high adsorption capacity, andhigh degree of surface reactivity.137 It is very effective for adsorbing cationic,mordant, and acid dyes and to a slightly lesser extent dispersed, direct, vat,pigment, and reactive dyes.179 However, the use of carbon adsorption fordecolorization of raw wastewater is impractical because of competition be-tween colored molecules and other organic/inorganic compounds. Hence itsuse has been recommended as a polishing step or as an emergency unit at theend of treatment stage to meet the discharge color standards.79 The fact thatactivated carbon is expensive and weight loss is inevitable during its costlyon-site regeneration (10% loss in the thermal regeneration process)99 impedesits widespread use. Utilization of nonconventional, economical sources (in-dustrial or agricultural by-products) rather than usual relatively expensivematerials (coconut shell, wood or coal) as precursors for activated carbonhas been proposed to achieve cost-effectiveness in its application.142,181

There has been considerable interest in using low-cost adsorbents fordecolorization of wastewater. These materials include chitosan, zeolite, andclay; certain waste products from industrial operations such as fly ash, coal,and oxides; agricultural wastes and lignocellusic wastes; and so on.14,151 Eachof the non-regenerable economical adsorbents has its specific drawbacks andadvantages; all, however, pose further disposal problem. To do away withthe disposal problem, easily regenerable adsorbent is required.99

As mentioned earlier, adsorption is a nondestructive method involvingonly phase change of pollutants, and hence imposes further problem in theform of sludge disposal. The high cost of adsorbent also necessitates its re-generation. Conversely, some catalytic oxidation/reduction systems appearto be more efficient when treating small volumes of concentrated dyes. So itappears attractive to combine adsorption with some other process in a systemwhere contaminants are preconcentrated on adsorbent and then separatedfrom water. The contaminants thus separated may subsequently be mineral-ized, for example, by wet air oxidation,191,223 or degraded to some extent, forinstance, with azo bond reduction by bisulfite-mediated borohydride117 soas to regenerate the adsorbent and reuse. In this way an economical processcoupling two treatment technologies eliminating their inherent drawbacks

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may be developed. If partial degradation is applied to regenerate the adsor-bent, it will still leave behind a small volume of wastewater (as comparedto the volume that existed before adsorption) to be treated. This again canbe conveniently taken care of by applying some AOP. Ince et al.89proposeda slightly modified version of the aforementioned so-called “phase-transferoxidation.” Their strategy was comprised of simultaneous operation of ad-sorption and AOP followed by periodic on-site destructive regeneration ofthe spent adsorbent. Adsorption concurrent with ozonation,132 UV–H2O2,91

or microwave-induced oxidation132 has been reported to yield mutual en-hancements like catalysis of AOP by adsorbent and simultaneous regenera-tion of adsorbent. A rather elaborate method involving solvent extraction andcatalytic oxidation has been documented in the literature.87,150 The methodconsists of dye extraction using an economical solvent followed by dye re-covery through chemical stripping. In this way the solvent is also regener-ated. Finally, treatment of the extraction raffinate can be achieved by catalyticoxidation.

3.3. Membrane-Based Combinations

Membrane separation endows the options of either concentrating thedyestuffs and auxiliaries and producing purified water,208 or removing thedyestuff and allowing reuse of water along with auxiliary chemicals,110,172,174

or even realizing recovery of considerable portion of dye, auxiliaries, andwater all together.171 Such recovery/reuse practice reduces many-fold therecurring cost for the treatment of waste streams. The fact that the dyeingbehavior of the residual dye should ideally be identical to that of the fresh dyemay restrict dye recovery and reuse to specific dye classes.35,65 Accordingly,water and/or electrolyte recovery from dye bath effluent has become the fo-cus of the contemporary literature. However, concentrated sludge productionand occurrence of frequent membrane fouling requiring costly membrane re-placement impede widespread use of this technology.36 Two distinct trendsare hence notable among the reported studies that couple membrane sepa-ration with other technologies. Some studies mainly focus on alleviation ofthe membrane-concentrate disposal problem, while others seek to offer com-plete hybrid systems wherein elimination of the limitations of the membranetechnology (e.g., fouling) and/or those of the counterpart technologies (e.g.,ultrafine catalyst separation in photocatalysis) may be expected.

Hybrid processes based on membrane and photocatalysis have beenreported to eradicate the problem of ultrafine catalyst to be separated fromthe treated liquid in case of slurry reactors, with the added advantage ofmembrane acting as selective barrier for the species to be degraded. Onthe other hand, in case of immobilized catalysis, membrane may play therole of support for the photocatalyst.145 For coupling with photocatalysis,membrane distillation, however, has been reported to be more beneficial in

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comparison with pressure-driven membrane process, as significant foulingmay be associated with the latter. Tay et al.204 proposed a photo-oxidative(UV/TiO2/H2O2) pretreatment prior to membrane filtration to partially breakdown the high-molecular-weight compounds that cause membrane fouling.The relatively smaller fragments produced therefrom were still retainable bymembrane, and ,unlike the parent compounds, they did not affect the chargeof the membrane surface.

Membrane contactors, involving mass transfer in the pores by diffusion(avoiding gas dispersion as macroscopic bubbles as in traditional ozonationsystems), offer the advantages of higher contact surface (equal to membranesurface, which may reach up to 30 km2/m3 H2O for hollow-fiber membranes),easy scale-up, no foam formation, and lower process cost (no requirementof ozone destruction, lower ozone loss).42,45

Numerous studies have reported on application of membrane filtration(ultrafiltration/nanofiltration, UF/NF) following coagulation/flocculation toproduce reusable water.25,26,139 Such application has the added advantageof minimizing membrane fouling. In this context, the hybrid coagulation-membrane reactor may offer another viable option. This treatment schememay also be placed subsequent to advanced oxidation processes in order toremove soluble degradation products.88

Application of separate technologies for segregated streams has beenrecommended by different researchers. For instance, Wenzel et al.219 recom-mended hot water reuse in rinsing after reclamation by membrane, and reuseof dye bath water and salts after adsorption of dyestuff and COD on activatedcarbon. Conversely, the hybrid adsorption-membrane reactor, offering syn-ergism in that the compounds too large to be adsorbed onto adsorbent aresuccessfully retained by the membrane while low-molecular-weight organicsare well adsorbed on adsorbent, is also worth mentioning.168

A considerable number of studies have been devoted to eradicationof the major drawback associated with membrane separation, that is, con-centrated residue remaining for disposal. As mentioned earlier, dyes in theconcentrate from the membrane separation unit, because of the usual qualityrequirements for the color shades in the dyed products, cannot be reused andmust be treated before discharge. In this respect, catalyzed wet air oxidation(WAO) has emerged as an efficient system.55,118 Sonification was found es-sential to make the membraneretentate from actual wastewater be amenableto subsequent WAO.54 On the other hand, augmentation of advanced oxida-tion process (e.g., ozonation) subsequent to membrane filtration has beenenvisaged as a scheme yielding several advantages, such as reducing wastevolume for oxidation while simultaneously recovering salt, and, in addition,limiting concentrated waste for disposal.222 A novel membrane-based inte-grated water management system for the exhausted dye bath and rinsingbath was proposed by Bruggen et al.34 The proposed scheme involved,in order of application, microfiltration membrane (pretreatment), loose

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nanofiltration membrane (NF-1, for organics removal), and another tighterNF membrane (NF-2, salt retention). According to that scheme, further sep-aration of organic fraction may be achieved by membrane distillation units,while retained salt may be recovered through membrane crystallization. Fi-nally, the organic sludge of high calorific value from the membrane distillationunit may be incinerated.

4. BIOLOGICAL TREATMENT-BASED COMBINATIONS

4.1. Combination Among Biological Processes

Conventionally a chemical coagulation step, preceded by229 or antecedentto57 biological treatment, is applied for dye wastewater. Combined treat-ment with municipal wastewaters is usually favored75 wherever applicable.Various biological treatment processes including activated sludge, fluidizedbiofilm,229 different fixed film systems,3 or combinations thereof230 have beenemployed. Although in case of aerobic bacteria cometabolic reductive cleav-age of azo dyes as well as utilization of azo compounds as sole source ofcarbon and energy (leading to mineralization) have been reported, dyes aregenerally very resistant to degradation under aerobic conditions.19,199 Toxic-ity of dye wastewater and factors inhibiting permeation of the dye throughthe microbial cell membrane reduce the effectiveness of biological degrada-tion. Dyestuff removal, hence, currently occurs in the primary settling tankof a wastewater treatment plant for the water-insoluble dye classes (disperse,vat, sulfur, azoic dyes), while the main removal mechanism for the water-soluble basic and direct dyes in conventional aerobic systems is adsorptionto the biological sludge. Reactive and acid dyes, however, adsorb very poorlyto sludge and are thus major troublemakers in relation to residual color indischarged effluents.160

Since reduction of the azo bond can be achieved under the reducingconditions prevailing in anaerobic bioreactors31 and the resulting colorlessaromatic amines may be mineralized under aerobic conditions,32 a combinedanaerobic-aerobic azo dye treatment system appears to be attractive. Trialswith various combinations, including simultaneous anaerobic/aerobic pro-cess (microbial immobilization on a matrix providing oxygen gradient113

or an anaerobic–aerobic hybrid reactor95), anoxic plus anaerobic/aerobicprocess,162 anaerobic/oxic system,5 and aerobic (cell growth)/anaerobic (de-colorization) system,37 have all been explored, involving fed batch, sequenc-ing batch, or continuous feeding strategies, with encouraging results.Bothcytoplasmic184 and membrane-bound114 unspecific azo-reductase activitiesunder anaerobic condition have been reported. Glucose, raw municipalwastewater, and yeast extract, among others, have been reported as examplesof an essential cosubstrate needed to obtain good anaerobic color removal.52

Different abiotic processes involving derivatives generated during bacterial

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metabolism (e.g., sulfide, amino acid cysteine, ascorbate) may contribute indecolorization under anaerobic conditions.227 The biotic process, however,dominates in high-rate anaerobic bioreactors.233 Addition of redox-mediatingcompounds like anthraquinone sulfonate or anthraquinone disulfonate hasbeen reported to greatly enhance both the biotic and abiotic processes.233

However, during posttreatment of anaerobically treated azo dye-containingwastewater, there will be competition between biodegradation and autoxi-dation of aromatic amines. This may be problematic not only because theformed products are colored but also because some of these compounds,such as azoxy compounds, may cause toxicity.232 It should be emphasizedthat in high-nitrogen waste waters it makes little sense to remove part ofCOD by anaerobic treatment in the first step when COD has to be addedagain to the effluent afterward in order to achieve nitrogen removal.52

Biological treatment is a cost-competitive and eco-friendly alternative.Researchers are hence persistent in their pursuit of minimizing the inher-ent limitations of biological dye wastewater treatments. Several innovativeattempts to achieve improved reactor design and/or to utilize special dye-degrading microbes or to integrate textile production with wastewater treat-ment have been documented in literature. Some of these innovative en-deavors include a two-stage activated sludge process (high-load first stage,achieving biosorption and incipient decomposition of high-molecular-weightorganic compounds, followed by a low-load polishing stage);104 high-rateanaerobic systems uncoupling hydraulic retention time from solids reten-tion time;125 two-phase anaerobic treatment wherein the acidic-phase biore-actor is also shared for textile production (integration of production withwastewater treatment);59 activated sludge pretreatment, to reduce organicnitrogen, before fungi decoloration;144 fungi pretreatment before anaero-bic treatment;58 combined fungi (biofilm) and activated sludge culture98 fordecoloration; activated algae reactor (with mixed population of algae andbacteria);13 activated sludge followed by over land flow;185 etc.

4.2. Hybrid Technologies Based on Biological Processes

Table 4 summarizes a broad spectrum of intriguing reports on hybrid tech-nologies having biological processes as the core.

4.2.1. BIOLOGICAL/PHYSICOCHEMICAL

As mentioned earlier, the literature is replete with examples of use of co-agulation complementary to biological decoloration. The choice between acoagulation–biological or biological–coagulation scheme depends on typeand dosage of coagulant, sludge quantity, and degree of inhibitory and non-biodegradable substances present in wastewater. Coagulation prior to biolog-ical treatment may be advantageous for alkaline wastewaters. After biologicaltreatment ferrous sulfate cannot be used because pH is close to neutral. On

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TAB

LE4

.Typ

ical

Exa

mple

sofCom

bin

atio

ns

Bet

wee

nB

iolo

gica

lTre

atm

entan

dO

ther

Tech

nolo

gies

Tech

nolo

gyD

ye/w

aste

wat

erD

etai

lsRef

eren

ce(y

ear)

Chem

ical

(NaO

Cl)/b

io(a

nae

robic

)K

raft

E1

effluen

t(c

onta

inin

glig

nin

and

oth

erco

lore

dco

mpounds

like

quin

ones

,ch

alco

nes

,st

ilben

es)

NaO

Cl(0

.1kg

Cl/

kgco

lor;

pH

=10

)ac

hie

ved

90%

colo

rre

mova

lw

ith50

%in

crea

sein

low

mole

cula

rm

ass

AO

X,w

hic

hw

asam

enab

leto

subse

quen

tan

aero

bic

trea

tmen

t,al

though

asi

multa

neo

us

smal

lam

ountofco

lor

reve

rsio

nocc

urr

edduring

anae

robic

stag

e.A

short-ter

mso

lutio

nfo

rco

mbin

eddec

olo

ratio

n&

dec

hlo

rinat

ion.

47(1

994)

Poly

ure

than

eim

mobili

zed

fluid

ized

bio

film

/coag

ula

tion

(alu

m)

Dye

ing

was

tew

ater

from

poly

este

rdew

eigh

ted

pro

cess

92%

CO

DM

n(initi

ally

824

mg/

L)re

mova

lby

bio

logi

cal(0

.16–

0.32

kgCO

DM

n/k

gVSS

.day

)fo

llow

edby

coag

ula

tion

(600

mg/

Lal

um

,pH

=6)

pro

cess

.Coag

ula

tion

(100

0m

g/L

alum

,pH

=6)

follo

wed

by

bio

logi

cal(0

.09–

0.19

kgCO

DM

n/k

gVSS

.day

)pro

cess

achie

ved

sim

ilar

rem

ova

l,butw

ith20

%m

ore

exce

sssl

udge

due

tom

ore

dis

solv

ed(in

additi

on

tosu

spen

ded

)su

bst

ance

rem

ova

lduring

coag

ula

tion.

229

(199

6)

Coag

ula

tion

(Na-

ben

tonite

)/ac

tivat

edsl

udge

Was

tew

ater

from

pla

nts

dye

ing

&finis

hin

gnat

ura

l/sy

nth

etic

fiber

s

Chem

ical

pre

trea

tmen

t(2

g/L)

prior

tobio

logi

calpro

cess

reduce

d40

%ofin

itial

bio

deg

radab

leas

wel

las

iner

tso

luble

CO

D,th

ereb

yre

duce

dpote

ntia

lof‘res

idual

iner

tCO

D(p

roduct

sfr

om

bio

deg

radab

leCO

D)’,w

hile

chem

ical

post

trea

tmen

tfo

llow

ing

bio

logi

cal,

achie

ved,des

pite

bet

ter

dec

olo

ratio

n,only

20%

resi

dual

solu

ble

CO

Dre

mova

l.

57(2

002)

Fluid

ized

bio

film

/coag

ula

tion/

elec

troch

emic

aloxi

dat

ion

Synth

etic

text

iledye

ing

was

tew

ater

Bio

film

ofsp

ecia

llyis

ola

ted

mic

robes

on

support

med

iaac

hie

ved

68.8

%CO

Dcr

(initi

al=

800–

1000

mg/

L)an

d54

.5%

colo

rre

mova

lw

hile

those

achie

ved

by

ove

rall

com

bin

edsy

stem

(FeC

l 3.6

H2O

dose

of3.

25x

10−3

mol/

L;Ele

ctro

oxi

dat

ion:2.

1m

A/c

m2

ofcu

rren

tden

sity

and

0.7

L/m

inflow

rate

)w

ere

95.4

%an

d98

.5%

,re

spec

tivel

y.

100

(200

2)

Fento

nor

pow

der

edac

tivat

edC

(PA

C)/

fixe

dbed

bio

film

/Fen

ton

Dis

per

sedye

stuff

was

tew

ater

Enhan

ced

rem

ova

lby

pre

viousl

yac

clim

atiz

edbio

mas

son

fixe

dbed

due

toin

crea

sed

bio

deg

radab

ility

(BO

D5:C

OD

from

0.06

to0.

432)

by

Fento

n(H

2O

2:Fe

SO4·7H

2O

=70

0:35

00,m

g/L)

or

PAC

pre

trea

tmen

t.CO

Dre

mova

l(initi

ally

1720

0m

g/L)

sepa

rate

lyat

pre

trea

tmen

t,bio

logi

cal&

post

trea

tmen

tw

ere

50%

,85

%&

85%

,re

spec

tivel

y.

3(1

999)

(Con

tin

ued

on

nex

tpa

ge)

341

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TAB

LE4

.Typ

ical

Exa

mple

sofCom

bin

atio

ns

Bet

wee

nB

iolo

gica

lTre

atm

entan

dO

ther

Tech

nolo

gies

(Con

tin

ued

)

Tech

nolo

gyD

ye/w

aste

wat

erD

etai

lsRef

eren

ce(y

ear)

Coag

ula

tion/

elec

troch

emic

aloxi

dat

ion/a

ctiv

ated

sludge

15dye

suse

din

apla

nt

mak

ing

prim

arily

cotton

and

poly

este

rfiber

san

dsm

allquan

tity

ofw

ool

Influen

t:CO

D=

800–

1600

mg/

L,Tra

nsp

aren

cy<

4cm

,Conduct

ivity

=20

00μ

mho/c

m,pH

=6–

9.CO

Dco

nce

ntrat

ion

(100

mg/

L)an

dtran

spar

ency

(30)

amply

satis

fies

the

gove

rnm

entsa

fedis

char

gest

andar

dby

emplo

ying

Poly

alum

inum

chlo

ride

(40

mg/

L,w

ithpoly

mer

conce

ntrat

ion

0.5

mg/

L),el

ectroch

emic

aloxi

dat

ion

(pH

≈7,

curr

entden

sity

=53

.4m

A/c

m2,1

L/m

inofflow

rate

)an

dth

esu

bse

quen

tac

tivat

edsl

udge

pro

cess

.

129

(199

6)

Bio

/ele

ctro

flocc

ula

tion/

flota

tion/fi

ltrat

ion

Was

tew

ater

from

pla

nts

dye

ing

&finis

hin

gnat

ura

l/sy

nth

etic

fiber

s

Alth

ough

elec

troflocc

ula

tion

isef

fect

ive

with

outbio

logi

cal

pre

trea

tmen

t,th

esa

me

enhan

ced

itsper

form

ance

,w

hile

subse

quen

tflota

tion

and

ben

tonite

filtr

atio

nco

mple

ted

sludge

rem

ova

l&

low

ered

Feco

nce

ntrat

ion,th

eco

mbin

edsy

stem

achie

ving

com

ple

teco

lor,

69%

CO

D&

appre

ciab

lesa

ltre

mova

l.A

l-el

ectrode

should

be

pre

ferr

edto

Fe-e

lect

rode

toav

oid

resi

dual

Fein

terf

erin

gre

use

of

was

tew

ater

for

dye

ing

lightco

lors

.

43(2

001)

O3/c

oag

ula

tion/a

ctiv

ated

sludge

Text

ilew

aste

wat

erCom

ple

tedec

olo

riza

tion

ofth

ete

xtile

effluen

t(C

OD

=18

00m

g/L,

JTU

tran

spar

ency

=2

cm)

acco

mplis

hed

with

10m

inozo

nat

ion

(rat

e13

.25

g/h).

With

out/

With

coag

ula

tion

(3m

lPA

C)

only

5%an

dup

to70

%CO

Dre

duct

ion,re

spec

tivel

y.

127

(199

3)

Coag

ula

tion/a

ctiv

ated

sludge

/ove

rlan

dflow

Cotton

text

ilew

aste

wat

erIn

putCO

D,TD

San

dTurb

idity

(200

9m

g/L,

2987

mg/

L,10

2N

TU

)re

duce

das

follo

ws:

After

Phys

icoch

emic

al[A

lum

416

mg/

L,lim

e 213

mg/

L,

poly

elec

troly

te11

mg/

L]:

(105

4m

g/L,

1540

mg/

L,52

NTU

);A

fter

Act

ivat

edsl

udge

[HRT

=20

hr,

CO

Dlo

adin

g-0.

9kg

CO

D/m

3,

MLS

S-30

73m

g/L,

sludge

recy

cle-

20%

]:(4

88m

g/L,

772

mg/

L,49

NTU

);A

fter

land

trea

tmen

t:(8

9m

g/L,

239

mg/

L,20

NTU

);

185

(199

6)

Bio

/ele

ctro

chem

ical

+H

2O

2/c

oag

ula

tion/i

on

exch

ange

Dye

ing

&finis

hin

gw

aste

wat

erEle

ctro

chem

ical

(DC

2.5A

;20

0m

g/L

H2O

2;pH

=3;

10m

in)

&co

agula

tion

(100

mg/

LPA

C,1

mg/

Lpoly

mer

)on

bio

logi

cally

pre

trea

ted

was

tew

ater

(CO

D=

111

mg/

L;Conduct

ivity

=48

50μ

mho/c

m)

achie

ved

72.8

%CO

D&

97.3

%co

lor

rem

ova

l,w

hile

subse

quen

tio

nex

chan

ge(c

atio

nic

=40

,an

ionic

=20

g/L)

reduce

dco

nduct

ivity

&CO

Dto

10μ

mho/c

m&

10m

g/L.

[Reu

sable

]

130

(199

6)

Coag

ula

tion/a

ctiv

ated

sludge

,A

S/filtr

atio

n/

dis

infe

ctio

n

Text

ilew

aste

wat

er[B

OD

5(m

g/L)

,CO

D,Conduct

ivity

(μs/

cm)]:In

fluen

t=

[940

,25

60,

3500

];A

fter

chem

ical

trea

tmen

t(F

eSO

4.7H

2O

=0.

72kg

/m3,

Poly

elec

troly

te=

0.2

g/m

3)=

[512

,12

50,29

40];

After

tertia

ry=

[15,

310,

2800

],re

usa

ble

for

irriga

tion.

155

(199

2)

342

Dow

nloa

ded

by [

Kan

sas

Stat

e U

nive

rsity

Lib

rari

es]

at 0

5:45

01

Dec

embe

r 20

13

Bio

(Ph

an

eroch

aet

ech

ryso

spori

um

fungi

)/O

3

Text

ilew

aste

wat

erD

ecre

ase

inhig

hm

ole

cula

rm

ass

frac

tion

ofte

xtile

effluen

tin

the

bio

logi

calpro

cess

(pH

=4.

5)&

low

mole

cula

rm

ass

frac

tion

during

subse

quen

tO

3trea

tmen

t(p

H=

11,15

L/h,80

min

)ac

com

pan

ied

by

40%

dec

olo

ratio

nin

each

step

,th

efinal

effluen

tsh

ow

ing

no

toxi

city

.

115

(200

1)

Bis

ulfi

te-c

atal

yzed

Na-

boro

hyd

ride

reduct

ion

/bio

Direc

tN

=Nre

d23

,D

isper

seN

=Nye

llow

5,A

cid

N=N

yello

w17

,B

asic

N=N

blu

e41

,Rea

ctiv

eN=N

ora

nge

13

Dye

:D

epen

din

gon

dye

(200

mg/

L),85

–98%

dec

olo

ratio

nw

ithin

10–3

0m

inby

chem

ical

reduct

ion.

Act

ua

lw

ast

ewa

ter

(CO

D=

770

mg/

L):[C

OD

&co

lor

rem

ova

l]:i)

Na 2

S 2O

5(2

00–2

50m

g/L)

–ca

taly

zed

NaB

H4

(50–

60m

g/L)

reduct

ion

=[7

3–86

%,8–

12%

];ii)

Subse

quen

tbio

logi

caloxi

dat

ion

=[7

4–87

%,74

–76%

].

71(2

003)

Bio

/photo

reac

tor

Rea

ctiv

e(C

ibac

ron

red

FB),

Dis

per

salYel

low

C-4

R,

Direc

t(S

olo

phen

ylO

range

T4R

L)

[CO

Dre

mova

l,ye

llow

/red

colo

rre

mova

l]:O

nly

bio

logi

cal

[HRT

3day

s,SR

T20

day

s]:[6

0%,10

–15%

/notsi

gnifi

cant];

Only

photo

reac

tor [4

gTiO

2/15

0g

zeolit

e,Li

ght

(365

nm

)in

tensi

ty30

W/m

2,20

0hrs

]:

[>90

%,co

mple

tely

dec

olo

roze

d],

bio

-photo

reac

tor [2

4h

illum

inat

ion]:

[>90

%;co

mple

tedec

olo

riza

tion]

121

(199

7)

Photo

chem

ical

/bio

(Fungi

)K

raft

E1

effluen

t(c

onta

inin

glig

nin

and

colo

red

com

pounds

like

quin

ones

,ch

alco

nes

,st

ilben

es)

Only

photo

cata

lysi

s[5

0m

gsa

nd-im

mobili

zed

ZnO

(10%

,w/w

)/1

0ml

effluen

t;Li

ght(2

54nm

)in

tensi

ty=

108W

/m2;pH

=6.

5;2h

r]:10

0%dec

olo

ratio

n,80

%CO

2fo

rmat

ion,90

%CO

Dre

duct

ion;O

nly

bio

=57

%dec

olo

ratio

n;photo

(10m

in)-

bio

(Le

nti

nu

laed

od

esfu

ngi

,96

h):

73%

dec

olo

ratio

n,;

bio

(5d

+3

d,2

cycl

es)-

photo

(20

min

):10

0%dec

olo

ratio

n

178

(199

8)

Thin

-film

photo

reac

tor

conta

inin

gphoto

synth

etic

bac

teria

Aci

dN

=Nblu

e92

TiO

2-c

oat

edre

acto

rirra

dia

ted

with

UV

and

fluore

scen

tlig

ht(3

ofea

chty

pe

at6

W)

faci

litat

eddec

olo

riza

tion

effici

ency

(80%

;15

mg

dye

/gM

LSS/

d)

ofphoto

synth

etic

bac

teria

(with

outan

yin

hib

ition

induce

dby

UV

radia

tion)

by

avoid

ing

alga

lgr

ow

than

dits

adhes

ion

on

reac

tor.

83(2

003)

Fe(I

II)/

photo

(sola

r)as

sist

edbio

logi

cal

syst

em

5-am

ino-6

-met

hyl

-2-

ben

zim

idaz

olo

ne

(AM

BI)

;dye

inte

rmed

iate

The

300

min

(shortes

tposs

ible

toyi

eld

the

bes

tco

mbin

edre

sult)

aera

ted,Fe

(III

)/lig

htpre

trea

tmen

t(F

e+3=

1m

mol/

L;40

0W

;80

mW

cm−2

)ac

hie

ved

100%

AM

BI(1

mm

ol/

L)deg

radat

ion

and

40%

DO

Cre

mova

l,w

hile

subse

quen

tim

mobili

zed

bio

logi

calco

lum

n(6

L/h)

com

ple

ted

the

min

eral

izat

ion.Pilo

t-sc

ale

inve

stig

atio

nunder

sola

rra

dia

tion

reco

mm

ended

Fe(I

II)/

H2O

2/l

ightfo

r10

times

fast

erre

actio

n.

187

(200

3)

(Con

tin

ued

on

nex

tpa

ge)

343

Dow

nloa

ded

by [

Kan

sas

Stat

e U

nive

rsity

Lib

rari

es]

at 0

5:45

01

Dec

embe

r 20

13

TAB

LE4

.Typ

ical

Exa

mple

sofCom

bin

atio

ns

Bet

wee

nB

iolo

gica

lTre

atm

entan

dO

ther

Tech

nolo

gies

(Con

tin

ued

)

Tech

nolo

gyD

ye/w

aste

wat

erD

etai

lsRef

eren

ce(y

ear)

Ele

ctro

n-b

eam

trea

tmen

t/bio

Mix

edra

ww

aste

wat

erpre

dom

inat

ely

from

dye

ing

pro

cess

&8%

from

poly

este

rfiber

pro

duct

ion

Pilo

tpla

ntin

vest

igat

ion

(flow

rate

=10

00m

3/d

)in

volv

ing

low

dose

(1kG

y)E-b

eam

pre

trea

tmen

tre

veal

eden

han

ced

bio

trea

tmen

tper

form

ance

requirin

gre

duce

d(h

alf)

resi

den

cetim

e(H

RT)

for

sam

edeg

ree

ofre

mova

l.W

ithth

ew

aste

wat

erbei

ng

origi

nal

lybio

deg

radab

le,th

ero

leofE-b

eam

was

,in

contras

tto

usu

alan

ticip

atio

nofco

nve

rsio

nofnonbio

deg

radab

leportio

n,to

conve

rtth

ebio

deg

radab

leportio

nto

further

easi

erfo

rms.

81(2

004)

AO

P(P

eroxo

n,O

3+

H2O

2;photo

-Fen

ton

with

ozo

ne,

O3+

H2O

2+

UV

+Fe

+2)

/bio

4,4′ -D

initr

ost

ilben

e-2,

2′ -dis

ulfonic

acid

(DN

S)C=C

,fluore

scen

tw

hite

nin

gag

entpre

curs

or

[Initi

al:CO

D=

2840

mg/

L;B

OD

28/C

OD

=0.

04].

Per

oxo

n(M

ola

rra

tio,

DO

C:O

3:H

2O

2=

1:1:

1/3)

or

photo

-Fen

ton

with

ozo

ne

(DO

C:O

3:H

2O

2:Fe

+2=

1:0.

3:1:

1/20

;U

V15

0W

)re

aliz

edsi

mila

r60

%CO

D,50

%D

OC

&60

%A

OX

rem

ova

l,w

hile

the

bio

deg

radat

ion

of

the

5tim

esdilu

ted

pre

oxi

diz

edsa

mple

achie

ved

ove

rall

80%

CO

Dre

mova

l.So

leozo

nat

ion,how

ever

,ac

hie

ved

bet

ter

dec

olo

ratio

nth

anth

eab

ove

two.In

situ

.OH

form

atio

nw

ithoutnee

dofU

Vre

com

men

ded

due

tost

rong

UV-a

bso

rbin

gco

mpounds

inth

isw

aste

wat

er.

85(2

003)

Bio

/AO

P(P

eroxo

n,

O3+H

2O

2)/

bio

Stilb

eneC

=C-b

ased

fluore

scen

tw

hite

nin

gag

ent

[Initi

al:CO

D=

1980

mg/

L;B

OD

28/C

OD

=0.

44].

AO

Ppre

trea

tmen

tprior

bio

logi

caltrea

tmen

tdid

nothav

ean

yim

pro

vem

entef

fect

ove

rso

lebio

deg

radat

ion;hen

cea

reve

rsed

sequen

cew

asad

opte

d.

Bio

logi

calpre

trea

tmen

tre

move

d60

%CO

D&

55%

DO

C(D

isso

lved

Org

anic

Car

bon)

while

the

final

bio

deg

radat

ion

follo

win

gth

ein

term

edia

teA

OP

(Mola

rra

tio,D

OC:O

3:H

2O

2=

1:1:

1/3)

trea

tmen

tac

hie

ved

anove

rall

84%

CO

D&

71%

DO

Cre

mova

l.

85(2

003)

Cla

riflocc

ula

tion/b

io/A

OP

(H2O

2/U

V)

Woolsc

ouring

effluen

tCla

riflocc

ula

tion

follo

wed

by

aero

bic

bio

logi

caltrea

tmen

tre

move

d>

90%

CO

D&

allB

OD

;how

ever

,re

mai

nin

gCO

D(1

000

mg/

L)&

inte

nse

colo

rw

arra

nte

dsu

bse

quen

tH

2O

2/U

V[M

ola

rra

tio,CO

D:

H2O

2=

1:1;

40W

]trea

tmen

tw

hic

h,des

pite

pre

sence

ofst

rong

UV

abso

rbin

gco

mpounds,

achie

ved

100%

dec

olo

ratio

n(3

0m

in),

75%

CO

D&

85%

TO

Cre

mova

l(6

0m

in)

irre

spec

tive

ofpH

.

170

(200

4)

344

Dow

nloa

ded

by [

Kan

sas

Stat

e U

nive

rsity

Lib

rari

es]

at 0

5:45

01

Dec

embe

r 20

13

Bio

/flocc

ula

tion/O

3+

H2O

2

Text

ilew

aste

wat

erA

ctiv

ated

sludge

trea

tmen

tfo

llow

edby

flocc

ula

tion

real

ized

85%

,99

.5%

&85

%D

OC,B

OD

&CO

Dcr

rem

ova

l(I

niti

alva

lues

,m

g/L,

277,

220,

780)

,w

hile

subse

quen

tO

3+

H2O

2trea

tmen

t(6

0m

in;

[H2O

2]:[

DO

C]=

1:1)

achie

ved

com

ple

tere

mova

lofB

OD

&ove

r50

%re

mova

lofre

sidual

DO

C,CO

Dcr

.Conve

rsel

y,si

ngl

eozo

nat

ion

resu

lted

inlo

wer

CO

Dre

mova

lan

din

crea

sed

BO

D(b

iodeg

radab

ility

).

126

(200

4)

[O3]/

bio

/[O

3]

Was

tew

ater

from

pla

nts

dye

ing

&finis

hin

gnat

ura

l/sy

nth

etic

fiber

s

Pre

ozo

nat

ion,due

tose

lect

ive

pre

fere

nce

ofO

3fo

rsi

mple

rorg

anic

com

pound,si

gnifi

cantly

dec

reas

edre

adily

bio

deg

radab

leCO

Dw

ithoutap

pre

ciab

lyaf

fect

ing

solu

ble

iner

tCO

D.Post

ozo

nat

ion

achie

ved

hig

her

colo

ran

din

ertCO

Dre

mova

lin

volv

ing

50%

less

ozo

ne

dose

com

par

edto

pre

ozo

nat

ion

atsa

me

conta

cttim

e&

ozo

ne

flux

rate

.

158

(200

2)

Bio

/san

dfilte

r(S

F)/O

3W

aste

wat

erfr

om

pla

nts

dye

ing

&finis

hin

gnat

ura

l/sy

nth

etic

fiber

s

Rem

ova

lofsu

spen

ded

solid

(&hen

ceCO

D)

by

bio

logi

cal&

SFpre

trea

tmen

ten

han

ced

subse

quen

ttw

ose

quen

ces

ofozo

nat

ion

(30

min

,40

g/m

3),

achie

ving,

inco

ntras

tto

60%

CO

Dre

mova

lby

ozo

nat

ion

alone

(with

outpre

trea

tmen

t),a

com

bin

ed65

%&

78%

CO

Dre

mova

laf

ter

firs

t&

seco

nd

ozo

nat

ion

cycl

e,re

spec

tivel

y.Com

ple

tedec

olo

ratio

nal

low

edw

aste

wat

erre

use

indye

ing

even

lightco

lors

.

43(2

001)

Bio

(anae

robic

/aer

obic

)/O

3/b

io(A

erobic

)Se

greg

ated

conce

ntrat

eddye

bat

hco

nta

inin

gC.I

reac

tive

Bla

ck5

&hig

hsa

ltco

nce

ntrat

ions.

Alth

ough

bio

logi

calpre

trea

tmen

tac

hie

ved

>70

%dec

olo

ratio

n,an

dozo

nat

ion

incr

ease

dbio

deg

radab

ility

info

llow

ing

aero

bic

reac

tor,

hig

hozo

ne

dose

of6

gO3/g

DO

Cw

asre

quired

toac

hie

veco

mbin

ed>

95%

dec

olo

ratio

n&

80%

DO

Cre

mova

lw

hile

notm

ore

than

30%

DO

Cw

asre

move

dby

bio

logi

calre

acto

r;in

tern

alre

cycl

ebet

wee

nozo

nat

ion

&ae

robic

stag

ere

com

men

ded

for

reduci

ng

ozo

ne

dose

.

124

(200

3)

Bio (a

nae

robic

–aer

obic

)/O

3

Colo

red

was

tew

ater

conta

inin

gm

elan

oid

ins

Ozo

nat

ion

(1.6

g/h–

11.5

g/h)

ofbio

logi

cally

(anae

robic

–aer

obic

)pre

trea

ted

was

tew

ater

(CO

D=

4580

,TO

C=

1000

,m

g/L)

achie

ved

71–9

3%dec

olo

ratio

n&

15–2

5%CO

Dre

mova

lin

30m

in

165

(200

3)

(Con

tin

ued

on

nex

tpa

ge)

345

Dow

nloa

ded

by [

Kan

sas

Stat

e U

nive

rsity

Lib

rari

es]

at 0

5:45

01

Dec

embe

r 20

13

TAB

LE4

.Typ

ical

Exa

mple

sofCom

bin

atio

ns

Bet

wee

nB

iolo

gica

lTre

atm

entan

dO

ther

Tech

nolo

gies

(Con

tin

ued

)

Tech

nolo

gyD

ye/w

aste

wat

erD

etai

lsRef

eren

ce(y

ear)

Bio

(anoxi

c/ae

robic

)/O

3Rea

ctiv

eN=N

bla

ck5

(vin

ylsu

lfonic

acid

),Rea

ctiv

eN=N

red

198

(vin

ylsu

lfonic

acid

&tria

zine)

,Rem

azolD

unke

lbla

uH

R(M

etal

lized

azo)N

=N,

Rem

azolG

old

gelb

RN

LN=N

,Rea

ctiv

eN=N

yello

w25

(Dic

hlo

roquin

oxa

line)

,Rea

ctiv

eN=N

Red

159

(Dic

hlo

rofluro

pyr

imid

ine)

Sequen

cing

anoxi

c/ae

robic

pro

cess

along

with

par

tialoxi

dat

ion

by

ozo

nat

ion

(concu

rren

tw

ithae

robic

phas

e)in

are

circ

ula

ted

syst

emyi

elded

com

ple

tedec

olo

ratio

nan

dsh

ow

edsy

ner

gist

icen

han

ced

bio

logi

calD

OC

rem

ova

l(9

0%)

asw

ellas

low

erco

nsu

mptio

nof

O3(5

mg/

mg

DO

C).

111

(199

8)

Bio

logi

cal+

phys

icoch

emic

al/O

3

Jean

sfinis

hin

gpla

nt

was

tew

ater

mix

edw

ithdom

estic

WW

(<30

%)

Pre

trea

tmen

tin

volv

ing

GA

C(2

00g/

8L)

&poly

elec

troly

tead

diti

on

inan

aero

bic

reac

tor

rest

ore

dnitr

ifica

tion

activ

ity&

impro

ved

sludge

settle

abili

tyofth

esu

bse

quen

tae

robic

reac

tor

with

acu

mula

tive

96%

CO

D&

88%

colo

rre

mova

l,w

hile

follo

win

gozo

nat

ion

achie

ved

70%

reusa

ble

wat

er.

205

(199

9)

Bio

/O3

Nap

hth

alen

e-1,

5-dis

ulfonic

acid

(NA

DSA

),a

dye

pre

curs

or

Com

bin

edfixe

d-b

edbio

reac

tor

(equip

ped

with

a1.

5μ

mm

embra

ne

for

solid

/liq

uid

separ

atio

n)

and

ozo

nat

ion

trea

tmen

tin

sem

icontin

uous

fash

ion

achie

ved

ca.80

%D

OC

rem

ova

l(I

niti

al=

170–

340

mg/

L)w

ith>

50%

reduct

ion

inozo

ne

consu

mptio

n(0

.8m

ol

O3/m

olD

OC)

asco

mpar

edto

singl

euse

ofozo

nat

ion

only

.

30(2

003)

Bio

/O3/g

ranula

rac

tivat

edC(G

AC)

Dom

estic

+te

xtile

indust

ry(5

0–70

%)

was

tew

ater

Feed

wat

er[o

nG

AC]:

CO

D=

128–

135

mg/

L,TO

C=

16–1

8m

g/L;

C-a

dso

rptio

nis

less

effe

ctiv

eaf

ter

the

ozo

nat

ion,re

sidual

CO

D(>

70)

&co

lor

(ove

roptic

aldet

ectio

n)

unsu

itable

for

reuse

;“B

io+F

locc

ula

tion+O

3+G

AC”

pro

pose

d.

23(1

999)

O3/b

iolo

gica

lac

tivat

edC

(BA

C)

Nat

ura

lco

loring

mat

ter

(Hum

icsu

bst

ance

s)B

iodeg

radab

leD

OC

incr

ease

dby

pre

ozo

nat

ion

was

subse

quen

tlybio

deg

raded

rath

erth

anbei

ng

sim

ply

adso

rbed

on

BA

Can

d,

ther

eby,

incr

ease

dB

AC

serv

ice

time.

221

(199

7)

Coag

ula

tion

or

cata

lytic

H2O

2/b

ioB

asic

dye

Chem

ical

pre

cipita

tion

(FeC

l 3=

400

mg/

L;pH

=9.

5),des

pite

resu

lting

in41

%CO

Dre

mova

lfr

om

raw

was

tew

ater

,co

uld

notim

pro

vebio

deg

radab

ility

.A

fter

par

tialoxi

dat

ion

(H2O

2/C

OD

=1;

Fe+3

=50

0m

g/L;

pH

=3.

5;1

day

)63

%CO

Dre

mova

l&

was

tew

ater

bio

deg

radab

ility

was

achie

ved.

15(1

999)

346

Dow

nloa

ded

by [

Kan

sas

Stat

e U

nive

rsity

Lib

rari

es]

at 0

5:45

01

Dec

embe

r 20

13

Bio

logi

calfixe

dG

AC

bed

Aci

dN

=N(T

ectil

on

Red

2B,

Tect

ilon

ora

nge

3G)

GA

Cbed

inocu

late

dw

ithsp

ecia

lch

rom

ophoric

bond-c

leav

ing

&ar

om

atic

ring-

clea

ving

bac

teria,

afte

rin

itial

accl

imat

izat

ion

per

iod,

outp

erfo

rmed

conve

ntio

nal

GA

Cbed

;th

ebac

terial

activ

ity,how

ever

,dec

reas

edaf

ter

certai

nper

iod

due

tola

ckofnutrie

ntan

d/o

rdis

solv

edoxy

gen.[D

ye=

100

mg/

L].

218

(199

6)

Bio

(anoxi

c/ae

robic

)/o

xyge

nen

rich

edB

AC

Mix

edte

xtile

dye

ing–

printin

g(R

eact

ive

blu

edye

)an

dal

kali

pee

ling

was

tew

ater

The

initi

alco

nta

ctbio

-film

syst

emim

pro

ved

bio

deg

radab

ility

while

subse

quen

tB

AC

syst

em,due

toen

han

ced

bio

deg

radat

ion

induce

dby

hig

hD

Ole

velm

ainta

ined

by

hig

hpre

ssure

(0.4

Mpa)

,ac

hie

ved

hig

htu

rbid

ity,co

lor,

CO

D,&

NH

3-N

rem

ova

lw

ithco

ncu

rren

tpro

longe

dca

rbon-b

edlif

e,th

eper

form

ance

esse

ntia

llybei

ng

bet

ter

than

norm

alB

AC

or

pure

GA

Cpro

cess

.

177

(200

4)

Bio

logi

calfluid

ized

GA

Cbed

Ble

ached

kraf

tm

illse

condar

yef

fluen

tco

nta

inin

gre

frac

tory

org

anic

slik

elig

nin

,w

hic

hm

aybe

consi

der

edto

be

repre

senta

tive

ofdye

stru

cture

.

57%

DO

Cre

mova

l(initi

al=

280–

330

mg/

L;0.

9g

DO

C/k

gA

C.d)

by

phys

ical

adso

rptio

non

GA

Can

dbio

mas

sfo

llow

edby

bio

deg

radat

ion

&des

orp

tion

achie

ving

par

tialbio

rege

ner

atio

nof

GA

Cw

asobse

rved

.Com

bin

ed‘b

iore

gener

atio

n/p

hys

ical

(US–

IR)–

par

tialre

gener

atio

n(5

0%ofG

AC

volu

me)

’ach

ieve

d30

–40%

impro

ved

rem

ova

lw

ith2%

wei

ghtlo

ss/r

egen

erat

ion,w

hic

his

smal

ler

than

loss

due

toso

lere

gener

atio

nby

phys

ical

met

hod.

217

(199

4)

Bio

+re

circ

ula

ted

pow

der

edac

tivat

edC

(PA

C)

/flocc

ula

tion

Dom

estic

effluen

tm

ixed

with

reac

tive

dye

(Cib

acorn

yello

wCR01

,Cib

acorn

yello

wF3

R,

Cib

acorn

red

C2G

,Cib

acorn

red

CR,

Cib

acorn

Red

FB,

Cib

acorn

blu

eFB

,Le

vafix

yello

wK

R,Le

vafix

red

KG

R,Rem

azolre

d,

Rem

azolbla

ck)

/sal

ts/a

uxi

liary

chem

.

[Initi

alCO

D=

775–

4035

,pH

=9–

12];

Rec

ircu

latio

nofPA

C(1

3m

g/L)

resu

lted

inef

fect

ive

rem

ova

lofdye

san

dhal

oge

nat

ed/r

efra

ctory

org

anic

sal

ong

with

optim

um

use

ofPA

Cw

hic

his

only

par

tially

load

edif

notre

cycl

ed.

156

(199

9)

Pow

der

edac

tivat

edca

rbon

or

org

anic

flocc

ula

ntad

diti

on

inbio

logi

calsy

stem

Cotton

text

ilew

aste

wat

erO

nly

bio

(SRT

=30

day

s,H

RT

=16

day

s):94

%CO

Dre

mova

l,36

%dec

olo

ratio

n.Com

bin

ed(P

AC

=20

0m

g/L

or

Org

anic

flocc

ula

nt=

120

mg/

L):D

ecolo

ratio

nim

pro

ved

up

to78

%,th

eorg

anic

flocc

ula

nt

pro

duci

ng

less

exce

sssl

udge

than

PAC.

161

(200

2)

Pow

der

edac

tivat

edca

rbon

additi

on

inbio

logi

calsy

stem

(PA

CT)

Aci

dN

=Nora

nge

7,C.I.15

510

The

beh

avio

rofCO

Dre

mova

lw

asth

esa

me

butth

edye

rem

ova

lw

asbet

ter

inth

ePA

CT

than

inth

eco

nve

ntio

nal

activ

ated

sludge

pro

cess

.49

(199

7)

(Con

tin

ued

on

nex

tpa

ge)

347

Dow

nloa

ded

by [

Kan

sas

Stat

e U

nive

rsity

Lib

rari

es]

at 0

5:45

01

Dec

embe

r 20

13

TAB

LE4

.Typ

ical

Exa

mple

sofCom

bin

atio

ns

Bet

wee

nB

iolo

gica

lTre

atm

entan

dO

ther

Tech

nolo

gies

(Con

tin

ued

)

Tech

nolo

gyD

ye/w

aste

wat

erD

etai

lsRef

eren

ce(y

ear)

Pow

der

edac

tivat

edca

rbon

additi

on

inbio

logi

calsy

stem

Aci

dN

=Nora

nge

7,C.I.

1551

0U

nder

ahig

her

bio

mas

sco

nce

ntrat

ion

(>3

g/L)

,th

eca

rbon

par

ticle

sar

etrap

ped

inth

efloc

mat

rix

and

lose

thei

rpro

per

ties

ofad

sorp

tion

hin

der

ing

mic

robia

lgr

ow

than

ddye

rem

ova

l.

141

(199

7)

Pow

der

edac

tivat

edca

rbon

additi

on

inbio

logi

calsy

stem

Dis

per

sed,direc

t,ac

id&

bas

icdye

s;an

ionic

/nonio

nic

det

erge

nts

.

Rem

ova

lef

fici

ency

rise

sfr

om

55.8

to75

.6%

(CO

D)

and

from

78to

98.5

%(T

OC).

The

nitr

ifica

tion–

den

itrifi

catio

nca

pac

ityofth

esy

stem

also

incr

ease

s,pro

bab

lydue

tohig

hco

nce

ntrat

ion

of

nitr

ifyi

ng–

den

itrifyi

ng

bac

teria

on

the

PAC

surf

ace.

197

(198

4)

Fluid

ized

bed

reac

tor

conta

inin

gco

mple

xpel

lets

ofw

hite

rot

fungu

s&

activ

ated

carb

on

Aci

dN

=Nvi

ole

t7

Com

ple

xm

ycel

ium

pel

lets

with

abla

ckco

reofac

tivat

edca

rbon

(pre

par

atio

n:5

mlin

ocu

lum

+0.

6g

A.C

+200

mlm

ediu

m),

by

reta

inin

gnec

essa

ryfu

nga

lm

etab

olit

es,outp

erfo

rmed

stan

dal

one

applic

atio

noffu

ngi

or

activ

ated

C,or

even

sim

ple

additi

on

of

activ

ated

Cin

fungi

reac

tor;

the

dec

olo

ratio

n(9

5%)

bei

ng

bet

ter

inre

pea

ted

bat

chre

acto

r(5

0g

wet

com

ple

xpel

let/

L;20

hre

tentio

n;

500

mg/

Ldye

)th

anin

contin

uous

reac

tor.

235

(200

0)

Act

ivat

edca

rbon

(AC)-

amen

ded

anae

robic

bio

reac

tor

Hyd

roly

zed

reac

tiveN

=Nre

d2,

Aci

dN

=Nora

nge

7A

C,in

additi

on

toits

adso

rptio

nca

pac

ity,as

abio

logi

cally

rege

ner

able

redox

med

iato

rdue

toquin

one

surf

ace

group

on

it,en

han

ced

azo

dye

reduct

ion,ac

hie

ving

97–9

0%dec

olo

ratio

nfo

r13

0day

s[4

2m

g/L

dye

;35

g/L

VSS

;H

RT

=5.

5hr;

10g/

LA

C].

234

(200

3)

Bio

/NF

Dilu

ted

wooldye

ing

bat

hco

nta

inin

gm

etal

com

ple

x&

acid

dye

(origi

nal

dye

conce

ntrat

ion

8g/

L)

Dilu

ted

dye

bat

h(C

OD

=2

g/L)

afte

rac

tivat

edsl

udge

trea

tmen

t(C

OD

=20

0m

g/L)

was

subje

cted

tonan

ofiltr

atio

nth

atre

sulte

din

reuse

stan

dar

dper

mea

te(f

urther

99%

colo

r&

88%

CO

Dre

mova

l)w

ithle

ssfo

ulin

gas

com

par

edto

that

for

direc

tnan

ofiltr

atio

nofdye

bat

hs.

Ozo

nat

ion

ofm

embra

ne–

rete

nta

tebef

ore

recy

clin

gto

activ

ated

sludge

pro

cess

was

reco

mm

ended

.

33(2

001)

Bio

/mem

bra

ne

(+al

um

inum

poly

chlo

ride)

Dom

estic

+Te

xtile

indust

ry(8

0%by

org

anic

load

)w

aste

wat

er

Mic

rofiltr

atio

n(3

00,0

00D

,cr

oss

-flow

)fo

llow

edby

nan

ofiltr

atio

n(1

50D

,10

bar

,sp

iral

wound)

along

with

alum

inum

poly

chlo

ride

(70

mg/

L)pro

duce

dre

cycl

able

wat

er(C

OD

<10

mg/

L,co

nduct

ivity

<40

us/

cm,neg

ligib

lere

sidual

colo

r)fr

om

the

seco

ndar

yef

fluen

t;al

tern

atel

y“c

lariflocc

ula

tion

(Dose

:4

ppm

,vo

l.)+

multi

med

iafiltr

atio

n+

low

-pre

ssure

RO

(58

D,4

bar

,10

L/m

2.h

,sp

iral

wound)”

seem

edpre

fera

ble

inte

chno-e

conom

ical

anal

ysis

.

183

(199

9)

348

Dow

nloa

ded

by [

Kan

sas

Stat

e U

nive

rsity

Lib

rari

es]

at 0

5:45

01

Dec

embe

r 20

13

‘Bio

+pow

der

edac

tivat

edC,

(BPA

C)’/M

icro

filtr

atio

n

Seco

ndar

yse

wag

eef

fluen

tco

nta

inin

gre

frac

tory

org

anic

slik

elig

nin

,w

hic

hm

aybe

consi

der

edto

be

repre

senta

tive

ofdye

stru

cture

.

PAC

dose

of0.

5g/

L.52

%TO

Cre

move

din

BPA

Cco

nta

ctor

(hig

her

than

PAC

only

),ad

diti

onal

16.8

%w

asre

ject

edby

mem

bra

ne.

189

(199

7)

Bio

/NF

or

O3

Was

tew

ater

from

printin

g,dye

ing

&finis

hin

gte

xtile

pla

nt

Bio

logi

cally

trea

ted:Conduct

ivity

(mS/

cm)

2.8–

3.33

;CO

D(m

g/L)

200–

400.

Folo

win

gbio

logi

caltrea

tmen

ti)

Nan

ofiltr

atio

n(fl

ow

rate

=20

0–40

0L/

h,TM

P=

20bar

):CO

D<

50m

g/L;

Conduct

ivity

=0.

39–0

.51

mS/

cm.ii)

O3:CO

D=

286

(30

min

),70

(210

min

)iii

)O

3+U

V:CO

D<

50(3

0m

in),

<50

(210

min

).O

zonat

ed(w

ith/w

ithoutU

V)

was

tew

ater

can’t

be

reuse

dfo

rrinsi

ng

due

toneg

ligib

leco

nduct

ivity

rem

ova

lal

though

the

pro

cess

isfr

eefr

om

reje

ctst

ream

gener

atio

n.

27(2

003)

Bio

/NF/

O3

Text

ilew

aste

wat

erm

ixed

with

dom

estic

(20%

)w

aste

wat

er

Ozo

nat

ion

(12

ppm

,2h

)ofm

embra

ne

conce

ntrat

es(C

OD

=59

5,TO

C=

190,

Conduct

ivity

=5

ms/

cm,B

OD

5=

0,EC

20=

34%

,pH

=7.

9)re

sulti

ng

from

nan

ofiltr

atio

n(1

0bar

,30

0L/

h)

ofbio

logi

cally

trea

ted

seco

ndar

yte

xtile

effluen

tac

hie

ved

30%

,50

%,an

d90

%re

duct

ion

inTO

C,CO

D,an

dto

xici

ty,re

spec

tivel

y,m

akin

gth

eef

fluen

tre

cycl

able

tobio

logi

caltrea

tmen

t.

134

(199

9)

Bio

/NF/

photo

cata

lytic

mem

bra

ne

reac

tor

Text

ilew

aste

wat

erVis

ible

Ligh

tm

edia

ted

Fento

n(N

afion-F

e+3m

embra

ne,

1.78

%;H

2O

2,

10m

M)

trea

tmen

t(3

h)

ofm

embra

ne

conce

ntrat

es(C

OD

=49

6,TO

C=

110,

pH

=8)

resu

lting

from

nan

ofiltr

atio

nofbio

logi

cally

trea

ted

seco

ndar

yte

xtile

effluen

tre

sulte

din

50%

,20

–50%

,an

d50

%re

duct

ion

inTO

C,ab

sorb

ance

,an

dto

xici

ty,re

spec

tivel

y.Fu

rther

deg

radat

ion

thro

ugh

bio

logi

caltrea

tmen

tposs

ible

atlo

wco

stdue

tobio

com

pat

ible

pH

ofth

eef

fluen

t.

17(1

999)

Bio

/cla

riflocc

ula

tion/G

AC

or

bio

/mem

bra

ne

(MF

→N

F)/O

3

Text

ilew

aste

wat

erm

ixed

with

dom

estic

(25–

30%

)w

aste

wat

er

Due

toco

stofm

embra

ne

and,CO

D&

salin

ityin

crea

sein

bio

logi

cal

pla

ntby

mem

bra

ne

rete

nta

te,te

chno-e

conom

ical

anal

ysis

favo

red

post

trea

tmen

tofbio

logi

cally

trea

ted

effluen

tby

‘cla

riflocc

ula

tion

follo

wed

by

GA

Cad

sorp

tion’o

ver‘m

embra

ne

filtr

atio

n(M

Ffo

llow

edby

NF)

follo

wed

by

ozo

nat

ion’,

alth

ough

the

latter

pro

duce

dbet

ter

&co

nst

antqual

ity(s

often

ed,co

lorles

s)re

cycl

able

effluen

t.

182

(199

9)

Bio

/san

dfiltr

atio

n(S

F)/m

embra

ne

(MF

follo

wed

by

NF)

Dye

ing

was

tew

ater

100%

SS,78

%tu

rbid

ity&

30%

CO

Dre

mova

lby

SF(2

bar

)&

MF

(3.5

bar

;40

0L/

h);

13%

colo

rre

mova

lby

MF,

and

rem

ainin

gCO

D&

colo

rre

mova

lby

NF

(6.5

–7bar

)co

ntrib

ute

dto

ove

rall

94%

colo

r&

82%

CO

Dre

mova

lal

ong

with

conduct

ivity

rem

ova

lm

akin

gth

etrea

ted

wat

erre

usa

ble

for

dye

ing.

139

(200

2)

349

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the other hand, the dose of coagulants and consequently the quantity of thechemical sludge after biological treatment are smaller compared to those incoagulation followed by biological treatment.57,75,100

Besides coagulation, a variety of other treatment processes may be com-bined with biological treatment. Very often a certain physicochemical processis placed before129 and/or after130 an advanced oxidation process. The bio-logical process is then applied either as the very first,100 penultimate,3 or asthe last129 treatment unit. In view of the abundance of bioresistant and toxiccontaminants in dye wastewater, physicochemical and advanced oxidativepretreatment prior to biological treatment appears to be a rational option. Thechoice between physicochemical and oxidative pretreatment, however, de-pends on the specific wastewater; usually an astute stream separation wouldfacilitate application of appropriate treatment system for different streams.3

On the contrary, especially isolated/acclimatized microbes are usually re-quired for effective biological pretreatment.100,115 In order to obtain reusablewater, an elaborate treatment train composed of conventional physicochemi-cal and advanced oxidation processes may be placed after biological pretreat-ment. While numerous such combinations have been reported in literature,the common underlying principle is to choose a combination so as to furnisha complete system eliminating limitations of the individual techniques. Forinstance, the fact that high concentrations of suspended or colloidal solids inthe wastewater may impede the advanced oxidation processes necessitatessufficient prior removal of these materials by physicochemical treatment.43,100

Conversely, enhancement of COD removal (e.g., after ozonation)127 or im-provement of settleability of sludge (e.g., after electrofloatation)43,130 mayrequire physicochemical treatment subsequent to AOPs.

4.2.2. INTEGRATED PARTIAL OXIDATION/BIODEGRADATION

In contrast to the conventional pre- or posttreatment concepts, where pro-cess designs of different components are independent of each other, a ratherinnovative approach is the so-called “integrated processes” where the effec-tiveness of combining biological and other treatments is specifically designedto be synergetic rather than additive.134 A typical example of such processesis combination of advanced oxidation with an activated sludge treatmentwhere the chemical oxidation is specifically aimed to partially degrade therecalcitrant contaminants to more easily biodegradable intermediates, therebyenhancing subsequent biological unit and simultaneously avoiding the highcosts of total mineralization by AOP. During recent years myriad studies deal-ing with partial preoxidation of dye wastewater, involving virtually all sortsof AOPs, have been reported. Some of these studies include partial oxida-tion by ozonation,39 H2O2,46 photocatalysis,178 photo (solar)-Fenton,207 wetair oxidation,169 combined photocatalysis and ozonation/H2O2,146,200 pho-toelectrochemical process,6 sub- and supercritical water oxidation,103 andelectron-beam treatment.81 The bulk of such studies report on improvement

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of biodegradability (as revealed by biological oxygen demand [BOD]/CODratio or partial oxidation parameter92) and reduction of toxicity (using bioas-say, e.g., bioluminescence test) following some AOP treatment without in-volving actual experiment in biological reactor. However, complete resultsfrom actual investigation in biological system following partial oxidation,as listed in Table 4, are also available. Careful consideration of character-istics of each AOP would facilitate selection of a proper preoxidation pro-cess for rendering wastewater more amenable to biological treatment. Forinstance, Fenton-like treatment using Nafion-Fe+3 membrane, rather than di-rect addition of iron salt,17 or immobilized TiO2 photocatalysis rather thanthe photo-Fenton process,164 would facilitate further biological treatment un-der biocompatible pH making neutralization redundant. Mantzavinos et al.138

have proposed a step-by-step approach to evaluate chemical pretreatmentfor integrated systems.

The combined oxidation and subsequent biodegradation make it nec-essary to set the optimal point of oxidative treatment. Further oxidation maynot lead to any significant changes in the molecular weight distribution, butresult in an increasing mineralization of low-molecular-weight biodegradablesubstances.92 Hence it is rational to adopt the shortest possible preoxidationperiod and remove the biodegradable portion using cost-effective biologicalprocess. Nonetheless, the extent of combined COD removal achievable withthis strategy may be limited in some cases, making utilization of a longer ox-idation period necessary and the following biological process redundant.170

An internal recycle between the oxidation and biological stage has beenrecommended for reducing chemical dose in such circumstances.124 Do-gruel et al.56 pointed to the selective preference of ozone for simpler readilybiodegradable soluble COD fractions, which leads to unnecessary consump-tion of the chemical. They suggested preozonation of segregated recalcitrantstreams from the dye house prior to biological treatment of the mixed wholeeffluent. If a considerable amount of biodegradable compounds originallyexists in the wastewater, the preoxidation step obviously will not lead toa significant improvement of biodegradability; rather, it will cause unnec-essary consumption of chemicals. In such a case a biological pretreatment(removing biodegradable compounds) followed by an AOP (converting non-biodegradable portion to biodegradable compounds with less chemical con-sumption) and a biological polishing step may prove to be more useful.85,213

4.2.3. BIODEGRADATION/ADSORPTION

Owing to limited effectiveness of conventional biological treatment for re-calcitrant textile wastewater composed of recalcitrant textile chemicals anddyes, various adsorbents and chemicals,161 predominantly activated carbon,have been directly added into the activated sludge systems in certain stud-ies. The fact that the additional removal of soluble organic matter (COD andtotal organic carbon, TOC ) in such a system over that in a conventional

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system cannot be explained by probable contribution of adsorbent as pre-dicted by adsorption isotherms141 has persuaded researchers to hypothe-size a synergistic relationship between activated carbon and microorganism(“enhanced microbial degradation and bioregeneration of adsorbent”).167 En-hanced biodegradation has been attributed to the ability of adsorbent to actas a modulator, by immediately adsorbing high concentrations of the toxiccompounds, and thus regulating the concentration of the free toxic material,together with providing an enriched environment for microbial metabolismon the liquid–solid surface, on which microbial cells, enzymes, organic ma-terials, and oxygen are adsorbed.1 Conversely, bioregeneration of activatedcarbon has been explained by extracellular biodegradation of adsorbed or-ganics by microbial enzymes excreted into carbon micropores.197,225 Themain step in dye removal for activated carbon-amended biological processis microbial degradation, which is higher than adsorption both on activatedcarbon and on biomass.49 Accordingly, although the dye removal in that pro-cess has frequently been reported to be better than in the conventional ac-tivated sludge process,161,197 the mode of COD removal may be the same.49

Under a higher biomass concentration (>3 g/L), the carbon particles are,however, trapped in the floc matrix and lose their properties of adsorption,thereby hindering microbial growth and dye removal.141 Although simultane-ous adsorption and biodegradation treatment occasionally has been demon-strated as a mere combination of adsorption and biodegradation without anymutual enhancement159 and has raised controversies in the bioregenerationhypothesis,225 application of this process to the treatment of textile wastew-aters is an important economic improvement. It allows the removal of CODand color from textile wastewater in a single step with no additional physic-ochemical treatment.141 To minimize reactor volume, a hydraulic retentiontime as low as possible is practically expected. This in turn, however, ren-ders powdered activated carbon (PAC) partially loaded. Its optimum use maybe realized by recirculation of PAC.156 In addition to its adsorption capac-ity, activated carbon has also been reported to enhance anaerobic azo dyereduction234 by acting as a biologically regenerable redox mediator due toquinone surface groups on it. Zhang et al.235 documented an innovative ap-proach involving a fluidized bed reactor containing complex pellets of whiterot fungus and activated carbon. The reactor, by retaining necessary fungalmetabolites, surpassed stand-alone application of fungi or activated C. Theprocess was claimed to be superior to simple addition of activated C in fungireactor.

Fixed granular activated carbon (GAC) beds inoculated with specialchromophoric bond-cleaving and aromatic ring- cleaving bacteria, after aninitial acclimatization period, have been reported to outperform the con-ventional GAC bed.218 However, the bacterial activity in the GAC bed maydecrease after a certain period due to lack of nutrient and/or dissolved oxy-gen (DO). Maintenance of a high DO level by a pressurized system may

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ensure achievement of stable removal (color and COD) with concurrentprolonged carbon-bed life.177 A novel approach entailing partial bioregener-ation (physical adsorption on fluidized biological GAC followed by biodegra-dation and desorption), coupled with complementary periodic physical re-generation of 50% of total GAC, has been reported by Vuoriranta et al.217

The system was observed to achieve an improved COD and color removalapart from reduction in regeneration cost and weight loss of GAC. Moreover,the system has the added advantage of allowing biological activity in GACmedium for subsequent use. Some means of improvement of biodegrad-ability, be it biological177 or advanced oxidation process221, will certainlyfortify biological activity in the subsequent biological GAC. However, in caseof oxidative degradation, subsequent substrate adsorption on carbon mayplummet.23 Carbon-biocatalyst amalgamation in adsorption cartridges for de-coloration has been commercialized (BIOCOL) in the United Kingdom.48

4.2.4. BIODEGRADATION/MEMBRANE FILTRATION

4.2.4.1. Chronological application. For reusable water production,researchers have recurrently referred to nanofiltration (or low-pressurereverse osmosis) of biologically treated colored wastewater, since thisoption involves less fouling as compared to that for direct nanofiltrationof dye baths.33 Some references have put forward inclusion of sandfiltration/multimedia filtration and/or microfiltration in between biologicaltreatment and nanofiltration.139,182 Site-specific techno-economical analysisis usually recommended to ascertain the best combination.183 Notwithstand-ing the disposal problem of the reject stream emanating from membraneseparation, it may be preferred to ozonation as a posttreatment to derivereusable water from secondary wastewater, in view of the fact that the latterwould realize negligible conductivity removal.27 Conversely, provision ofadvanced oxidation of biologically treated wastewater before sending itfor nanofiltration has been reported to yield further increased membranelife.28,96 Addition of facility for partial oxidative degradation (e.g., ozonation)of membrane concentrate to the aforementioned treatment train of nanofil-tration of secondary wastewater may furnish a quasi-“closed loop” system, inthat the partially oxidized products (detoxified) may be recycled to biologicaltreatment.120,134 Such practice may, however, give rise to concern aboutsalinity increase in biological plant. Wu et al.224 reported a cost-competitivedye wastewater reclamation system involving deep aeration activated sludgeprior to bioactivated carbon and nanofiltration, which, in addition to yield-ing prolonged membrane life and recovery/reuse potential, allowed directdischarge of concentrated membrane retentate. Illustrations of chronologicalapplication of membrane and biological treatment in the case of segregatedtextile wastewater streams are also available. Rinsing water may be reused af-ter reclamation by membrane, while the concentrated waste may be degradedin anaerobic digester.219 This example may be further extended to filtration of

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the segregated dye bath effluent utilizing a membrane of appropriate molec-ular cutoff size that allows passage of salt but retains dye. Consequently,dye bath water containing salt may be reused for dye bath reconstruction,while the membrane concentrate may be degraded in an anaerobic digester.

4.2.4.2. Membrane bioreactors. The membrane bioreactor (MBR),a remarkable improvement over the conventional activated sludgetreatment,214 has been set forth as a promising option in colored wastew-ater treatment. MBR for decoloration has often been envisioned in con-junction with simultaneous adsorption.189 A treatment scheme comprisingan activated carbon-amended anaerobic reactor preceding aerobic MBR re-alizes stable decoloration along with high TOC removal, with concurrentimprovement in activated sludge dewaterability and reduction in filtrationresistance.157 For reuse purpose, MBRs have occasionally been envisagedas the main treatment process prior to a polishing nanofiltration step,188

or even as the core of a rather elaborate treatment train including anaer-obic/aerobic pretreatment prior to MBR and ozonation following it.112 Aninnovative approach notable in contemporary literatures involves the mem-brane (submerged78/sidestream62,102)-separated fungi reactor, which couplesthe excellent degradation capability (due to nonspecific extracellular oxida-tive enzymes) of white-rot fungi with the inherent advantages of membranebioreactor. The MBR system has been envisaged to be capable of coping withthe impedances in implementation of white-rot fungi in large-scale industrialwaste treatment, such as rather slow fungal degradation,147 loss of the ex-tracellular enzymes and mediators with discharged water,235 and excessivegrowth of fungi.236 Development of such a system offering stable 99% decol-oration and 97% TOC removal from synthetic textile wastewater along withavoidance of membrane fouling has been recently documented.78

5. COST ANALYSIS

The overall costs are represented by the sum of the capital costs, the operatingcosts, and maintenance costs. Most costs are very site specific, and for a full-scale system these costs strongly depend on the flow rate of the effluent, theconfiguration of the reactor, the nature (concentration) of the effluent, andthe pursued extent of treatment. The location is also important, not only forits obvious influence on land price but also due to its climatic influence, forexample, duration and intensity of sunlight influencing efficiency of solar-Fenton process.187 Table 5 lists some cost values quoted in different studies.

Studies generally show that AOPs and membrane processes are morecostly than biological processes. However, because of the numerous site-specific factors and assumptions inevitably made in such estimates, a directcomparison is difficult. Especially, indiscriminate comparison of costs (inper cubic meter or per kilogram contaminant) of segregated versus mixedstreams would be simply misleading, as the latter remove significantly less

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TAB

LE5

.Cost

Info

rmat

ion

Per

tain

ing

toD

iffe

rentCom

bin

atio

ns

Purp

ose

&te

chnolo

gyCost

Dye

/was

tew

ater

Rem

arks

Ref

eren

ce(y

ear)

Direc

tnan

ofiltr

atio

nfo

rre

use

US$

0.53

–1.1

9a

m–3

Segr

egat

eddye

ing

and

rinsi

ng

was

tew

ater

Runnin

gco

st(1

5bar

,flow

rate

=4.

5m

/s,flux

=0.

2–1.

1m

3/h

)only

;sa

ving

ofw

ater

supply

cost

due

tore

cycl

ing

not

consi

der

ed.

215

(200

1)

Direc

tnan

ofiltr

atio

nfo

rre

use

US$

0.81

m−3

Was

tew

ater

from

dye

bat

hco

nta

inin

gac

id,dis

per

sean

dm

etal

com

ple

xdye

Cost

incl

udes

both

capita

l&

oper

atin

gco

st(fl

ow

rate

=10

00m

3/d

).Sa

ving

ofw

ater

supply

cost

(2–3

US$

m−3

)due

tore

cycl

ing

notco

nsi

der

ed.

108

(200

1)

Direc

tnan

ofiltr

atio

nfo

rre

use

ofw

ater

and

dye

bat

hsa

lt

US$

1.36

m−3

Rea

ctiv

edye

bat

hw

aste

wat

erco

nta

inin

ghig

ham

ountofN

aCl

Flow

rate

=20

0m

3/d

;quote

dco

sthas

bee

nca

lcula

ted

usi

ng

the

oper

atin

gan

din

vest

men

tco

stm

entio

ned

inth

ere

fere

nce

(ass

um

ing

10-y

rin

vest

men

t).A

pay

bac

kofin

vest

men

tco

stm

aybe

expec

ted

inle

ssth

an2

yrs

with

the

savi

ng

ofw

ater

supply

cost

,w

aste

wat

erdis

posa

lco

st,N

aClan

dhea

ten

ergy

.

110

(200

4)

Reu

seofw

ater

and

chem

ical

resi

dues

by

(i)

mem

bra

ne

filtr

atio

n,

(ii)

chem

ical

pre

cipita

tion,(iii)

activ

ated

C,(iv)

counte

rcurr

ent

evap

ora

tion

US$

m−3

(i)1

,(ii)1–

2,(iii)

10–1

5,(iv)

10–1

5

Rea

ctiv

edye

ing

ofco

tton

Cost

incl

udes

oper

atin

gan

din

vest

men

tco

st.

219

(199

6)

Ele

ctro

coag

ula

tion

asso

letrea

tmen

tU

S$0.

1–0.

3(k

gCO

Dre

move

d)−1

Mix

ture

ofex

hau

stdye

ing

solu

tions

Oper

atin

gco

st(incl

udin

gen

ergy

and

mat

eria

lco

st)

for

iron

and

alum

inum

elec

trode,

resp

ectiv

ely.

Labor,

mai

nte

nan

ce,an

dso

lid/l

iquid

separ

atio

nco

stnotco

nsi

der

ed.[W

aste

wat

erCO

D=

3422

mg/

L;ar

ound

70%

rem

ova

l.]

21(2

004)

Com

bin

edtrea

tmen

tw

ithH

2O

2/O

3/U

VU

S$6.

54m

−3W

aste

wat

erco

nta

inin

gdis

per

sedye

stuff

&pig

men

ts

Cost

ofco

nsu

mab

les

only

.Le

ssye

tsa

tisfa

ctory

(>90

%)

CO

Dre

mova

lby

Fento

n’s

reag

entat

alo

wer

(0.2

3U

S$)

unit

cost

.12

(200

4)

Com

bin

edtrea

tmen

tw

ithO

3/e

lect

ron

bea

mto

mee

tdis

char

gest

andar

d

US$

3.17

m−3

Mola

sses

pro

cess

ing

was

tew

ater

(inte

nse

lyco

lore

dan

dre

calc

itran

t)

Cost

incl

udes

both

capita

l&

oper

atin

gco

st(fl

ow

rate

=50

m3/h

).69

(199

8)

(Con

tin

ued

on

nex

tpa

ge)

355

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TAB

LE5

.Cost

Info

rmat

ion

Per

tain

ing

toD

iffe

rentCom

bin

atio

ns

(Con

tin

ued

)

Purp

ose

&te

chnolo

gyCost

Dye

/was

tew

ater

Rem

arks

Ref

eren

ce(y

ear)

Com

bin

edtrea

tmen

tw

ithm

ulti

stag

eco

agula

tion/O

3

1.57

CU

S$to

n−1

h−1

Dye

man

ufa

cturing

was

tew

ater

Appro

xim

ate

cost

consi

der

ing

elec

tric

ityco

stofozo

ne

gener

atio

nonly

(chem

ical

cost

mad

esm

allco

ntrib

utio

n).

86(1

998)

Com

bin

edtrea

tmen

tw

ithad

sorp

tion

+U

V–H

2O

2

US$

1m

−3Rea

ctiv

eEve

rzolB

lack

-GSP

Oper

atin

gco

st(c

onsu

mab

les

and

mai

nte

nan

ce)

for

dec

olo

ratio

n&

50%

TO

Cre

mova

lfr

om

36ppm

dye

solu

tion.

91(2

002)

Com

bin

edtrea

tmen

tw

ithcl

arifl

occ

ula

-tio

n/o

zonat

ion/m

embra

ne

(UF)

for

reusa

ble

wat

er

US$

0.52

bm

−3W

aste

wat

erfr

om

carb

oniz

ing,

dye

ing

and

fulli

ng

pro

cess

Flow

rate

=15

00m

3/d

;Cost

incl

udes

oper

atin

gan

din

vest

men

tco

st.A

pay

bac

kofin

vest

men

tco

stm

aybe

expec

ted

in3

yrw

ithth

esa

ving

ofw

ater

supply

cost

.

139

(200

2)

Photo

(sola

r)-F

ento

npre

trea

tmen

t(f

or

subse

quen

tbio

logi

cal

trea

tmen

t)

US$

22m

−3D

yein

term

edia

te(5

-am

ino-6

-met

hyl

-2-

ben

zim

idaz

olo

ne

AM

BI)

-conta

inin

gw

aste

wat

er;4

gC/L

Cost

(for

1.2

Lh

−1m

−2)

incl

udes

annual

ized

capita

l,co

nsu

mab

les

&m

ainte

nan

cebutex

cludes

hig

hla

nd

cost

(US$

200–

400

m−2

)in

Switz

erla

nd.Eco

nom

ical

than

wet

air

oxi

dat

ion

or

inci

ner

atio

n(U

S$20

0m

−3).

Further

cost

reduct

ion

poss

ible

for

dilu

ted

was

tew

ater

ata

loca

tion

pro

vidin

ghig

her

sunny

hours

.

187

(200

3)

Couple

dphoto

-Fen

ton

and

bio

logi

cal

trea

tmen

t

US$

71m

−3p-n

itroto

luen

e-ortho-

sulfonic

acid

(conta

ined

indye

man

ufa

cturing

was

tew

ater

),1

g/L

or

330

mg

C/L

Cost

of70

min

(0.6

8L/

h)

photo

-Fen

ton

pre

trea

tmen

tusi

ng

400

Wla

mp

(0.1

2U

S$/K

WH

)prior

tobio

logi

caltrea

tmen

t,co

mbin

edD

OC

rem

ova

lbei

ng

91%

.Com

mer

cial

lam

ps,

bei

ng

far

more

effici

ent,

would

incu

rle

ssco

st.

175

(199

9)

Com

bin

edtrea

tmen

tw

ithO

3/b

io(a

erobic

,ro

tatin

gdis

cre

acto

r)

US$

94.7

bm

−3Se

gre

ga

ted

conce

ntrat

eddye

bat

hco

nta

inin

gC.I

reac

tive

Bla

ck5

&hig

hsa

ltco

nce

ntrat

ions.

Cost

incl

udes

both

capita

l&

oper

atin

gco

st(fl

ow

rate

=50

L/h).

Hig

her

valu

eas

com

par

edto

those

from

oth

erst

udie

s.e.

g.,

mem

bra

ne

separ

atio

n(1

1.68

US$

m−3

),ad

sorp

tion

follo

wed

by

aero

bic

bio

logi

caltrea

tmen

t(2

.6U

S$m

−3),

pre

cipita

tion/fl

occ

ula

tion

follo

wed

by

activ

ated

carb

on

adso

rptio

n(5

.19

US$

m−3

)in

dic

ates

the

ambig

uousn

ess

aris

ing

from

stra

ightforw

ard

com

par

ison

ofco

sts

ofse

greg

ated

vs.m

ixed

stre

ams.

124

(200

3)

356

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ded

by [

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at 0

5:45

01

Dec

embe

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13

UV

/H2O

2trea

tmen

tof

seco

ndar

yte

xtile

effluen

tto

mee

tdis

char

gest

andar

d

US$

0.85

m−3

Text

ilew

aste

wat

erO

per

atin

gco

stin

cludin

gla

mp

repla

cem

ent,

chem

ical

and

elec

tric

alco

st.(D

isch

arge

stan

dar

d:CO

D<

100

mg/

L;co

lor<

400

AD

MIunit)

123

(200

0)

Post

trea

tmen

tof

seco

ndar

yte

xtile

effluen

tby

(i)

ozo

nat

ion,(ii)

mem

bra

ne

filtr

atio

n

US$

m−3

(i)

0.19

,(ii)

0.69

Text

ilew

aste

wat

erco

nta

inin

gdirec

tan

dre

activ

edye

s

Cost

incl

udes

both

capita

l&

oper

atin

gco

st(e

xcep

tth

ere

ject

dis

posa

lco

stin

case

ofm

embra

ne

filtr

atio

n).

Flow

rate

,(a

)20

00m

3/d

;(b

)10

00m

3/d

.

108

(200

1)

Com

bin

edtrea

tmen

tw

ithco

agula

tion/

elec

troch

emic

aloxi

dat

ion/a

ctiv

ated

sludge

US$

0.34

ton

−1Te

xtile

was

tew

ater

conta

inin

g15

dye

suse

din

apla

ntm

akin

gprim

arily

cotton

and

poly

este

rfiber

san

dsm

all

quan

tity

ofw

ool

Mai

nly

cost

ofco

nsu

mab

les

incl

uded

.Eco

nom

ical

than

the

conve

ntio

nal

trea

tmen

tpro

cess

(US$

0.45

ton

−1)

use

dat

that

time

inTai

wan

.

129

(199

6)

Com

bin

edtrea

tmen

tw

ithco

agula

tion/F

ento

n’s

reag

ent/

activ

ated

sludge

US$

0.4

m−3

Text

ilew

aste

wat

erRunnin

gco

st,ex

cludin

gth

atfo

rsl

udge

dis

posa

l.Eco

nom

ical

than

the

conve

ntio

nal

trea

tmen

tpro

cess

use

dat

that

time.

128

(199

5)

Com

bin

edtrea

tmen

tw

ithCoag

ula

tion/A

ctiv

ated

sludge

/Filt

ratio

n/

Dis

infe

ctio

n

US$

0.19

–0.

22m

−3Te

xtile

was

tew

ater

Oper

atin

gco

st(c

onsu

mab

les

and

mai

nte

nan

ce)

155

(199

2)

Com

bin

edtrea

tmen

tw

ithbio

/san

dfilte

r(S

F)/O

3

for

reusa

ble

wat

er

US$

0.13

bm

−3W

aste

wat

erfr

om

pla

nts

dye

ing

&finis

hin

gnat

ura

l/sy

nth

etic

fiber

s

Cost

men

tioned

isfo

roper

atio

n&

mai

nte

nan

ce.In

cludin

gin

vest

men

tco

st,it

may

amountup

to0.

52U

S$m

−3

dep

endin

gon

amountofw

ater

trea

ted,al

though

inve

stm

ent

may

be

repai

din

ash

ort

time

due

tosa

ving

ofco

stofw

ater

supply

(0.5

2–1.

3U

S$m

−3).

43(2

001)

Com

bin

edtrea

tmen

tw

ithbio

/cla

riflocc

ula

tion/

GA

Cfo

rre

usa

ble

wat

er

US$

0.45

4bm

−3Te

xtile

was

tew

ater

mix

edw

ithdom

estic

(25–

30%

)w

aste

wat

er

Flow

rate

=25

,000

m3/d

.Cost

incl

udes

both

capita

l&

oper

atin

gco

st.

182

(199

9)

Com

bin

edtrea

tmen

tw

ithbio

/mem

bra

ne

(MF→

NF)

/O3

for

reusa

ble

wat

er

US$

1.69

-1.9

5b

m−3

Text

ilew

aste

wat

erm

ixed

with

dom

estic

(25–

30%

)w

aste

wat

er

Flow

rate

=25

,000

m3/d

.Cost

incl

udes

both

capita

l&

oper

atin

gco

st.The

syst

emm

aypote

ntia

llybec

om

eco

st-e

ffec

tive

with

dec

line

inm

embra

ne

cost

,th

em

ain

cost

-contrib

utin

gfa

ctor.

182

(199

9)

(Con

tin

ued

on

nex

tpa

ge)

357

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Dec

embe

r 20

13

TAB

LE5

.Cost

Info

rmat

ion

Per

tain

ing

toD

iffe

rentCom

bin

atio

ns

(Con

tin

ued

)

Purp

ose

&te

chnolo

gyCost

Dye

/was

tew

ater

Rem

arks

Ref

eren

ce(y

ear)

Com

bin

edtrea

tmen

tw

ithbio

/san

dfiltr

atio

n(S

F)/m

embra

ne

(MF

follo

wed

by

NF)

for

reusa

ble

wat

er

US$

0.44

bm

−3D

yein

gw

aste

wat

erFl

ow

rate

=15

00m

3/d

;Cost

incl

udes

oper

atin

gan

din

vest

men

tco

st.A

pay

bac

kofin

vest

men

tco

stm

aybe

expec

ted

in3

yrs

with

the

savi

ng

ofw

ater

supply

cost

.

139

(200

2)

Com

bin

edtrea

tmen

tw

ithbio

/san

dfiltr

atio

n(S

F)/m

embra

ne

(UF

follo

wed

by

RO

)fo

rre

usa

ble

wat

er

US$

1.26

bm

−3W

aste

wat

erfr

om

pla

nts

dye

ing

&finis

hin

gnat

ura

l/sy

nth

etic

fiber

s

Flow

rate

=10

00m

3/d

;Cost

incl

udes

both

oper

atin

gan

din

vest

men

tco

sts.

44(2

001)

Com

bin

edtrea

tmen

tw

ithdee

pae

ratio

nac

tivat

edsl

udge

/BA

C/m

embra

ne

(NF)

for

50%

recy

clin

g

US$

0.29

4C

m−3

Was

tew

ater

from

pla

nts

dye

ing

&finis

hin

gsy

nth

etic

fiber

s

Flow

rate

=50

m3/d

;Cost

men

tioned

isfo

roper

atio

n&

mai

nte

nan

ce.

224

(200

5)

Com

bin

edtrea

tmen

tw

ithbio

/san

dfiltr

atio

n(S

F)/o

zonat

ion

for

50%

recy

clin

g

US$

0.57

bm

−3W

aste

wat

erfr

om

pla

nts

fulli

ng

&dye

ing

nat

ura

l/sy

nth

etic

fiber

s

Flow

rate

=20

00m

3/d

;O

per

atin

gco

stonly

.Req

uired

fres

hw

ater

supply

(50%

ofto

tal)

incu

rsa

further

cost

of0.

92U

S$m

−3.

42(2

001)

Reu

seaf

ter

mem

bra

ne

filtr

atio

n(i),

follo

wed

by

UV

/H2O

2(ii),

concu

rren

tw

ithre

use

afte

rm

embra

ne

conce

ntrat

etrea

tmen

tby

wet

air

oxi

dat

ion

(iii)

and

bio

logi

cal(iv)

US$

m−3

(i)

0.53

(ii)2.

6(iii)

4.4

(iv)

0.13

Text

ilew

aste

wat

erFl

ow

rate

=40

0m

3/d

.In

dic

ated

cost

sar

eoper

atin

gan

dm

ainte

nan

ceco

sts

for

each

stag

eofth

ein

tegr

ated

syst

em.

Annual

ized

tota

lin

stal

latio

nco

stis

US$

243,

000

while

savi

ng

gener

ated

from

wat

erre

use

isU

S$98

,000

.

120

(200

1)

Mem

bra

ne

bio

reac

tor

US$

0.27

3m

−3M

unic

ipal

was

tew

ater

dFl

ow

rate

=2.

4m

3/h

;co

stm

entio

ned

incl

udes

allso

rts

of

capita

l&

oper

atin

gco

sts.

With

expec

ted

dec

line

inm

embra

ne

cost

toU

S$50

m−2

in20

04,th

eunit

cost

would

reduce

toU

S$0.

181

m−3

.

228

(200

4)

a,b

,cO

rigi

nal

reported

valu

esin

Deu

tsch

eM

arks

,Euro

and

Tai

wan

ese

dolla

rhav

ebee

nco

nve

rted

toU

S$by

multi

ply

ing

with

afa

ctorof0.

6633

48,1

.297

30,0

.032

2134

,re

spec

tivel

y.dD

ata

give

nfo

rco

mpar

ison

ofM

BR

tech

nolo

gyw

ithoth

ers

only

.

358

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contaminant due to dilution. The fact that treatment schemes based on segre-gated waste streams coupled with process water recycling have the potentialto save quite a bit of money even with high costs per cubic meter shouldbe considered while evaluating process viability.124 Nevertheless, the impor-tance of reporting such values cannot be overlooked as they always givesome rough idea on different scenarios and may as well form the base forfurther improved cost estimation. Plausible analyses of the cost data followin the next paragraph.

Treatment trains composed of conventional physicochemical and bio-logical systems involve sustainable cost155; however, their removal perfor-mance may not satisfy contemporary stricter regulations. Membrane filtrationof biologically pretreated dye wastewater109 has been occasionally reportedto require less cost than that for direct membrane filtration108 of dye bath,presumably as the former involves less membrane fouling. However, boththe processes furnish potential of water reuse, thereby achieving furthercost savings. Other membrane-based combinations, especially, membranebioreactors,78,228 are potential contenders among present-day dye wastewatertreatment processes. At the present stage of development of AOPs, sole ap-plication of AOP or even combinations among AOPs themselves are unlikelyto yield satisfactory effluent with reasonable cost.12 AOP pretreatment priorto biological treatment is certainly more cost-effective than complete miner-alization by AOP. Conversely, according to the examples in Table 5, AOP asa posttreatment incurs less cost as compared to that as pretreatment.109,187

Notwithstanding this fact, it should be emphasized that application of AOPpretreatment on segregated recalcitrant stream may avoid unnecessary con-sumption of chemicals by biodegradable compounds, thereby impartingcost-effectiveness to the integrated system.124 Combination of AOP withadsorption,91 membrane separation,139 or other physicochemical86 systemsmay be cost-competitive. It is intriguing to notice that integrated systemscombining a wide variety of technologies, for instance, membrane, AOP,WAO, and biological processes, when accomplishing water and/or auxiliarychemicals reuse, appear to be feasible, in that capital cost can be recoveredwithin a few years.43,120,139

6. PROPOSED HYBRID PROCESS

Based on the array of potential hybrid technologies and the available costinformation, a conceptual on-site textile dye wastewater treatment system, aspresented in Figure 3, may be proposed. Two distinct cases have been con-sidered here: (1) an integrated textile processing plant involving essentiallyall steps of textile processing, starting from conversion of fiber to cloth andextending up to dyeing and finishing, and (2) a segregated plant concerningonly dyeing and finishing. Additionally, an ideal state of practice of recovery

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FIGURE 2. Different stages of textile wet processing and associated scopes of materialrecovery.127,220

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FIGURE 3. Layout of a conceptual on-site textile dye wastewater treatment scheme (Contin-uation from Figure 2).

and reuse of textile chemicals (sizing agent, detergent, lanolin from raw woolscouring, caustic for cotton mercerizing, dye bath electrolyte), energy (heat),and water by using appropriate membranes has been assumed (Figure 2).This assumption was prompted by the fact that such practice realizes costsavings through reduction in production of waste and consumption of freshchemicals/water, and consequently the usual payback period of the highcapital investment associated with it is 2–3 years or less.151,180 Furthermore,available technoeconomical analyses indicate that inclusion of a comprehen-sive energy and water reuse plan within the treatment scheme would be moreviable as compared to full end-of-pipe treatment with limited or no recov-ery/reuse strategy.51 Nevertheless, initial investment costs and site-specificconditions will obviously play a role in whether or to what extent a plantdecides to proceed with a recycling concept. It is worth mentioning here thatrecovery/reuse of both chemicals and water is different from that of only wa-ter, in that the former entails handling of the point sources separately, whilethe latter may be achieved by following usual end-of-pipe strategy (mixingdifferent streams).

A submerged microfiltration membrane bioreactor (MBR) implementinga mixed microbial culture predominantly composed of white-rot fungi con-stitutes the core of the proposed hybrid dye wastewater treatment scheme.The fungi MBR78 couples the excellent recalcitrant compound degradabilityof white-rot fungi with the inherent advantages of an MBR. To sustain an un-interrupted supply of nonspecific extra cellular enzyme by fungi, the reactorrequires operation under a quasi-controlled environment (acidic pH) withsimultaneous supply of an easily biodegradable carbon source (e.g., starchused in textile sizing). In the case of an integrated textile plant, after thechemical and water recoveries as indicated in Figure 2, the concentrates anddiscarded streams may be fed to the MBR. Depending on the case-specific

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requirement, the MBR may be augmented by a subsequent advanced oxi-dation facility (e.g., solar photocatalysis187). An internal recycle strategy be-tween the MBR and the photoreactor may prove to be further beneficial.Depending on the site-specific quality achievement, the final effluent may bereused with or without mixing with fresh water. In the case of a plant deal-ing only with dyeing and finishing, however, a slightly changed approachof water and electrolyte recovery is recommended. In this case since otherstreams except the dyeing and finishing streams are absent, the concentratedreject stream generated after water and salt recovery from segregated dyebath effluent and rinse water cannot be diluted. Under this condition, thedye bath effluent and rinse water may be directly fed to the MBR–AOP se-quence, and then desalinated by membrane (RO/NF), with the concentrate(salt) and permeate (water) being reused.

Due to declining membrane costs,34 recovery and reuse of chemicalsand water using membranes is expected to gain rapid acceptability in nearfuture. The concentrates generated therefrom and discarded streams (includ-ing dye), however, entail further effective economical treatment. This maybe realized by an on site membrane separated fungi reactor. Requirementof small plant size is one of the inherent advantages of MBR process. Thefungi MBR,78 in addition, can achieve excellent effluent quality. Besides,posttreatment of the MBR permeate by an AOP will ensure complete de-coloration. Moreover, use of the AOP for posttreatment will minimize itslight penetration limitation, which would be significant if it were used forpretreatment. Last but not least, the approach of utilizing solar light for pho-tocatalysis adds to the effort to conserve energy sources. Based on this rea-soning, the proposed conceptual integrated treatment scheme appears to beattractive.

This article intends to underscore the indispensability of hybrid tech-nology for dye wastewater treatment and endorses the inclusion of energyand water reuse plan within the treatment scheme. However, the proposedlayout is certainly not claimed to be a panacea for textile dye wastewa-ter. It is rather a demonstration of one of the probable suitable combina-tions. In line with the broad spectrum of hybrid technologies portrayedin this article, some additions/modifications to the proposed scheme mayalso be considered. For instance, simultaneous addition of adsorbent in theMBR,189 utilization of concurrent AOP adsorption systems,91,132 etc. are worthexploring.

Other approaches may enjoy case-specific superiority over the proposedscheme. For example, with more advancement in the reactor design for AOPs,the partial preoxidation by AOP (may be combination among AOPs them-selves) prior to MBR treatment may appear to be more appropriate in nearfuture. Conversely, incineration/wet air oxidation of dye bath concentrate(possessing high calorific value34) remaining after material and water recov-ery by membrane may also furnish an attractive solution.

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7. CONCLUSION

Residual dyes along with other auxiliary chemical reagents used for process-ing, impurities from the raw materials, and other hazardous materials appliedin the finishing process impose massive load on wastewater treatment sys-tem. This eventually leads to a poor color and COD removal performance.The release of colored wastewater in the ecosystem is a remarkable sourceof esthetic pollution, eutrophication, and perturbations in aquatic life. Theseconcerns have led to new and/or stricter regulations concerning coloredwastewater discharges, rendering the decolorization process further difficultand costly. To combat this problem, researchers have put forward a widevariety of hybrid decolorization techniques. Based on the array of potentialhybrid technologies and the available cost information, it can be concludedthat hybrid technologies having biological processes as the core appear to bethe most prospective ones. It should also be emphasized here that inclusionof energy and water reuse plan within the treatment scheme is an imperative.In this context, membrane technology has an immense role to play. Mem-brane bioreactors implementing special dye-degrading microorganisms andinvolving simultaneous addition of adsorbent in MBR may surface as poten-tial contenders among present-day dye wastewater treatment processes. TheMBR technology may also be combined with advanced oxidation facilities.Case-specific selection of the appropriate hybrid technology is the key torealization of a feasible system.

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Hybrid Treatment Systems for Dye Wastewater

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