Textile Dyeing Wastewater Treatment by Single and Intregated Processes of Coagulation, Chemical Oxidation and Biological Degradation

Tex ile Dy
In eg a ed P ocesses o Coagula ion, Chemical Oxida ion and
Ca men Susana de Deus Rod igues
Disse a ion
p esen ed o he Ph.D. Deg ee in En i onmen al Enginee ing a he Facul y o
Enginee ing, Uni e si y o Po o, Po ugal
Labo a o y o Sepa a ion and Reac ion Enginee ing/
Labo a o y o P ocess, En i onmen al and Ene gy Enginee ing
Facul y o Enginee ing, Uni e si y o Po o
Tex ile Dy
e
ing Was ewa e T ea men by Single and
In eg a ed P ocesses o Coagula ion, Chemical Oxida ion and
Biological Deg ada ion
Ca men Susana de Deus Rod igues
p esen ed o he Ph.D. Deg ee in En i onmen al Enginee ing a he Facul y o
Enginee ing, Uni e si y o Po o, Po ugal
Supe iso s
Rui Al edo da Rocha Boa en u a
Luís Miguel Palma
Madei a
Labo a o y o Sepa a ion and Reac ion Enginee ing/
Associa ed Labo a
o y
Labo a o y o P ocess, En i onmen al and Ene gy Enginee ing
(LEPAE)
Chemical Enginee ing Depa men
Facul y o Enginee ing, Uni e si y o Po o
Po o, Sep embe 2013
ing Was ewa e T ea men by Single and
In eg a ed P ocesses o Coagula ion, Chemical Oxida ion and
p esen ed o he Ph.D. Deg ee in En i onmen al Enginee ing a he Facul y o
Rui Al edo da Rocha Boa en u a
Madei a
o y
LSRE/LCM
(LEPAE)
i
Acknowledgmen s
To my supe iso es, Doc o Rui Boa en u a and P o . Miguel Madei a, in pa esponsible
o my in e es in scien i ic esea ch, I wan o hank he oppo uni y o pe o m his wo k,
as well as all he suppo , mo i a ion, unde s anding and emendous willingness o e he
yea s ha we wo ked oge he . Also hanks o all sugges ions, c i icisms, complimen s
and encou agemen o do mo e and be e .
I’m also g a e ul o all o ganiza ions and people wi hou which his wo k would no ha e
been possible:
Fundação pa a a Ciência e a Tecnologia (FCT) o he PhD schola ship
(SFRH/BD/46704/2008).
Facul y o Engenee ing, Uni e si y o Po o (FEUP) and, pa icula y, he Labo a o y o
Sepa a ion and Reac ion Enginee ing – LSRE, he Labo a o y o P ocess, En i onmen al
and Ene gy Enginee ing – LEPAE, and he Depa men o Chemical Enginee ing, o
making a ailable he esou ces and acili ies o ca y ou his wo k.
E oc - Acabamen os Têx eis S.A., namely M . A mando Ama o and M . Vi gilio
Guima ães, and DyS a (Po o), namely M s. Go e i Quinaz, o gen ly supplying he
chemicals and dyes and he in o ma ion equi ed o e luen s simula ion.
Tex il Luís Simões, ha p o ided a eal e luen sample used in his s udy. Pa icula ly I
wan o hank M s. Susana Cos a o kindly ecei ing me, and o all he in o ma ion and
aluable assis ance in collec ing he e luen sample.
Quimi écnica, namely M . Luís Quelhas, and Ri az Química, o supplying he locculan s,
as well as he p ices o he chemicals used in his wo k.
M . Claúdio Cos a om T a a e and M s. Ca la Aze edo om Rabada WWTP, o
p o iding he biomass used in he deg ada ion es s and in he acclima iza ion o he
biological eac o
.
ii
P o . Fe nando Pe ei a om he Labo a o y o Ca alysis and Ma e ials (LCM) a FEUP o
he help in es ablishing con ac wi h he ex ile indus y, as well as, in he las phase o he
wo k, o he access o he Labo a o y o En i onmen al Sciences.
P o esso Joaquim Fa ia and Doc o Claudia Sil a om LCM a FEUP o kindly p o iding
he ac inome y da a and supplying he me cu y lamp TQ 150 o pho o-Fen on
expe imen s.
Luís Ca los and Nuno Gue ei o om he Depa amen o Chemical Enginee ing a FEUP
o he p omp ness in sol ing some p oblems conce ning he expe imen al se up o he
Sequencing Ba ch Reac o (SBR) and he pilo plan o Fen on p ocess
.
Doc o Salomé Soa es om LCM, M s. Dionísia Po ela om Cen o Tecnológico das
Indús ias Têx il e do Ves uá io de Po ugal (CITEVE) and M s. Pa ícia Al es o
p o iding scien i ic li e a u e, encou agemen , sha ing o knowledge, bu a he by he
iendship demons a ed since he 1s yea o he g adua ion in Chemical Enginee ing.
Doc o Nídia Cae ano, Doc o Olga F ei as and Doc o Sónia Figuei edo om he
Chemical Enginee ing Depa men , School o Enginee ing, Poly echnic Ins i u e o Po o,
o he
iendship, encou agemen and knowledge sha ing.
Liliana Pe ei a, Sil ia Faia, Paula Pinhei o, Ma ia do Céu, Se a im Pe ei a, no only o
p o iding he bes wo king condi ions a he Labo a o y o En i onmen al Sciences, bu
also o he iendship, he p ecious help and he use ul ad ices.
I am also g a e ul o all people (so many ha I canno nomina e all o hem…) ha I me a
LSRE du ing his pe iod o my li e o he help, companionship and all he wo ds o
encou agemen . Thanks o Filipa Dua e and Cá ia Feliz om LEPAE o he e y special
iendship, companionship, help, con e sa ions and con idences, and o all good ime we
spen oge he .
Finally my e e nal g a i ude o my pa en s, my husband, my daugh e , my b o he , my
sis e , my sis e in law and my niece, o he lo e, he uncondi ional suppo , he op imis ic
iew o li e and o making me a be e pe son.
iii
P e ace
This PhD hesis was ca ied ou a he Labo a o y o Sepa a ion and Reac ion
Enginee ing, Associa ed Labo a o y LSRE/LCM, and a he Labo a o y o P ocess,
En i onmen al and Ene gy Enginee ing (LEPAE) o he Depa men o Chemical
Enginee ing, a he Facul y o Enginee ing – Uni e si y o Po o.
The hesis is s uc u ed in o i e pa s di ided in chap e s wi h he ollowing con en :
Pa I – The backg ound and mo i a ion o his s udy a e desc ibed in chap e 1,
and he wo k o be pe o med in o de o achie e he objec i es is also e e ed o.
A b ie cha ac e iza ion o he ex ile sec o in Po ugal and he ea men
echnologies o his ype o was ewa e a e also p esen ed. Chap e 2 p esen s
he s a e o he a o ex ile was ewa e ea men by chemical
coagula ion/ loccula ion, ad anced chemical oxida ion wi h Fen on’s eagen ,
pho o-Fen on p ocess and biological oxida ion in sequencing ba ch eac o s
(SBR).
Pa s II consis s in one chap e (chap e 3) conce ning he p epa a ion o syn he ic
was ewa e s and hei cha ac e iza ion as well as he cha ac e iza ion o he ex ile
indus ial was ewa e . The ma e ials and me hods used and he expe imen al
p ocedu es a e also desc ibed.
Pa III is di ided in 7 chap e s p esen ing he expe imen al esul s ob ained in he
ea men o syn he ic dyeing was ewa e s ei he by single o combined p ocesses.
Pa IV (Chap e 11) ega ds he ea men o a eal co on dyeing e luen by an
in eg a ed p ocess o coagula ion/ loccula ion plus Fen on’s oxida ion, Fen on’s
eagen alone and a combina ion o Fen on’s oxida ion, coagula ion/ loccula ion
and biological deg ada ion in SBR.
Pa V poin s ou he main conclusions om his s udy and some sugges ions o
u u e wo k.

i
The pa s III and IV co espond o chap e s 4 o 11, which a e based on 8 scien i ic
pape s, 3 o which al eady published/accep ed in scien i ic jou nals, 3 unde e iew and 2
submi ed.
Abs ac
Coagula ion/ loccula ion using e ous sulpha e (FeSO
4
.7H
2
O) as coagulan was s udied in
his wo k o he emo al o o ganic compounds and colo om simula ed co on, ac ylic
and polyes e dyeing was ewa e s. The e ec o he coagulan dose, empe a u e, pH,
s i ing speed and s i ing ime on he emo al o dissol ed o ganic ca bon (DOC) and
colo was assessed o each e luen . Then he e ec o he s i ing speed, s i ing ime
and locculan (Magna loc 155 o Supe loc C-573) dose on loccula ion was also
e alua ed a he op imal condi ions p e iously de e mined in he coagula ion s age. The
ob ained esul s allowed concluding ha he op imal ope a ing condi ions a y wi h he
e luen and ha he o e all p ocess (coagula ion/ loccula ion) is e y e icien as ega ds
colo emo al (91.4% o co on, 93.8% o ac ylic e luen s; polyes e e luen is p ac ically
colo less). Howe e , he DOC emo al is no e y signi ican (33.3%, 45.4% and 28.3%
o polyes e , co on and ac ylic dyeing e luen s, espec i ely). On he o he hand, one
can ake ad an age o he emaining dissol ed i on con en o u he in eg a ing his
ea men wi h an i on ca alyzed Fen on p ocess, hus educing he consump ion o
chemicals in he o e all ea men ; such educ ion depends on he e luen na u e, bu he
use o his p e ious ea men s age acili a es he chemical oxida ion in he subsequen
one. A simila coagula ion/ loccula ion ea abili y s udy was conduc ed using e ic
sulpha e (Fe
2
(SO
4
)
3
) as coagulan . The in luence o pH and Fe
3+
concen a ion in bo h
colo and DOC emo al om he same e luen s was assessed in he coagula ion s age.
The e ec o he ype and locculan dose was also e alua ed a he be e ope a ing
condi ions ound in he coagula ion s ep. Once again he op imum pH and he be e
coagulan and locculan doses we e ound o depend on he e luen unde s udy.
Maximum DOC emo als o 40.2, 43.0 and 16.5% we e ound o polyes e , co on and
ac ylic dyeing was ewa e s, espec i ely. The colo emo al o he ac ylic dyeing e luen
(44.7%) was sligh ly highe han o he co on one (33.2%); bo h we e howe e much
smalle as compa ed o he use o e ous sal .
O he ea men app oaches we e applied o he same e luen s. The Fen on's eagen
was applied o he ac ylic e luen p e iously ea ed by coagula ion/ loccula ion (App oach
1) o o ganic ma e and colo emo al, while imp o ing he biodeg adabili y. The ini ial
i on load a ied om he esidual soluble i on esul ing om coagula ion/ loccula ion (275
mg Fe/L) up o 400 mg/L, by adding e ous sul a e. The combina ion o he wo
ea men s led o o e all emo als o 99.8, 84.2 and 78.6% o colo , DOC and chemical
i
oxygen demand (COD), espec i ely, and o a inal e luen ha mee s he legisla ed
discha ge limi s. The Fen on p ocess was also di ec ly applied o he same e luen
(App oach 2). Unde he op imal condi ions, he colo emo al (99.5%) was simila o ha
ob ained in he combined p ocess, bu DOC and COD emo als we e lowe (66.5 and
65.1%, espec i ely). An imp o emen o he was ewa e biodeg adabili y was obse ed,
bo h in e ms o he speci ic oxygen up ake a e and biochemical oxygen
demand:chemical oxygen demand (BOD
5
:COD) a io. The e luen oxici y (inhibi ion o V.
Fische i) also dec eased. The use o Fen on’s eagen ollowed by coagula ion/ loccula ion
(App oach 3) a he op imal condi ions led o he highe colo and o ganic ma e emo als
o his e luen (99,7, 75,8 e 80,1% o colo , COD and DOC, espec i ely). Howe e , he
App oach 1 pe mi s o each a ea ed e luen mee ing he discha ge s anda ds a he
smalles ope a ing cos (~7 €/m
3
).
Rega ding he co on e luen , he ope a ing cos is also highe in App oach 2 and
App oach 3 due o he equi ed dose o hyd ogen pe oxide. The applica ion o he
Fen on’s p ocess be o e coagula ion/ loccula ion p o ided an e luen ha mee s he
discha ge limi s, wi h global o ganic ma e emo als o 55.6% o COD, 42.7% o BOD
5
and 70.4% o DOC, and almos comple e colo educ ion (99.6%). Howe e , he
combina ion o coagula ion/ loccula ion wi h Fen on’s oxida ion (App oach 1) also exhibi s
high o e all e iciencies (61.7%, 25.8% and 71.2% o COD, BOD
5
and DOC emo al,
espec i ely, and almos comple e decolo iza ion) wi h lowe cos s associa ed wi h
chemicals consump ion (0.83 €/m
3
).
The same ea men app oaches we e also applied o he simula ed polyes e dyeing
e luen . The e ec o Fe
2+
dose, ini ial H
2
O
2
concen a ion and empe a u e on o ganic
ma e by Fen on’s oxida ion was e alua ed in App oaches 1 and 2, while in App oach 3
only he in luence o pH and locculan dose was assessed in he coagula ion/ loccula ion
p ocess. A sligh inc ease in he speci ic oxygen up ake a e (SOUR) o he e luen was
obse ed in App oaches 1 and 2 ( om 27.0 o 28.5-30.0 mgO
2
/(g
VSS
h)) and he inhibi ion
o Vib io Fische i was elimina ed a e Fen on’s oxida ion. In all cases, an e luen ha
complies wi h discha ge s anda ds was ob ained; howe e , App oach 3 leads o smalle
ope a ing cos s wi h chemicals. The use o dissol ed i on esul ing om Fen on’s
oxida ion as coagulan in he second s age is hus an e icien and economically a ac i e
s a egy o ea ing his e luen .
ii
The simula ed e luen s we e also subjec ed o he pho o-Fen on p ocess, aiming a
educing he consump ion o chemicals, as compa ed o he da k Fen on p ocess, while
simul aneously minimizing he ene gy cos s by using sola adia ion. The educ ion o he
hyd ogen pe oxide dose is limi ed by he need o achie ing ea ed e luen s complying
wi h discha ge limi s. The cos s associa ed wi h he use o a i icial adia ion in he pho o-
Fen on p ocess (17.4, 9.6 and 2.9 €/m
3
o ac ylic, co on and polyes e e luen s,
espec i ely) a e s ill oo high. The use o (simula ed) sola ligh allows ob aining high
emo als o colo (>98-99%) and signi ican COD (30.1-72.0%) and DOC (46.2-71.5%)
aba emen s a an ope a ing cos educed by a ac o o ca. 3. T ea ed e luen s by he
sola pho o-Fen on p ocess also mee he discha ge s anda ds.
As he ac ylic dyeing e luen is p ac ically non biodeg adable, only he biological
ea abili y o polyes e and co on dyeing e luen s was e alua ed. The biodeg ababili y
a e Fen on’s oxida ion was also assessed o all e luen s. Raw and chemically oxidized
(p e- ea ed) was ewa e s we e ed o a Sequencing Ba ch Reac o (SBR) du ing 10
cycles (i.e., up o pseudo s eady-s a e condi ions). In he in eg a ed chemical-biological
p ocess op imum doses o Fe(II) and H
2
O
2
( o biodeg adabili y enhancemen and
maximiza ion o colo and DOC emo als) we e de e mined o Fen on’s oxida ion, wi h
he simul aneous objec i e o minimizing he ope a ing cos s. The in eg a ion o Fen on’s
oxida ion wi h a downs eam SBR p o ides much be e emo als o o ganic ma e (87.7
– 98.2% o COD, 83.2 – 94.5% o BOD
5
and 91.2 – 98.4% o DOC, depending on he
pa icula ex ile e luen ) and colo (>98.5%) han he biological o chemical ea men
alone. Besides, such in eg a ed ea men allows o mee he discha ge limi s wi h a
educ ion o he ope a ing cos s, in he ange 24-44 % compa a i ely o Fen on’s oxida ion
alone.
This s udy also ocused on he ea abili y e alua ion o indus ial dyeing was ewa e s; due
o ime limi a ions only one co on dyeing was ewa e was used. Fou ea men
app oaches, including single and in eg a ed p ocesses, we e s udied, namely:
coagula ion/ loccula ion pe se and i s combina ion wi h Fen on oxida ion (App oach 1),
Fen on’s p ocess alone (App oach 2) and i s in eg a ion wi h ei he
coagula ion/ loccula ion (App oach 3) o biological oxida ion in SBR (App oach 4).
Biological deg ada ion o he aw was ewa e in SBR was no es ed because he a io
BOD
5
:COD and he alue o SOUR a e e y small, which indica es low biodeg adabili y.
All he conside ed app oaches p o ided a was ewa e ha mee s he discha ge limi s,
howe e App oaches 1 and 3 led o smalle ope a ing cos s (0.83 and 0.87 €/m
3
,
xi
3.2 Tex ile Dyeing Was ewa e s ............................................................................65
3.2.1
Simula ed Tex ile Dyeing Was ewa e s ................................................................ 65
3.2.1.1 Dyes………………………..…………………………………….………………………..65
3.2.1.2 Auxilia y Chemicals….....………………………………………………………………..66
3.2.1.3 P epa a ion o he Simula ed Tex ile Dyeing E luen s…….………………………..69
3.2.2
Real Co on Dyeing Was ewa e .......................................................................... 75
3.3 Analy ical Me hods ..........................................................................................77
3.3.1
Alkalini y ............................................................................................................... 77
3.3.2
Biodeg adabili y .................................................................................................... 77
3.3.3
Biochemical Oxygen Demand .............................................................................. 77
3.3.4
Chemical Oxygen Demand .................................................................................. 78
3.3.5
Chlo ides, Dissol ed Phospho us, Ni a es and Sul a es ..................................... 78
3.3.6
Colo ..................................................................................................................... 78
3.3.7
Conduc i i y .......................................................................................................... 79
3.3.8
Dissol ed I on ....................................................................................................... 79
3.3.9
Dissol ed Oxygen Ca bon .................................................................................... 79
3.3.10
Hyd ogen Pe oxide ............................................................................................... 79
3.3.11
Inhibi ion o Vib io Fische i ................................................................................... 79
3.3.12
pH ......................................................................................................................... 80
3.3.13
To al Ni ogen ....................................................................................................... 80
3.3.14
To al Phospho us ................................................................................................. 80
3.3.15
To al Suspended Solids and Vola ile Suspended Solids ..................................... 80
3.3.16
HPLC Analyses .................................................................................................... 81
3.3.17
Zahn-Wellens Tes ............................................................................................... 81
3.4 Expe imen al P ocedu e ..................................................................................82
3.4.1
Coagula ion/Floccula ion ...................................................................................... 82
3.4.2
Fen on´s Reac ion ................................................................................................ 83
3.4.3
Pho o-Fen on Oxida ion........................................................................................ 84
3.2.1.1 Pho o-Fen on wi h A i icial Radia ion……..……..…………………………………………..85
3.2.1.1 Pho o-Fen on using Simula ed Sola Radia ion……....……..…………….………………..87
3.4.4
Biological Oxida ion in Sequencing Ba ch Reac o .............................................. 87
3.5 Re e ences .......................................................................................................89
Pa III – Simula ed Dyeing Was ewa e s T ea men
4
Coagula ion/Floccula ion wi h Fe
2+
as Coagulan ................................. 95
4.1 In oduc ion ......................................................................................................95
4.2 Ma e ials and Me hods ....................................................................................95
4.2.1
P epa a ion o Simula ed Tex ile Was ewa e s .................................................... 95
4.2.2
Coagula ion/Floccula ion Expe imen s ................................................................. 95
4.2.3
Analy ical Me hods ............................................................................................... 96

x
4.3 Resul s and Discussion ..................................................................................96
4.3.1
E ec o S i ing Speed and Time on he Coagula ion S age............................... 97
4.3.2
E ec o he Tempe a u e on he Coagula ion S age ........................................... 97
4.3.3
E ec o he pH on he Coagula ion S age ........................................................... 98
4.3.4
E ec o he Coagulan (Fe
2+
) Concen a ion ..................................................... 100
4.3.5
In luence o he S i ing Speed and Time in he Floccula ion S age .................. 102
4.3.6
In luence o he Flocculan Type and Dosage .................................................... 102
4.4 Conclusions ................................................................................................... 107
4.5 Re e ences ..................................................................................................... 107
5
Coagula ion/Floccula ion wi h Fe
3+
as Coagulan ............................... 113
5.1 In oduc ion .................................................................................................... 113
5.2 Ma e ials and Me hods .................................................................................. 114
5.2.1
P epa a ion o Simula ed Tex ile E luen s ......................................................... 114
5.2.2
Coagula ion/Floccula ion Expe imen s ............................................................... 114
5.2.3
Analy ical Me hods ............................................................................................. 114
5.3 Resul s and Discussion ................................................................................ 115
5.3.1
In luence o pH ................................................................................................... 115
5.3.2
In luence o he Fe
3+
Concen a ion.................................................................... 116
5.3.3
In luence o he Flocculan Na u e and Dose ..................................................... 118
5.3.4
O e all P ocess E iciency .................................................................................. 123
5.4 Conclusions ................................................................................................... 126
5.5 Re e ences ..................................................................................................... 126
6
In eg a ion o Physical-Chemical and Oxida ion P ocesses o Ac ylic
E luen T ea men ............................................................................................ 131
6.1 In oduc ion .................................................................................................... 131
6.2 Ma e ials and Me hods .................................................................................. 131
6.2.1
P epa a ion o he Simula ed Tex ile E luen ..................................................... 131
6.2.2
Expe imen al P ocedu e ..................................................................................... 131
6.2.3
Analy ical Me hods ............................................................................................. 132
6.3 Resul s and Discussion ................................................................................ 132
6.3.1
Combina ion o Coagula ion/Floccula ion plus Fen on´s oxida ion and Fen on´s
oxida ion alone ....................................................................................................................... 132
6.3.1.1 E ec o he Fe ous Ion Concen a ion……………………….………………………………….133
6.3.1.2 E ec o he Hyd ogem Pe oxide Concen a ion …………….………………………………….135
6.3.1.3 E ec o he Tempe a u e……….…………..………………….………………………………….137
6.3.1.4 In luence o pH …………………………………………….……………………………………….140
6.3.1.5 Op imized T ea men o Simula ed Dyeing Was ewa e …..………………………………….141
6.3.2
Fen on´s Reac ion Followed by Coagula ion/Floccula ion ................................. 145
x i
6.3.2.1 E ec o he pH ……………………………………………….....………………………………….146
6.3.2.2 E ec o Suppe loc C-573 Doses …..…………………………………………………...……….147
6.3.2.3 O e all P ocess E iciency ……………………………………..………………………………….148
6.4 Conclusions ................................................................................................... 150
6.5 Re e ences ..................................................................................................... 151
7
In eg a ion o Physical-Chemical and Oxida ion P ocesses o Co on
Dyeing E luen T ea men ............................................................................... 157
7.1 In oduc ion .................................................................................................... 157
7.2 Ma e ials and Me hods .................................................................................. 157
7.2.1
P epa a ion o he Simula ed Tex ile E luen ..................................................... 157
7.2.2
Expe imen al P ocedu e ..................................................................................... 158
7.2.3
Resea ch S a egy .............................................................................................. 158
7.2.4
Analy ical Me hods ............................................................................................. 160
7.3 Resul s and Discussion ................................................................................ 160
7.3.1
Combina ion o Coagula ion/Floccula ion and Fen on’s Reagen (App oach 1) 160
7.3.1.1 In luence o Fe ous Ion Concen a ion ………….…………...………………………………….161
7.3.1.2 E ec o he Ini ial Hyd ogen Pe oxide Concen a ion ….....………………………………….162
7.3.1.3 E ec o he Tempe a u e..……………………………………..………………………………….163
7.3.1.4 Op imized T ea men Pe o mance …………………………...………………………………….165
7.3.2
Fen on Oxida ion (App oach 2) .......................................................................... 166
7.3.2.1 In luence o Fe ous Ion Concen a ion ………….…………...………………………………….167
7.3.2.2 E ec o he Ini ial Hyd ogen Pe oxide Concen a ion ……………….....……….…………….168
7.3.2.3 E ec o he Tempe a u e..……………………………………..………………………………….170
7.3.2.4 Op imized T ea men o he Simula ed Co on Dyeing Was ewa e ….……………………….172
7.3.3
Fen on’s Oxida ion Followed by Coagula ion/Floccula ion (App oach 3) ........... 173
7.3.3.1 In luence o pH …………………………….……….…………...………………………………….174
7.3.3.2 E ec o Magna loc 155 Doses …………………………….....………………………………….175
7.3.3.3 O e all P ocess E iciency ……………………………………..………………………………….176
7.3.4
Cos s E alua ion ................................................................................................. 178
7.4 Conclusions ................................................................................................... 180
7.5 Re e ences ..................................................................................................... 181
8
In eg a ion o Physical-Chemical and Oxida ion P ocess o Polyes e
Dyeing E luen T ea men ............................................................................... 185
8.1 In oduc ion .................................................................................................... 185
8.2 Ma e ials and Me hods .................................................................................. 185
8.2.1
P epa a ion o Syn he ic Tex ile Was ewa e s ................................................... 185
8.2.2
Expe imen al P ocedu e ..................................................................................... 186
8.2.3
Analy ical Me hods ............................................................................................. 186
8.3 Resul s and Discussion ................................................................................ 187
8.3.1
Combina ion o Coagula ion/Floccula ion and Fen on Reagen (App oach 1) ... 187
x ii
8.3.1.1 In luence o Fe ous Ion Concen a ion Added Du ing he Chemical Oxida ion S age
……………………………………………………………….…………...………………………………….188
8.3.1.2 E ec o he Ini ial Hyd ogen Pe oxide Concen a ion on he Chemical Oxida ion
S age……..……………………………………………..…………….....………………………………….189
8.3.1.3 E ec o he Tempe a u e Du ing he Chemical Oxida ion S age ….………………………….190
8.3.1.4 Op imized In eg a ed Coagula ion/Floccula ion plus Fen on's Oxida ion ……..…………….191
8.3.2
Fen on’s Oxida ion (App oach 2) ........................................................................ 193
8.3.2.1 In luence o Fe ous Ion Concen a ion ………….…………...………………………………….194
8.3.2.2 E ec o he Ini ial Hyd ogen Pe oxide Concen a ion ….....………………………………….195
8.3.2.3 E ec o he Tempe a u e.….…………………………………..………………………………….197
8.3.2.4 Op imized T ea men by Fen on's Oxida ion……..…………...………………………………….198
8.3.3
Fen on’s Oxida ion ollowed by Coagula ion/Floccula ion (App oach 3) ............ 200
8.3.3.1 In luence o pH in he Coagula ion P ocess….….…………...………………………………….201
8.3.3.2 E ec o Supe loc C-573 Doses ………………………….....……………….………………….202
8.3.4
Ope a ing Cos s .................................................................................................. 205
8.4 Conclusions ................................................................................................... 207
8.5 Re e ences ..................................................................................................... 208
9
Simula ed Dyeing Tex ile E luen s T ea men by he Pho o-Fen on
P ocess ............................................................................................................. 213
9.1 In oduc ion .................................................................................................... 213
9.2 Ma e ials and Me hods .................................................................................. 213
9.2.1
P epa a ion o Simula ed Tex ile Was ewa e s .................................................. 213
9.2.2
Expe imen al P ocedu e ..................................................................................... 213
9.2.3
Analy ical Me hods ............................................................................................. 214
9.3 Resul s and Discussion ................................................................................ 214
9.3.1
Pho o eac o wi h A i icial Radia ion .................................................................. 214
9.3.1.1 Compa ison Be ween Di ec Pho olysis, UV- isible+H2O2 and Pho o-Fen on P ocesses
………………………….…………..…………………………………….………………………………….216
9.3.1.2 Pho o-Fen on P ocess….……………….………………….………….………………………….218
9.3.1.2.1 E ec o Hyd ogen Pe oxide Concen a ion….……….…………………………………………………..218
9.3.1.2.2 E ec o Radia ion In ensi y …………………………………….………………………………..………….222
9.3.1.2.3 Ope a ing Cos s ………………………………………………….………….………………………………….224
9.3.2
Pho o eac o wi h Simula ed Sola Radia ion ..................................................... 227
9.4 Conclusions ................................................................................................... 232
9.5 Re e ences ..................................................................................................... 233
10
Simula ed Tex ile Dyeing E luen s T ea men by SBR alone and
Combined wi h Fen on’s Oxida ion ................................................................ 237
10.1 In oduc ion .................................................................................................... 237
10.2 Ma e ials and Me hods .................................................................................. 237
10.2.1
P epa a ion o he Simula ed Tex ile E luen s ................................................... 237
x iii
10.2.2
Expe imen al P ocedu e ..................................................................................... 237
10.2.3
Analy ical Me hods ............................................................................................. 238
10.3 Resul s and Discussion ................................................................................ 238
10.3.1
Biological T ea men ........................................................................................... 238
10.3.2
In eg a ion o Fen on’s Reagen Followed by Biological T ea men ................... 243
10.3.3
Cos s E alua ion ................................................................................................. 251
10.4 Conclusions ................................................................................................... 252
10.5 Re e ences ..................................................................................................... 253
Pa IV – Real Co on Dyeing Was ewa e
11
Co on Dyeing Was ewa e T ea men .................................................. 259
11.1 In oduc ion .................................................................................................... 259
11.2 Ope a ing Cos s ............................................................................................. 261
11.3 Ma e ials and Me hods .................................................................................. 262
11.3.1
Expe imen al P ocedu e ..................................................................................... 262
11.3.2
Analy ical Me hods ............................................................................................. 262
11.4 Resul s and Discussion ................................................................................ 263
11.4.1
Tex ile Deying Was ewa e ................................................................................. 263
11.4.2
Coagula ion/Floccula ion plus Fen on’s Reac ion (App oach 1) ........................ 263
11.4.3
Fen on’s Oxida ion (App oach 2) ........................................................................ 266
11.4.4
In eg a ion o Fen on’s Oxida ion and Coagula ion/ Floccula ion (App oach 3) . 269
11.4.5
Combina ion o Fen on´s Reac ion and SBR (App oach 4) ............................... 272
11.5 Conclusions ................................................................................................... 275
11.6 Re e ences ..................................................................................................... 276
Pa I – Conclusions and Sugges ion o Fu u e Wo k
12
Concluding Rema ks and Fo hcoming Wo k ...................................... 283
12.1 Concluding Rema ks ..................................................................................... 283
12.1.1
Simula ed Tex ile Dyeing E luen s ..................................................................... 283
12.1.2
Indus ial Co on Dyeing Was ewa e ................................................................. 285
12.1.3
B ie Compa ison o P ocesses .......................................................................... 285
12.2 Fo hcoming Wo k ......................................................................................... 287
Appendix ........................................................................................................... 291
A.1 Suppo ing In o ma ion o Chap e 4 ……………………...…………….………291
A.2 Suppo ing In o ma ion o Chap e 9 ………………………………...….………293
xix
Lis o Figu es
Pa I – In oduc ion and S a e o A
Figu e 1.1 – Tex ile indus y geoghaphic dis ibui ion in Po ugal …………………………………….. 7
Figu e 1.2 – Rep esen a i e lowcha o ex ile and clo hing manu ac u ing p ocess ……………… 9
Pa II – Expe imen al Sec ion
Figu e 3.1 – Scheme o polyes e ibe s dyeing: a) ibe p epa a ion, b) dyeing and c) educ ion
washing…………………………………………………………………...………………………………… 72
Figu e 3.2 – Scheme o ac ylic ibe s dyeing …………………………………………….………….… 73
Figu e 3.3 – Scheme o co on ibe s dyeing: a) ibe p epa a ion, b) dyeing and c) washing
……………………………………………………...………………………………………….………….… 73
Figu e 3.4 – UV/ isible spec um o polyes e , ac ylic and co on was ewa e s ……..…………… 75
Figu e 3.5 – UV/ isible spec um o eal co on dyeing was ewa e ……...………………………… 76
Figu e 3.6 – Diag am o he Ja - es se -up ……………………………….…………………………… 82
Figu e 3.7 – Diag am o Fen on’s oxida ion se -up ……………………….…………………………… 83
Figu e 3.8 – Diag am o he pho o-Fen on se -up wi h me cu y lamp TQ 150 …………………….. 84
Figu e 3.9 - Va ia ion o he adia ion in ensi y wi h he Solophenyl G een BLE 155% concen a ion
ci cula ing in he pho o- eac o jacke …………………………………………………………………... 86
Figu e 3.10 – Diag am o he sun- es se -up ………………………………………………………..… 87
Figu e 3.11 – Diag am o he SBR se -up ……………………………………………………………… 88
Pa III – Simula ed Dyeing Was ewa e s T ea men
Figu e 4.1 – Va ia ion o DOC (a) and colo (b) emo als wi h empe a u e in he coagula ion s age
o he di e en simula ed e luen s (
coagula ion
=150 pm,
coagula ion
=3 min, [Fe
2+
]=200 mg/L and
pH=8.3). ………………………………………………….………………………………………………… 98
Figu e 4.2 – In luence o pH on DOC (a) and colo (b) emo als by coagula ion applied o he
di e en simula ed e luen s (
coagula ion
=150 pm,
coagula ion
=3 min, [Fe
2+
]=200 mg/L and T
=T
ambien
=22-23 ºC) ........................................................................................................................ 99
Figu e 4.3 – Va ia ion o DOC (a) and colo (b) emo als wi h he concen a ion o coagulan (Fe
2+
)
o he di e en simula ed e luen s (
coagula ion
=150 pm,
coagula ion
=3 min, T=T
ambien
=23-25 ºC and
pH
polyes e
=8.3, pH
co on
=9.4 and pH
ac ylic
=7.2) ..................................................................................100
Figu e 4.4 - Va ia ion o DOC (a) and colo (b) emo als wi h he dose o locculan (Magna loc
155) o he di e en simula ed e luen s (
coagula ion
=150 pm,
coagula ion
=3 min, T=T
ambien
=23-25 ºC,
pH
polyes e
=8.3, pH
co on
=9.4, pH
ac ylic
=7.2, [Fe
2+
]
polyes e
=[Fe
2+
]
co on
=200 mg/L, [Fe
2+
]
ac ylic
=3000 mg/L,
loccula ion
=20 pm and
loccula ion
=15 min) ........................................................................................ 101

xx
Figu e 4.5 - Va ia ion o DOC (a) and colo (b) emo als wi h he dose o locculan (Supe loc C-
573) o he di e en simula ed e luen s (
coagula ion
=150 pm,
coagula ion
=3 min, T=T
ambien
=23-25 ºC,
pH
polyes e
=8.3, pH
co on
=9.4, pH
ac ylic
=7.2, [Fe
2+
]
polyes e
=[Fe
2+
]
co on
=200 mg/L, [Fe
2+
]
ac ylic
=3000 mg/L,
loccula ion
=20 pm and
loccula ion
=15 min) ........................................................................................ 104
Figu e 5.1 – In luence o pH in DOC (a) and colo (b) emo al om he di e en e luen s (
coagula ion
= 150 pm,
coagula ion
= 3 min, [Fe
3+
]
polyes e
= [Fe
3+
]
co on
= 200 mg/L, [Fe
3+
]
ac ylic
= 500 mg/L and
T=T
ambien
= 22-23 ºC) .................................................................................................................... 116
Figu e 5.2 – E ec o Fe
3+
concen a ion on DOC (a) and colo (b) emo al om he di e en
e luen s (
coagula ion
= 150 pm,
coagula ion
= 3 min, T=T
ambien
= 23-25 ºC and pH
polyes e
= 9.4, pH
co on
=
5.0 and pH
ac ylic
= 8.3) ................................................................................................................... 117
Figu e 5.3 – E ec o Magna loc155 concen a ion on DOC (a) and colo (b) emo al om he
di e en e luen s (
coagula ion
= 150 pm,
coagula ion
= 3 min, T=T
ambien
= 23-26 ºC, pH
polyes e
= 9.4,
pH
co on
= 5.0, pH
ac ylic
= 8.3, [Fe
3+
]
polyes e
= 500 mg/L, [Fe
3+
]
co on
= 200 mg/L, [Fe
3+
]
ac ylic
= 1000 mg/L,
loccula ion
= 20 pm and
loccula ion
= 15 min) ..................................................................................... 119
Figu e 5.4 – E ec o Supe loc C-573 concen a ion on DOC (a) and colo (b) emo al om he
di e en e luen s (
coagula ion
= 150 pm,
coagula ion
= 3 min, T = T
ambien
= 23-26 ºC, pH
polyes e
= 9.4,
pH
co on
= 5.0, pH
ac ylic
= 8.3, [Fe
3+
]
polyes e
= 500 mg/L, [Fe
3+
]
co on
= 200 mg/L, [Fe
3+
]
ac ylic
= 1000 mg/L,
loccula ion
= 20 pm and
loccula ion
= 15 min) ..................................................................................... 120
Figu e 6.1 - Va ia ion o DOC emo al and k’ wi h he o al i on concen a ion, in he i s (a) and c),
espec i ely) and second expe imen (b) and (d), espec i ely) (ini ial pH=3.5, T=30 °C, ini ial
[H
2
O
2
]=5 g/L) …………………………………………………………………………………………….. 134
Figu e 6.2 - In luence o he H
2
O
2
concen a ion on DOC emo al and k’ in he i s (a) and c),
espec i ely) and second expe imen (b) and d), espec i ely) (ini ial pH=3.5, T=30 °C, ini ial
[Fe]=350 mg/L) …………………………………………………………………………………………... 136
Figu e 6.3 - E ec o empe a u e on DOC emo al and k’ in he i s (a) and c), espec i ely) and
second expe imen (b) and d), espec i ely) (ini ial pH=3.5, [Fe]=350 mg/L, [H
2
O
2
]
1s
exp=3.5 g/L,
[H
2
O
2
]
2nd
exp=20 g/L) ………………………………………………………………………………….... 139
Figu e 6.4 - E ec o empe a u e on he esidual hyd ogen pe oxide concen a ion in he i s (a)
and second expe imen (b) (ini ial pH=3.5, [Fe]=350 mg/L, [H
2
O
2
]
1s
exp=3.5 g/L, [H
2
O
2
]
2nd
exp=20
g/L) ………………………………………………………………………………………………………... 140
Figu e 6.5 - Va ia ion o DOC emo al (a) and k’ (b) wi h he ini ial pH in he i s expe imen (T=50
°C, [Fe]=350 mg/L and [H
2
O
2
]=3.5 g/L) ……………………………………………………………….. 140
Figu e 6.6 - E olu ion o he inhibi ion o Vib o ische i o samples aken along 60 min o Fen on’s
eac ion o con ac imes o 5, 15 and 30 min in he i s (a) and second expe imen (b) (pH= 3.5,
T=50 °C, [Fe]=350 mg/L and [H
2
O
2
]
1s
exp=3.5 g/L, [H
2
O
2
]
2nd
exp=20 g/L) ……………………..… 143
Figu e 6.7 - Time e olu ion o HPLC ch oma og am in he i s (a) and second expe imen (b) (pH=
3.5, T=50 °C, [Fe]=350 mg/L and [H
2
O
2
]
1s
exp=3.5 g/L, [H
2
O
2
]
2nd
exp=20 g/L) ………………….. 143
Figu e 6.8 – Va ia ion o DOC (a) and colo (b) emo als wi h pH in he coagula ion s age o
di e en doses o hyd ogen pe oxide applyed in he p e ious Fen on’s p ocess - uns #1, #2 and #3
(
coagula ion
=150 pm,
coagula ion
=3 min, [Fe dissol ed]
un #1
= 75.5 mg/L, [Fe dissol ed]
un #2
=118.1
mg/L, [Fe dissol ed]
un #3
=275 mg/L and T =T
ambien
= 22-24 ºC) ………………………………….… 146
Figu e 6.9 – Va ia ion o DOC (a) and colo (b) emo als wi h locculan concen a ion in he
loccula ion s ep o di e en hyd ogen pe oxide doses applyed in he p e ious Fen on’s p ocess -
uns #1, #2 and #3 (
coagula ion
=150 pm,
coagula ion
=3 min, [Fe dissol ed]
un #1
=75.5 mg/L, [Fe
xxi
dissol ed]
un #2
=118.1 mg/L, [Fe dissol ed]
un #3
=275 mg/L and T =T
ambien
= 22-24 ºC,
loccula ion
=20
pm,
loccula ion
=15 min) …………………………………………………………………………………... 147
Figu e 7.1 - Schema ic diag am o p ocess con igu a ions adop ed ………………………………. 159
Figu e 7.2 – Va ia ion o dissol ed o ganic ca bon (a) and colo (b) emo al along ime wi h he i on
dose du ing he Fen on eac ion a e he coagula ion/ loccula ion s age – App oach 1 (ini ial
pH=3.5, T=30 ºC, [H
2
O
2
]
o
=500 mg/L) ………...……………………………………………………….. 161
Figu e 7.3 – Va ia ion o dissol ed o ganic ca bon (a) and colo (b) emo al along ime wi h he
concen a ion o H
2
O
2
added du ing he Fen on’s eac ion a e he coagula ion/ loccula ion s age –
App oach 1 (ini ial pH=3.5, T=30 ºC, [Fe]=100 mg/L) ………...………………………………………163
Figu e 7.4 – Va ia ion o dissol ed o ganic ca bon (a) and colo (b) emo al along ime wi h he
empe a u e du ing he Fen on eac ion a e he coagula ion/ loccula ion s age – App oach 1 (ini ial
pH=3.5, [Fe]=100 mg/L and [H
2
O
2
]
o
=500 mg/L) ………………………...…………………………… 165
Figu e 7.5 – Va ia ion o dissol ed o ganic ca bon (a), colo (b) emo al and speci ic oxygen up ake
a e (c) along ime wi h he ini ial concen a ion o Fe
2+
du ing he Fen on eac ion – App oach 2
(ini ial pH=3.5, T=30 ºC, [H
2
O
2
]
o
=5 g/L) ………………………………………………………………..168
Figu e 7.6 – Va ia ion o dissol ed o ganic ca bon (a), colo (b) emo al and speci ic oxygen up ake
a e (c) along ime wi h he ini ial concen a ion o H
2
O
2+
du ing he Fen on eac ion – App oach 2
(ini ial pH=3.5, T=30 ºC, [Fe
2+
]
o
=300 mg/L) …………………………………………………………... 169
Figu e 7.7 – Va ia ion o dissol ed o ganic ca bon (a), colo (b) emo al and speci ic oxygen up ake
a e (c) along ime wi h he empe a u e du ing he Fen on eac ion – App oach 2 (ini ial pH=3.5,
[Fe
2+
]
o
=300 mg/L and [H
2
O
2
]
o
=10 g/L) ………………………………………………………………… 171
Figu e 7.8 – Va ia ion o DOC (a) and colo (b) emo als wi h pH du ing he coagula ion s age –
App oach 3 – o di e en doses o hyd ogen pe oxide employed in he p e ious Fen on’s p ocess
in uns #1, #2 and #3 (
coagula ion
=150 pm,
coagula ion
=3 min, [Fe
dissol ed
]
un #1
=52.1 mg/L, [Fe
dissol ed
]
un
#2
=85.6 mg/L, [Fe
dissol ed
]
un #3
=167 mg/L and T =T
ambien
=23-25 ºC) ……………………………….. 173
Figu e 7.9 – Va ia ion o DOC (a) and colo (b) emo als wi h he locculan concen a ion du ing
he loccula ion s ep – App oach 3 – o he di e en doses o hyd ogen pe oxide employed in he
p e ious Fen on’s p ocess in uns #1, #2 and #3 (
coagula ion
=150 pm,
coagula ion
=3 min, T=T
ambien
=23-
25 ºC, pH=5.0, [Fe
dissol ed
]
un #1
=52.1 mg/L, [Fe
dissol ed
]
un #2
=85.6 mg/L, [Fe
dissol ed
]
un #3
=167 mg/L,
loccula ion
=20 pm and
loccula ion
=15 min) ……………………………………………………………….. 175
Figu e 7.10 – E ec o Fe and H
2
O
2
doses in he o al ope a ing cos o was ewa e ea men by
coagula ion/ loccula ion plus Fen on p ocesses – App oach 1 (a), Fen on’s eagen – App oach 2
(b) and in luence o Magna loc 155 and H
2
O
2
concen a ion in he o al ea men cos s by Fen on’s
p ocess ollowed by coagula ion/ loccula ion – App oach 3 (c) …………………………………….. 179
Figu e 8.1 – Va ia ion o DOC emo al (a) and pe cen age o H
2
O
2
consump ion (b) along ime,
wi h he i on dose added du ing he 2
nd
s age – Fen on oxida ion in App oach 1 (ini ial pH=3.5,
T=30 ºC, ini ial [H
2
O
2
]= 500 mg/L) …………………………………………………………………….. 188
Figu e 8.2 – E ec o H
2
O
2
dose in DOC emo al (a) and pe cen age o H
2
O
2
consump ion (b)
along ime du ing he 2
nd
s age i.e. Fen on oxida ion in App oach 1 (ini ial pH=3.5, T=30 ºC,
[Fe]=200 mg/L) …………………………………………………………………..………………………. 190
Figu e 8.3 – Va ia ion o DOC emo al (a) and pe cen age o H
2
O
2
consump ion (b) along ime
wi h he eac ion empe a u e du ing he 2
nd
s age – Fen on oxida ion in App oach 1 (ini ial pH=3.5,
[Fe]=200 mg/L and ini ial [H
2
O
2
]=1000 mg/L) …………………………….………………………….. 191
xxii
Figu e 8.4 – E olu ion o he inhibi ion o V. ische i a 5, 15 and 30 minu es o con ac (a) and
HPLC ch oma og ams (b) o samples aken along ime du ing he 2
nd
s age – Fen on oxida ion in
App oach 1 (ini ial pH=3.5, T=50 ºC, ini ial [Fe]=200 mg/L and ini ial [H
2
O
2
]=1000 mg/L)
……………………………………………………………………………………………………………... 192
Figu e 8.5 – Va ia ion o DOC emo al (a), pe cen age o H
2
O
2
consump ion (b) and k’(c) along
ime wi h he ini ial Fe
2+
dose du ing Fen on’s eac ion in App oach 2 (ini ial pH=3.5, T=30 ºC, ini ial
[H
2
O
2
]= 5.0 g/L) ………………………………………………………………………………………….. 193
Figu e 8.6 – Va ia ion o DOC emo al (a), pe cen age o H
2
O
2
consump ion (b) and k’(c) along
ime wi h he ini ial H
2
O
2
dose du ing Fen on’s eac ion in App oach 2 (ini ial pH=3.5, T=30 ºC,
ini ial [Fe
2+
]=350 mg/L) ………………………………………………………………………………….. 196
Figu e 8.7 – Va ia ion o DOC emo al (a), pe cen age o H
2
O
2
consump ion (b) and k’(c) along
ime wi h he eac ion empe a u e du ing Fen on’s eac ion in App oach 2 (ini ial pH=3.5, ini ial
[Fe
2+
]=350 mg/L and ini ial [H
2
O
2
]=2.5 g/L) …………………………………………………………... 198
Figu e 8.8 – E olu ion o V. ische i inhibi ion a e 5, 15 and 30 minu es o con ac (a) and HPLC
ch oma og ams (b) o samples aken along ime du ing Fen on’s oxida ion in App oach 2 (ini ial
pH=3.5, T=50 ºC, ini ial [Fe
2+
]=350 mg/L and ini ial [H
2
O
2
]=2.5 g/L) ………………………………. 199
Figu e 8.9 – Va ia ion o DOC emo al wi h pH du ing he coagula ion s age – App oach 3 – o he
di e en doses o hyd ogen pe oxide employed in he p e ious Fen on’s p ocess in uns #1, #2 and
#3 (
coagula ion
=150 pm,
coagula ion
=3 min, [Fe]
dissol ed
un #1
= 64.8mg/L, [Fe]
dissol ed un #2
=88.5 mg/L,
[Fe]
dissol ed un #3
=222 mg/L and T =T
ambien
=22-24 ºC) ……………………………………………..… 201
Figu e 8.10 – Va ia ion o DOC emo al wi h he locculan concen a ion du ing he loccula ion
s ep – App oach 3 – o he di e en doses o hyd ogen pe oxide employed in uns #1, #2 and #3
o he p e ious Fen on’s p ocess (
coagula ion
=150 pm,
coagula ion
=3 min, T=T
ambien
=22-24 ºC, pH=5.0,
[Fe]
dissol ed
un #1
= 64.8mg/L, [Fe]
dissol ed un #2
=88.5 mg/L, [Fe]
dissol ed un #3
=222 mg/L,
loccula ion
=20
pm and
loccula ion
=15 min) ………………………………………………………………………………. 203
Figu e 8.11 – E ec o Fe and H
2
O
2
doses on he ope a ing cos o was ewa e ea men by:
coagula ion/ loccula ion plus Fen on p ocesses – App oach 1 (a) o Fen on’s eagen – App oach 2
(b), and in luence o [Supe loc C-573] and [H
2
O
2
] on he ope a ing cos o Fen on’s p ocess
ollowed by coagula ion/ loccula ion – App oach 3 (c) ………………………………………………. 206
Figu e 9.1 – E olu ion o DOC and colo emo al o ac ylic (a), co on (b) and polyes e (c)
was ewa e du ing 120 minu es o di ec pho olysis, H
2
O
2
-assis ed
pho olysis ([H
2
O
2
]
ac ylic
=20 g/L,
[H
2
O
2
]
co on
=10 g/L and [H
2
O
2
]
polyes e
=2.5 g/L) o pho o-Fen on ([H
2
O
2
]
ac ylic
=20 g/L, [H
2
O
2
]
co on
=10
g/L and [H
2
O
2
]
polyes e
=2.5 g/L, [Fe
2+
]
co on
=300 mg/L, [Fe
2+
]
ac ylic
=[Fe
2+
]
polyes e
=350 mg/L). In all cases
adia ion in ensi y = 500 W/m
2
, pH=3.5, T=50ºC …………………………………………………….. 216
Figu e 9.2 – E ec o H
2
O
2
dose on DOC and colo emo al in he pho o-Fen on p ocess o ac ylic
(a), co on (b) and polyes e (c) was ewa e s ( adia ion in ensi y = 500 W/m
2
, T=50 ºC, pH=3.5,
Fe
2+
:H
2
O
2 ac ylic
=1:57, Fe
2+
:H
2
O
2 co on
=1:33, Fe
2+
:H
2
O
2 polyes e
=1:7 – w . a ios) ………………… 219
Figu e 9.3 – E ec o adia ion in ensi y on DOC and colo emo al o he ac ylic e luen du ing he
pho o-Fen on p ocess o di e en dosages o hyd ogen pe oxide: 6.5 g/L (a), 10.0 g/L (b) o 20.0
g/L (c) (T=50 ºC, Fe
2+
:H
2
O
2
=1:57 and pH=3.5) ……………………………………………………… 223
Figu e 9.4 – E ec o hyd ogen pe oxide doses and adia ion in ensi y on he o al ope a ing cos
associa ed wi h he pho o-Fen on p ocess wi h TQ 150 lamp o ea ing ac ylic (a), co on (b) and
polyes e (c) was ewa e s ………………………………………………………………………………. 226
xxiii
Figu e 9.5 – E ec o H
2
O
2
dose on DOC and colo emo al wi h simula ed sola adia ion a
in ensi y o 253 W/m
2
o ac ylic (a), co on (b) and polyes e (c) was ewa e s (T=50 ºC, Fe
2+
:H
2
O
2
ac ylic
=1:57, Fe
2+
:H
2
O
2 co on
=1:33 Fe
2+
:H
2
O
2 polyes e
=1:7, pH=3.5) ……………………………….… 228
Figu e 9.6 – E ec o H
2
O
2
and Fe
2+
doses on he o al ope a ing cos associa ed wi h he pho o-
Fen on wi h simula ed sola adia ion o ea ing ac ylic (a), co on (b) and polyes e (c)
was ewa e s ……………………………………………………………………………………………… 231
Figu e 10.1 – E olu ion o pe cen age o COD deg ada ion along ime in Zahn-Wellens es o
ac ylic was ewa e ………………………………………………………………………………………. 233
Figu e 10.2 - Va ia ion o COD (a), BOD
5
(b), DOC (c), o al ni ogen (d) and colo (e) emo als
along 10 cycles o SBR ope a ion o polyes e and co on was ewa e s ……………………….… 240
Figu e 10.3 - Va ia ion o COD (a), BOD
5
(b), DOC (c), o al ni ogen (d) and colo (e) emo als
du ing 10 cycles o SBR ope a ion o ac ylic e luen , p e iously ea ed by Fen on’s oxida ion.
Runs#1 o #3 ep esen expe imen s wi h dec easing doses o chemicals in he Fen on’s s age
...……………………………………………………………………………...……………………………. 248
Figu e 10.4 - Va ia ion o COD (a), BOD
5
(b), DOC (c), o al ni ogen (d) and colo (e) emo als
du ing 10 cycles o SBR ope a ion o syn he ic co on dyeing e luen , p e iously ea ed by
Fen on’s eac ion. Runs#1 o #3 ep esen expe imen s wi h dec easing doses o chemicals in he
Fen on’s s age …………………………………………………………………………………………… 249
Figu e 10.5 - E olu ion o COD (a), BOD
5
(b), DOC (c) and o al ni ogen (d) emo als du ing 10
cycles o SBR ope a ion o polyes e dyeing was ewa e , p e iously ea ed by Fen on’s eac ion.
Runs#1 o #3 ep esen expe imen s wi h dec easing doses o chemicals in he Fen on’s s age
....................................................................................................................................................... 250
Figu e 10.6 - To al ope a ing cos s o biological, Fen on alone and in eg a ed ea men o ac ylic,
co on and polyes e dyeing was ewa e s …………………………………………………………….. 252
Pa IV – Real Co on Dyeing Was ewa e
Figu e 11.1 - Schema ic diag am o all p ocess con igu a ions adop ed ………………………….. 260
Figu e 11.2 - E ec o H
2
O
2
concen a ion on COD, BOD
5
, DOC and colo emo als du ing
Fen on’s oxida ion (App oach 2) (ini ial pH=3.5, T=50 ºC, = 60 min and [Fe
2+
]
= 300 mg/L) ….. 266
Figu e 11.3 - E ec o Fe
2+
concen a ion on COD, BOD
5
, DOC and colo emo als du ing Fen on’s
oxida ion (App oach 2) (ini ial pH=3.5, T=50 ºC, = 60 min and [H
2
O
2
]
= 1.25 g/L) ……………… 268
Figu e 11.4 - Va ia ion o COD (a), DOC (b), BOD
5
(c), colo (d) o al ni ogen (e) and o al
phospho us ( ) emo als along 10 cycles o SBR ope a ion, a e ea men by Fen on’s oxida ion.
Runs #3 o #1 e e o Fen on’s s age wi h p og essi ely dec easing doses o chemicals ……… 273
Figu e 11.5 - Ope a ing cos s o Fen on alone and Fen on plus SBR o ea men o a eal co on
dyeing was ewa e ………………………………………………………………………………………. 275
Appendix
Figu e A.1 – In luence o he s i ing a e on he coagula ion s age o DOC (a) and colo (b)
emo al om polyes e and co on simula ed e luen s (
coagula ion
=3 min, T=T
ambien
=23-25 ºC,
[Fe
2+
]=200 mg/L and pH=8.3) ....................................................................................................... 291
KTN Kjeldhal To al Ni ogen [mg/L]
P Powe [W]
SRT Sludge Re en ion Time [day]
SOUR o k’ Speci ic Oxygen Up ake Ra e [mg O
2
/(g
VSS
.h)]
V
coagula ion
S i ing Speed in Coagula ion S ep [ pm]
V
loccula ion
S i ing Speed in Floccula ion S ep [ pm]
T Tempe a u e [ºC]
T
amb
Ambien Tempe a u e [ºC]
T Time [min]
eed
Time o Feeding [days]
coagula ion
Time o Coagula ion S age [min]
loccula ion
Time o Floccula ion S age [min]
eac ion
Time o eac ion [min]
TDS To al Dissol ed Solids [mg/L]
TOC To al O ganic Ca bon [mg C/L]
TS To al Solids [mg/L]
TSS To al Suspensed Solids [mg/L]
G Veloci y g adien [s
-1
]
VSS Vola il Suspensed Solids [mg/L]
[mg MLSS/L]
G eek Le e s
Symbol Designa ion Uni y
λ Wa eleng h [nm]
λ
max
Wa eleng h o Maximum Abso bance Value [nm]

xxxi
Abb e ia ions
Abb e ia ion Designa ion
AA – SBR Ae obic - Anae obic Sequen ial Ba ch Reac o
AOP Ad anced Oxida ion P ocess
E.L.V. Emission Limi Value
FCS Fe ic Chlo ide Sludge
GAC G anula Ac i a ed Ca bon
HPLC High Pe o mance Liquid Ch oma og aphy
R O ganic compound
M.A.V. Maximum Allowable Value
MLSS Mixed Liquo Suspensed Solids
PDMDAAC Polidime ildialilamonium Chlo ide
PAC Polyaluminum Chlo ide
PFC Poly e ic Chlo ide
PAS Polyalumimium Sul a e
SBR Sequen ial Ba ch Reac o
UV Ul a- iole
hν Radia ion
V. ische i Vib io ische i
WWTP Was ewa e T ea men Plan
Pa I
In oduc ion and S a e o A
Chap e 1
Thesis F amewo k

Pa I
5
1 Thesis F amewo k
1.1 In oduc ion
This chap e p esen s he ou line and mo i a ion o he hesis, a b ie o e iew o he
ex ile indus y in Po ugal, a sho desc ip ion o he indus ial p ocess, he
cha ac e iza ion o he ex ile was ewa e s gene a ed and he iden i ica ion o he majo
en i onmen al impac s associa ed wi h he discha ge o ex ile e luen s.
1.2 Ou line and Mo i a ion
En i onmen al p o ec ion and co ec ion o en i onmen al dys unc ions a e key issues o
e ec i ely imp o ing he quali y o li e and sus ainable de elopmen . The wa e is used o
e y di e se pu poses, which include domes ic and public supply, i iga ion, anspo ,
indus ial p ocesses, ec ea ion and o he human ac i i ies. These ac i i ies gene a e
hea ily con amina ed was ewa e s, ha i discha ged wi hou any ea men can cause
s ong nega i e impac s on he ecei ing bodies.
The ex ile indus y is known as one o he mos pollu ing indus ial sec o s [Vande i e e
e al., 1998], gi en he la ge amoun s o was ewa e ejec ed, he composi ion o he
e luen s and he ac ha dyes a e he mos no o ious pollu an s, and o en oxic
[Figuei edo, 2002].
The adop ion o legisla ion ha add esses he need o con ol he con amina ion by
educing he pollu an s discha ged (2000/60/EC Di ec i e) and he imposi ion o emission
limi alues (E.L.V.) by Dec ee - Law No. 236/98 o 1 Augus and maximum allowable
alues (M.A.V.) o he discha ge o ex ile e luen s (O dinance No. 423/97 o 25 June)
makes he s udy o new ea men p ocesses a need inc easingly u gen . Mo eo e , he
possibili y o eusing he ea ed e luen in indus ial p ocesses mus necessa ily be
exploi ed, since i allows he minimiza ion o wa e consump ion as well as he elimina ion
o pollu an s discha ge [Sil a, 2003].
Fo he ea men o ex ile e luen s, chemical, biological o a combina ion o bo h
p ocesses a e gene ally en isaged. The biological ea men by ac i a ed sludge is
e icien in emo ing he biodeg adable o ganic ma e , bu o en ine ec i e in emo ing
Chap e 1
-
F amewo k
6
he colo om was ewa e s, since his is only emo ed by loccula ion and adso p ion o
he dyes o locs o mic oo ganisms [Halliday and Beszedi s, 1986]. Chemical
coagula ion/ loccula ion is also no ully e ec i e in emo ing ce ain dyes [Rod igues,
2007].
As a con ibu ion o o e come his p oblem i was decided o s udy he combina ion o
coagula ion/ loccula ion, chemical oxida ion by Fen on’s eagen – bo h in da kness and
unde a i icial o sola (simula ed) adia ion (pho o-Fen on oxida ion) – and an ae obic
biological p ocess (SBR - sequen ial ba ch eac o ) o imp o e decolo iza ion and o ganic
ma e emo al.
Resea ch was ocused on h ee simula ed e luen s ( esul ing om he dyeing o ac ylic,
co on and polyes e ibe s) and he ea abili y o each e luen was assessed by he
indi idual p ocesses men ioned abo e and hei in eg a ion in o de o ob ain a ea ed
e luen complying wi h he discha ge limi s imposed by O dinance No. 423/97 o 25 June
a he lowes ope a ion cos . Taking in o accoun he esul s ob ained when ea ing a
simula ed co on dyeing was ewa e , a combina ion o coagula ion/ loccula ion and
Fen on’s oxida ion, Fen on’s oxida ion alone and an in eg a ed p ocess consis ing in
Fen on’s oxida ion plus coagula ion/ loccula ion o biological oxida ion in SBR, we e
applied o a eal co on dyeing was ewa e ha ing also in mind he need o mee he
discha ge limi s a he lowes ope a ing cos s.
1.3 The Tex ile Indus y
1.3.1 Economic Pe spec i e and Tex ile Indus y Dis ibu ion in
Po ugal
The Eu opean ex ile and clo hing indus y, which ep esen s app oxima ely 7% o
employmen and 4% o o al manu ac u ing ou pu in he E.U. [Commission o he
Eu opean Communi ies, 2003], is in a di icul economic si ua ion due o he high
compe i ion om Asian coun ies like China, India and Pakis an and he aboli ion o impo
quo as by Janua y 1
s
2005. In ac , he e was a decline in he p oduc ion (8.7%) and in
he employmen (8.4%) in 2001 and 2002 [Commission o he Eu opean Communi ies,
2003]. In 2003 he dec ease was 4.4% and 7.1% o p oduc ion and employmen ,
espec i ely [Commission o he Eu opean Communi ies, 2004].
Pa I
7
In Po ugal, he ex ile and clo hing indus y has a la ge ep esen a ion in he indus ial
s uc u e wi h a p ominen ole in e ms o employmen and weigh in he na ional
economy [Vasconcelos, 2006]. Acco ding o he Tex ile and Clo hing Associa ion [ATP,
2013], in 2011 he e we e, in Po ugal, abou 7000 companies labo ing in all ex ile and
clo hing sub-sec o s, which accoun ed o 10% o Po uguese expo s, 19% o
employmen in manu ac u ing indus y, 8% o u no e and 8% o p oduc ion. Na ional
s eng hs lie in geog aphical and cul u al p oximi y o he Eu opean ma ke , adi ion and
accumula ed "know-how", mode a e wage cos s as ega ds he Eu opean le els, g owing
in e na ional ecogni ion o he p oduc s, p og essi e de elopmen o a cul u e o quali y
and apid esponse [Vasconcelos, 2006].
The ex ile sec o in Po ugal also el p essu e om he Asian ma ke and he aboli ion o
impo quo as led o a conside able dec ease o o al expo s since 2007 [ATP, 2013].
The ex ile indus ies in Po ugal a e loca ed mainly in h ee egions: No h, Cen e and
Tagus Valley, and he e has been in ecen yea s an inc ease in he ela i e weigh o he
No h and Cen e, o he de imen o Lisbon, as can be seen in Figu e 1.1 [Vasconcelos,
2006].
Figu e 1.1 – Tex il indus y geog a ic dis ibui ion in Po ugal (adap ed om Vasconcelos, 2006).
In Po ugal, he e a e wo majo concen a ions o he ex ile indus y. The i s one,
conce ning he subsec o s o co on and syn he ic ibe s, is ound in he no he n egion,
0
1000
2000
3000
4000
No e Cen o Lisboa e
Vale do
Tejo
Alen ejo Alga e Aço es Madei a
Nº Emp esas
1999
2000
2001
2002
2003
Numbe o Indus ies
No h Cen e Lisbon Alen ejo Alga e Aço es Madei a
Chap e 1
-
In oduc ion
14
The uncon olled discha ge wi hou any p io ea men o such hea ily con amina ed
e luen s (c . Table 1.4) gene a es nega i e impac s on he en i onmen , namely:
 pH inc ease o he ecei ing wa e s, causing damage o auna and lo a;
 P esence o high le els o dissol ed solids can gene a e inc eased salini y and
u bidi y associa ed wi h he p oli e a ion o mic oo ganisms o eu ophiza ion
o he wa e esou ces;
 Possible occu ence o low dissol ed oxygen concen a ion in wa e due o i s
consump ion by ae obic mic oo ganisms ha oxidize he biodeg adable
o ganic ma e p esen in he e luen , hen causing he dea h o aqua ic
o ganisms; he o ganic ma e may also be deg aded anae obically, yielding
oxic and unpleasan odo ous compounds (such as hyd ogen sul ide);
 One o he mos impo an ad e se e ec s esul ing om he discha ge o
ex ile was ewa e comes om non- ixed dyes o he ibe . Because dyes
p esen a g ea chemical and pho oly ic s abili y [Sil a, 2003] and a e isible a
low concen a ions (1 mg/L) [O'Neill e al., 1999], hey p e en he use o wa e
o ce ain uses, pa icula ly o p oducing d inking wa e and o ec ea ional
pu poses [Rod igues, 2007 and San os, 2009]; mo eo e , when inges ed hey
pose isks associa ed wi h ch onic bio ans o ma ions, as speci ic enzymes can
p oduce ca cinogenic and mu anogenic compounds (a oma ic amines such as,
oluidines, ac i e adicals, e c.), which may cause de ma i is when in con ac
wi h he skin [Sil a, 2003].
 Ano he nega i e impac o dyes is associa ed wi h a dec ease in sunligh
pene a ion, a ec ing pho osyn hesis and plan g ow h [Rod igues, 2007;
San os, 2009], and wi h dis u bances in he solubili y o gases causing damage
o he aqua ic auna [Sil a, 2003].
The compe en au ho i ies ha e been de elopping legisla ion ha limi s he concen a ion
o hese pollu an s in e luen s discha ged, o minimize en i onmen al impac s. Fo he
ex ile sec o , excluding he wool subsec o , he Po uguese Legisla ion (O dinace No.
423/97 o 25 June) imposes maximum allowable alues (M.A.V.) o pH, COD, BOD
5
and
isibile colo a e dilu ion 1:40 (Table 1.5).

Pa
I
15
Table 1.5 – Maximum allowable alues o he ex ile sec o , excluding he wool subsec o .
Pa ame e Maximum Allowable Values
pH 5.5 – 9.0
BOD
5
100 mgO
2
/L
COD 250 mgO
2
/L
Colo no isible a e dilui ion 1:40
The alues o pH, COD, BOD
5
and colo ypically do no comply wi h he alues
es ablished by law, so i is necessa y o ea he ex ile e luen s be o e dischage. Va ious
s udies conce ning he ea men o hese e luen s, namely, by physical p ocesses
(coagula ion/ loccula ion, adso p ion and memb ane sepa a ion), ad anced chemical
oxida ion, biological oxida ion and chemical educ ion, a e epo ed in he li e a u e
[Lou enço e al., 2001; Figuei edo, 2002; Walke e al., 2002; Malik e al., 2003; Fe si e
al., 2005; Rami ez e al., 2005; Joo e al., 2007; Rod igues, 2007].
In his hesis, coagula ion/ loccula ion, Fen on and pho o-Fen on oxida ion, and biological
p ocesses we e selec ed o ea ex ile dyeing was ewa e s. The nex chap e p esen s a
desc ip ion o hese echnologies and he easons o hei choice.
1.4 Re e ences
Ab aha , E.N. (1977). Dyes and Thei In e media es. 2
nd
Edi ion, Edwa d A nold L d, London.
Al-Kadasi, A.; Id is, A.; Saed, K.; Guan, C.T. (2004). T ea men o ex ile was ewa e by ad anced
oxida ion p ocess – a e iew. In e na ional Jou nal, 6 (3), 222-230.
AMAVE – Associação de Municípios do Vale do AVE, S.I.D.V.A. – Sis ema In eg ado de
Despoluição do Vale do A e (2002).
And ade, F. (2003). Remoção de co de e luen es êx eis com a amen o de lodos a i ados e um
polielec óli o o gânico. Disse ação de Mes ado em Engenha ia Ambien al, Depa amen o de
Engenha ia Sani á ia, Uni e sidade Fede al de San a Ca a ina, Flo ianópolis. (acess:
h p://www. ede.u sc.b / eses/PGEA0163.pd ).
A aújo, M. e Cas o, E. M. (1984). Manual de Engenha ia Têx il, olume II. Lisboa: Fundação
Calous e Gulbenkian.
ATP (2013). Associação Têx il e Ves uá io de Po ugal. h p://www.a p.p /gca/index.php?id=18.
(las acess 23/03/2013).
Chap e 1
-
In oduc ion
16
Bisschops, I.; Spanje s, H. (2003). Li e a u e Re iew on Tex ile Was ewa e Cha ac e isa ion.
En i onmen al Technology, 24, 1399-1411.
Commission o he Eu opean Communi ies (2003). O u u o do sec o dos êx eis e do Ves uá io na
União Eu opeia ala gada. Communica ion om he Council Commission, he Eu opean Pa liamen ,
he Eu opean Economic and Social Commi ee and he Commi ee o he Regions, B ussels.
Commission o he Eu opean Communi ies (2004). O sec o dos êx eis e do Ves uá io após 2005
– Recomendações do G upo de Al o Ní el pa a os Têx eis e o Ves uá io. Communica ion om he
Council Commission, he Eu opean Pa liamen , he Eu opean Economic and Social Commi ee
and he Commi ee o he Regions, B ussels.
2000/60/CE Di ec i e o Eu opean Pa liamen Council, 23 Oc obe 2000, es ablishing a amewo k
o Communi y ac ion in he ield o wa e policy.
Eas on, J. R. (1995). The dye make 's iew. In Colou in Dyehouse E luen , P. Coope (Ed.).
Ox o d, The Socie y o dye s and Colou is s, The Alden P ess, 9-21.
Fa ia, P.C.C. (2008). Ca aly ic Ozona ion o E luen s om he Tex ile Indus y. PhD hesis,
Uni e si y o Po o – Facul y o Enginee ing.
Fe si, C.; Gza a, L;. Dhahbi, M. (2005). T ea men o ex ile e luen s by memb ane echnologies.
Desalina ion, 185 (1-3), 399-409.
Figuei edo, J.M.; Rod igues, F.; Co eia, A.; Ba os, M. (2000). Guia Técnico do Sec o Têx il.
Lisbon.
Figuei edo, S. A. R. C. (2002). Remoção de co an es êx eis em solução aquosa usando ma e iais
na u ais con endo qui ina. PhD hesis, Uni e si y o Po o – Facul y o Enginee ing.
Gao, B.-Y.; Wang, Y.; Yue, Q.-Y.; Wei, J.-C.; Li, Q. (2007). Colo emo al om simula ed dye wa e
and ac ual ex ile was ewa e using a composi e coagulan p epa ed by ploy e ic chlo ide and
polydime hyldiallylammonium chlo ide. Sepa a ion and Pu i ica ion Technology, 54, 157-163.
Halliday, P.J.; Beszedi s, S. (1986). Colo Remo al om Tex ile Mill Was ewa e . Canadian Tex ile
Jou nal, Ap il, 78-84.
Hi, S.H.; Peng, C.F. (1994). T ea men o ex ile was ewa e by elec ochemical me hod, Wa e
Resea ch 28 (2), 277–282.
Joo, D.J.; Shin, W.S.; Choi,J.-H.; Choi, S. J.; Kim, M.-C.; Han, M.H.; Ha, T. W.; Kim, Y.-H. (2007).
Decolou iza ion o eac i e dyes using ino ganic coagulan s and syn he ic polyme . Dyes and
Pigmen s, 73, 59-64.
Kim, T.-H.; Pa k,C.; Yang,J.;Kim, S. (2004) Compa ison o dispe se and eac i e dye emo als by
chemical coagula ion and Fen on oxida ion. Jou nal o Haza dous Ma e ials, B 112, 95-103.
Lou enço, N.D.; No ais, J.M.; Pinhei o, H.M. (2001). E ec o some ope a ional pa ame e s on
ex ile dye biodeg ada ion in a sequen ial ba ch eac o . Jou nal o Bio echnology, 89, 163-174.
Malik, P.K.; Saha, S.K. (2003). Oxida ion o di ec dyes wi h hyd ogen pe oxide using e ous ion
ca alys . Sepa a ion and Pu i ica ion Technology, 31, 241-250.
Pa
I
17
Mokh a i, J., Phillips, D. A. S., Taylo , J. A. (2005). Syn hesis and e alua ion o a se ies o isazo
he e obi- unc ional eac i e dyes o co on. Dyes and Pigmen s, 64 (2), 163-170.
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Mas e disse a ion in en i onmen al enginee ing, Uni e si y o Po o – Facul y o Enginee ing.
O'Neill, C., Hawkes, F. R., Hawkes, D. L., Lou enco, N. D., Pinhei o, H. M. e Delee, W. (1999),
Colou in ex ile e luen s – sou ces, measu emen , discha ge consen s and simula ion: a e iew.
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Ves uá io. B aga, Po ugal, 26 de Ou ub o de 2006.
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T ea men o dye was e. Wa e Pollu ion Con ol, 78, 12-26.
Chap e 2
S a e o he A

Pa I
21
2 S a e o he A
2.1 In oduc ion
In he p esen chap e he p ocesses o coagula ion/ loccula ion, Fen on and pho o-
Fen on’s oxida ion and biological deg ada ion in sequencing ba ch eac o (SBR) a e
e iewed, pa icula ly hei applica ion o ex ile was ewa e ea men .
The selec ion o hese ea men p ocesses ook in o accoun he ease o ope a ion, he
abili y o elimina e pollu an s and he ope a ing cos .
2.2 Coagula ion/Floccula ion
Na u al wa e s and was ewa e s con ain suspended o colloidal insoluble pa icles.
Colloids a e pa icles wi h diame e in he ange o 0.1-1 nm [Ecken elde , 2000], usually
nega i ely cha ged. The su ace a ac s opposi ely cha ged ions in solu ion, he eby
o ming a ixed S e n laye . The emaining ions p esen in solu ion o m a di use laye
a ound he S e n laye . The combina ion o he wo laye s is called a double laye
[Ecken elde , 2000].
The colloids a e s able owing o epulsi e elec os a ic o ces which p e en hei
agglome a ion o loccula ion [Ecken elde , 2000]. Acco dingly, hese pa icles p esen a
e y low se ling a e and hus canno be emo ed by adi ional g a i ic p ocesses
[Ecken elde , 2000; Samye e al., 1994]. Colloids also exhibi a ac i e o ces, wi h
smalle ampli ude han he epulsi e ones (Van de Waals o ces), wi h he abili y o
agg ega e pa icles ha su ound hemsel es enough.
Fo he occu ence o such pa icles emo al i is necessa y o agglome a e hem, o ming
la ge pa icles. Thus, he coagula ion/ loccula ion p ocess is based on he des abiliza ion
o colloids and subsequen o ma ion o locs ( ha occu s a e addi ion o a polyelec oly e
o an ino ganic coagulan - no mally aluminium o i on sal s) and makes use o a polyme
o p omo e he locs agg ega ion, which a e u he sepa a ed by sedimen a ion
[Cãniza es e al., 2009].
Chap e 2
–
S a e o he A
22
The coagula ion s age is a somewha complica ed p ocess in ol ing a se ies o physical-
chemical in e ac ions: elec os a ic a ac ion, so p ion, b idging ( ela ed o high molecula
weigh polyme s) and inclusion in me al p ecipi a es [Pea y e al., 1985; Sawye e al.,
1994; Ecken elde , 2000; Al es, 2007]. No mally he des abiliza ion o he colloids in wa e
and was ewa e ea men p ocesses is achie ed h ough mechanisms o cha ge
neu aliza ion and inclusion in me al p ecipi a es. These mechanisms a e a ec ed by
a ious pa ame e s such as: ype o coagulan , coagulan dose, pH, s i ing a e and
con ac ime [Me cal & Eddy, 2003; Al es, 2007].
To de e mine he op imum alues o he pa ame e s o coagula ion i is necessa y o
pe o m labo a o y expe imen s, since hey depend on he cha ac e is ics o he e luen o
be ea ed and he ype o coagulan used. Howe e , in he li e a u e can be ound ypical
alues o s i ing speed a ound 100 pm [Sa e ield, 2004; Bose, 2010; Poland and
Pagano, 2010] and s i ing ime in he o de o 1-3 minu es [Pea y,198; Ecken elde ,
2000; Bose, 2010; Poland and Pagano, 2010]. Fo he ea men o ex ile e luen s, doses
o 250-1000 mg/L and pH alues om 3 o 11 o Fe
2
(SO
4
) and doses o 250-750 mg/L
and pH alues o 5 o 10 o Al
2
(SO
4
)
3
.18H
2
O ha e been epo ed [Ecken elde , 2000].
A e s abiliza ion o colloids he agg ega ion o pa icles mus be p omo ed o ob ain
pa icles wi h highe diame e , which acili a es hei sedimen a ion ( loccula ion s ep). This
is achie ed h ough collisions be ween pa icles and can be igge ed by wo mechanisms,
pe ikine ic o o hokine ic loccula ion [Vigneswa an and Vis ana han, 1995; Al es, 2007].
In he loccula ion s ep i is necessa y o ake in o accoun he ype and dose o locculan ,
s i ing speed and con ac ime. The op imal alues o hese a iables a e also de e mined
by pe o ming labo a o y es s and mainly a ying he ype and dose o locculan , since
hey depend on he cha ac e is ics o he was ewa e , as in he coagula ion s ep [Al es,
2007]. Values o 10 o 45 minu es o he con ac ime [Pea y e al., 1985; Al es, 2007;
Bose, 2010; Poland and Pagano, 2010] and 25 o 35 pm [Phipps & Bi d, 1995; La leu ,
1997; Ecken elde , 2000; Bose, 2010; Poland and Pagano, 2010] o he s i ing speed,
ha e been epo ed.
The main ad an ages o his ea men p ocess a e he ollowing ones: low
esidence/con ac ime, lexibili y and e iciency o mos classes o dyes, low capi al cos s,
use o ela i ely simple equipmen and simul aneous emo al o o he pollu an s ( o
example allows he COD educ ion). Howe e , his echnique has some disad an ages,
such as: use o locculan s o inc ease he e iciency o he p ocess, conside able olume
Pa I
23
o chemical sludge p oduced, necessi y o adding chemicals, ela i ely high ope a ing
cos s, and some ca ionic o ganic polyme s can be oxic o ishes, e en a low
concen a ions [Eas on, 1995].
In he li e a u e a e epo ed s udies whe e coagula ion/ loccula ion o a combina ion o
his echnique wi h o he p ocess has been applied in he ea men o ex ile e luen s. In
he wo nex sec ions a b ie desc ip ion o hese s udies is p esen ed.
2.2.1 Tex ile Was ewa e T ea men by Coagula ion/Floccula ion
In he las yea s a ious wo ks ha e been epo ed in he open li e a u e ega ding he
ea men o dye solu ions and simula ed o eal ex ile was ewa e s by
coagula ion/ loccula ion. Table 2.1 summa izes some o hose wo ks.
Table 2.1 – Resea ch wo ks on he applica ion o coagula ion/ loccula ion o ea ing dye solu ions
and ex ile e luen s.
Dye solu ion o
E luen ype
Op imal Ope a ing Condi ions
E iciencies
(%)
Re e ence
Blue Sunc on RD-400
dye
V
coagula ion
= 250 pm
coagula ion
= 2 min
V
loccula ion
= 40 pm
loccula ion
= 15 min
sedimen a ion
= 30 min
pH = 6
[FeCl
3
.6H
2
O] = 0.93 mM
COD = 84
Dye = 98
Kim e al. [2004]
Yellow Sunc on 3GE-
200 dye
V
coagula ion
= 250 pm
coagula ion
= 2 min
V
loccula ion
= 40 pm
loccula ion
= 15 min
sedimen a ion
= 30 min
pH = 5
[FeCl
3
.6H
2
O] = 0.74 mM
COD = 88
Dye = 100
Kim e al. [2004]
Blue Sunc on P-3R dye
V
coagula ion
= 250 pm
coagula ion
= 2 min
V
loccula ion
= 40 pm
loccula ion
= 15 min
sedimen a ion
= 30 min
pH = 7
[FeCl
3
.6H
2
O] = 2.78 mM
COD = 25
Dye = 61
Kim e al. [2004]
Chap e 2
–
S a e o he A
30
HO
•
+ H
2
O
2
→ H
2
O + HO
2•
(2.3)
HO
•
+ Fe
2+
→Fe
3+
+ HO
-
(2.4)
Fe
3+
+ H
2
O
2
→ Fe
2+
+ HO
2•
+ H
+
(2.5)
The Fen on p ocess e iciency is in luenced by se e al a iables, including pH,
empe a u e, concen a ion o e ous ion and hyd ogen pe oxide. The pH is a c ucial
pa ame e in he Fen on p ocess. The dec ease in eac ion e iciency a pH abo e 4 is
associa ed wi h he o ma ion o complexes o Fe
2+
[Beni ez e al., 2001], p ecipi a ion o
Fe(OH)
3
, which inhibi s he egene a ion o Fe
2+
(Equa ion 2.5), and also wi h he
decomposi ion o hyd ogen pe oxide in wa e and oxygen [Szpy kowicz e al., 2001]. A
pH below 2, he gene a ion o hyd oxyl adicals dec eases, and is almos o ally
supp essed a pH 1. Fo so low pH alues he hyd ogen pe oxide o ms H
3
O
2+
, educing
he eac i i y wi h Fe
2+
[Schi man and Dela a enne, 1979, ci ed in Mo ais, 2005]. On he
o he hand, he concen a ion o Fe
3+
, esponsible o he con inued oxida ion (Equa ion
2.5) is small [Pigna ello, 1992] as he e ic i on is in he o m o Fe(OH)
2+
and Fe(OH)
2+
.
Va ious au ho s indica ed op imal alues o his pa ame e in he ange 2-5 [Sims, 1983;
Ri as e al., 2001; Zhu e al., 2001], o mo e speci ically pH a ound 3 [Neyens and
Baeyens, 2003], ega dless he cha ac e is ics o he e luen o ea [Mo ais, 2005].
The eac ion a e inc eases wi h inc easing empe a u e, since i inc eases he kine ic
cons an s acco ding o he A henius law, and pa icula ly be ween 5 and 30-40 °C
[Flahe y and Huang, 1992]. Howe e , he ex en o eac ion dec eases o empe a u es
abo e 40-50 °C because occu s he he mal decomposi ion o hyd ogen pe oxide in o
wa e and oxygen. In he li e a u e he e a e se e al wo ks epo ing op imal ope a ing
empe a u es be ween 20 and 50 °C [Gulkaya e al., 2006; Tekin e al., 2006; Sun e al.,
2007].
The Fen on´s eac ion also depends on he e ous ion dose, he minimum equi ed o he
eac ion o p oceed a easonable a e being be ween a ound 3 o 15 mg/L [Mo ais, 2005].
Howe e , he subs a e emo al inc eases wi h he ca alys concen a ion up o a poin
beyond which he eac ion o excess o e ous ion wi h he hyd oxyl adical occu s
(Equa ion 2.4) [Walling, 1975] – he so-called sca enging e ec . The equi ed ca alys
dose depends on he ype o e luen o be ea ed; howe e Mo ais [2005] indica es
alues o 1:10 o 1:50 o he Fe
2+
:subs a e a io (w:w).

Pa I
31
Finally, he e iciency o Fen on’s oxida ion inc eases wi h he hyd ogen pe oxide
concen a ion bu when his eagen is in excess, i eac s wi h he adicals (Equa ion 2.3
[Waling, 1975]). The equi ed dose o H
2
O
2
o be used depends on he amoun o o ganic
compounds, bu i is necessa y o add an excess o e he s oichiome ic amoun o
compensa e he quan i y o hyd ogen pe oxide which decomposes in o wa e and oxygen
and also he one consumed in pa allel / undesi ed eac ions [Sou hwo h and Voelke ,
2003].
This homogeneous p ocess has se e al ad an ages such as high e iciency, simple
applicabili y, ope a ion a oom empe a u e and a mosphe ic p essu e, and non-
selec i i y, i.e. abili y o oxidize a ious pollu an s a he same ime. Howe e , he main
disad an age is he gene a ion o e ic i on sludge which equi es sepa a ion and
disposal and/o euse [Hsueh e al., 2005].
2.3.1 Tex ile Was ewa e T ea men by Homogeneous Fen on’s
Oxida ion
The Fen on p ocess has been widely applied in he ea men o ex ile e luen s. Recen
s udies a e summa ized below.
Malik and Saha [2003] s udied he deg ada ion o wo di ec dyes (Blue 2B – B54 and Red
12B - R31) by he Fen on p ocess. A pa ame ic s udy was pe o med o e alua e he
e ec o a ious pa ame e s. The maximum dye emo al (97%) was achie ed o pH=3,
[H
2
O
2
]=1.47 and 2.94 mM o B54 and R31, espec i ely, [Fe
2+
]=8.93x10
-2
mM, T=40 ºC
and =30 minu es. The au ho s also assessed he e ec o he p esence o chlo ides and
sul a es in he emo al e iciency and ound ha up o 600 mg/L he sul a e ion had no
e ec on he emo al o he wo dyes, bu he chlo ide ion nega i ely a ec ed he dyes
emo al, because his anion “sca enges” he hyd oxyl adical.
O he au ho s [Swamina han e al., 2003] e alua ed he e ec o p ocess a iables on he
decolo iza ion and deg ada ion o wo comme cial azo dyes (Red M5B and Blue MR) and
H-acid dye, by he Fen on’s eac ion. Fo he Red M5B dye he maximum colo (~100%)
and DOC (78%) emo als we e achie ed by using 10 mg/L o Fe
2+
, 400 mg/L o H
2
O
2
,
pH=3 and 120 minu es o eac ion ime. Fo he Blue MR dye high colo and COD
emo als we e ob ained (99% o COD and ~100% o colo ) in he ollowing condi ions:
Chap e 2
–
S a e o he A
32
20 mg/L, 500 mg/L, 3 and 20 minu es o Fe
2+
dose, H
2
O
2
concen a ion, pH and eac ion
ime, espec i ely. Finally 99% o COD and ~100% o colo emo als we e achie ed o
he H-acid dye by using 25 mg Fe
2+
/L, 500 mg H
2
O
2
/L, pH=3 and =120 minu es.
Decolo iza ion ollowed 1
s
o de kine ics and he compu ed a e cons an was g ea e o
H-acid dye (k = 0.0106 min
-1
) ollowed by ed M5B dye (k = 0.0413 min
-1
) and inally blue
MR (k = 0.0727 min
-1
). The sul a e concen a ion in H-acid and Blue MR solu ions and he
concen a ion o chlo ides and sul a es in Red M5B solu ions inc eased wi h eac ion ime
allowing he au ho s o conclude ha hese anions a e eplaced in he s uc u e o he
dyes when he HO
•
species b eaks he molecula bonds.
Many mo e s udies a e epo ed in he li e a u e. Table 2.3 p esen s he op imal ope a ing
condi ions used in hese s udies and he maximum emo als achie ed.
Table 2.3 – S udies on he ea men o dye solu ions and ex ile e luen s by Fen on’s eac ion.
Dye solu ion o
E luen ype Op imal Ope a ing
Condi ions E iciencies
(%) Commen s Re e ence
Real e luen o
ace a e and
polyes e deying
pH = 5
[FeSO
4
] = 500 mg/L
[H
2
O
2
] = 300 mg/L
Colo = 94
COD = 96
Azba e al. [2004]
Reac i e Black 5
dye solu ion
pH = 3
T= 40 ºC
[dye] = 100 mg/L
[FeSO
4
] = 100 mg/L
[H
2
O
2
] = 400 mg/L
Colo = 99
COD = 71
Me iç e al. [2004]
Reac i e Black 5
dye solu ion
pH = 3
T= 40 ºC
[dye] = 200 mg/L
[FeSO
4
] = 225 mg/L
[H
2
O
2
] = 1000 mg/L
Colo = 99
COD = 84
Me iç e al. [2004]
Reac i e O ange 4
dye solu ion
pH = 5
[Fe
2+
] = 0.075 mM
[H
2
O
2
] = 15 mM
Dye = 97
Mu iganandham and
Swamina han, [2004]
Blue Sunc on RD-
400 dye solu ion [Fe
2+
] = 0.38 mM
[H
2
O
2
] = 2.48 mM
COD = 60
Dye = 90
Kim e al. [2004]
Yellow Sunc on
3GE-200 dye
solu ion
[Fe
2+
] = 0.41 mM
[H
2
O
2
] = 1.91 mM
COD = 48
Dye = 90
Kim e al. [2004]
Blue Sunc on P-3R
dye solu ion [Fe
2+
] = 1.61 mM
[H
2
O
2
] = 4.41 mM
COD = 80
Dye = 90
Kim e al. [2004]
Yellow Sunc on
E4R-H dye solu ion [Fe
2+
] = 0.23 mM
[H
2
O
2
] = 1.15 mM
COD = 70
Dye = 90
Kim e al. [2004]
Pa I
33
Table 2.3 – S udies on he ea men o dye solu ions and ex ile e luen s by Fen on’s eac ion.
(con .)
Dye solu ion o
E luen ype Op imal Ope a ing
Condi ions E iciencies
(%) Commen s Re e ence
O ange II dye
pH = 3
T= 29 ºC
= 120 min
[H
2
O
2
] = 10 mM
Fe
2+:
H
2
O
2
a io (w/w) = 0.08
Colo = 100
Rami ez e al.
[2005]
O ange II dye
pH = 3
T= 50 ºC
= 120 min
[H
2
O
2
] = 13.8 mM
Fe
2+:
H
2
O
2
a io (w/w) = 0.05
TOC = 71 Rami ez e al.
[2005]
Reac i e Black 5
pH = 5
= 120 min
[dye]
0
= 1.0x10
-4
M
[Fe
2+
] = 1.5x10
-4
M
[H
2
O
2
]
0
= 7.3x10
-4
M
Colo = 98
TOC = 22 Lucas and Pe es
[2006]
Syn he ic Dyeing
e luen
con aining acid
dyes
pH = 3
= 30 min
[Fe
2+
] = 10 mM
[H
2
O
2
] = 30 mM
Colo = 92
COD = 24
Low oxici y o
bac e ia om
ac i a ed sludge
Ala on and Teksoy
[2007]
Remazol
Tu quoise Blue
G-133 dye
solu ion
pH = 3
= 45 min
[Fe
2+
] = 25 mg/L
[H
2
O
2
] = 50 mg/L
Colo = 99 k = 0,0102 L
mg
-1
min
-1
Bali and
Ka agozoglu [2007]
Acid Yellow 23
dye solu ion
pH = 3
[Fe
2+
] = 0.1 mmol
[H
2
O
2
] = 500 mg/L
Colo ~ 100 Modi shahla e al.
[2007]
Real e luen om
polye hylene
ibe s p ocessing
pH = 3
= 24 h
[Fe
2+
] = 40 mg/L
[H
2
O
2
] = 30 mg/L
Colo = 72
COD = 45
BOD
5
= 60
TOC = 40
BOD
5
:COD ≤
0.15 (a e
ea men )
Papadopoulos e al.
[2007]
Amido Black 10B
dye solu ion
pH = 3.5
[dye]
0
= 50 mg/L
[Fe
2+
]
0
= 0.025 mM
[H
2
O
2
]
0
= 0.50 mM
Dye = 99 Sun e al. [2007]
Chap e 2
–
S a e o he A
34
Table 2.3 – S udies on he ea men o dye solu ions and ex ile e luen s by Fen on’s eac ion.
(con .)
Dye solu ion o
E luen ype Op imal Ope a ing
Condi ions E iciencies
(%) Commen s Re e ence
P ocion Red H-
EXL g an dye
solu ion
pH = 3.5
= 120 min
[dye] = 100 mg/L
T= 73.6 ºC
[Fe
2+
] = 0.12 mM
[H
2
O
2
] = 2.9 mM
Colo = ~100
TOC = 58 Rod igues [2007]
Was ewa e om
ac ylic ibe
manu ac u ing
pH = 3
= 2 h
[Fe
2+
] = 300 mg/L
[H
2
O
2
] = 500 mg/L
COD = 66
BOD
5
:COD =
0.5 (a e
ea men ) Li e al. [2012]
Real ex ile
e luen
pH = 6.6
T = 35 ºC
[FeSO
4
] = 0.75 g/L
[H
2
O
2
] = 15 g/L
Colo = 98
COD = 39
BOD
5
:COD =
0.45 (a e
ea men )
Wu and Wang
[2012]
Real d y-spun
ac ylic ibe
e luen
pH = 3
T = 30 ºC
= 120 min
[Fe
2+
] = 20 mM
[H
2
O
2
] = 90 mM
COD = 47
TOC = 35
BOD
5
:COD =
0.69 (a e
ea men ) Wei e al. [2013]
Real d y-spun
ac ylic ibe
e luen
pH = 3
T = 50 ºC
= 120 min
[Fe
2+
] = 20 mM
[H
2
O
2
] = 90 mM
k = 0.265 min
-1
Wei e al. [2013]
2.3.2 Tex ile Was ewa e T ea men by In eg a ion o Homogeneous
Fen on’s Oxida ion wi h Sequencing Ba ch Reac o
T ea abili y s udies o ex ile e luen s by Fen on´s oxida ion combined wi h sequencing
ba ch eac o (SBR) a e succinc ly desc ibed in his sec ion.
Fongsa i kul e al. [2004] e alua ed he in eg a ion o Fen on’s eagen wi h biological
oxida ion in SBR o ea ing was ewa e gene a ed in he ex ile indus y. Expe imen al
condi ions we e pH 3, T = 28-30 °C, eac ion ime abou 30 minu es and o al dose o
eagen s be ween 25 mg/L and 300 mg/L (FeSO
4
.7H
2
O and H
2
O
2
- 1:1 mola a io).
Pa I
35
Maximum colo and COD emo als (~ 70% and ~ 30%, espec i ely) we e achie ed o
eagen doses o 75 mg/L. To inc ease he e iciency o o ganic ma e emo al, he
au ho s es ed he combina ion Fen on’s oxida ion plus SBR. The biological ea men was
pe o med a pH 7, he ope a ing cycle o SBR was 24 hou s, dis ibu ed as ollows: 4
hou s eeding, 2 hou s anoxic, 4 hou s ae obic, 7 hou s anoxic, 4 hou s ae obic, 1.5 hou s
sedimen a ion, 0.5 hou s d aw and 1 hou sludge emo al. The global e iciency was gi en
by: 90% COD emo al, ~ 80% maximum colo emo al, 81 phospho us emo al and 92%
KTN emo al. A e wa ds he ea abili y o he e luen by he combina ion o SBR wi h
chemical oxida ion was also in es iga ed. The SBR was ope a ed unde he same
condi ions desc ibed abo e and was ed o 50 days. The biological p ocess was able o
emo e ~ 80% COD, ~50% colo , ~ 82% KTN and ~ 58% o al phospho us. Then he
biologically ea ed e luen was subjec ed o chemical oxida ion, a e adjus ing he pH o
3. The dose o eagen a ied in he ange 25-200 mg/L. Remo als inc eased wi h he
dose o eagen , eaching 27 and 60% o COD and colo , espec i ely, using 200 mg/L o
eagen . The combina ion SBR plus Fen on’s oxida ion led o o e all e iciencies o 87%
o COD, 68% o colo , 91% o KTN and 80% o o al phospho us.The is combina ion
o p ocesses (Fen on’s oxida ion ollowed by SBR) yielded be e esul s, because he p e-
ea men inc eased he biodeg adabili y o he e luen o be subjec ed o biological
ea men .
Mo e ecen ly Lodha and Chaudha i [2007] e alua ed he ea abili y o azo dyes
(Reac i e Black 5 dye - RB5 - Reac i e Blue 13 - RB13 - and Acid O ange 7 - AO7)
solu ions. The Fen on p ocess was op imized by a ying he pH (2-7), [H
2
O
2
] (be ween 25
and 150 mg/L) and [Fe
2+
] ( om 5 o 50 mg/L) and se ing he eac ion ime wi hin 30
minu es. The condi ions ha maximized colo (>97% o all dyes es ed) and COD (63, 89
and 68% o RB5, RB13 and AO7, espec i ely) emo als we e pH = 3, [Fe
2+
] = 15 mg/L
and [H
2
O
2
] = 50 mg/L. Fo he biological ea men , he biomass was p e iously
acclima ized. Thus, o a pe iod o 20 days, he SBR was ed wi h 0.5 L o a solu ion
con aining 0.4 g o dex ose, al e na ing he nex day wi h 0.5 L o p e ea ed e luen . The
solids con en in he SBR was main ained in 3000 mg MLSS/L. The SBR eached s eady
s a e a e 40 days (20 days o acclima iza ion and 20 ed wi h p e-oxidized e luen ),
achie ing COD emo als o 82, 89 and 84% o RB5, RB13 and AO7 dyes, espec i ely.
An in eg a ed p ocess (chemical oxida ion wi h Fen on's eagen ollowed by biological
oxida ion) was also pe o med yielding o al decolo iza ion (> 99% o all dyes) and highe
COD emo als (93, 99 and 95% o RB5, RB13 and AO7, espec i ely).

Chap e 2
–
S a e o he A
36
Mo e s udies can be ound in he li e a u e ega ding he ea men o ex ile e luen s o
dye solu ions by he combina ion o Fen on´s eac ion wi h SBR. Table 2.4 b ie ly p esen s
he bes ope a ing condi ions o bo h p ocesses and he o e all e iciencies achie ed.
Table 2.4 – S udies on he in eg a ion Fen on’s eac ion wi h SBR.
Dye solu ion
o E luen
ype
Ope a o y
Condi ions in
Fen on
Ope a o y
Condi ions in
SBR
O e all
E iciencies
(%)
Commen s Re e ence
Reac i e
Black 5
solu ion
pH = 3
T = 25-30 ºC
[Fe
2+
] = 1.05 mM
[H
2
O
2
] = 72 mM
eed
= 20 days
HRT = 96 h
SRT = 45 days
COD = 82
The SBR
was
p e iously
acclima ed
by eeding
dex ose
solu ion
Tana ak and
Chaudha i
[2007]
Reac i e Blue
13 solu ion
pH = 3
T = 25-30 ºC
[Fe
2+
] = 1.05 mM
[H
2
O
2
] = 72 mM
eed
= 20 days
HRT = 96 h
SRT = 45 days
COD = 86
The SBR
was
p e iously
acclima ed
by eeding
dex ose
solu ion
Tana ak and
Chaudha i
[2007]
Acid O ange 7
solu ion
pH = 3
T = 25-30 ºC
[Fe
2+
] = 1.05 mM
[H
2
O
2
] = 72 mM
eed
= 20 days
HRT = 96 h
SRT = 45 days
COD = 78
The SBR
was
p e iously
acclima ed
by eeding
dex ose
solu ion
Tana ak and
Chaudha i
[2007]
Syn he ic
co on deying
e luen
pH = 3.5
T = 73.6 ºC
[Fe
2+
] = 11 mM
[H
2
O
2
] = 305 mM
1.1 h eed
6 h eac ion
3.5 h
sedimen a ion
0.9 h
supe na an
discha ge
[O
2
] ~3 mg/L
pH ~7
T ~25 ºC
[VSS] ~5 g/L
BOD
5
= 96
COD = 90
Colo = 97
Rod igues
[2007]
2.4 Pho o-Fen on P ocess
The pho o-Fen on p ocess is based on p inciples ha a e common o he da k Fen on
one, namely he gene a ion o ex emely eac i e hyd oxyl adicals ( ha will unselec i ely
Pa I
37
a ack he o ganic compounds) by b eaking hyd ogen pe oxide molecules, in acidic
medium, making use o a ca alys like e ous ion (Equa ion 2.6) [Walling, 1975], bu wi h
simul aneous use o ul a- iole / isible adia ion. Thus, he pho o-Fen on p ocess is as e
and enables educing he consump ion o chemicals as he hyd oxyl adicals gene a ion
occu s by h ee di e en mechanisms: i) he decomposi ion o hyd ogen pe oxide by he
Fe
2+
ca alys (Equa ion 2.6); ii) he incidence o ul a iole adia ion, wi h λ<360-365 nm,
decomposes he hyd ogen pe oxide in o hyd oxyl adicals (Equa ion 2.7) [Gal ez and
Rod iguez, 2003]; and iii) by using adia ion wi h wa eleng hs in he ange 290 <λ< 410
nm [Sun and Pigna ello, 1993], he e is he addi ional p oduc ion o HO
•
adicals upon
Fe
2+
egene a ion ei he by Equa ion 2.8 o by pho olysis o i on (III) hyd oxides (Equa ion
2.9); inally, Equa ion 2.10 s ill e e s o Fe
2+
egene a ion by pho olysis o complexes
o med be ween he o ganic compounds o hei in e media es wi h Fe
3+
[Gal ez and
Rod iguez, 2003; Mo ais, 2005; Huang e al., 2008]. The egene a ion o Fe
2+
species by
se e al eac ions is ano he eason o he as e a e o he pho o-Fen on p ocess as
compa ed o he da k one, whe e ca alys egene a ion is commonly a e-limi ing.
Fe
2+
+ H
2
O
2
→ Fe
3+
+ HO
•
+ OH
−
(2.6)
H
2
O
2
+ hν → 2HO
•
(2.7)
Fe
3+
+ H
2
O
2
+ hν → Fe
2+
+ HO
•
+ H
+
(2.8)
Fe(OH)
2+
+ hν → Fe
2+
+ HO
•
(2.9)
[Fe(RCO
2
)]
2+
+ hν → Fe
2+
+ CO
2
+ R
•
(R= o ganic compound) (2.10)
The Fe(OH)
2+
complex is p edominan unde acidic condi ions (pH in he ange 2-3
[To ades e al., 2004]), and plays an impo an ole in he pho o-Fen on p ocess since i is
he compound wi h g ea e abili y o gene a e hyd oxyl adicals by abso bing UV/ isible
adia ion. The pho olysis o hyd ogen pe oxide (Equa ion 2.7), which has low abso p i i y
(19.6 M
-1
cm
-1
a 254 nm [Engwall e al., 1998]), has a limi ed con ibu ion owa ds he
o ma ion o adicals when i on complexes a e p esen in solu ion.
The pho o-Fen on p ocess is in luenced by many a iables, such as pH, hyd ogen
pe oxide concen a ion, e ous ion concen a ion and adia ion in ensi y (and na u e). A
pH > 6 he Fe
3+
o ms insoluble oxides [Pé ez e al., 2002]. In e y acidic pH alues he
complex Fe(OH)
2+
is p esen in a educed amoun , and he wo mo e pho o eac i e
Chap e 2
–
S a e o he A
38
compounds (Fe(OH)(H
2
O)
52+
and Fe(OH)
2
(H
2
O)
4+
) a e p esen in smalle quan i ies o
gene a e he adicals and egene a e he ca alys [Mo ais, 2005; Noguei a, 2007],
howe e he Fe(H
2
O)
63+
species is p esen in g ea e amoun bu i has lowe abso p i i y,
which limi s he abso ion o adia ion [Noguei a e al., 2007]. Mo eo e , pH < 2.5 allows o
occu he sca enging eac ion be ween he hyd oxyl adical and H
+
(Equa ion 2.11)
[Noguei a e al., 2007]:
HO
•
+ H
+
+ e
-
→H
2
O (2.11)
Fo hese easons, op imum pH alues in he ange 2-3 ha e been poin ed ou [Pigna ello,
1992; Kim, 1997; Wu e al., 1999; Elmolla and Chaudhu i, 2009]. Ac ually, in his ange
inc eased amoun s o pho o eac i e species (Fe
3+
and Fe(OH)
2+
) a e p esen in solu ion.
Fo emo al o dyes some au ho s ha e sugges ed pH alues o 3-5 [Kang e al., 2000;
Liu e al., 2007; Modi shahla e al., 2007].
The amoun o ca alys o be used mus be de e mined and op imized, since i depends on
he na u e o he e luen o be ea ed. None heless, i is no ad isable o use an excess
o Fe
2+
because his gene a es u bidi y which hinde s he abso p ion o he adia ion and,
on he o he hand, as in da k Fen on, occu s he sca enging eac ion o hyd oxyl adicals
wi h he excess Fe
2+
(Equa ion 2.4).
The pollu an emo al is ela ed o he amoun o hyd ogen pe oxide, hus i is necessa y
o de e mine he op imum dose o eagen conside ing ha : i) when i s concen a ion is
low he oxida ion deg ee is low and he e is he possible o ma ion o undesi able
in e media e compounds, ii) i s excess eac s wi h hyd oxyl adicals gene a ing HO
2.
adicals wi h lowe oxida i e po en ial and iii) an excess is equi ed o compensa e he
decomposi ion in o wa e and oxygen and o he pa allel /undesi able eac ions.
The adia ion in ensi y o pho onic lux is ela ed o he lamp powe i.e. he capaci y o emi
pho ons. In gene al, an inc ease in he adia ion in ensi y leads o an inc ease in he
eac ion a e, hence an inc eased deg ada ion o o ganic compounds.
Acco ding o Mala o e al. [2002], he ad an ages o he pho o-Fen on p ocess, compa ed
o o he pho ochemical echniques, a e he ope a ion a UV o nea UV wa eleng hs (300-
400 nm), he sensi i i y o ligh up o wa eleng s ≤ 600 nm, which makes possible he use
o sola adia ion, he ligh pene a ion is deepe and he con ac be ween pollu an and
oxidizing agen is in ima e, because o he homogenous phase. The majo disad an ages
Pa I
39
o his p ocess a e associa ed wi h he use o low pH (<4) o ob ain he maximum
e iciency and he gene a ion o chemical sludge con aining i on.
2.4.1 Tex ile Was ewa e T ea men by Homogeneous Pho o-Fen on
P ocess
A lo o s udies can be ound in he li e a u e using he pho o-Fen on p ocess o dyes
emo al in aqueous solu ion, as well as in he ea men o e luen s om he ex ile
indus y. A b ie desc ip ion o some o hese s udies is p esen ed below.
Kang e al. [2000] e alua ed he emo al o colo om a syn he ic ex ile dyeing e luen
(con aining 100 mg/L o poly inyl alcohol – PVA – and 100 mg/L o Reac i e R94H dye)
by he pho o-Fen on p ocess. Unde op imal condi ions (pH = 4, [H
2
O
2
] = 100 mg/L, [Fe
2+
]
= 20 mg/L, lamp powe = 64 W and = 30 min) he au ho s ob ained 95% colo emo al.
Subsequen ly, he e ec o he PVA concen a ion was e alua ed by a ying i s
concen a ion (COD be ween 200 o 620 mg/L) and i was ound ha he inc ease o COD
showed no e ec on colo emo al. Compa ing pho o-Fen on a pH o 4 and 7 wi h Fen on
a pH 4 and pho olysis a pH 4, i was obse ed ha pho o-Fen on p ocess a pH 4 led o a
highe emo al (93%) o a eac ion ime o 30 min, ollowed by pho olysis (82% colo
emo al in he same pe iod), hen pho o-Fen on a pH 7 (73% colo emo al) and inally
da k Fen on a pH 4 (64% colo emo al).
Pé ez e al. [2002] s udied he ea abili y o a eal ex ile e luen by he pho o-Fen on
p ocess. The au ho s s a ed he s udy by e alua ing he e ec o Fe
2+
, H
2
O
2
and
combina ion o he wo eagen s. Va ying he empe a u e (25-70 °C) highe emo als o
TOC we e achie ed a 70 ºC. The e ec o e ous ion (up o 400 mg/ L) and hyd ogen
pe oxide (up o 10 g/L), se ing he pH a 3 and empe a u e a 40 °C, was also analyzed.
Maximum TOC emo al (70% a e 2 hou s o eac ion) was achie ed when using 100
mg/L o Fe
2+
and H
2
O
2
be ween 2.5 and 5 g/L. A hese ope a ing condi ions, he e ec o
he ype o adia ion (ligh om luminescen black lamp o 6 W, sunligh and xenon lamp o
250 W) was assessed. Fo he i s 60 min o eac ion TOC emo al was high when using
xenon and sola adia ion, bu o >60 min he luminescen black lamp showed be e
emo al e iciency. The au ho s s a e ha an in ense i adia ion a o s he exhaus ion o
Chap e 2
–
S a e o he A
46
(anae obic/ae obic SBR). The 1
s
sys em ope a ed du ing 48 h pe cycle, comp ising
se e al minu es o eeding he was ewa e , 20 h-anae obic eac ion, 4h-se le, 20 h-
ae obic eac ion, 4 h-se lle/d aw. In he 2
nd
sys em he anae obic and ae obic eac ion
occu ed in sepa a ed eac o s, and each cycle o 48 h was di ided as ollows: se e al
minu es o eeding he e luen in o he anae obic eac o , 20 h-anae obic eac ion, 2 h-
se le and 2 h o d aw he supe na an ha ed he ae obic eac o o 2 h, 20 h o eac ion
and 4 h-se le/d aw. The maximum decolo iza ion (80.8% a e 36 cycles) was ob ained
when anae obic and ae obic eac ions occu ed sepa a ely (2
nd
sys em).
Lou enço e al. [2001] also s udied he deg ada ion o Remazol B illian Viole 5R and
Remazol Black B dyes by AA-SBR. Fo Remazol B illian Viole 5R he au ho s ob ained
90% dye emo al when ope a ing 24 h pe cycle (50 min- ill, 11 h-anae obic eac ion, 10
h-ae a ion, 60 min-se le, 55 min-d aw and 15 min-idle) and 10 days o SRT (sludge
e en ion ime), while o Remazol Black B eached 75% o dye emo al using 24 h pe
cycle (53 min- ill, 11 h-anae obic eac ion, 10 h-ae a ion, 50 min-se le, 65 min-d aw and
10 min-idle) and 15 days o SRT.
Table 2.6 p esen s op imal ope a ing condi ions and e iciencies a ained in o he
esea ch wo ks conce ning he ea men o dye solu ions and ex ile e luen s in SBR.
Table 2.6 – S udies on he ea abili y o dye solu ions and ex ile e luen s by SBR.
Dye solu ion o
E luen ype Op imal Ope a ing
Condi ions E iciencies
(%) Commen s Re e ence
Simula ed e luen
con aining
Remazol Red RR
dye
5 min ill
12 h anae obic eac ion
11 h eac ion
30 min se le
10 min d aw
[Dye] = 60 mg/L
[COD]
0
= 800 mg/L
SRT = 15 days
Colo = 95
COD = 70
Addi ion o
phospha es,
sul a es and
glucose o he
e luen
Kapdan and Oz uk
[2005]
Syn he ic
was ewa e
con aining Va
Yellow 1 dye
1 h ill (wi h ae a ion)
19 h eac
3 h se le
0.5 h d aw
0.5 h idle (in anoxic condi ions)
HRT = 3 days
[VSS] = 2000 mg MLSS/L
Colo = 99
COD = 97
BOD
5
= 99
KTN = 93
Addi ion o u ea,
glucose,
KH
2
PO
4
and
o he nu ien s
o he e luen
Si iamun apiboon e
al. [2006]

Pa I
47
Table 2.6 – S udies on he ea abili y o dye solu ions and ex ile e luen s by SBR (con .).
Dye o E luen
ype Op imal Ope a ing
Condi ions E iciencies
(%) Commen s Re e ence
Real was ewa e
plus 0.89 g/L o
glucose
1 h ill (wi h ae a ion)
19 h eac
3 h se le
0.5 h d aw
0.5 h idle (in anoxic condi ions)
Colo = 75
COD = 71
BOD
5
= 97
KTN = 63
Si iamun apiboon
e al. [2006]
Syn he ic
was ewa e
con aining Acid
Black 210 dye
30 min ill
23 h ae a ion wi h eci cula ion
15 min se le
15 min d aw
Colo = 100
COD = 92
Addi ion o
glucose and
nu ien s o he
was ewa e
Mohan e al.
[2007]
Simula ed e luen
con aining
Remazol B illian
Viole 5R dye
3 min ill
12 h anae obic eac ion
11.9 h ae obic eac ion
3 min d aw
Colo = 72
COD = 75
Benzene
based
a oma ic
amines = 92
Addi ion o
glucose and
nu ien s o he
dye solu ion
Çina e al. [2008]
Syn he ic
was ewa e
con aining
Reac i e Red 195
dye
[Dye] = 40 mg/L
[COD]
0
= 800 mg/L
SRT = 50 days
24 h pe cycle
Colo > 90
COD > 90
Addi ion o
nu ien s and
ace ic acid o he
was ewa e
k
colo
in anae obic
eac ion
= 0.135 h
-1
k
COD
in anae obic
eac ion
= 0.043 h
-1
Fa abegoli e al.
[2010]
Syn he ic
Was ewa e
con aining
Reac i e Blue
Bezak i S-GLD
150 dye
15 min ill
23 h ae obic eac ion
30 min se le
15 min d aw
SRT = 30 days
Volume ic dye a e 15 g/(m
3
d)
Colo = 88-
97
COD = 95-
98
Addi ion o
glucose,
(NH
4
)
2
SO
4
and
KH
2
PO
4
o he dye
solu ion
The inocula we e
acclima ized
du ing 30 days
unde ae obic
condi ions
Khouni e al.
[2011 b)]
Simula ed e luen
con aining Acid
Black 10B dye
15 min ill
2820 min ae a ion eac ion
wi h eci cula ion
30 min se le
15 min decan
Colo
a e 18
cycles
= 67
COD
a e 10
cycles
= 88
Addi ion o
glucose and
nu ien s o he
e luen
Mohan e al.
[2012]
O he au ho s [Kapdan and Oz ekin, 2006] e alua ed he e ec o he anae obic s age
ime (2-19h) and ini ial COD concen a ion (400-1800 mg/L) on he pe o mance o a SBR
sys em ea ing a simula ed was ewa e con aining Remazol Red RR dye, phospha es,
Chap e 2
–
S a e o he A
48
sul a es and glucose. The colo emo al, in he anae obic phase, was comple ed in he
i s 4-6 h, achie ing 90% decolo iza ion. Ope a ing he ae obic phase o 19-20 h, 80%
COD emo al was achie ed, while 50% was eached in he anae obic s age. The ae obic
s age was e icien e en when educing he pe iod o he anae obic s age (2-4 h).
Finally, Vaigan e al. [2009] e alua ed he e ec o B ill Blue KN-R dye concen a ion in
he pe o mance o SBR. The eac o ope a ed du ing 36 cycles (5 o sludge
acclima iza ion and 31 o no mal ope a ion) wi h 24 h pe cycle comp ising 2 min o ill,
22.5 h o ae a ed eac ion, 1 h se ling, 2 min o d aw and 25 min o idle. Colo emo al
dec eased om 57.0% o 31.0% when he dye concen a ion inc eased om 20 o 40
mg/L, howe e COD emo al was p ac ically cons an (~97%) o all concen a ions.
2.5.2 Tex ile Was ewa e T ea men by Combina ion o SBR and O he
Techniques
In his sec ion a e p esen ed some s udies conce ning he ea abili y o simula ed
e luen s con aining dyes o eal ex ile was ewa e s by biological oxida ion in SBR
in eg a ed wi h o he ea men me hods.
K ull and Hempel [2001] e alua ed he colo and COD emo als and oxici y educ ion o
dye-house liquo by combining SBR wi h ozona ion. A e he chemical ea men he
e luen was in oduced in o he SBR and subjec ed o ae obic deg ada ion. By in eg a ing
he wo p ocesses he au ho s ob ained 90 and 98% o COD and colo emo als,
espec i ely, and oxici y was educed by 99%, as de e mined by bioluminescence es s.
O he au ho s [Zu iaga-Agus i e al., 2010] e alua ed he ea men o a simula ed ex ile
was ewa e (con aining 20 mg/L o Remazol Yellow RR, Remazol Red RR and Remazol
Blue RR, glucose and nu ien s) by combining biological oxida ion in SBR wi h
nano il a ion. The SBR was ope a ed a 2.5 days o HRT and 20 h pe cycle comp ising
0.2 h- ill, 9 h-anae obic eac , 8 h-ae obic eac , 2 h-se le, 0.3 h-d aw and 0.5 h-idle. In
he i s 55 cycles he SBR was ed wi h syn he ic was ewa e and emo als o 80 o 90%
we e achie ed o Red and Blue dyes and 70 o 80% o Yellow dye. A e wa ds he SBR
was ed wi h h ee di e en mix u es: i) 4.0 L o syn he ic ex ile was ewa e (STW) and
1.0 L o nano il a ion ejec ion (NFR), ii) 3.5 L o STW and 1.5 L o NFR and iii) 2.5 L o
Pa I
49
bo h e luen s. I was ound ha highe amoun s o NFR in he eed s eam caused a mo e
ma ked decay in he e iciency o dye emo al, due o conduc i i y inc ease.
Blanco e al. [2012] s udied he applicabili y o Fen on´s eac ion and combina ion o SBR
wi h Fen on’s eagen o ea ing a eal ex ile was ewa e . In he Fen on p ocess alone,
he au ho s e alua ed he e ec o H
2
O
2
dose (1650-4950 ppm), Fe
2+
dose (109-540 ppm)
and empe a u e (25-35 ºC) and achie ed maximum TOC emo al (64%) and Esche ichia
coli educ ion (>99%) in he ollowing condi ions: 25 ºC, 3, 1650 mg/L and 216 mg/L o T,
pH, [H
2
O
2
] and [Fe
2+
], espec i ely. The ea men in SBR alone was ca ied ou a e pH
adjus men o 6.5-7.5, addi ion o nu ien s, oxygen a 3 mgO
2
/L and T=25 ºC. 75% TOC
emo al was eached o HRT=1 day. Finally, using he combina ion o biological oxida ion
ollowed by Fen on p ocess (pH=3, [H
2
O
2
]=1518 mg/L and [Fe
2+
]=66.5 mg/L) ema kable
emo al e iciencies o 92 and 99% o TOC and E. coli, espec i ely, we e achie ed,
showing he in e es in in eg a ing bo h p ocesses.
Addi ional s udies ocused on he combina ion o SBR wi h adso p ion by GAC a e
epo ed in he li e a u e and summa ized in Table 2.7, whe e he ope a ing condi ions and
global emo al e iciencies a e also p esen ed.
Table 2.7 – S udies on he in eg a ion o SBR wi h o he p ocesses o ea ing dye solu ions and
ex ile e luen s.
Dye solu ion o
E luen ype Ope a ing Condi ions
in SBR
O he P ocess O e all
E iciencies
(%) Commen s Re e ence
Dispe se Red 60
dye
1 h ill
19 h eac ion
3 h se le
0.5 h d aw
0.5 h idle
HRT = 3 days
[dye] = 80 mg/L
G anula Ac i a ed
Ca bon
BOD
5
= 97
COD = 97
KTN = 90
Si iamun a
piboon and
S iso nsak
[2007]
Real was ewa e
con aining
Dispe se Red 60
and Dispe se Blue
60 dyes
1 h ill
19 h eac ion
3 h se le
0.5 h d aw
0.5 h idle
SRT = 67 days
HRT = 5 days
G anula Ac i a ed
Ca bon
Colo = 95
BOD
5
= 94
COD = 94
KTN = 59
Addi ion o
glucose o
he
was ewa e
No
p oduc ion o
excess
sludge
Si iamun a
piboon and
S iso nsak
[2007]
Chap e 2
–
S a e o he A
50
Table 2.7 – S udies on he in eg a ion o SBR wi h o he p ocesses o ea ing dye solu ions and
ex ile e luen s (con .).
Dye solu ion o
E luen ype Ope a ing Condi ions
in SBR
O he P ocess O e all
E iciencies
(%) Commen s Re e ence
Di ec Red 23 and
Di ec Blue 201
dyes solu ions
1 h ill
19 h eac ion
3 h se le
0.5 h d aw
0.5 h idle
G anula Ac i a ed
Ca bon
BOD
5
,
COD and
KTN in he
o de 89-99
Si ianun ap
boon e al.
[2007]
Real was ewa e
con aining Di ec
Red 23 and Di ec
Blue 201 dyes
1 h ill
19 h eac ion
3 h se le
0.5 h d aw
0.5 h idle
G anula Ac i a ed
Ca bon
Colo = 76
BOD
5
= 84
COD = 86
KTN = 68
Addi ion o
glucose o
he
was ewa e
No
p oduc ion o
excess
sludge
Si ianun ap
boon e al.
[2007]
Simula ed e luen
con aining Di ec
Blue 201
1 h ill
19 h eac ion
3 h se le
0.5 h d aw
0.5 h idle
HRT = 7.5 days
SRT = 22 days
[VSS] = 3000 mg
MLSS/L
G anula Ac i a ed
Ca bon
BOD
5
, COD
and KTN
>93
Addi ion o
u ea,
glucose and
nu ien s o
he e luen
Si ianun ap
boon and
Sansak
[2007]
Simula ed e luen
con aining Di ec
Red 23 dye
1 h ill
19 h eac ion
3 h se le
0.5 h d aw
0.5 h idle
HRT = 7.5 days
SRT = 22 days
[VSS] = 3000 mg
MLSS/L
G anula Ac i a ed
Ca bon
BOD
5
,
COD and
KTN >93
Addi ion o
u ea,
glucose and
nu ien s o
he e luen
Si ianun ap
boon and
Sansak
[2007]
Real e luen
1 h ill
19 h eac ion
3 h se le
0.5 h d aw
0.5 h idle
SRT = 28 days
G anula Ac i a ed
Ca bon
BOD
5
,
COD and
KTN >93
Addi ion o
glucose o
he e luen
Si ianun ap
boon and
Sansak
[2007
Real e luen
1 h ill
19 h eac ion
3 h se le
0.5 h d aw
0.5 h idle
SRT = 28 days
G anula Ac i a ed
Ca bon
BOD
5
,
COD and
KTN >93
Addi ion o
ice
was ewa e
o he
e luen
Si ianun ap
boon and
Sansak
[2007
Pa I
51
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Mohan, S.V.; Babu, P.S.; Na esh, K.; Vel izhi, G.; Madamwa , D. (2012). Acid azo dye emedia ion
in anoxic-ae obic-anoxic mic oen i onmen unde pe iodic discon inuous ba ch ope a ion: Bio-
elec o kine ics and mic obial in en o y. Bio esou ce Technology, 119, 362-372.
Mohseni, B.A.; Baza i, H. (2004). Biological ea men o dai y was ewa e by sequencing ba ch
eac o . I anian Jou nal o En i onmen al Heal h Science & Enginee ing, 1, 65-69.
Mo ais, L.C.P. (2005). A aliação da T a abilidade de E luen es da Indús ia de Cu umes po
Oxidação Química e Biológica. Disse a ion o doc o deg ee in chemical enginee ing, Uni e si y o
Po o – Facul y o Enginee ing.
Mo ling, S. (2010). No ogen emo al and hea y me als in leacha e ea amen using SBR
echnology. Jou nal o Haza dous Ma e ials, 174, 679-686.

Chap e 3
Ma e ials and Me hods
Pa II
65
3 Ma e ials and Me hods
3.1 In oduc ion
This pa o he hesis ega ds he p epa a ion and cha ac e iza ion o syn he ic e luen s
as well as he cha ac e iza ion o a eal co on dyeing e luen . A b ie desc ip ion o he
analy ical me hods and expe imen al p ocedu es is also p esen ed.
3.2 Tex ile Dyeing Was ewa e s
3.2.1
Simula ed Tex ile Dyeing Was ewa e s
Once he ea abili y o a gi en e luen depends on he cons i uen s p esen he ein and
hei espec i e concen a ion, his s udy s a ed by es ablishing a con ac wi h he ex ile
dyeing company E oc – Acabamen os Têx eis S.A. (loca ed in Famalicão) – so as o
collec in o ma ion ega ding he amoun s o dyes and auxilia y p oduc s used in dyeba hs
o syn he ic (polyes e and ac ylic) and na u al (co on) ibe s and he deg ee o ixa ion o
each chemical on he ibe s. This way one could p edic he concen a ion o each
indi idual chemical in he inal (and complex) e luen and p epa e he co esponding
simula ed was ewa e s.
3.2.1.1 Dyes
Two dispe se (Dianix Blue K-FBL and Dianix O ange K3G), one basic (As azon Blue
FGGL 03 300%) and wo eac i e (P ocion Yellow H-EXL g an and P ocion Deep Red H-
EXL g an) dyes we e selec ed o he p epa a ion o he simula ed e luen s, as hey a e
commonly used o dyeing polyes e , ac ylic and co on ibe s, espec i ely.
Table 3.1 shows he s uc u es (a ailable om he manu ac u e ) o he dyes p esen in
each e luen as well as some o he cha ac e is ics such as he dye class and he
expe imen ally de e mined wa eleng h o maximum abso bance in he isible egion. The
chemical s uc u e and gene ic name o he P ocion deep ed H-EXL g an dye is no
Chap e 3
–
Ma e ials and Me hods
66
p esen ed as his dye is a mix u e o wo dyes ( eac i e yellow 138:1 and ano he eac i e
azo dye). These dyes we e kindly p o ided by DyS a -Anilinas Têx eis Unipessoal Lda.
The selec ion o hese dyes also ook in o accoun he ollowing aspec s: i) he eac i e
dyes, which a e used in la ge amoun s o dyeing ibe s in Po ugal, dese e special
a en ion because o hei low deg ee o ixa ion on he ibe s, so ha conside able
quan i ies a e ejec ed and will be p esen in he e luen ; u he mo e, some eac i e dyes
a e no easily emo ed by con en ional p ocesses, such as biological ea men and
coagula ion/ loccula ion using ino ganic coagulan s; ii) he basic dyes exhibi an inc ease
in consump ion due o hei high in o ial alue and inc eased consump ion o ac ylic
ibe s; iii) he consump ion o dispe se dyes has been ising ollowing he inc ease in
demand o polyes e ibe s.
3.2.1.2 Auxilia y Chemicals
The dyeing auxilia ies we e also supplied by DyS a – Anilinas Têx eis Unip. Lda. Table
3.2 p esen s he auxilia y p oduc s used in he p epa a ion o he dyeba hs o each ibe
conside ed and hei main cha ac e is ics.
Table 3.1-
Cha ac e is ics o he dyes p esen in each simula ed e luen .
Comme cial name
Gene ic name
Dianix Blue K-FBL
Dispe se Blue 56
Dianix O ange K3G
Dispe se O ange 30
As azon Blue FGGL 300% 03
Basic Blue 41
P ocion Yellow H-EXL g an
Reac i e Yellow 138:1
P ocion Deep Red H-EXL g an n.a.
*
*
no a ailable.
Cha ac e is ics o he dyes p esen in each simula ed e luen .
Gene ic name
Class Mola mass (g/mol)
Chemical s uc u e
Polyes e e luen
Dispe se Blue 56
An h aquinone 304.14
Dispe se O ange 30
Azo 450.27
Ac ylic e luen
Basic Blue 41
Azo 482.57
Co on e luen
Reac i e Yellow 138:1
Azo
n.a.
*
n.a.
Azo n.a.
*
n.a.
Pa II
67
Chemical s uc u e
λ
max
(nm)
600
450
610
n.a.
*
420
n.a.
*
520

Chap e 3
–
Ma e ials and Me hods
68
Table 3.2 - Gene al cha ac e is ics o he auxilia y p oduc s used o dyeing polyes e , ac ylic and
co on ibe s.
Come cial name Dyeing s ep Func ion Chemical cha ac e is ic
Polyes e e luen
Ad anol NL Fibe p epa a ion An i-oil -
An ibacol R Fibe p epa a ion/Dyeing An i-c ease -
T isodium phospha e Fibe p epa a ion Elec oly e Sal
Se a Gal PLP Dyeing Equalizing/dispe san Alkyl polyglycol e he
solu ion
Ammonium sul a e Dyeing Elec oly e Sal
Ace ic acid Dyeing Acid gene a o Acid
Sodium hyd oxide 32%
(w/ ) Washing Alkaline sys em Base
Sodium hyd osul i e Washing Reduce sys em Reduce
Ac ylic e luen
Se a Con N-VS Dyeing Acid gene a o Ca boxylic acid es e
solu ion
Se a Spe se M-IW Dyeing Dispe san Alkyl polyglycol e he
solu ion
Se a Ta d A-AS Dyeing Re a de N-alkyl-N, N-
dime hylbenzylammonium
Sodium sul a e Dyeing Elec oly e Sal
Se a Lube M-CF Dyeing An i-c ease/lub ican Polyme ic amides solu ion
Co on e luen
Mouillan BG/JT Fibe p epa a ion An i-oil Composi ion based in
alipha ic e hoxyla es
An icassu e BG/BD Fibe p epa a ion An i-c ease Ac yamide aqueous solu ion
Sodium hyd oxide 50%
(w/ ) Fibe p epa a ion Alkaline sys em Base
Hyd ogen pe oxide 200
ol. Fibe p epa a ion Oxidizing he dye Oxidan eagen
Ace ic acid Fibe p epa a ion Acid gene a o
Acid
Ze ox Fibe p epa a ion Hyd ogen pe oxide
neu alize Ca alase
Enzyme BG/FB Fibe p epa a ion Bleaching Fungal cellulase
Sequion M150 Dyeing Wa e co ec o Composed by
phosphana es/ca boxyla es
Sodium chlo ide Dyeing Elec oly e Elec oly e
Sodium ca bona e Dyeing Alkalyne sys em Base
Sandozin NRW LIQ ALT C Washing De e gen Polye hylene glycol
iso idecyl e he
Pa II
69
3.2.1.3 P epa a ion o he Simula ed Tex ile Dyeing E luen s
The e luen s we e p epa ed aking in o accoun ha o e e y p ocess he e a e se e al
s ages, namely ibe p epa a ion, dyeing and washing (al hough he ibe p epa a ion
s age is no used in ac ylic dyeing). Mo eo e , i is wo h men ioning ha in each pa icula
case di e en olumes o wa e and chemicals a e employed along he p ocess, as shown
in Table 3.3, and ha he a io be ween he amoun o ibe o be dyed and he wa e used
in he ba h was assumed o be 1:10 (kg:L). Finally, he pe cen age o hese p oduc s
un ixed in he ex ile ibe s (and he e o e eleased in o he wa e ) should be also aken
in o accoun . This in o ma ion was p o ided by a dye-house (E oc-Acabamen os Têx eis
S.A. - Famalicão, Po ugal) and by DyS a Anilinas Têx eis, Unip L d (Po ugal), and is
summa ized in Table 3.3 along wi h he es ima ed concen a ion o each eagen in he
simula edl e luen s (polyes e , ac ylic and co on), which was based in he o al olume o
wa e employed in all s ages. Figu es 3.1 o 3.3 show he empe a u e p o iles o he
espec i e dyeing p ocesses and he momen o addi ion o each componen .
Chap e 3
–
Ma e ials and Me hods
70
Table 3.3 - Es ima ed concen a ion o each componen in he polyes e , ac ylic o co on simula ed e luen s.
Chemical Dyeing s age Dyeing s age
Concen a ion Rejec ion** Concen a ion in he inal
e luen om each s ep Concen a ion in he
global e luen
Polyes e e luen
Ad anol NL Fibe p epa a ion 1 g/L 100% 1 g/L 0.33 g/L
An ibacol R Fibe p epa a ion 1 g/L 100% 1 g/L 0.33 g/L
T issodic phospha e Fibe p epa a ion 1 g/L 90% 0.9 g/L 0.30 g/L
Se a Gal PLP Dyeing 0.5 g/L 100% 0.5 g/L 0.17 g/L
An ibacol R Dyeing 1 g/L 100% 1 g/L 0.33 g/L
Ammonium sul a e Dyeing 2 g/L 90% 1.8 g/L 0.60 g/L
Ace ic acid Dyeing 0.5 g/L 100% 0.5 g/L 0.17 g/L
Dianix Blue KFBL Dyeing 0.71%* 5% 0.036 g/L 0.012 g/L
Dianix O ange K3G Dyeing 1.2%* 5% 0.06 g/L 0.02 g/L
Sodium hyd oxide 32% (w/ ) Washing 3 g/L 100% 3 g/L 1.0 g/L
Sodium hyd osul i e Washing 3 g/L 90% 2.7 g/L 0.90 g/L
Ac ylic e luen
Se a con N-VS Dyeing 0.4 mL/L 100% 0.4 mL/L 0.13 mL/L
Se a spe se M-IW Dyeing 0.5 g/L 100% 0.5 g/L 0.17 g/L
Se a a d A-AS Dyeing 1 g/L 100% 1 g/L 0.33 g/L
Sodium sul a e Dyeing 3 g/L 90% 2.7 g/L 0.90 g/L
Se a lube M-CF Dyeing 2 g/L 100% 2 g/L 0.67 g/L
As azon Blue FGGL 300%
03 Dyeing 1.5%* 5% 0.025 g/L 0.008 g/L
Co on e luen
Mouillan BG/JT Fibe p epa a ion 0.7 mL/L 90% 0.21 mL/L 0.09 mL/L
An icassu e BG/BD Fibe p epa a ion 0.5 mL/L 90% 0.15 mL/L 0.06 mL/L
Pa II
71
Table 3.3 - Es ima ed concen a ion o each componen in he polyes e , ac ylic o co on simula ed e luen s. (con .)
Chemical Dyeing s age Dyeing s age
Concen a ion Rejec ion** Concen a ion in he inal
e luen om each s ep Concen a ion in he
global e luen
Co on e luen
Sodium hyd oxide 50% (w/ ) Fibe p epa a ion 4 mL/L 100% 1.3 mL/L 0.57 mL/L
Hyd ogen pe oxide 200 ol. Fibe p epa a ion 1.5 mL/L 85% 0.4 mL/L 0.18 mL/L
Ace ic acid Fibe p epa a ion 0.8 mL/L 100% 0.26 mL/L 0.11 mL/L
Ze ox Fibe p epa a ion 0.6 mL/L 90% 0.18 mL/L 0.08 mL/L
Enzyme BG/FB Fibe p epa a ion 0.4 mL/L 90% 0.12 mL/L 0.05 mL/L
Sequion M150 Dyeing 1 mL/L 100% 1 mL/L 0.14 mL/L
Sodium chlo ide Dyeing 9 g/L 90% 8.1 g/L 1.16 g/L
Sodium ca bona e Dyeing 20 g/L 90% 18 g/L 2.6 g/L
P ocion Yellow H-EXL g an Dyeing 0.45%* 10% 0.045 g/L 0.006 g/L
P ocion Deep Red H-EXL
g an Dyeing 2.8 %* 10% 0.28 g/L 0.04 g/L
Sandozin NRW LIQ ALT C Washing 0.9 mL/L 90% 0.27 mL/L 0.12 mL/L
* w dye/w ibe ;
** Pe cen age o dyes and auxilia y p oduc s no ixed by he ibe s.
Chap e 3
–
Ma e ials and Me hods
78
3.3.4 Chemical Oxygen Demand
The de e mina ion o he COD was pe o med acco ding o me hod 5220 B [APHA, 1998],
which quan i ies he K
2
C
2
O
7
educ ion by oxidizable o ganic and ino ganic compounds in
an open e lux diges e (G.VITTADINI Reco d/6Tes diges e ), a 150 °C o 2 hou s. The
emaining dich oma e was de e mined by i a ion wi h ammonium i on sulpha e. COD
was also de e mined by he closed e lux me hod (Me hod 5220 D [APHA, 1998]), a 150
ºC (The mo eac o TR 300 om Me ck) o 2 hou s, hen measu ing he abso bance
(Spec oquan No a 60) co esponding o he educed ch omium.
The samples wi h concen a ions o chlo ides highe han he maximum pe missible by he
me hod (2000 mg/L), such as he simula ed co on e luen , we e i s ly dilu ed.
3.3.5 Chlo ides, Dissol ed Phospho us, Ni a es and Sul a es
Chlo ides, ni a es, dissol ed phospho us and sul a es we e measu ed by ion
ch oma og aphy (Dionex DX 120) using a Dionex Ionpac AS9-HC 4 mm (10-32) column
and sodium ca bona e 9 mM as eluen – Me hod 4110 B [APHA, 1998].
3.3.6 Colo
The colo o he samples was quan i ied by measu ing he abso bance a he wa eleng h
o maximum abso bance (520, 600 and 610 nm o syn he ic co on, eal co on and
syn he ic ac ylic e luen s, espec i ely), using a molecula abso p ion spec opho ome e
(Pye Unicam, model He
l
ios α). As he abso bance o he was ewa e s a ies wi h pH, he
pH in he ea ed e luen was adjus ed o he ini ial alue, whene e necessa y, be o e
abso bance measu emen .
To e alua e de compliance wi h he discha ge limi as de ined in O dinance No. 423/97 o
25 June, he samples we e dilu ed 40 imes and isually checked he p esence o
absence o colo .

Pa II
79
3.3.7 Conduc i i y
The conduc i i y a 20 ºC was de e mined using a conduc i i y p obe (WTW Te aCon
325) and a conduc i i y me e (WTW LF538) - Me hod 2510 B [APHA, 1998].
3.3.8 Dissol ed I on
The dissol ed i on was de e mined by he a omic abso p ion spec ome y- lame me hod
(AAS GBC model 932 AB Plus) - Me hod 3111 B [APHA, 1998], a e il a ion o he
samples h ough cellulose ni a e memb anes (Albei ) wi h po e size o 0.45
µ
m.
3.3.9 Dissol ed Oxygen Ca bon
The DOC o he samples was ob ained, a e il a ion h ough nylon il e memb anes wi h
po e diame e o 0.45 µm, by ca aly ic oxida ion a 680 ºC using a 5000 A - Shimadzu
To al Ca bon analyze , ollowed by quan i ica ion o he CO
2
o med by in a- ed
spec ome y as desc ibed in Me hod 5310 D [APHA, 1998]. DOC was calcula ed as he
di e ence be ween he o al dissol ed ca bon (TDC) and he ino ganic ca bon (IC) in he
liquid sample.
3.3.10 Hyd ogen Pe oxide
The quan i ica ion o he hyd ogen pe oxide was pe o med as desc ibed by Selle s
[1980]. The me hod is based on he measu emen o he in ensi y o he yellow-o ange
colo esul ing om he eac ion o hyd ogen pe oxide wi h i anium oxala e. The samples
we e p e iously il e ed h ough nylon il e memb anes wi h po e diame e o 0.45 µm.
3.3.11 Inhibi ion o Vib io Fische i
The inhibi ion es o bac e ium Vib io ische i was pe o med acco ding o he s anda d
DIN/EN/ISO 11348-3 [In e na ional O ganiza ion o S anda diza ion, 2005]. The samples
Chap e 3
–
Ma e ials and Me hods
80
we e added o V. ishe i cul u e medium a 15 ºC and he bioluminescence was measu ed
a e 5, 15 and 30 minu es in a Mic o ox Model 500 analyze . The samples we e i s
neu alized o pH ~ 7 wi h HCl o NaOH 1N.
3.3.12 pH
The pH was measu ed wi h a combined elec ode (Hanna Ins umen s HI 1230)
connec ed o a pH-me e (Hanna Ins umen s HI 8424)- Me hod 4500 H
+
B [APHA, 1998].
3.3.13 To al Ni ogen
To al ni ogen was quan i ied by po assium pe sul a e diges ion (Me hod 4500 N. C
[APHA, 1998]), which con e s o ganic ni ogen, ammonia and ni i e in o ni a e, wi h
subsequen de e mina ion o ni a e by molecula abso p ion spec opho ome y a e
eac ion wi h b ucine (Me hod D992-71 o ASTM [1973]).
3.3.14 To al Phospho us
The o al phospho us was quan i ied by measu ing he in ensi y o blue colo esul ing
om he eac ion o o hophospha e wi h asco bic acid, a e acid diges ion wi h
ammonium pe sul a e o con e all phospho us in o o hophospha e (Me hod 4500 P. E
[APHA, 1998]).
3.3.15 To al Suspended Solids and Vola ile Suspended Solids
To al suspended solids (TSS) and ola ile suspended solids (VSS) we e e alua ed by
g a ime y - Me hod 2540 B and Me hod 2540 E [APHA, 1998], espec i ely.
Pa II
81
3.3.16 HPLC Analyses
Fo he high pe o mance liquid ch oma og aphy (HPLC) analyses (in a VWR
ch oma og aph, Eli e Lach om model) o he in e media es o med du ing oxida ion, a
Pu osphe S a RP-18 (5 µm) column was used, a a empe a u e o 30 ºC, wi h a mix u e
o ace oni ile (A) and wa e (W) as eluen , low a e o 1 mL/min in g adien mode (a =0
min, 30% o A and 70% o W, =20 min, 63% o A and 37% o W, =22 min, 63% o A and
37% o W, =23 min, 30% o A and 70% o W and =30 min, 30% o A and 70% o W). The
peak ampli ude was measu ed wi h a diode a ay de ec o (DAD) (a 254 nm o ac ylic
e luen and 200 nm o polyes e e luen ).
3.3.17 Zahn-Wellens Tes
The Zahn–Wellens es was pe o med acco ding o me hod 302B o OECD [1992]. A
olume o 250 mL o was ewa e was added o an open glass essel, magne ically s i ed
(Velp Scien i ica model Mul i15 S i e ) and kep in he da k inside a he mos a ic
e ige a o (PSelec a model HOTCOLD - M) a 25 ºC. Then 0.25 g o ac i a ed sludge
om he ae a ion ank o a WWTP ea ing ex ile e luen s (Rabada, San o Ti so),
p e iously cen i uged, and mine al nu ien s (KH
2
PO
4
, K
2
HPO
4
, Na
2
HPO
4
, NH
4
Cl, CaCl
2
,
MgSO
4
and FeCl
3
) we e added o he samples. The con ol and blank expe imen s we e
p epa ed subs i u ing he e luen by lau yl sul ona e (0.2 g/L) and dis illed wa e ,
espec i ely. The pe cen age o biodeg ada ion (D
) was de e mined by Equa ion 3.1:
(3.1) 100 *
C - C
C - C
- 1 D
BAA
B






=
whe e C
A
and C
BA
a e he DOC concen a ions (mg/L) o he mix u e and blank, measu ed
3 h a e he beginning o he expe imen , C
and C
B
a e he DOC (mg/L) o he mix u e
and blank, measu ed a he sampling ime .
Chap e 3
–
Ma e ials and Me hods
82
3.4 Expe imen al P ocedu e
3.4.1 Coagula ion/Floccula ion
The coagula ion/ loccula ion expe imen s we e ca ied ou in a Ja - es appa a us (Isco)
(Figu e 3.6). A olume o 300-500 mL o e luen was used and he pH adjus ed using
NaOH (1 o 10 N) o H
2
SO
4
(1 N), depending on he pH equi ed o he coagula ion s age
and on he e luen na u al pH. A high s i ing speed (which was a ied in he pa ame ic
s udies in he ange 100-200 pm, co esponding o a eloci y g adien , G, be ween 237
and 669 s
-1
) was hen p omo ed and he coagulan (FeSO
4
.7H
2
O – Me ck, 99% o pu i y –
o Fe
3
(SO
4
)
2
– Rieden Häen, 99% o pu i y) added. Immedia ely a e his, he pH was
eadjus ed (i necessa y) and he agi a ion was p olonged o he in ended ime (
coagula ion
).
A e he coagula ion, he locculan was added jus be o e he beginning o he slow
s i ing s age (20-50 pm, co esponding o a eloci y g adien be ween 21 and 84 s
-1
).
This s age p oceeded o a gi en ime (
loccula ion
= 15-45 minu es) in o de o acili a e he
locs agg ega ion o an easie sedimen a ion. The expe imen s we e pe o med a
con olled empe a u e by placing he Ja - es appa a us (VELP P4) inside a
he mos a ized chambe (Velp Scien i ica FOC 225E), he addi ion o he coagulan being
done only a e empe a u e s abiliza ion.
Figu e 3.6 – Diag am o he Ja - es se -up.
Pa II
83
3.4.2 Fen on´s Reac ion
Fen on’s oxida ion was ca ied ou in an 1 L-capaci y jacke ed ba ch eac o connec ed o
a he mos a ic ba h (G an Y6) o wa e ci cula ion (Figu e 3.7), in o de o main ain he
empe a u e inside he eac o a he desi ed alue.
Figu e 3.7 – Diag am o he Fen on’s oxida ion se -up.
In all uns, 500 mL o aw was ewa e o p e- ea ed e luen was loaded in o he eac o
and a e empe a u e s abiliza ion, he pH was adjus ed o a p ede ined alue wi h 1 N
H
2
SO
4
o 1 o 10 N NaOH. When equi ed, e ous sul a e hep ahyd a e was added and
he eac ion s a ed wi h he addi ion o H
2
O
2
, 30% (w/ ). All eagen s we e om Me ck,
analy ical g ade.
The oxida ion eac ion p oceeded unde cons an s i ing, using a magne ic ba and a s i
pla e (Falc). Pe iodically, samples we e aken om he eac o and he eac ion s opped in
he lasks by he addi ion o la ge excess sodium sul i e ( ha eac s ins an aneously wi h
emaining hyd ogen pe oxide) o measu ing he dissol ed o ganic ca bon (DOC) as
desc ibed abo e. As ega ds o he pa ame e s, namely chemical oxygen demand (COD),
biochemical oxygen demand a e 5 days (BOD
5
), pH, colo , speci ic oxygen up ake a e
(SOUR o k’) and oxici y (inhibi ion o Vib io ische i), he eac ion was s opped by
elimina ing he esidual H
2
O
2
and by p ecipi a ion o he i on ca alys . Fo ha , he pH o
he inal e luen was aised o 12.3 by addi ion o 10 N NaOH, he sample was hea ed a
80 °C o 10 minu es and inally neu alized ( o pH ~7.0) wi h conc. H
2
SO
4
. The samples
o oxici y assessmen we e neu alized wi h HCl 1N, ins ead o H
2
SO
4
, as p oposed by

Chap e 3
–
Ma e ials and Me hods
84
he analy ical me hodology. In his case sodium sul i e was no used because i leads o
deac i a ion o V. ische i and consequen ly o a decay in he luminescence.
The supe na an esul ing om he Fen on´s oxida ion was acidi ied o pH 1 wi h conc.
HNO
3
o ensu e ha he i on was kep dissol ed o he subsequen s age o
coagula ion/ loccula ion. The analyses o he e luen we e pe o med immedia ley.
3.4.3 Pho o-Fen on Oxida ion
3.4.3.1 Pho o-Fen on wi h A i icial Radia ion
The es s ook place in a closed cylind ical eac o o 1-li e capaci y, which was loaded
wi h 800 ml o e luen o be ea ed. The eac o was equipped wi h a UV/ isible lamp
(150 W high p essu e me cu y apo - He aeus TQ 150, co esponding o 500 W/m
2
-
which emi s UV/ isible adia ion a wa eleng hs om 200 o ~600 nm), loca ed axially
inside a dip imme sion qua z ube (c . Figu e 3.8). The jacke ed qua z ube was
connec ed o a he mos a ic ba h (GRANT Y6) o empe a u e con ol h ough wa e
eci cula ion. The eac o was also p o ided wi h a magne ic s i pla e (Falc).
Figu e 3.8 – Diag am o he pho o-Fen on se -up wi h me cu y lamp TQ 150.
Pa II
85
In uns using a i icial adia ion, he eac o was loaded wi h 800 ml o e luen o be
ea ed. A e he e luen eached he desi ed empe a u e, he pH was adjus ed o he
es abilished alue wi h 1N H
2
SO
4
. In he case o di ec pho olysis expe imen s, he lamp
was hen connec ed, and samples collec ed a p e-es ablished pe iods o measu e he
abso bance and dissol ed o ganic ca bon (DOC). In uns whe e one in ended o combine
UV/Vis adia ion wi h H
2
O
2
(30% w/ om Me ck), he me cu y lamp was swi ched on a
he same ime ha he eagen (H
2
O
2
) was added. In his case, be o e analyzing he
samples, he emaining hyd ogen pe oxide was emo ed by he addi ion o la ge excess
o sodium sul i e (six imes he s oichiome ic alue co esponding o he amoun o
hyd ogen pe oxide added a he beginning o he es ).
In pho o-Fen on expe imen s, he adop ed p ocedu e was basically he same, wi h one
in e media e s ep o adding e ous sul a e hep ahyd a e (Me ck) be o e u ning on he
lamp and adding hyd ogen pe oxide. Again, hyd ogen pe oxide was elimina ed om he
samples aken h oughou he eac ion by adding sodium sul i e, be o e DOC and he
abso bance measu emen . In he samples collec ed a e 60 minu es o eac ion o he
subsequen de e mina ion o COD and BOD
5
, he eac ion was s opped by aising he pH
o 12.3 wi h he addi ion o 10 M NaOH ( om Me ck), hea ing he samples a 80 °C o 10
minu es and neu alizing wi h concen a ed H
2
SO
4
un il pH ~ 7.0; his p ocedu e was
adop ed because sodium sul i e in e e es wi h hose analy ical de e mina ions.
In pho o-Fen on es s he ligh lux ha eached he was ewa e was a ied by ci cula ing,
in he jacke o he qua z ube, a solu ion o dye Solophenyl G een BLE 155% a di e en
concen a ions, as desc ibed by Sil a and Fa ia [2009]. These concen a ions ha e been
p e iously de e mined by po assium e ioxala e ac inome y [Kuhn e al., 2004]. Figu e
3.9 shows he a ia ion o he adia ion in ensi y (measu ed wi h a Kipp & Zonen B.V.,
model CUV 5 UV adiome e , and a Del a OHM, model D9221 isible adiome e - placed
ou side he eac o and a mid-heigh o he dip imme sion qua z ube) ha eaches he
solu ion o be ea ed as a unc ion o he dye concen a ion in he solu ion ci cula ing in
he jacke .
Chap e 3
–
Ma e ials and Me hods
86
Figu e 3.9 - Va ia ion o he adia ion in ensi y wi h he Solophenyl G een BLE 155% concen a ion
ci cula ing in he pho o- eac o jacke .
3.4.3.2 Pho o-Fen on using Simula ed Sola Radia ion
The pho o eac o using simula ed sola adia ion ac ually comp ises wo eac o s (Figu e
3.10): i) an 1-li e capaci y closed cylind ical eac o equipped wi h a jacke o wa e
eci cula ion om a he mos a ic ba h (RW-0525G he Lab Companion) o empe a u e
con ol and ii) a ubula eac o ( olume o ~ 0.78 L, 100% olume i adia ed) placed inside
he Sola box (ATLAS, model SUNTEST XLS+). The Sola box has a Xenon lamp o 1700
W ha emi s adia ion a wa eleng hs om 300 o 800 nm.
In uns wi h simula ed sola adia ion he cylind ical eac o was ed wi h 800 mL o
e luen and he pH adjus ed o he p ede ined alue wi h 1 N H
2
SO
4
. The solu ion was
con inuously pumped o he ubula eac o and eci cula ed back in o he cylind ical one
(wi h he aid o a pe is al ic pump - Ecoline VC-380 II Isma ec), a a low a e o 0.65 L/min
(~ 0.12 min esidence ime in he ubula eac o ). A e eaching he desi ed empe a u e,
hep ahyd a ed e ous sul a e (Me ck) and hyd ogen pe oxide (30% w/ – Me ck) we e
added o he cylind ical eac o . Then he lamp was swi ched on. Du ing he eac ion he
cylind ical eac o con en s we e s i ed by a magne ic ba and s i pla e (Velp Scien i ica,
model ARE).
Samples we e aken a p e-de ined imes and he eac ion was s opped as desc ibed in
he p e ious sec ion o da k Fen on expe imen s. The adia ion in ensi y in he ange 300
0
100
200
300
400
500
0 100 200 300 400 500
In ensi y (W/m2)
)
)
)
[Dye] (mg/L)
Pa II
87
- 400 nm was measu ed in he ubula eac o by an UV adiome e (Kipp & Zonen B.V.,
model CUV 5).
Figu e 3.10 – Diag am o he sun- es se -up.
3.4.4 Biological Oxida ion in Sequencing Ba ch Reac o
The SBR is a jacke ed cylinde (20 cm in e nal diame e , 45 cm o al heigh and 30º slope
conical bo om; e ec i e wo king olume = 5.0 L) connec ed o a he mos a ic ba h (Isco
GTR 90, om I aly). Figu e 3.11 shows he ins alla ion se -up. The biological eac o was
ope a ed a cons an empe a u e (25 °C) du ing 12 hou s pe cycle (1 h eeding, 6 h
eac ion, 4 h sedimen a ion, 0.8 h discha ge and 0.2 h idle), up o 10 cycles (i.e., when he
pa ame e s analysed in he ea ed e luen and desc ibed below showed nea ly con an
alues om cycle o cyle – pseudo s eady-s a e condi ions). In he i s cycle he eac o
was ed wi h 2.5 L o was ewa e wi h pH p e iously adjus ed o ~7.0 using 1M H
2
SO
4
and
10 M NaOH, a e adding phospho us (as phospha e bu e ) o ni ogen (as u ea)
whene e necessa y o ensu e he minimum quan i y equi ed o biological ea men

Pa III
95
4 Coagula ion/Floccula ion wi h Fe
2+ as Coagulan
4.1 In oduc ion
The p esen chap e ocuses on de e mining he bes ope a ing condi ions o he
coagula ion/ loccula ion p ocess using i on (II) as coagulan o ea di e en ypes o
syn he ic ex ile was ewa e s simula ing co on, ac ylic and polyes e dyeing. I is
e alua ed he e ec o s i ing speed, con ac ime, empe a u e, pH and doses o
coagulan ( e ous sulpha e) and locculan s (Magna loc 155 o Supe loc C-573) in colo
and dissol ed o ganic ca bon (DOC) emo al om he was ewa e s. The selec ed
locculan s a e commonly employed in he ea men o ex ile dyeing was ewa e s.
Howe e , he use o an i on sal as coagulan is ela ed o he possibili y o in eg a ing he
coagula ion/ loccula ion p ocess wi h a subsequen Fen on-like oxida ion ea men in
which he soluble emaining i on is used as ca alys , hus dec easing he o e all
consump ion o chemicals. The use o he soluble i on esul ing om he
coagula ion/ loccula ion in he pa ial mine aliza ion o o ganic compounds by such
oxida ion ea men is add essed in chap e s 6-8.
4.2 Ma e ials and Me hods
4.2.1
P epa a ion o Simula ed Tex ile Was ewa e s
The simula ed e luen s we e p epa ed as desc ibed in sec ion 3.2 o chap e 3 and he
main cha ac e is ics o he syn he ic e luen s a e epo ed in Table 3.4 (c . sec ion 3.2.1).
4.2.2 Coagula ion/Floccula ion Expe imen s
The expe imen al p ocedu e conce ning he coagula ion/ loccula ion expe imen s was
desc ibed in sec ion 3.4.1 – Ma e ials and Me hods.
The e luen p e- ea ed by coagula ion employing he op imal condi ions was hen
subjec ed o loccula ion expe imen s. Magna loc, an anionic polyac ylamide (molecula
weigh a ound 5×10
6
, densi y ~750 kg/m
3
, incolo solid) and Supe loc C-573, a ca ionic
Chap e 4
–
Coagula ion/Floccula ion wi h Fe
2+
as Coagulan
96
polyamine (molecula weigh a ound 10
4
, densi y 1.14-1.18 kg/m
3
, yellow liquid), we e
es ed as locculan s, since hey ha e been conside ed as sui able polyme s o ea his
kind o was ewa e s.
The samples o supe na an we e collec ed a e 30 minu es o sedimen a ion and he
dissol ed o ganic ca bon (DOC) de e mined immedia ely (despi e DOC alues in he
supe na an o he same samples analysed a e 24 h o sedimen a ion we e iden ical o
hose ob ained a e 30 minu es). The abso bance was, howe e , ead a e one day o
sedimen a ion o minimize he numbe o e y small pa icles o i on hyd oxide in
suspension. Mo eo e , he supe na an sample o colo measu emen was cen i uged
(Mini Spin Eppendo ) a 13400 pm o 2 minu es.
4.2.3 Analy ical Me hods
The expe imen al me hods used in his s udy we e al eady men ioned in sec ion 3.3 o
Chap e 3.
The pa ame e s we e measu ed in duplica e and he a ia ion coe icien s we e less han
2% o DOC, < 1% o abso bance, < 9% o BOD
5
and < 3% o he o he pa ame e s.
4.3 Resul s and Discussion
In his chap e a e epo ed expe imen s ca ied ou o de e mine he e ec o s i ing a e
and ime on he colo and DOC emo al du ing he coagula ion p ocess. Howe e , hese
a iables we e no e y e ec i e, as shown below om he esul s ob ained o he
polyes e and co on e luen s. Fu he , he e ec o o he mo e ele an ope a ing
condi ions as empe a u e, pH and e ous sal concen a ion on he colo and DOC
emo al e iciency was analyzed o he h ee e luen s.
The same app oach was adop ed o he loccula ion s age a e being submi ed o
coagula ion a he op imal condi ions. Thus, he in luence o s i ing speed and ime is
discussed o wo e luen s, bu o he mo e signi ican a iables ( locculan ype and
concen a ion) a e analyzed in u he de ail o all e luen s.
Pa III
97
4.3.1 E ec o S i ing Speed and Time on he Coagula ion S age
The s i ing a e in he coagula ion s age should be high and acco ding o p e ious
wo ke s alues a ound 100 pm we e p oposed [Sa e ield, 2004; Bose, 2010; Poland
and Pagano, 2010]. Thus, expe imen s we e pe o med changing his a iable in he
ange 100 - 200 pm (G be ween 237 and 669 s
-1
) o co on and polyes e e luen s.
Values om 1 minu e o 3 minu es [Ecken elde , 2000; Bose, 2010; Poland and Pagano,
2010] ha e been p oposed o he du a ion o his ini ial s age. To s udy he e ec o his
a iable, he s i ing ime (
coagula ion
) was a ied be ween 1 o 5 minu es. I was ound ha
bo h a iables do no a ec he colo o he DOC emo al o bo h e luen s (c . Appendix -
Figu es. A1 and A2). DOC emo als we e ~27% and ~30% o he polyes e and co on
e luen s, espec i ely. A ound 74% o colo emo al was ob ained o he co on e luen
wha e e he s i ing a e and ime ( he polyes e is colo less). These esul s allow
concluding ha hese a iables, s i ing a e and ime, do no play an impo an ole in he
coagula ion s age.
4.3.2 E ec o he Tempe a u e on he Coagula ion S age
In his s udy he e ec o empe a u e in he coagula ion p ocess was analyzed; al hough i
has no been commonly in es iga ed in he open li e a u e, Edeline [1992] epo ed he
empe a u e as being a a iable o ake in o accoun . Thus, he empe a u e was a ied
be ween 15 and 50 ºC while he p e ious a iables we e ixed a
coagula ion
= 150 pm (G =
435 s
-1
) and
coagula ion
= 3 min.
Figu e 4.1 shows ha o he polyes e was ewa e , he DOC emo al is almos
independen o empe a u e, emaining nea ly cons an (~27%) in he s udied ange; he
same applies wi h he co on e luen . In he ac ylic was ewa e a sligh inc ease is no iced
in he empe a u e ange om 15 o 22 ºC, hen emaining nea ly cons an . Remo al o
o ganic ca bon is highe in he co on and lowe in he ac ylic compa ed o he polyes e
e luen . The e ec o empe a u e on colo emo al is much mo e ma ked, inc easing
om 11.4% and 4.7% a 15 ºC up o ~74% and ~32% a 22 ºC o co on and ac ylic
was ewa e s, espec i ely, bu pe o mance is no u he imp o ed a 50 ºC (Figu e 4.1 b).
Thus, subsequen uns we e pe o med a oom empe a u e. The inc eased pe o mance
wi h empe a u e may be a consequence o he imp o ed kine ics as occu s in mos
Chap e 4
–
Coagula ion/Floccula ion wi h Fe
2+
as Coagulan
98
chemical eac ions (A henius dependency). The e ec o empe a u e on coagula ion has
been analyzed by Duan and G ego y [2003], indica ing ha a lowe empe a u es he
coagula ion wi h hyd olyzing me als is less e icien . Tempe a u e e ec s may be due o
physical o chemical ac o s, whe e physically he empe a u e a ec s he iscosi y and
consequen ly he anspo o collision a es. On he o he hand, he chemical in luence is
on he le el o hyd olysis eac ions, p ecipi a ion and solubili y o he me al hyd oxide.
Figu e 4.1 – Va ia ion o DOC (a) and colo (b) emo als wi h empe a u e in he coagula ion s age
o he di e en simula ed e luen s (
coagula ion
=150 pm,
coagula ion
=3 min, [Fe
2+
]=200 mg/L and
pH=8.3).
4.3.3 E ec o he pH on he Coagula ion S age
One o he mos impo an a iables in he coagula ion p ocess using ino ganic sal s is he
pH. This occu s because he coagulan (i on sal in his case) is con e ed in o di e en
ionic species as he pH alue changes hus, in luencing he coagula ion. In alkaline pH,
depending on he edox po en ial, some i on (II) p ecipi a es as a hyd oxide (g een us )
capable o abso bing anions because o he p esence o posi i e elec ical cha ges on i s
su ace. Howe e , o pH<10 he p edominan i on species a e Fe
2+
(p ac ically he only
species o pH<7) and Fe(OH)
+
. In his wo k, he pH was changed in he ange om 3.5 o
10.4 bu in he ac ylic e luen expe imen s a pH abo e 8.3 was no used because a
change o he blue colo o ligh g ey was obse ed.
Figu e 4.2 shows ha he e a e op imum pH alues o he DOC and colo emo al which
changes om one e luen o ano he . In gene al, he op imum pH alue is he same o
0
10
20
30
40
50
60
15 22 50
DOC emo al (%)
T(ºC)
Ac ylic Polyes e Co on
a)
0
20
40
60
80
100
15 22 50
Colo emo al (%)
T (ºC)
Ac ylic
Co on
b)
Pa III
99
ei he DOC o colo emo al o each was ewa e used. I can be summa ized ha o he
polyes e e luen he e is no DOC emo al a all a pH 3.5 o 5, bu an op imum exis s a
pH 8.3 (27.6% emo al). Fo he co on e luen , a pH o ca. 9.4 led o he g ea es DOC
and colo emo als (40.3% and 90.1%, espec i ely). As o he ac ylic e luen , he DOC
emo al a a pH o 3.5 and 5 was low and he highe emo als we e obse ed a a pH o
7.2 (~10% o DOC and 55.3% o colo ). I is wo h men ioning ha he op imal pH ollow
he o de o he e luen 's na u al pH alues; ac ylic < polyes e < co on (c . Table 3.4 in
sec ion 3.2.1.3).
Figu e 4.2 – In luence o pH on DOC (a) and colo (b) emo als by coagula ion applied o he
di e en simula ed e luen s (
coagula ion
=150 pm,
coagula ion
=3 min, [Fe
2+
]=200 mg/L and T
=T
ambien
=22-23 ºC).
The op imum pH alues ob ained, which will be adop ed in he subsequen uns, a e close
o he alues commonly appoin ed in o he s s udies wi h he same coagulan o ex ile
e luen s, bu he op imum pH depends s ongly on he na u e o he was ewa e o be
ea ed. Fo example, pH alues o 5.0 and 6.0 ha e been epo ed o whi e and ed wine
e luen s, espec i ely [B az e al., 2010], 7.4 o mechanical pulping e luen coagula ion
[S ephenson and Du , 1996], a ound 8.0 o dai y was ewa e [Kushwaha e al., 2010]
and cosme ic manu ac u ing was ewa e [Pe digón-Melón e al., 2010], 8.5 o pu i ied
e aph halic acid was ewa e [Ve ma e al., 2010] and 9.4 o e luen om pe sonnel ca e
p oduc s manu ac u ing [El-Goha y e al., 2010] . O he au ho s ixed he pH a 9.0 [Golob
e al., 2005] o 9.5 [Selcuk, 2005] o dye con aining was ewa e s.
0
10
20
30
40
50
60
3.5 5 7.2 8.3 9.4 10.4
DOC emo al (%)
pH
Ac ylic Polyes e Co on
a)
0
20
40
60
80
100
3.5 5 7.2 8.3 9.4 10.4
Colo emo al (%)
pH
Ac ylic
Co on
b)

Chap e 4
–
Coagula ion/Floccula ion wi h Fe
2+
as Coagulan
100
4.3.4 E ec o he Coagulan (Fe
2+
) Concen a ion
The dose o coagulan necessa y o he ea men o e luen s by coagula ion, and
pa icula ly hose om ex ile indus ies, depends on he cha ac e is ics o he
was ewa e s [Ecken elde , 2000]. The e o e, i is necessa y o e alua e he e ec o he
coagulan dose (Fe
2+
), which was he ein changed in he ange o 15 o 1000 mg/L o
polyes e and co on e luen s and om 200 o 4000 mg/L o ac ylic ones. These anges
we e enough o ind op imum doses, and he o he s a iables ha in luence he p ocess
we e ixed a he op imum alues ob ained be o e.
The esul s o DOC emo al (Figu e 4.3 a) pe mi ed concluding ha o co on
was ewa e s, he op imum Fe
2+
dose is 200 mg/L and highe doses a e also no equi ed
o educing he colo o such e luen s (Figu e 4.3 b). Fo he ac ylic, he op imum is
shi ed owa ds a much highe coagulan dose; 3000 mg/L o DOC emo al while o he
colo emo al i inc eased up o 500 mg/L and hen emained almos unchanged. The
highe concen a ion o Fe
2+
equi ed is p obably a consequence o he highe load o
o ganic ma e in his e luen (Table 3.4 in sec ion 3.2.1.3). Fo he polyes e , Figu e 4.3 a
shows ha he DOC emo al inc eases wi h he Fe
2+
concen a ion up o a dosage o 200
mg/L, and ha o highe doses he e iciency emains nea ly cons an . The op imum dose
o Fe
2+
in his case is qui e simila o ha obse ed wi h he co on e luen , which migh be
ela ed o he simila o ganic ca bon con en o bo h was ewa e s (Table 3.4 o sec ion
3.2.1.3). In he selec ed condi ions, a ound 90% o colo emo al was eached o co on
and 65.8% o ac ylic, while e iciencies o 40.3%, 17.7% and 27.6% we e ob ained o
DOC emo al in co on, ac ylic and polyes e e luen s, espec i ely. O he s udies epo
he occu ence o an op imal in coagulan dose o ea was ewa e s by chemical
coagula ion/ loccula ion [Amok ane e al., 1997 Ta si e al., 2003].
Pa III
101
Figu e 4.3 – Va ia ion o DOC (a) and colo (b) emo als wi h he concen a ion o coagulan (Fe
2+
)
o he di e en simula ed e luen s (
coagula ion
=150 pm,
coagula ion
=3 min, T=T
ambien
=23-25 ºC and
pH
polyes e
=8.3, pH
co on
=9.4 and pH
ac ylic
=7.2).
Geo gious e al. [2003] achie ed he bes esul s o colo and COD elimina ion om
co on dyeing was ewa e using a combina ion o lime (800 mg/L) and FeSO
4
.7H
2
O (1000
mg/L). On he o he hand, Golob e al. [2005] achie ed almos ull decolou iza ion o
dyeba h e luen s (co on/poliamide blends) using 20 mg/L o FeSO
4
.7H
2
O bu TOC was
only educed by 25%. In spi e o using a e ic sal , Joo e al. [2007] concluded ha 3000
mg/L was he equi ed dose o maximizing he colo emo al and 4000 mg/L o
maximizing he COD emo al o a eac i e dye syn he ic was ewa e . These and o he
published da a show ha he coagulan dose is highly a iable, depending on he
was ewa e cha ac e is ics, dye concen a ion and o e all o ganic con en , in ag eemen
wi h ou indings. Addi ionally, i mus be emphasized ha excess o coagulan can
p omo e he undesi able s abiliza ion o colloids, which has been obse ed in di e en
s udies [Aziz e al., 2007; Liang e al., 2009].
In he p esen s udy, o he ac ylic dyeing was ewa e , a dose a ound 500 mg/L should be
adequa e o maximize he colo emo al bu i was inc eased o maximize DOC emo al
(in spi e o no exceeding 17.7% wi hou locculan addi ion). O cou se, o p ac ical
pu poses o he c i e ia should be also aken in o accoun , namely he ex a cos o he
coagulan dose, and balanced wi h he bene i in e ms o p ocess pe o mance.
0
10
20
30
40
50
60
15 50 100 200 500 1000200030004000
DOC emo al (%)
[Fe
2+
] (mg/L)
Ac ylic Polyes e Co on a)
0
20
40
60
80
100
15 50 100 200 500 1000200030004000
Colo emo al (%)
[Fe
2+
] (mg/L)
Ac ylic Co on
b)
Chap e 4
–
Coagula ion/Floccula ion wi h Fe
2+
as Coagulan
102
4.3.5 In luence o he S i ing Speed and Time in he Floccula ion
S age
Usually he s i ing speed in he loccula ion s age a ies in he ange 25-35 pm [Bose,
2010; Poland and Pagano, 2010] and las s be ween 12 and 35 min [Phipps & Bi d, 1995;
La leu , 1997; Ecken elde , 2000; Bose, 2010; Poland and Pagano, 2010]. Fo e alua ing
he e ec o s i ing speed on he loccula ion, his pa ame e (
loccula ion
) was a ied in he
ange 20-50 pm, i.e., G be ween 21 and 84 s
-1
(a a ixed ime o 15 min and a Magna loc
155 concen a ion o 2.5 mg/L). Then, u he expe imen s we e pe o med while changing
he loccula ion ime om 15 o 45 min. Wi h hese expe imen s i was concluded ha
loccula ion
and
loccula ion
do no ha e any app eciable in luence on ei he colo o DOC
emo al (c . Figu es A.3 and A.4 in Appendix). The e o e, in subsequen expe imen s
hese a iables we e ixed a 20 pm (G = 39 s
-1
) and 15 min, espec i ely.
4.3.6 In luence o he Flocculan Type and Dosage
Small dosages o a polyelec oly e (0.5-3 mg/L and 1-5 mg/L) pe mi he o ma ion o la ge
locks and accele a e sedimen a ion [G au, 1991; Poland and Pagano, 2010]. Two se ies
o expe imen s we e hen pe o med o each syn he ic e luen using wo locculan s:
Magna loc 155 (dose in he ange 0.25 - 5 mg/L) and Supe loc C-573 ( om 0.25 o 5
mg/L o co on and polyes e e luen s and om 0.1 o 5 mg/L o he ac ylic one) in o de
o s udy he in luence o he locculan ype and dosage on he loccula ion s age.
Figu e 4.4 shows ha he op imum doses o Magna loc 155 a e as ollows: ca. 1 mg/L o
polyes e and 0.5 mg/L o bo h co on and ac ylic e luen s. The o e all DOC emo als
using he op imum doses we e 33.3, 45.4 and 21.4% o polyes e , co on and ac ylic
e luen s, espec i ely, while colo emo als we e o 91.4% and 78.9%, espec i ely o
co on and ac ylic e luen s.
Pa III
103
Figu e 4.4 - Va ia ion o DOC (a) and colo (b) emo als wi h he dose o locculan (Magna loc
155) o he di e en simula ed e luen s (
coagula ion
=150 pm,
coagula ion
=3 min, T=T
ambien
=23-25 ºC,
pH
polyes e
=8.3, pH
co on
=9.4, pH
ac ylic
=7.2, [Fe
2+
]
polyes e
=[Fe
2+
]
co on
=200 mg/L, [Fe
2+
]
ac ylic
=3000 mg/L,
loccula ion
=20 pm and
loccula ion
=15 min).
Doses o Supe loc C-573 o maximum DOC emo als we e 0.5 mg/L o co on and
polyes e e luen s and 0.25 mg/L o he ac ylic one, hese doses leading o DOC
emo als o 43.2%, 32.0%, and 28.3%, espec i ely (Figu e 4.5 a). Mo eo e , Figu e 4.5 b
shows ha colo emo al in co on was ewa e (~90%) is almos independen o he
locculan dose, bu o he ac ylic e luen he bes o e all e iciency o colo educ ion
(93.8%) was ob ained using a Supe loc dose o 0.25 mg/L. Simila doses we e
de e mined by o he au ho s o dyes con aining was ewa e s, al hough di e en
locculan s we e used [Bes-Piá e al., 2002; Joo e al., 2007; El-Goha y and Taw ik, 2009].
0
10
20
30
40
50
60
0 0.25 0.5 1.0 2.5 4.0 5.0
DOC emo al (%)
[Magna loc 155] (mg/L)
Ac ylic Polyes e Co on
a)
0
20
40
60
80
100
0 0.25 0.5 1.0 2.5 4.0 5.0
Colo emo al (%)
[Magna loc 155] (mg/L)
Ac ylic Co on
b)

* This Chap e is based on he publica ion “Rod igues C.S.D.; Madei a, L.M.; Boa en u a, R.A.R. Syn he ic
Tex ile Was ewa e s T ea men Using Fe ic Sal as Coagulan ”. Submi ed o En i onmen al
Enginee ing and Managemen Jou nal.
Chap e 5
Coagula ion/Floccula ion wi h Fe
3+
as Coagulan
*
Pa III
113
5 Coagula ion/Floccula ion wi h Fe
3+ as Coagulan
5.1 In oduc ion
The combina ion o coagula ion/ loccula ion and Fen on oxida ion p ocesses has been
al eady applied o was ewa e s om he ex ile indus y [Kang e al., 2002; Wang e al.,
2008] and o he e luen s [Ma ins e al., 2005]. Howe e , when using i on sal s as
coagulan s, he esidual soluble i on con ibu es o a educ ion in he ope a ing cos s
associa ed wi h Fen on’s oxida ion, o en used downs eam om coagula ion/ loccula ion,
whe ein he esidual i on is used as ca alys .
The pu pose o his chap e is o assess he applicabili y o e ic sulpha e as coagulan in
combina ion wi h an anionic (Magna loc 155) o ca ionic (Supe loc C-573) locculan o
he emo al o o ganic ma e and colo om polyes e , co on and ac ylic dyeing syn he ic
was ewa e s. In spi e o he ecommenda ions o he manu ac u e s (Allied Colloids and
Ame ican Cyanamid Co., espec i ely), Magna loc 155 and Supe loc C-573 ha e no
been used so a o ex ile dyeing was ewa e ea men . Op imized condi ions o key
a iables as pH, Fe
3+
and locculan doses we e also de e mined. This wo k is he
con inua ion o a p e ious one (chap e 4) whe e e ous sulpha e was used as coagulan
and he e o e i allows compa ing he pe o mances o Fe(II) and Fe(III) sal s o each
syn he ic e luen , hus aiming o in e i he same sal could be bene icially used in all
cases o no . The main objec i e o bo h s udies was o ake ad an age o he dissol ed
i on p esen in he e luen esul ing om he coagula ion p ocess in a downs eam i on-
ca alysed oxida ion – he well-known Fen on´s ad anced oxida ion p ocess, add essed in
subsequen chap e s. This addi ional ea men , alone o supplemen ed by a biological
p ocess, is jus i ied by he limi ed capabili y o coagula ion/ loccula ion o p oducing pe
se an e luen ha mee s he discha ge limi s ( o pH, COD, BOD
5
and colo ) imposed by
he Po uguese legisla ion (O dinance No. 423 o June 25, 1997, o discha ge o ex ile
was ewa e s).
Chap e 5
–
Coagula ion/Floccula ion wi h Fe
3+
as Coagulan
114
5.2 Ma e ials and Me hods
5.2.1 P epa a ion o Simula ed Tex ile E luen s
The simula ed e luen s used in he wo k epo ed in his chap e we e p epa ed as
desc ibed in sec ion 3.2.1 o chap e 3.
5.2.2 Coagula ion/Floccula ion Expe imen s
I on sul a e (Fe
2
(SO
4
)
3
; CAS: 10028-22-5) used as coagulan was supplied by
Quimi écnica S.A. (Po ugal) as a b own solu ion wi h pH = 2.0±0.5 and speci ic g a i y =
1.56 ± 0.2 a 20 ºC. The wo king solu ion was p epa ed by dilu ing he comme cial p oduc
wi h dis illed wa e o ob ain a solu ion wi h 50 g Fe
3+
/L.
Magna loc 155 is an anionic polyac ylamide (molecula weigh a ound 5×10
6
, densi y
~750 kg/m
3
, whi ish-yellow solid) om Allied Colloids (England) and Supe loc C-573 is a
ca ionic polyamine (molecula weigh a ound 10
4
, densi y 1.14-1.18 kg/m
3
, yellow liquid)
om Ame ican Cyanamid Co (USA), bo h used as locculan s in his wo k.
The op imum pH as well as he op imal coagulan and locculan doses we e de e mined
om expe imen s pe o med in a Ja - es appa a us acco ding o he desc ip ion gi en in
sec ion 3.4.1.
Fo ei he DOC o colo analyses he supe na an was p e iously cen i uged (Mini Spin
Eppendo , Ge many) a 13400 pm o 2 minu es.
5.2.3 Analy ical Me hods
The analy ical p ocedu es we e pe o med as desc ibed in sec ion 3.3 o chap e 3.
Pa III
115
5.3 Resul s and Discussion
In a p e ious wo k (chap e 4) i was ound ha some ope a ing condi ions, namely he
s i ing speed and s i ing ime du ing he coagula ion s age, ha e almos no e ec on
ei he colo o DOC educ ion om syn he ic ex ile dyeing e luen s. So, hose pa ame e s
we e kep cons an a 150 pm and 3 min, espec i ely, while de e mining he e ec o
bo h pH and Fe
3+
concen a ion on colo and o ganic ma e emo al in he coagula ion
s age. The esponses selec ed in his pa ame ic s udy we e colo and DOC educ ion
because hey a e as e o assess; besides, hey a e closely ela ed o legisla ed
pa ame e s (pH, COD, BOD
5
and colo ), which a e ne e heless assessed a e op imizing
p ocess condi ions o see i he inal e luen mee s legisla ed s anda ds.
5.3.1 In luence o pH
As ound p e iously wi h a Fe
2+
sal (chap e 4), he pH is one o he mos impo an
ac o s o ake in o accoun in he coagula ion p ocess. In his wo k, whe e a Fe
3+
sal was
used as coagulan , he pH was a ied om 3.5 o 10.4 o polyes e and co on e luen s.
Fo he ac ylic e luen no esul s a e p esen ed o pH > 8.3 because i was obse ed a
change in he colou o he e luen ( om blue o ligh g ey).
The ob ained esul s conce ning he e ec o he pH a e shown in Figu e 5.1. They allow
concluding ha he e a e op imal pH alues o DOC emo al (Figu e 5.1 a): 9.4 o he
polyes e e luen (33.4% o DOC educ ion) and 5.0 o he co on e luen (38.7% o DOC
educ ion). Fo he ac ylic e luen he emo al inc eased wi h he pH, bu a pH 8.3 only a
educ ion o 13.6% in DOC was ob ained. Rega ding colo emo al (Figu e 5.1 b), he
op imum occu ed a pH = 5.0 (32.0% o colo educ ion) o he co on e luen and
inc eased wi h pH, in he ange s udied, o he ac ylic e luen , wi h maximum colo
emo al o 41.2% a pH = 8.3.
A he op imum condi ions, and o he co on e luen , he coagula ion occu s mos
p obably by cha ge neu aliza ion and inclusion in an amo phous hyd oxide p ecipi a e
(sweep loccula ion), because a pH 5.0 he species p esen in solu ion a e Fe
3+
ions and
hyd olysable species (Fe(OH)
2+
and Fe(OH)
3
) [Duan and G ego y, 2003]. Fo he ac ylic
and polyes e e luen s, wi h op imum coagula ion pH in he alkaline zone, Fe(OH)
3
and
Fe(OH)
4-
a e he main species p esen in solu ion (Duan and G ego y, 2003), and one can

Chap e 5
–
Coagula ion/Floccula ion wi h Fe
3+
as Coagulan
116
conside ha he coagula ion p incipally occu s by inco po a ion in i on hyd oxide
p ecipi a es.
Figu e 5.1 – In luence o pH in DOC (a) and colo (b) emo al om he di e en e luen s (
coagula ion
= 150 pm,
coagula ion
= 3 min, [Fe
3+
]
polyes e
= [Fe
3+
]
co on
= 200 mg/L, [Fe
3+
]
ac ylic
= 500 mg/L and
T=T
ambien
= 22-23 ºC).
The op imum pH alues ob ained o he co on and polyes e e luen s a e wi hin he
anges indica ed by Edeline (1992) when using Fe
2
(SO
4
)
3
as coagulan : 3.5-7 and > 9.
The bes pH o he ac ylic e luen was no de e mined due o he colo change o pH >
8.3, as abo e men ioned. The op imum pH o he co on e luen (5.0) is also close o ha
ob ained in o he s udies wi h he same coagulan , e en applied o di e en was ewa e s.
Fo ins ance, Joo e al. (2007) poin ed ou an op imum pH be ween 4 o 7 o he
ea men o ex ile e luen s, while Aziz e al. (2007) and Liang e al. (2009) ob ained he
maximum e iciency a pH 4 in he ea men o land ill leacha e and molasses
was ewa e s.
5.3.2 In luence o he Fe
3+
Concen a ion
The e ec o he coagulan dose was assessed by a ying he dosage in he ange 15 -
1000 mg/L o polyes e and co on e luen s and 200 - 4000 mg/L o he ac ylic one. The
o he a iables o he p ocess we e ixed a he op imal alues de e mined be o e, namely
he pH.
0
10
20
30
40
50
60
3.5 5.0 7.2 8.3 9.4 10.4
DOC emo al (%)
pH
Ac ylic Polyes e Co on
a)
0
10
20
30
40
50
60
3.5 5.0 7.2 8.3 9.4 10.4
Colo emo al (%)
pH
Ac ylic Co on b)
Pa III
117
The esul s ob ained (Figu e 5.2) show a Fe
3+
op imum dose o 500 mg/L o he polyes e
was ewa e , leading o 35.1% DOC emo al. Fo he co on e luen bo h he colo and
DOC emo als inc ease wi h [Fe
3+
] up o 200 mg/L, dec easing o highe concen a ions.
Maximum emo als o 38.7 and 32.0% we e achie ed o DOC and colo , espec i ely. An
op imal concen a ion o 1000 mg/L was ound o he ac ylic e luen , yielding 44.7%
decolo iza ion and a DOC educ ion o only 16.5%. The exis ence o op imum Fe
3+
doses
has been also epo ed in o he s udies [Kim e al., 2004; Joo e al., 2007; Anouzla e al.,
2009] and has been a ibu ed o he ac ha when he coagulan dosage is in excess, he
es abiliza ion o colloids can occu [Aziz e al., 2007].
Figu e 5.2 – E ec o Fe
3+
concen a ion on DOC (a) and colo (b) emo al om he di e en
e luen s (
coagula ion
= 150 pm,
coagula ion
= 3 min, T=T
ambien
= 23-25 ºC and pH
polyes e
= 9.4, pH
co on
=
5.0 and pH
ac ylic
= 8.3).
In a p e ious wo k using a Fe
2+
sal as coagulan (chap e 4) i was obse ed ha o each
ex ile dyeing e luen he highes educ ions bo h in colo and DOC we e in gene al
ob ained o he same pH and coagulan dose. A simila esul was ob ained in his s udy
using Fe
3+
. The dose o coagulan necessa y o he coagula ion p ocess is ela ed o he
o ganic load o he e luen . Fo he ac ylic e luen , wi h highe o ganic load (c . Table 3.4,
sec ion 3.2.1.3), a highe dosage o e ic sal is needed. Howe e , he coagulan dose
also depends on he global was ewa e cha ac e is ics, as epo ed by o he au ho s. Fo
ins ance, Liang e al. (2009) epo ed an op imum dose o 3 g/L o e ic sul a e o he
ea men o a molasses e luen wi h a COD o 975±25 mg O
2
/L while Joo e al. (2007)
0
10
20
30
40
50
60
15 50 100 200 500 1000200030004000
DOC emo al (%)
[Fe3+]
Ac ylic Polyes e Co on
a)
0
20
40
60
80
100
15 50 100 200 500 1000 200 30004000
Colo emo al (%)
[Fe
3+
]
Ac ylic Co on b)
Chap e 5
–
Coagula ion/Floccula ion wi h Fe
3+
as Coagulan
118
ob ained he op imum a 4 g/L o e ic sal o he ea men o a ex ile e luen wi h a
much highe COD load (2968 mg O
2
/L).
5.3.3 In luence o he Flocculan Na u e and Dose
Some ope a ing condi ions, namely he s i ing speed and s i ing ime du ing he
loccula ion s age, ha e almos no e ec in ei he colo o DOC educ ion o he es ed
e luen s (chap e 4). So, a e he coagula ion s age, he in luence o he na u e and
concen a ion o locculan on colo and DOC emo al was e alua ed, in he loccula ion
s age, bu speed and s i ing ime we e kep cons an a 20 pm and 15 min, espec i ely.
The locculan s (Magna loc 155 and Supe loc C-573) we e employed in concen a ions
a ying be ween 0.25 o 5 mg/L. The loccula ion s udy was pe o med using e luen s p e-
ea ed by coagula ion a he bes ope a ing condi ions p e iously de e mined (c . Table
5.1).
Figu e 5.3 p esen s he esul s ob ained using Magna loc 155. As ega ds he polyes e
e luen i can be seen ha he DOC emo al sligh ly inc eases wi h he locculan
concen a ion up o 2.5 mg/L (39.9% o DOC emo al), bu highe doses do no imp o e
he p ocess pe o mance. The e is also a e y sligh inc ease in DOC educ ion o he
co on dyeing was ewa e when Magna loc 155 dose is inc eased om 0.25 o 0.5 mg/L
(41.2%), bu hen emains nea ly cons an o is somewha smalle . Colo educ ion is
nea ly independen o he locculan dose (in he ange s udied) o his e luen (a e age
educ ion ~32.5%). DOC and colo emo al o he ac ylic e luen a e low compa ed o
hose ob ained du ing he coagula ion s ep, which could be due o he exis ence o an
in e ac ion o he locculan wi h he locs o med du ing he coagula ion and,
consequen ly, he o ganic compounds and dye a e edissol ed. I is no ewo hy ha hese
uns we e epea ed se e al imes and he same e ec on DOC and colo emo al was
always obse ed.
Pa III
119
Figu e 5.3 – E ec o Magna loc155 concen a ion on DOC (a) and colo (b) emo al om he
di e en e luen s (
coagula ion
= 150 pm,
coagula ion
= 3 min, T=T
ambien
= 23-26 ºC, pH
polyes e
= 9.4,
pH
co on
= 5.0, pH
ac ylic
= 8.3, [Fe
3+
]
polyes e
= 500 mg/L, [Fe
3+
]
co on
= 200 mg/L, [Fe
3+
]
ac ylic
= 1000 mg/L,
loccula ion
= 20 pm and
loccula ion
= 15 min).
In expe imen s wi h Supe loc C-573 (Figu e 5.4), he educ ion o he DOC (and also
colo ) emo al is again obse ed, as compa ed o he coagula ion s ep, o he ac ylic
e luen . DOC emo al sligh ly inc eases up o 1 mg/L (40.2%) o he polyes e dyeing
e luen and emains cons an o highe doses. A e y small inc ease occu s a 0.5 mg/L
(maximum DOC emo al o 43.0%) o he co on e luen . Colo emo al is again cons an
in he dose ange s udied (a e age ~32.5%).
Figu e 5.4 – E ec o Supe loc C-573 concen a ion on DOC (a) and colo (b) emo al om he
di e en e luen s (
coagula ion
= 150 pm,
coagula ion
= 3 min, T = T
ambien
= 23-26 ºC, pH
polyes e
= 9.4,
pH
co on
= 5.0, pH
ac ylic
= 8.3, [Fe
3+
]
polyes e
= 500 mg/L, [Fe
3+
]
co on
= 200 mg/L, [Fe
3+
]
ac ylic
= 1000 mg/L,
loccula ion
= 20 pm and
loccula ion
= 15 min).
0
10
20
30
40
50
60
0 0.25 0.5 1.0 2.5 4.0 5.0
DOC emo al (%)
[Magna loc 155] (mg/L)
Ac ylic Polyes e Co on
a)
0
20
40
60
80
100
0 0.25 0.5 1.0 2.5 4.0 5.0
Colo emo al (%)
[Magna loc 155] (mg/L)
Ac ylic Co on b)
0
10
20
30
40
50
60
0 0.25 0.5 1.0 2.5 4.0 5.0
DOC emo al (%)
[Supe loc C-573] (mg/L)
Ac ylic Polyes e Co on
a)
0
20
40
60
80
100
0 0.25 0.5 1.0 2.5 4.0 5.0
Colo emo al (%)
[Supe loc C-573] (mg/L)
Ac ylic Co on b)
Chap e 9
–
Simula ed Dyeing Tex ile E luen s T ea men by he Pho o
-
Fen on P ocess
222
9.3.1.2.2 E ec o Radia ion In ensi y
In o de o minimize he ene gy cos s o he pho o-Fen on p ocess, i was decided o
analyze he e ec o he adia ion in ensi y (be ween 7 and 500 W/m
2
– co esponding o
lamp powe s be ween 2.1 o 150 W) wi h he doses o eagen s es ed p e iously ha
allowed complying wi h discha ge s anda ds. Fo example, and acco ding wi h he da a o
Table 9.1, o he ac ylic e luen he ligh adia ion could be less han 500 W/m
2
o H
2
O
2
doses in he ange 6.5-20.0 g/L bu no o [H
2
O
2
] = 2.5-5.0 g/L because in he la e
condi ions COD o he e luen was abo e he legisla ed s anda d o 250 mgO
2
/L.
Figu e 9.3 shows he emo al o DOC and colo o he di e en adia ion in ensi y es ed
in he assays wi h 6.5, 10 and 20 g/L o H
2
O
2
o he e luen esul ing om dyeing o
ac ylic ibe s. I can be seen ha in all es s he colo emo al is e y as , equi ing only 1-
5 minu es o adia ion o each nea ly comple e descolo iza ion, and is almos
independen o he adia ion lux eaching he solu ion. Rega ding he emo al o DOC, i
can be seen ha , in gene al, and wha e e he adia ion lux and pe oxide dose, i is e y
as in he i s 15 minu es, hen sligh ly dec eases ill 60 minu es o eac ion, a e which
DOC emains app oxima ely cons an . Howe e , he emo al o o ganic compounds
inc eases wi h inc easing adia ion in ensi y o all hyd ogen pe oxide concen a ions, in
ag eemen wi h o he s udies [Kang e al., 2000; Mu uganandhan and Swaninan han,
2004; Modi shahla e al., 2007]. Fo he maximum adia ion used o 500 W/m
2
73, 83 and
96.7% o DOC emo al was eached o H
2
O
2
doses o 6.5, 10 and 20 g/L, espec i ely.
Simila expe imen s we e pe o med o he o he e luen s, and he conclusions eached
a e qui e simila , o cou se wi h di e en pe o mances. Resul s ob ained a e shown in
Figu es A.5 and A.6 o he Appendix o he co on and polyes e was ewa e s,
espec i ely.

Pa III
223
a)
b)
c)
Figu e 9.3 – E ec o adia ion in ensi y on DOC and colo emo al o he ac ylic e luen du ing he
pho o-Fen on p ocess o di e en dosages o hyd ogen pe oxide: 6.5 g/L (a), 10.0 g/L (b) o 20.0
g/L (c) (T=50 ºC, Fe
2+
:H
2
O
2
=1:57 and pH=3.5).
0
20
40
60
80
100
0 20 40 60 80 100 120
DOC emo al (%)
I adia ion ime (min)
0
20
40
60
80
100
0 20 40 60 80 100 120
Colo emo al (%)
I adia ion ime (min)
253 W/m2
500 W/m2
0
20
40
60
80
100
0 20 40 60 80 100 120
DOC emo al (%)
I adia ion ime (min)
0
20
40
60
80
100
0 20 40 60 80 100 120
Colo emo al (%)
I adia ion ime (min)
7 W/m2
107 W/m2
220 W/m2
253 W/m2
500 W/m2
0
20
40
60
80
100
0 20 40 60 80 100 120
DOC emo al (%)
I adia ion ime (min)
0
20
40
60
80
100
0 20 40 60 80 100 120
Colo emo al (%)
I adia ion ime (min)
7 W/m2
107 W/m2
253 W/m2
500 W/m2
Chap e 9
–
Simula ed Dyeing Tex ile E luen s T ea men by he Pho o
-
Fen on P ocess
224
Again, in all assays pe o med in his sec ion he inal e luen was cha ac e ized in e ms
o legisla ed pa ame e s. As illus a ed in Table 9.1, in all es s he colo was no isible in
he e luen s a e he equi ed dilu ion. Besides, o e e y e luen and oxidan dose, i is
no iced ha he lowe he adia ion in ensi y, he lowe a e he pe o mances eached in
e ms o COD emo al, so ha inal alues o his pa ame e a e 60 min o i adia ion a e
highe ; o BOD
5
his no always obse ed ( he small a ia ions obse ed in his pa ame e
a e associa ed wi h unce ain ies in i s de e mina ion), bu he alues eached a e always
below he legisla ed s anda d o 100 mgO
2
/L. This means ha o each dose o hyd ogen
pe oxide, o a gi en ype o e luen , he e is aa adia ion in ensi y h eshold bellow which
e luen ’s cha ac e is ics do no comply wi h legisla ed s anda ds. Fo ins ance, and aking
in o he accoun he alues es ed, o he ac ylic one hese alues a e 500 W/m
2
o
[H
2
O
2
] = 6.5 g/L, 220 W/m
2
o [H
2
O
2
] = 10.0 g/L and 7 W/m
2
o [H
2
O
2
] = 20.0 g/L. O
cou se, he highe he oxidan concen a ion, he lowe is he adia ion in ensi y equi ed o
each COD alues below 250 mgO
2
/L. The ques ion emaining is which se o alues is
mo e ad an ageous o indus ial implemen a ion; he answe can be gi en by compa ing
associa ed cos s, as de ailed in he ollowing sec ion.
9.3.1.3 Ope a ing Cos s
The o e all cos s o he ea men p ocess a e ep esen ed by he sum o he capi al,
ope a ing and main enance cos s. Fo a ull-scale sys em hese cos s depend on he low
a e o he e luen , he na u e o was ewa e , as well as he con igu a ion o he eac o s,
among o he issues. In his s udy we conside ed only he cos s wi h he chemicals, i.e.,
he cos s o eagen s, and he cos s o ene gy. The i s we e ob ained om Quimi écnica
S.A., he a e age alues conside ed being as ollows: H
2
O
2
(49.5% w/ , densi y a 25 ºC =
1.2 g/cm
3
) - 365 €/ on; FeSO
4
.7H
2
O (93 % o pu i y) – 233.7 €/ on, while he la e is abou
0.10 €/(kWh). The p ices o acid (H
2
SO
4
) and base (NaOH) we e no conside ed, because
he quan i ies consumed a e insigni ican .
The ope a ing cos was calcula ed by he sum o cos s o hyd ogen pe oxide, e ous
sul a e and ene gy consump ion, as shown by Equa ion 9.1. The pa ial cos s we e
calcula ed acco ding o Equa ions. 9.2 - 9.4.
Pa III
225
Ope a ing
Cos
=
Cos
H
2
O
2
+
Cos
F
e
2
+
+
Cos
ene gy
(
9
.
1
)
Cos
H
2
O
2
=P ice H
2
O
2
൬ €
on൰ሾH
2
O
2
ሿ∗ 10
−3
ቀ on
m
3
ቁ ∗ ρ
H
2
O
2
(kg
L)
%
H
2
O
2
100 (kg
L) (9.2)
Cos
Fe
2+
=P ice FeSO
4
.7H
2
O ൬ €
on൰ሾFe
2+
ሿ∗ 10
−6
ቀ on
m
3
ቁ ∗ MM
FeSO
4
.7H
2
O
MM
Fe
2+
%
o pu i y
100
(
9.3
)
Cos
ene gy
=
Powe o lamp∗ 10
−3
(kW)∗ P ice ene gy ൬ €
kWh൰ ∗ ime
eac ion (h)
Volume
ea ed
e luen
(
m
3
)
(
9
.
4
)
Figu e 9.4 shows he e ec o hyd ogen pe oxide dose and he adia ion in ensi y in he
o al ope a ing cos s o ea ing he ac ylic (a), co on (b) and polyes e (c) e luen s; in
each case, he H
2
O
2
:Fe
2+
a io was kep cons an , so ha changing he oxidan dose
implies also a change in he ca alys concen a ion. As expec ed, he cos inc eases wi h
inc easing doses o chemicals and powe applied. The o e all cos is highe o he
ea men o ac ylic e luen , ollowed by co on and he polyes e , which is ela ed o he
amoun o hyd ogen pe oxide used ( he ac ylic equi es a highe concen a ion o his
eagen and he polyes e a lowe dose). Fo his eason, he weigh o he chemicals in
he o e all cos also a ies om e luen o e luen , being e y ele an in he ac ylic one,
while in he polyes e he adia ion in ensi y is p eponde an .
Chap e 9
–
Simula ed Dyeing Tex ile E luen s T ea men by he Pho o
-
Fen on P ocess
226
a)
b)
c)
Figu e 9.4 – E ec o hyd ogen pe oxide doses and adia ion in ensi y on he o al ope a ing cos
associa ed wi h he pho o-Fen on p ocess wi h TQ 150 lamp o ea ing ac ylic (a), co on (b) and
polyes e (c) was ewa e s.
0
10
20
0
10
20
30
40
0167 333 500
Ope a ing Cos (€/m
3
)
Ligh lux (W/m
2
)
30-40
20-30
10-20
0-10
0
5
10
0
10
20
30
40
0167 333 500
Ope a ing Cos (€/m
3
)
Ligh lux (W/m
2
)
30-40
20-30
10-20
0-10
0
1.25
2.5
0
10
20
30
40
0167 333 500
Ope a ing Cos (€/m
3
)
Ligh lux (W/m
2
)
30-40
20-30
10-20
0-10
Pa III
227
The main pu pose o his analysis was o ind which se o condi ions desc ibed in he
p e ious sec ion and ha allow eaching a inal e luen complying wi h legisla ed
s anda ds p o ide a smalle cos . Values ob ained o such cos s a e included in Table
9.1. I can be seen ha he condi ions p o iding smalle cos s o each e luen bu s ill
complying wi h legisla ion a e he ollowing: i) ac ylic – [H
2
O
2
] = 10.0 g/L, in ensi y = 220
W/m
2
, cos = 17.4 €/m
3
; ii) co on – [H
2
O
2
] = 10.0 g/L, in ensi y = 7 W/m
2
, cos = 9.6 €/m
3
;
iii) polyes e – [H
2
O
2
] = 2.5 g/L, in ensi y = 7 W/m
2
, cos = 2.9 €/m
3
. Fo all e luen s, bu
pa icula ly o he ac ylic and co on ones, he ea men cos s a e qui e high. The e o e,
wi h he pu pose o minimizing he cos s, namely in e ms o ene gy, he wo k p oceeded
by es ing he pho o-Fen on p ocess wi h simula ed sola adia ion ( o which ene gy cos s
a e null).
9.3.2 Pho o eac o wi h Simula ed Sola Radia ion
Tes s we e ca ied ou as when using lamp TQ 150 wi h he pu pose o no exceeding he
maximum allowable alues o he ea ed e luen s, wi h he excep ion ha wi h he
Sola box i was no possible o dec ease he adia ion in ensi y bellow 253 W/m
2
(lamp
powe = 76 W ). On he o he hand, alues abo e 500 W/m
2
(lamp powe = 150 W) we e
also no es ed. Fi s , o compa e wi h da a ob ained wi h TQ lamp, bu also o keep a
easonable le els he powe co esponding o he adia ion in ensi y close o eal
condi ions (150 W co espond o ~ 60 W/m
2
a wa eleng hs in he ange 300-400 nm,
which is only sligh ly abo e he ypical maximum adia ion in ensi y in he no h o Po ugal
– 50 W/m
2
).
9.3.2.1 E ec o Hyd ogen Pe oxide Concen a ion
Resul s o colo and DOC emo als ob ained o uns wi h he Sola box employing a
adia ion in ensi y o 253 W/m
2
a di e en dosages o oxidan a e shown in Figu e 9.5.
Fo bo h he ac ylic and co on dyeing was ewa e s he colo emo al is e y apid (only 1-
2 minu es a e equi ed o comple e decolo iza ion a all doses es ed). Howe e , o DOC
emo al i is necessa y mo e ime, and again a e ~60 minu es he maximum
pe o mance is eached, which is no u he imp o ed. Be e pe o mances a e eached

Chap e 9
–
Simula ed Dyeing Tex ile E luen s T ea men by he Pho o
-
Fen on P ocess
228
o highe H
2
O
2
doses: 82.4% o 20 g/L o H
2
O
2
in he ac ylic; 54.6% o 10 g/L in he
co on, and 66.3% o 2.5 g/L o he polyes e .
a)
b)
c)
Figu e 9.5 – E ec o H
2
O
2
dose on DOC and colo emo al wi h simula ed sola adia ion a
in ensi y o 253 W/m
2
o ac ylic (a), co on (b) and polyes e (c) was ewa e s (T=50 ºC, Fe
2+
:H
2
O
2
ac ylic
=1:57, Fe
2+
:H
2
O
2 co on
=1:33 Fe
2+
:H
2
O
2 polyes e
=1:7, pH=3.5).
0
20
40
60
80
100
0 20 40 60 80 100 120
DOC emo al (%)
I adia ion ime (min)
0
20
40
60
80
100
0 20 40 60 80 100 120
Colo emo al (%)
I adia ion ime (min)
10 g/L H2O2
20 g/L H2O2
0
20
40
60
80
100
0 20 40 60 80 100 120
DOC emo al (%)
I adia ion ime (min)
0
20
40
60
80
100
0 20 40 60 80 100 120
Colo emo al (%)
I adia ion ime (min)
5 g/L H2O2
10 g/L H2O2
0
20
40
60
80
100
0 20 40 60 80 100 120
DOC emo al (%)
I adia ion ime (min)
1.25 g/L H2O2
2.5 g/L H2O2
Pa III
229
Again, he inal COD, BOD
5
and isible colo (a e dilu ion o 1:40) a e 60 minu es o
eac ion we e measu ed o each e luen (see Table 9.2). I is wo h no ing ha in all es s
wi h adia ion in ensi y o 253 W/m
2
he e luen s does no exhibi isible colo , and he
alues o he o he wo pa ame e s a e smalle han he maximum allowable alues. So, i
is possible o dec ease he oxidan dose in each case, possibly equi ing howe e a
highe adia ion in ensi y. This does no imply howe e highe cos s, once we a e now
using sola adia ion (al hough simula ed).
Table 9.2 – Values o COD, BOD
5
and isible colo (1:40 dilu ion) a e 60 minu es o oxida ion o
di e en doses o H
2
O
2
and adia ion in ensi yes using simula ed sola i adia ion (in bold:
condi ions ha allow mee ing he discha ge limi s a he minimum cos ).
[H
2
O
2
] (g/L) Radia ion
in ensi y
(W/m
2
) COD (mgO
2
/L) BOD
5
(mgO
2
/L)
Visible colo
a e dilu ion
1:40
To al Cos s
(€/m
3
)
Ac ylic
6.5 500 232.1 32.4 no isible 5.8
10.0 253 242.0 44.6 no isible 9.2
500 143.2 33.1 no isible 9.2
20.0 253 150.6 40.8 no isible 18.3
500 101.2 55.8 no isible
Co on
3.75 500 244.5 76.3 no isible 3.5
5.0 253 207.8 75.0 no isible 4.7
500 183.4 80.9 no isible 4.7
10.0 253 158.9 79.3 no isible 9.3
500 134.5 83.5 no isible 9.3
Polyes e
0.938 150 231.0 66.4 no isible 1.0
1.25 76 221.1 74.3 no isible 1.3
150 206.4 61.4 no isible 1.3
2.5 76 179.4 60.8 no isible 2.7
150 167.1 57.6 no isible 2.7
Chap e 9
–
Simula ed Dyeing Tex ile E luen s T ea men by he Pho o
-
Fen on P ocess
230
The ends eached wi h he maximum sola adia ion in ensi y o 500 w/m
2
o di e en
hyd ogen pe oxide doses a e nea ly he same as be o e (c . Figu e A.7 in Appendix): colo
emo al is e y quick, equi ing only 1 o 5 minu es o exposu e o adia ion o each
alues > 99%; emo al o DOC is again e y as mainly in he i s 15 minu es, and nea ly
s abilizes a e 60 minu es o i adia ion; highe pe o mances a e eached o inc eased
amoun o eagen s used. Mine aliza ion achie ed was 91.7% o he ac ylic e luen using
20 g/L o H
2
O
2
; ~64% o he co on one wi h 10 g H
2
O
2
/L and 71.2% a a dose o 2.5 g
H
2
O
2
/L o he polyes e one. As expec ed, DOC emo als a e highe a 500 W/m
2
s. 253
W/m
2
, o he same doses o eagen s.
Fo all e luen s and a e exposu e o i adia ion du ing 60 minu es, he emaining loads o
COD, BOD
5
and isible colo isible a e shown in Table 9.2. Again, in all es s he
e luen s a e colo less, and he alues o he o he wo pa ame e s a e s ill smalle han
he legisla ed s anda ds (100 mgO
2
/L o BOD
5
and 250 mgO
2
/L o COD).
Finally, i is wo h men ioning ha pe o mances eached (in e ms o COD, BOD
5
, DOC
and colo emo al) in he all es s pe o med wi h he simula ed sola adia ion a e e y
close o hose ob ained wi h he TQ150 lamp (o cou se da a mus be compa ed o
iden ical condi ions, i.e., doses o chemicals and adia ion in ensi y, o e e y e luen ).
9.3.2.2 Ope a ing Cos s
In he ea men o he was ewa e s by pho o-Fen on oxida ion wi h simula ed sola
adia ion, as s a ed ea lie , o he calcula ion o he o al cos o ope a ion only he
consump ion o eagen s was aken in o accoun (Equa ions. 9.2 and 9.3), while he
ene gy cos s (Equa ion 9.4) we e assumed o be null.
Figu e 9.6 shows he e ec o hyd ogen pe oxide and e ous ion concen a ions in he
was ewa e s ea men cos . Bo h eac an s inc ease o al cos s, howe e his is a mo e
in luenced by he H
2
O
2
dose. Ob iously, o he ac ylic highe cos s a e eached, while he
smalle a e o he polyes e , because o he di e en anges o hyd ogen pe oxide
concen a ions employed. I is also no ewo hy ha he cos s a e much smalle han in he
pho o-Fen on using he TQ 150 lamp (Figu e 9.5), whe e ene gy cos s we e also aken
in o accoun .
Pa III
231
a)
b)
c)
Figu e 9.6 – E ec o H
2
O
2
and Fe
2+
doses on he o al ope a ing cos associa ed wi h he pho o-
Fen on wi h simula ed sola adia ion o ea ing ac ylic (a), co on (b) and polyes e (c)
was ewa e s.
0
10
20
0
5
10
15
20
0175 350
Ope a ing Cos (€/m
3
)
[Fe
2+
] (mg/L)
15-20
10-15
5-10
0-5
0
5
10
0
3
5
8
10
0150 300
Ope a ing Cos (€/m
3
)
[Fe
2+
] (mg/L)
8-10
5-8
3-5
0-3
0
1.25
2.5
0.0
0.5
1.0
1.5
2.0
2.5
3.0
0175 350
Ope a ing Cos (€/m
3
)
[Fe
2+
] (mg/L)
2.5-3.0
2.0-2.5
1.5-2.0
1.0-1.5
0.5-1.0
0.0-0.5
Chap e
10
–
Simula ed Tex ile Dyeing E luen s T ea men by SBR alone and
Combined wi h Fen on’s Oxida ion
238
10.2.3 Analy ical Me hods
The analy ical me hods used o he de e mina ion o he a ious pa ame e s a e
desc ibed in sec ion 3.3 o chap e 3.
All de e mina ions we e pe o med in duplica e and he coe icien s o a ia ion we e less
han o 2% o DOC, 8% o BOD
5
, 4% o COD and SOUR, 3% o inhibi ion o V. ishe i
and 5% o he o he pa ame e s.
10.3 Resul s and Discussion
The mo e ele an cha ac e is ics o he syn he ic ac ylic, co on and polyes e dyeing
was ewa e s used in his s udy a e epo ed in Table 3.4. Co on and ac ylic was ewa e s
a e colo ed e en a 1:40 dilu ion bu polyes e e luen is p ac ically colo less. The o ganic
load (exp essed as COD o DOC) is mode a e o all was ewa e s bu he biodeg adabili y
is low as indica ed by he BOD
5
:COD a io and he alues o SOUR; ac ually, he ac ylic
was ewa e can be classi ied as non biodeg adable and he o he was ewa e s can be
conside ed as only sligh ly biodeg adable. Ac ylic and polyes e e luen s s ongly inhibi
V. ishe i ac i i y, which p o es hei oxici y. Taking in o accoun he low biodeg adabili y
and he high oxici y (excep o he co on was ewa e ), a biological ea men o hese
was ewa e s does no p obably allow mee ing he discha ge limi s, as es ablished by he
Po uguese legisla ion (c . Table 3.4). E en so, he easibili y o using a biological p ocess
(SBR) alone o downs eam om a chemical oxida ion p ocess (Fen on’s eac ion) o
achie e he discha ge limi s was in es iga ed in his s udy.
The esul s ob ained when applying his s a egy o ea ing he h ee di e en kinds o
ex ile dyeing was ewa e s a e shown in he nex sec ions.
10.3.1 Biological T ea men
The biological deg ada ion was only applied o aw polyes e and co on e luen s because
he ac ylic one p esen s e y low biodeg adabili y (BOD
5
/COD a io <0.0012 and SOUR

Pa III
239
<0.2 – Table 3.4), also con i med by he Zhan Wellens es (see Figu e 10.1), which
indica ed ha he deg ada ion ob ained a e 28 days does no exceed 15%.
Figu e 10.1 – E olu ion o pe cen age o COD deg ada ion along ime in Zahn-Wellens es o
ac ylic was ewa e .
Figu e 10.2 shows he COD, BOD
5
, DOC, o al ni ogen and colo emo als ob ained in 10
successi e cycles o SBR ea men o polyes e and co on e luen s; no u he cycles
we e applied because nea ly s eady-s a e condi ions we e eached in all cases, i.e., s able
pe o mances in consecu i e cycles. The polyes e e luen exhibi s a conside able
inc ease o COD, BOD
5
, DOC and o al ni ogen emo al du ing he i s 5 cycles ha
con inue o inc ease, albei mo e slowly, up o he 7 h cycle, and hen emain almos
cons an wi h a e age alues o 24.2, 39.4, 39.7 and 16.4% o COD, BOD
5
, DOC and
ni ogen, espec i ely. Fo he co on e luen he emo als also inc ease du ing he i s 5
cycles and hen he emo al a e dec eases o main ains cons an leading o a e age inal
alues o 19.9, 19.6, 19.9 and 20.5% o COD, BOD
5
, DOC and ni ogen, espec i ely.
The low e iciencies achie ed can be explained by he p esence in he e luen s o a
signi ican p opo ion o e ac o y o only sligh ly biodeg adable compounds, as could be
in e ed om he low BOD
5
/COD a ios and SOUR alues, pa icula ly o he co on one
(c . Table 3.4). As ega ds colo emo al, in he co on was ewa e he alues o
abso bance a 520 nm dec eased in he i s 4 cycles and kep cons an in he
subsequen ly cycles, achie ing an a e age alue o 50.6% o decolo iza ion. The emo al
may be he esul o some biological deg ada ion o he ex ile dyes p esen in he e luen
0
20
40
60
80
100
0 2 4 6 8 10 12 14 16 18 20 22 24 26 28
D (%)
(days)
Con ol Subs ance
Was ewa e
Chap e
10
–
Simula ed Tex ile Dyeing E luen s T ea men by SBR alone and
Combined wi h Fen on’s Oxida ion
240
bu he adso p ion on o he biomass locs p obably also con ibu es o colo elimina ion
[Wa e s, 1995]. The colo emo al ob ained o co on was ewa e is simila o ha
epo ed by Vaigan e al. [2009]. These au ho s achie ed colo emo als o 31-57% when
ea ing 20 o 40 mg/L o eac i e Blue B-16, espec i ely, in an SBR.
Figu e 10.2 - Va ia ion o COD (a), BOD
5
(b), DOC (c), o al ni ogen (d) and colo (e) emo als
along 10 cycles o SBR ope a ion o polyes e and co on was ewa e s.
0
20
40
60
0 1 2 3 4 5 6 7 8 9 10
COD emo al (%)
Numbe o Cycles
a)
0
20
40
60
0 1 2 3 4 5 6 7 8 9 10
BOD
5
emo al (%)
Numbe o Cycles
b)
0
20
40
60
0 1 2 3 4 5 6 7 8 9 10
DOC emo al (%)
Numbe o Cycles
c)
0
20
40
60
012345678910
N o al emo al (%)
Numbe o Cycles
d)
0
20
40
60
012345678910
Colo emo al (%)
Numbe o Cycles
e)
Polyes e Co on
Pa III
241
Wi h ega d o o he moni o ed pa ame e s, whose alues a e no p esen ed in Figu e
10.2, i was no ed ha du ing all SBR cycles he concen a ions in he ea ed e luen s
we e in he ange 2.4 - 2.9 mg P/L, 22 – 29 mg TSS/L and 2530-2970 mg VSS/L o he
polyes e e luen and 5.7 - 5.9 mg P/L, 27 - 32 mg TSS/L and 2350-2680 mg VSS/L o
he co on one.
The pseudo-s eady s a e was eached a e ca. 7 cycles o bo h co on and polyes e
e luen s. Table 10.1 p esen s he a e age alues o di e en pa ame e s a e eaching
he pseudo-s eady s a e. I can be concluded ha he e luen s esul ing om biological
ea men do no mee he discha ge limi s, since he alues o COD (392.4 and 280.4
mg/L o polyes e and co on, espec i ely) a e abo e 250 mg/L and he colo o he
co on e luen is isible a e 1:40 dilu ion. So, a p e- ea men o subsequen ea men is
equi ed. We choose o apply he chemical oxida ion by Fen on’s eagen as p e- ea men
o enhance he biodeg adabili y and emo e colo and, hen, subjec he was ewa e o
biological ea men . The esul s ob ained om he combined p ocess a e p esen ed in he
ollowing sec ion.
Chap e
10
–
Simula ed Tex ile Dyeing E luen s T ea men by SBR alone and Combined wi h Fen on’s Oxida ion
242
Table 10.1 – Cha ac e is ics o he simula ed dyeing aw was ewa e s and a e SBR ea men and espec i e emo al e iciencies.
Pa ame e
Ac ylic Polyes e Co on Maximum
Allowable
Value*
Raw
Was ewa e
Raw
Was ewa e A e SBR Remo al
(%)
Raw
Was ewa e A e SBR Remo al
(%)
pH 6.8 8.3 7.10 --- 11.4 7.15 --- 5.5-9.0
Conduc i i y a 20 ºC (mS/cm) 1503.0 2.9 n.d. --- 23.2 n.d. ---
To al suspended solids (mg/L) 16.0 21.7 25.1 67.0 28.3
To al ni ogen (mg N/L) 16.4 15.9 13.3 16.4 3.9 3.1 20.5
Ni a es (mg NO
3-
/L) 15.7 7.5 n.d. --- 4.25 n.d. ---
To al phospho us (mg P/L) 0.2 3.0 2.4 20.0 5.9 5.7 3.4
Dissol ed phospho us (mg P/L) < 0.06 2.7 n.d. --- 0.1 n.d. ---
COD – Chemical oxygen demand (mg O
2
/L) 828.1 517.9 392.4 24.2 350.0 280.4 19.9 250
BOD
5
– Biochemical oxygen demand (mg O
2
/L) < 1.0 130.7 79.1 39.4 77.5 62.3 19.6 100
DOC – Dissol ed o ganic ca bon (mg C/L) 334.1 143.1 86.3 39.7 117.5 94.1 19.9
Sul a es (mg/L) 598.0 885.8 n.d. --- 41.0 n.d. ---
Chlo ides (mg Cl
-
/L) 44.1 17.3 n.d. --- 7981.8 n.d. ---
Alkalini y (mg CaCO
3
/L) 51.8 774.4 n.d. --- 4425.0 n.d. ---
SOUR – Speci ic oxygen up ake a e (mg O
2
/(g
VSS
.h)) < 0.2 27.0 n.d. --- 5.6 n.d. ---
BOD
5
:COD a io < 0.0012 0.26 0.20 --- 0.22 0.22 ---
Maximum abso bance wa eleng h, λ
max
(nm) 610 --- n.d. --- 520 n.d.
Abso bance a λ
max
(a.u.) 1.592 --- n.d. --- 0.437 0.179 50.6**
Visible colo a e dilu ion 1:40 Visible no isible no isible --- Visible isible --- no isible
Vib io ische i Inhibi ion 5 min (%) 94.0 74.5 n.d. --- 0.0 n.d. ---
Vib io ische i Inhibi ion 15 min (%) 96.0 82.5 n.d. --- 0.0 n.d. ---
Vib io ische i Inhibi ion 30 min (%) 97.0 84.5 n.d. --- 0.0 n.d. ---
n.d. – no de e mined
* Po uguese legisla ion o discha ge o ex ile was ewa e s (O dinance No. 423/97 o 25 June ).
** calcula ed om he abso bance o aw was ewa e a pH 7.0 (0.3617 abs. uni s)
Pa I
II
243
10.3.2 In eg a ion o Fen on’s Reagen Followed by Biological T ea men
As he oxida ion p ocess allows inc easing he biodeg adabili y o he ac ylic and co on
e luen s while educing he oxici y o he ac ylic and polyes e e luen s, as shown below (c .
Tables 10.2-10.4), he combina ion o Fen on eac ion wi h he biological oxida ion in SBR
was s udied. Aiming educing he doses o chemicals, and inhe en ly he ope a ing cos s
(desc ibed in he ollowing sec ion), h ee expe imen s we e pe o med, i.e., he p elimina y
Fen on eac ion s age was pe o med wi h di e en doses o eagen s. The 1s un was
pe o med a he bes condi ions o maximizing colo and DOC emo als and imp o ing
biodeg adabili y al eady de e mined in p e ious s udies (chap e s 6-8): [H
2
O
2
]=20 g/L and
[Fe
2+
]=350 mg/L o ac ylic, [H
2
O
2
]=10 g/L and [Fe
2+
]=300 mg/L o co on and [H
2
O
2
]=2.5 g/L
and [Fe
2+
]=350 mg/L o polyes e was ewa e s, all a pH 3.5 and 50 ºC. In uns #2 and #3
he doses o hyd ogen pe oxide and e ous i on we e educed o 3/4 and 1/2 o ac ylic and
1/2 and 1/4 o polyes e and co on e luen s, espec i ely, wi h he aim o dec easing he
ea men cos (associa ed wi h he consump ion o chemicals in he Fen on’s p ocess) while
ob aining a inal e luen ha should mee he discha ge limi s imposed by he na ional
legisla ion o he ex ile indus y. Resul s ob ained du ing Fen on’s oxida ion ha e been
epo ed p e iously (in he wo ks men ioned abo e) and only o e all pe o mances eached
a e desc ibed he ein – un #1 in Tables 10.2, 10.3 and 10.4 o he ac ylic, co on and
polyes e e luen s, espec i ely.

Chap e
10
–
Simula ed Tex ile Dyeing E luen s T ea men by SBR alone and Combined wi h Fen on’s Oxida ion
244
Table 10.2 – Cha ac e is ics o he syn he ic ac ylic dyeing was ewa e s a e Fen on eac ion and SBR and espec i e emo al e iciencies
(wi hin b acke s) and global emo als. Runs#1 o #3 ep esen expe imen s wi h dec easing doses o chemicals in he Fen on’s s age.
Pa ame e
Run #1 – Op imal dose o chemicals Run #2 – 0.75 o op imal dose o chemicals Run #3 – 0.5 o op imal dose o chemicals Maximum
Allowable
Value*
Fen on
( emo al
(%))
SBR
( emo al
(%))
Global
Remo al
(%)
Fen on
( emo al
(%))
SBR
( emo al
(%))
Global
Remo al
(%)
Fen on
( emo al
(%))
SBR
( emo al
(%))
Global
Remo al (%)
pH 7.10 7.15 --- 7.06 7.09 --- 7.01 6.98 --- 5.5-9.0
To al ni ogen (mg N/L) 16.0 (2.4) 8.8 (45.0) 46.3 16.1 (2.4) 9.3 (41.9) 43.3 16.3 (2.4) 12.4 (22.5) 24.4
To al phospho us (mg P/L) 0.2 (0.0) 0.61 (47.9**) 47.9 0.2 (0.0) 0.20 (74.7**) 74.7 0.2 (0.0) 0.16 (68.0**) 68.0
COD (mg O
2
/L) 289.0 (65.1) 14.6 (94.9) 98.2 294.5 (64.4) 104.3 (64.6) 87.4 349.7 (57.7) 273.7 (21.8) 66.9 250
BOD
5
(mg O
2
/L) 116.5 6.4 (94.5) 94.5 78.8 12.0 (84.8) 84.8 46.8 14.5 (69.0) 69.0 100
DOC (mg C/L) 112.0 (66.5) 5.4 (95.2) 98.4 124.7 (62.7) 34.5 (72.3) 89.7 132.3 (60.4) 109.3 (17.4) 67.3
SOUR – Speci ic oxygen up ake a e
(mg O
2
/(g
VSS
.h)) 17.9 n.d. --- 10.2 n.d. --- 2.7 n.d. ---
BOD
5
:COD a io 0.40 0.46 --- 0.27 0.12 --- 0.13 0.05 ---
Abso bance a λ
max
(a.u.) 0.0079
(99.5***) 0.0025
(68.4****) 99.8 0.0080
(99.5***) 0.0025
(68.8****) 99.8 0.0089
(99.4***) 0.0025(71.9**
**) 99.8
Visible colo a e dilu ion 1:40 no isible no isible --- no isible no isible --- no isible no isible --- no isible
Vib io ische i Inhibi ion 5 min (%) 29 n.d. --- 38 n.d. --- 77 n.d. ---
Vib io ische i Inhibi ion 15 min (%) 27 n.d. --- 41 n.d. --- 81 n.d. ---
Vib io ische i Inhibi ion 30 min (%) 29 n.d. --- 41 n.d. --- 82 n.d. ---
n.d. – no de e mined.
* Po uguese legisla ion o discha ge o ex ile was ewa e s (O dinance No. 423/97 o 25 June).
** calcula ed om o al phospho us in e luen a e Fen on eac ion a e adding phospha e bu e (1.17, 0.79, 0.5 mg P/L in un #1, #2, #3, espec i ely).
*** calcula ed om he abso bance a 610 nm o aw was ewa e a pH 3.5 (1.624 abs. uni s).
**** calcula ed om he abso bance a 610 nm o was ewa e a e Fen on a pH 7.0 (0.0079, 0.0080 and 0.0089 abs. uni s in un #1, #2 and #3, espec i ely).
Pa III
245
Table 10.3 – Cha ac e is ics o he syn he ic co on dyeing was ewa e a e Fen on eac ion and SBR and espec i e emo al e iciencies
(wi hin b acke s) and global emo als. Runs#1 o #3 ep esen expe imen s wi h dec easing doses o chemicals in he Fen on’s s age.
Pa ame e
Run #1– Op imal dose o chemicals Run #2 – 0.5 o op imal dose o chemicals Run #3 – 0.25 o op imal dose o chemicals Maximum
Allowable
Value*
Fen on
( emo al
(%))
SBR
( emo al
(%))
Global
Remo al
(%)
Fen on
( emo al
(%))
SBR
( emo al
(%))
Global
Remo al
(%)
Fen on
( emo al
(%))
SBR
( emo al
(%))
Global
Remo al (%)
pH 6.99 7.05 --- 7.04 7.10 --- 7.09 7.03 --- 5.5-9.0
To al ni ogen (mg N/L) 3.9 (0.0) 1.2 (82.4) 82.4 3.9 (0.0) 2.1 (62.5) 62.5 3.8 (2.6) 3.7 (15.9) 18.1
To al phospho us (mg P/L) 5.9 (0.0) 4.8 (18.6) 18.6 5.9 (0.0) 5.2 (11.9) 11.9 5.8 (1.7) 5.6 (3.4) 5.1
COD (mg O
2
/L) 262.1 (25.1) 43.2 (83.5) 87.7 281.9 (19.5) 113.2 (59.8) 67.7 318.6 (9.0) 261.8 (17.8) 25.2 250
BOD
5
(mg O
2
/L) 135.7 (0.0) 22.8 (83.2) 83.2 112.9 (0.0) 45.1 (60.1) 60.1 88.0 (0.0) 72.3 (17.8) 17.8 100
DOC (mg C/L) 60.2 (48.8) 9.95 (83.5) 91.5 94.1 (19.9) 37.6 (60.0) 68.0 100.3 (14.6) 82.0 (18.2) 30.2
SOUR – Speci ic oxygen up ake a e
(mg O
2
/(g
VSS
.h)) 15.51 n.d. --- 8.11 n.d. --- 2.54 n.d. ---
BOD
5
:COD a io 0.52 0.53 --- 0.40 0.40 --- 0.33 0.28 ---
Abso bance a λ
max
(a.u.) 0.0331
(89.9***) 0.0037
(86.6****) 98.6 0.0310
(90.5***) 0.0053
(81.9****) 98.3 0.0349
(89.3***) 0.0126
(65.8****) 96.3
Visible colo a e dilu ion 1:40 no isible no isible --- no isible no isible --- no isible no isible --- no isible
Vib io ische i Inhibi ion 5 min (%) 0.0 n.d. --- 0.0 n.d. --- 0.0 n.d. ---
Vib io ische i Inhibi ion 15 min (%) 0.0 n.d. --- 0.0 n.d. --- 0.0 n.d. ---
Vib io ische i Inhibi ion 30 min (%) 0.0 n.d. --- 0.0 n.d. --- 0.0 n.d. ---
n.d. – no de e mined.
* Po uguese legisla ion o discha ge o ex ile was ewa e s (O dinance No. 423/97 o 25 June).
** calcula ed om o al phospho us in e luen a e Fen on eac ion a e adding u ea ( 6.8, 5.6, 4.4 mg N/L in un #1, #2, #3, espec i ely).
*** calcula ed om he abso bance a 520 nm o aw was ewa e a pH 3.5 (0.3615 abs. uni s).
**** calcula ed om he abso bance a 520 nm o was ewa e a e Fen on a pH 7.0 ( 0.0276, 0.0293 and 0.0368 abs. uni s in un #1, #2 and #3, espec i ely).
Chap e
10
–
Simula ed Tex ile Dyeing E luen s T ea men by SBR alone and Combined wi h Fen on’s Oxida ion
246
Table 10.4 – Cha ac e is ics o he syn he ic polyes e dyeing was ewa e s a e Fen on eac ion and SBR and espec i e emo al e iciencies
(wi hin b acke s), and global emo als. Runs#1 o #3 ep esen expe imen s wi h dec easing doses o chemicals in he Fen on’s s age.
Pa ame e
Run #1 – Op imal dose o
chemicals Run #2 – 0.5 o op imal dose o
chemicals Run #3– 0.25 o op imal dose o
chemicals Maximum
Allowable
Value*
Fen on
( emo al
(%))
SBR
( emo al
(%))
Global
Remo al
(%)
Fen on
( emo al
(%))
SBR
( emo al
(%))
Global
Remo al
(%)
Fen on
( emo al
(%))
SBR
( emo al
(%))
Global
Remo al
(%)
pH 7.05 7.10 --- 7.11 7.08 --- 7.15 7.10 --- 5.5-9.0
To al ni ogen (mg N/L) 15.1 (5.0) 12.3
(18.5) 22.6 15.3 (3.8) 12.4 (19.0) 22.0 15.9 (0.0) 13.3 (16.4) 16.4
To al phospho us (mg P/L) 2.8 (6.7) 2.2 (20.0) 25.3 2.9 (3.3) 2.2 (22.8) 25.3 3.0 (0.0) 2.4 (20.3) 20.3
COD (mg O
2
/L) 221.1
(57.3) 44.4
(79.9) 91.4 291.7 (43.7) 104.3 (64.2) 79.9 389.7 (24.7) 267.7 (31.3) 48.3 250
BOD
5
(mg O
2
/L) 62.8 (52.0) 11.4
(81.8) 91.3 80.2 (38.6) 29.4 (63.4) 77.5 103.8 (20.6) 54.3 (47.7) 58.5 100
DOC (mg C/L) 63.4 (55.7) 12.6
(80.1) 91.2 80.6 (43.7) 27.7 (65.6) 80.6 106.9 (25.3) 58.1 (45.7) 59.4
SOUR – Speci ic oxygen
up ake a e (mg O
2
/(g
VSS
.h)) 30.0 n.d. --- 29.0 n.d. --- 28.1 n.d. ---
BOD
5
:COD a io 0.28 0.26 --- 0.28 0.28 --- 0.27 0.20 ---
Visible colo a e dilu ion
1:40 no isible no
isible --- no isible no isible --- no isible no isible --- no isible
Vib io ische i Inhibi ion 5
min (%) 0.0 n.d. --- 10.4 n.d. --- 43.3 n.d. ---
Vib io ische i Inhibi ion 15
min (%) 0.0 n.d. --- 15.0 n.d. --- 55.8 n.d. ---
Vib io ische i Inhibi ion 30
min (%) 0.0 n.d. --- 17.6 n.d. --- 59.4 n.d. ---
n.d. – no de e mined.
* Po uguese legisla ion o discha ge o ex ile was ewa e s (O dinance No. 423/97 o 25 June).
Pa III
247
Rega ding he esul s ob ained in he SBR, Figu e 10.3 shows he emo al pe o mances
achie ed, in e ms o COD, BOD
5
, DOC, o al ni ogen and colo , o he ac ylic
was ewa e . I can be obse ed ha emo als inc eased du ing he i s 4 cycles, al hough
he imp o emen is mo e no o ious in he 1
s
and 2
nd
uns; he e o e, we can say ha he
pseudo-s eady s a e was eached a end o 4-5 cycles. A e eaching he pseudo-s eady
sa e, he a e age emo als achie ed in he SBR o he pa ame e s analyzed a e highe
in un #1 (94.9, 94.5, 95.2, 45.0 and 68.4% o COD, BOD
5
, DOC, o al ni ogen and colo ,
espec i ely), ollowed by un #2 (64.6, 84.8, 72.3, 41.9 and 68.8% o COD, BOD
5
, DOC,
o al ni ogen and colo , espec i ely) and hen by un #3 (21.8, 69.0, 17.4, 22.5 and
71.9% o COD, BOD
5
, DOC, o al ni ogen and colo , espec i ely). The eason is ha
om un #1 o un #3 less chemicals we e used in he Fen on’s s age, so ha he e luen
ed o he SBR is less biodeg adable (c . Table 10.2). In uns #1 and #2 i was possible o
each, a e he in eg a ed ea men , an e luen ha is eady o discha ge in o wa e
bodies – see Table 10.2. On he o he hand, al hough in un #3 less chemicals we e
employed in he Fen on’s s age as compa ed o un #2, i was no possible o ul ill he
limi s imposed by he na ional legisla ion o he discha ge o ex ile e luen s, namely in
e ms o COD (c . Table 10.2).
The emo als ob ained du ing 10 cycles o SBR o he co on e luen p e iously ea ed
by Fen on’s oxida ion a e shown in Figu e 10.3. Du ing he i s 6 cycles an inc ease was
obse ed o all uns, and hen he emo als emain nea ly cons an , which means ha he
pseudo-s eady s a e was eached. In uns #1 and #2 he a e age alues o COD, BOD
5
and isible colo (a e dilu ion o 1:40) a he ou le o he SBR, du ing he las 4 cycles o
ope a ion, a e smalle han he maximum allowable discha ge alues (see Table 10.3).
This is howe e no he case o un #3, in which e y low doses o chemicals we e used in
he Fen on’s oxida ion (25% o hose employed in un #1); hus, inal e luen shows COD
alues no complying wi h he legisla ed s anda d.

Pa IV
Real Co on Dyeing Was ewa e
* This Chap e is based on he publica ion “Rod igues C.S.D.; Madei a, L.M.; Boa en u a, R.A.R.
Decon amina ion o an indus ial co on dyeing was ewa e by chemical and biological p ocesses”.
Submi ed
o
Indus ial & Enginee ing Chemis y Resea ch.
Chap e 11
Co on Dyeing Was ewa e T ea men *
Pa IV
259
11 Co on Dyeing Was ewa e T ea men
11.1 In oduc ion
This wo k aimed a e alua ing ou app oaches o ea ing a eal co on dyeing
was ewa e (see Figu e 11.1). In App oach 1 coagula ion/ loccula ion was combined wi h
Fen on’s eac ion (as coagula ion/ loccula ion pe se is no e ec i e o comply wi h
legisla ed discha ge s anda ds o ex ile was ewa e unde s udy, as de ailed below). In
App oach 2 only Fen on’s oxida ion was applied and in App oaches 3 and 4 he
was ewa e was p e- ea ed by Fen on’s oxida ion and hen ea ed by
coagula ion/ loccula ion and a biological p ocess (SBR), espec i ely. In all si ua ions i
was in ended o ob ain he lowes ope a ing cos and an e luen ha mee s he discha ge
limi s imposed by he na ional legisla ion o ex ile e luen s. The e o e, o educe cos s,
pa o he ca alys used in he Fen on’s eac ion o App oach 1 was he esidual dissol ed
i on esul ing om coagula ion/ loccula ion ( his me hodology has been al eady applied o
indus ial was ewa e s o he han ex ile dyeing ones) [Pe es e al., 2004; Xing and Sun,
2009; Pe digon-Melon e al., 2010]. In he same way, in App oach 3 he coagulan used
was he esidual i on esul ing om he Fen on’s eac ion; howe e , in his case he inal
e luen clea ly complied wi h legisla ed s anda ds, and so he Fen on’s s age was also
pe o med wi h doses o chemicals educed o 3/4 and 1/2 o he op imum alue ound in
App oach 2 ( his me hodology has no ye been desc ibed in he li e a u e). In App oach 4
he doses o eagen s used in he Fen on’s oxida ion we e also educed, as desc ibed
abo e, and he esul ing e luen was subjec ed o a biological p ocess. I has been
epo ed in li e a u e [Olle e al., 2011] he need o using oxida i e p ocesses as a p e-
ea men s ep o indus ial ex ile was ewa e s wi h he aim o gene a ing a biodeg adable
e luen wi hou ex ensi e es ing he beha io o he biological p ocess. Recen wo ks
al eady in eg a ed bo h p ocesses, pa icula ly combining Fen on’s oxida ion and
biological deg ada ion in SBR [Rod igues e al., 2009 a); Blanco e al., 2012; Elmolla and
Chaudhu i, 2012; Sanchis e al., 2013; Wu e al., 2013]. The ul ima e choice o he
echnology o adop should ake also in o accoun economic indica o s, and so a cos
analysis was pe o med o each ea men s a egy, as de ailed in he nex sec ion.

Chap e 11
–
Co on Dyeing Was ewa e T ea men
260
App oach 1: Coagula ion/ loccula ion ollowed by Fen on’s eac ion App oach 2: Fen on’s oxida ion
alone
App oach 3: Fen on’s oxida ion ollowed by coagula ion/ loccula ion App oach 4: In eg a ion o Fen on’s oxida ion
plus SBR
Figu e 11.1 - Schema ic diag am o all p ocess con igu a ions adop ed.
Run #1: 18.8 mg/L Fe
2+
and 0.625 mg/L H
2
O
2
in Fen on’s oxida ion
Run #2: 28.2 mg/L Fe
2+
and 0.938 mg/L H
2
O
2
in Fen on’s oxida ion
Run #3: 37.5 mg/L Fe
2+
and 1.25 mg/L H
2
O
2
in Fen on’s oxida ion
App oaches 3 and 4
Fen on
Fen on
Coagula ion
/Floccula io
200 mg/L Fe
2+
98.3 mg/L Fe
2+
37.5 o 300 mg/L Fe
2+
0.938
-
10 g/L H
2
O
2
E luen
Real Dyeing E luen
Real Dyeing
Fe
2+
H
2
O
2
SBR
Fen on
Coagula ion/
Floccula ion
Fen on
2.5 mg/L Magna loc 155
E luen
Real Dyeing
Fe
2+
H
2
O
2
E luen
Real Dyeing
Pa IV
261
11.2 Ope a ing Cos s
To selec he be e in eg a ion o s ages o was ewa e ea men , bu ensu ing ha he
gene a ed e luen mee s he discha ge s anda ds, he ope a ing cos s associa ed o he
consump ion o chemicals and ene gy we e also assessed. Fo he la e i was
conside ed he ene gy consumed in agi a ion (powe equi ed = 0.61 W) and ai
insu la ed (powe = 4.5 W) in he SBR s age. The cos s o acids and base we e no
conside ed as hey a e almos negligible compa ed o he o he chemicals.
In he economic analysis he cos s o eagen s we e hose gi en by Quimi écnica S.A. and
Ri az Química S.A.: H
2
O
2
(49.5% (w/ ), densi y a 25 ºC = 1.2 g/cm
3
) – 365 €/ on;
FeSO
4
.7H
2
O (93 w .% o pu i y) – 233.7 €/ on; and Magna loc 155 – 3850 €/ on. Fo
ene gy i was conside ed he a e age alue o 0.10 €/(kW h)).
The ope a ing cos o he coagula ion/ loccula ion s ep is he sum o cos s o Fe
2+
(Equa ion 11.1) and Magna loc 155 (Equa ion 11.2), while o Fen on’s eac ion is he sum
o cos s o Fe
2+
(Equa ion 11.1) and H
2
O
2
(Equa ion11.3) consump ion; inally, o SBR is
he cos o ene gy (Equa ion 11.4) only.
(11.4)
)
3
(m
e luen ea ed
Volume
(h)
ae a ion
ime * h) (kW
ene gy
P ice * (kW)
3-
10* )
agi a ion
equi ed Powe
dinsu la e ai
(Powe
ene gy
Cos
(11.3)
(kg/L)
100
2
O
2
H
%
)
L
kg
(
2
O
2
H
ρ * )
3
m
on
(
3
10*
2
O
2
H * )
on
€
(
2
O
2
H
P ice
2
O
2
H
Cos
(11.2) )
3
m
on
(
6
10*155Magna loc * )
on
€
(
155Magna loc
P ice
155Magna loc
Cos
(11.1)
100
pu i y o %
2
Fe
MM
O
2
7H
4
FeSO
MM
* )
3
m
on
(
6
10*
2
Fe * )
on
€
(
O
2
7H
4
FeSO
P ice
2
Fe
Cos
+
=
−
=
−
=
+
−+
=
+




















































Chap e 11
–
Co on Dyeing Was ewa e T ea men
262
In he p e ious Equa ions, [i] ep esen s he concen a ion o species i (in g/L o H
2
O
2
and
mg/L o Fe
2+
and Magna loc 155), MM
i
s ands o mola mass (in g/mol) and he powe
equi ed o agi a ion is exp essed in W.
The o al ope a ing cos s o he in eg a ed p ocesses a e calcula ed by he sum o cos s
associa ed wi h each p ocess in ol ed.
11.3 Ma e ials and Me hods
11.3.1 Expe imen al P ocedu e
The coagula ion/ loccula ion, Fen on’s eac ion and SBR expe imen s we e pe o med as
de ailed in sec ions 3.4.1, 3.4.2 and 3.4.4, espec i ely.
The supe na an esul ing om coagula ion/ loccula ion was collec ed and acidi ied wi h
HNO
3
(68%, om Me ck, Ge many) o pH < 4 o keep he i on dissol ed ( o be la e used
as ca alys in he Fen on’s eac ion), when ea ing he e luen by he combina ion o
coagula ion/ loccula ion plus Fen on’s eac ion.
When applying Fen on’s oxida ion ollowed by coagula ion/ loccula ion, he e luen om
he oxida ion s age was acidi ied o pH ≈ 1 o keep he i on dissol ed o he
coagula ion/ loccula ion s udy, while simul aneously slowing down o inhibi ing he
Fen on’s eac ion. The analyses o he e luen we e pe o med immedia ely.
All coagula ion/ loccula ion expe imen s we e conduc ed a oom empe a u e (22-24 ºC).
All ope a ing condi ions we e se aking in o accoun p e ious esul s achie ed wi h a
simila simula ed e luen (chap e 7).
11.3.2 Analy ical Me hods
All analy ical pa ame e s we e de e mined as desc ibed in sec ion 3.3 o chap e 3.
The analy ical de e mina ions we e pe o med in duplica e, and he coe icien s o
a ia ion we e less han 2% o DOC, 6% o BOD
5
, 4% o COD and k’, and 5% o he
o he pa ame e s.
Pa IV
263
11.4 Resul s and Discussion
11.4.1 Tex ile Deying Was ewa e
The indus ial co on deying wa ewa e was p o ided by Têx il Luis Simões S.A. and i s
main cha ac e is ics a e epo ed in Table 3.5 (sec ion 3.2.2).
11.4.2 Coagula ion/Floccula ion plus Fen on’s Reac ion (App oach 1)
This s udy s a ed wi h he applica ion o coagula ion/ loccula ion o he aw was ewa e ,
using e ous sul a e and Magana loc 155 as coagulan and locculan , espec i ely. The
ope a ing condi ions used we e he op imal ones de e mined in a p io s udy on he
ea men o a syn he ic co on was ewa e (chap e 4): V
coagula ion
=150 pm,
coagula ion
= 3
min, [Fe
2+
]= 200 mg/L, pH= 9.4, V
loccula ion
=20 pm,
loccula ion
= 15 min, [Magna loc 155] = 0.5
mg/L. The cha ac e is ics o he was ewa e a e ea men a e p esen ed in Table 11.1.
One can conclude ha coagula ion/ loccula ion is e y e icien as ega ds colo emo al
(95.1% - pe cen emo al e iciencies a e wi hin b acke s in he able), leads o a
conside able emo al o o ganic ma e (36.9% and 39.4% espec i ely o COD and
DOC) and phospho us (47.2%), bu i is qui e ine icien conce ning he emo al o BOD
5
(17.2%) and ni ogen (1.9%). Mo eo e , he alues o COD and BOD
5
in he inal e luen
a e abo e he discha ge s anda ds imposed by he Po uguese legisla ion, which makes
necessa y an addi ional ea men .
So, o inc easing he e iciency o o ganic ma e emo al, he e luen om he
coagula ion/ loccula ion s age was subjec ed o Fen on’s oxida ion, applying he ope a ing
condi ions al eady op imized when ea ing a syn he ic e luen by he same in eg a ed
p ocess (chap e 7): T= 50 ºC, pH= 3.5, = 60 min, [H
2
O
2
]= 500 mg/L and [Fe
2+
]
added
= 98.3
mg/L ( o al i on
concen a ion = 100 mg/L, aking in o accoun ha 1.7 mg Fe/L emained
om he coagula ion/ loccula ion s ep). Resul s included in Table 11.1 poin ou ha
Fen on’s oxida ion applied o he p e- ea ed e luen allowed ob aining COD, BOD
5
and
DOC emo als o 53.7, 36.7 and 44.1%, espec i ely, colo educ ion o 89.3% and
smalle dec eases in o al phospho us and o al ni ogen concen a ions (29.7 and 2.7%,
espec i ely).
Chap e 11
–
Co on Dyeing Was ewa e T ea men
270
#1 o #3). The COD, DOC and colo emo als eached in Fen on’s eac ion a e in all
s a egies highe han in he coagula ion/ loccula ion s age, bu BOD
5
shows an opposi e
beha io . As expec ed, much be e ea men e iciencies a e eached in un #3, whe e
doses o chemicals in he Fen on’s s age a e highe (69.2, 60.4, 72.4, and 96.6% o
COD, BOD
5
, DOC and colo , espec i ely).
Final COD alues below he discha ge s anda ds we e only eached in uns#2 and #3,
whe e g ea e H
2
O
2
(and Fe
2+
) doses we e used. Howe e , despi e he sligh ly lowe
o ganic ma e emo al e iciency, he chemical dosages used in un #2 we e selec ed
because hey o igina e smalle ope a ing cos s (0.87 €/m
3
), compa a i ely o un #3 (1.2
€/m
3
), which is associa ed wi h he lowe H
2
O
2
and Fe
2+
concen a ion employed, wi hou
comp omising compliance wi h he legisla ed discha ge s anda ds.
The use o dissol ed i on esul ing om Fen on p ocess as coagulan in he subsequen ly
s age o coagula ion/ loccula ion ep esen s an economic ad an age, since he ope a ing
cos is educed by 27.5% compa a i ely o Fen on’s oxida ion alone.

Pa IV
271
Table 11.3 - Cha ac e is ics o he co on dyeing was ewa e a e Fen on’s oxida ion and coagula ion/ loccula ion (App oach 3) and global emo al o he
combined p ocess ( uns #1 o #3 co espond o di e en dosages o hyd ogen pe oxide in he Fen on’s s age; pe cen emo al e iciencies a e gi en wi hin
b acke s o each isola ed p ocess).
Pa ame e
Run #1 – 0.625 g H
2
O
2
/L Run #2 – 0.938 g H
2
O
2
/L Run #3 – 1.25 g H
2
O
2
/L
Fen on’s
oxida ion
Coagula ion
&
loccula ion
Global
emo al
(%)
Fen on’s
oxida ion
Coagula ion
&
loccula ion
Global
emo al
(%)
Fen on’s
oxida ion
Coagula ion
&
loccula ion
Global
emo al
(%)
Discha ge
limi ***
pH 1.20 7.0 - 1.25 7.02 - 1.10 7.03 - 5.5-9.0
Chemical oxygen
demand (mg O
2
/L) 347.5 (29.8) 270.0 (22.3) 45.5 292.5
(40.9) 185.0 (36.8) 62.6 260.0
(47.5) 152.5 (41.3) 69.2 250
Biochemical oxygen
demand (mg O
2
/L) 116.3 (8.8) 91.8 (21.1) 28.0 106.4
(16.5) 66.9 (37.1) 47.5 85.3 (33.1) 50.5 (40.8) 60.4 100
Dissol ed o ganic
ca bon (mg C/L) 124.9 (28.5) 94.9 (24.0) 45.7 98.4 (43.7) 62.2 (36.8) 64.4 82.4 (52.8) 48.3 (41.4) 72.4 -
BOD
5
:COD a io 0.33 0.34 - 0.36 0.36 - 0.33 0.33 - -
Abso bance a λ
max
(abs. uni s) 0.0407
(94.0*) 0.0234
(43.2**) 96.6 0.0392
(94.2*) 0.0230
(41.6**) 96.6 0.0387
(94.3*) 0.0233
(40.4**) 96.6 -
Visible colo a e
dilu ion 1:40 no isible no isible - no isible no isible - no isible no isible - no isible
* calcula ed om he abso bance o was ewa e a pH 3.5 (0.6805 abs. uni s).
** calcula ed om he abso bance a e Fen on a pH 5.0 (0.0412, 0.0394 and 0.0391 abs. uni s o un #1, #2 and #3, espec i ely).
*** Po uguese legisla ion o discha ge o ex ile was ewa e s (O dinance No. 423/97 o 25 June).
Chap e 11
–
Co on Dyeing Was ewa e T ea men
272
11.4.5 Combina ion o Fen on´s Reac ion and SBR (App oach 4)
As he biodeg adabili y o he aw was ewa e (in e ms o BOD
5
:COD a io and k') sligh ly
inc eased a e Fen on’s oxida ion ( om 0.26 and 8.85 mg O
2
/(g
ss
h) o 0.36 and 9.5 mg
O
2
/(g
ss
h), espec i ely), and he e was also a educ ion in Vib o ische i inhibi ion, as
shown in Tables 11.1 and 11.2, he al e na i e in eg a ed p ocess consis ing o Fen on’s
eac ion ollowed by SBR was s udied.
Th ee expe imen s we e pe o med using di e en doses o chemicals in Fen on’s
oxida ion s age. One expe imen ( un #3) was pe o med unde he op imal condi ions
de e mined in App oach 2 (37.5 mg/L Fe
2+
and 1.25 g/L H
2
O
2
); in he o he uns he doses
o H
2
O
2
and Fe
2+
we e educed o 3/4 and 1/2, espec i ely, wi h he objec i e o educing
he ope a ing cos s ( uns #2 and #1, espec i ely) (see Figu e 11.1).
Figu e 11.4 shows he COD, DOC, BOD
5
, colo , o al ni ogen and o al phospho us
emo als du ing 10 cycles o SBR ope a ion o he 3 uns; one can conclude ha he
emo als o all pa ame e s analyzed emained p ac ically cons an a e 6 cycles in all
uns/s a egies es ed, which means ha a pseudo-s eady s a e was eached. The
e iciencies inc eased wi h he doses o chemicals used in he Fen on’s eac ion ( un #3 >
un #2 > un #1), simul aneously wi h a signi ican decay o oxici y and a sligh inc ease o
biodeg adabili y (see also Table 11.4). Pa icula ly he inhibi ion o Vib io ische i
dec eased om 44.5-49.2% in un # 1 o 0.0 (non-inhibi ion) in un # 3. The a e age
emo als achie ed in he las 4 cycles a e p esen ed in Table 11.4. BOD
5
emo al was
g ea e in SBR p obably due o he b eakdown o he mo e ecalci an compounds by
chemical oxida ion.
As ega ds decolo iza ion, abou 94% o he abso bance o aw
was ewa e was emo ed by he Fen on’s eac ion and only 38-40% o he esidual
abso bance was emo ed in he SBR.
Pa IV
273
Figu e 11.4 - Va ia ion o COD (a), DOC (b), BOD
5
(c), colo (d) o al ni ogen (e) and o al
phospho us ( ) emo als along 10 cycles o SBR ope a ion, a e ea men by Fen on’s oxida ion.
Runs #3 o #1 e e o Fen on’s s age wi h p og essi ely dec easing doses o chemicals.
0
20
40
60
80
100
0 1 2 3 4 5 6 7 8 9 10
COD emo al (%)
Numbe o Cycles
Run # 1
Run # 2
Run # 3
a)
0
20
40
60
80
100
0 1 2 3 4 5 6 7 8 9 10
DOC emo al (%)
Numbe o Cycles
Run # 1
Run # 2
Run # 3
b)
0
20
40
60
80
100
0 1 2 3 4 5 6 7 8 9 10
BOD
5
emo al (%)
Numbe o Cycles
Run # 1
Run # 2
Run # 3
c)
0
20
40
60
80
100
0 1 2 3 4 5 6 7 8 9 10
Colo emo al (%)
Numbe o Cycles
Run # 1
Run # 2
Run # 3
d)
0
5
10
15
0 1 2 3 4 5 6 7 8 9 10
To al Ni ogen emo al
(%)
Numbe o Cycles
Run # 1
Run # 2
Run # 3
e)
0
5
10
15
20
0 1 2 3 4 5 6 7 8 9 10
To al Phospho us
emo al (%)
Numbe o Cycles
Run # 1
Run # 2
Run # 3
)
Chap e 11
–
Co on Dyeing Was ewa e T ea men
274
Table 11.4 – Cha ac e is ics o he co on dyeing was ewa e a e Fen on´s eac ion and SBR (App oach 4) and a e age (las ou cycles o SBR) and
global emo als ( espec i e emo al e iciencies a e gi en wi hin b acke s o each p ocesses).
Pa ame e
Run #1 – 0.625 g H
2
O
2
/L Run #2 – 0.938 g H
2
O
2
/L Run #3 – 1.25 g H
2
O
2
/L Discha ge
limi ***
Fen on SBR Global
Remo al
(%) Fen on SBR Global
Remo al
(%) Fen on SBR Global
Remo al
(%)
pH 7.12 7.17 --- 7.05 7.15 --- 7.09 7.17 --- 5.5-9.0
To al ni ogen (mg N/L) 1021.8 (4.0) 1005.4
(1.6) 5.5 1021.8
(4.0) 929.1
(9.1) 12.7 1021.8
(4.0) 905.5
(11.4) 14.9
To al phospho us (mg P/L) 4.2 (1.2) 3.8 (8.4) 9.5 4.2 (1.7) 3.7
(10.4) 11.9 4.2 (1.2) 3.6 (13.3) 14.3
COD (mg O
2
/L) 346.5 (30.0) 281.8
(18.7) 43.1 294.1
(40.6) 183.3
(37.7) 63.0 232.8
(53.0) 79.2 (66.0)
84.0 250
BOD
5
(mg O
2
/L) 114.2 (10.4) 93.4 (18.2) 26.7 103.4
(18.9) 64.4
(37.7) 49.5 84.7
(32.6) 28.6 (66.2) 77.6 100
DOC (mg C/L) 124.7 (28.5) 103.3
(17.2) 40.8 98.0 (43.8) 61.7
(37.0) 64.6 82.5
(52.7) 28.1 (65.9) 83.9
SOUR – Speci ic oxygen up ake
a e (k’) (mg O
2
/(g
VSS
.h)) 8.9 n.d. --- 9.1 n.d. --- 9.5 n.d. ---
BOD
5
:COD a io 0.33 0.33 --- 0.35 0.35 --- 0.36 0.36 ---
Abso bance a λ
max
(a.u.) 0.0410 (94.0*) 0.0257
(38.1**) 96.3 0.0393
(94.2*) 0.0240
(39.5**) 96.5 0.0386
(94.3*) 0.0234
(40.0**) 96.6
Visible colo a e dilu ion 1:40 no isible no isible --- no isible no
isible --- no
isible no isible --- no isible
Vib io ische i Inhibi ion 5 min (%) 44.5 n.d. --- 11.0 n.d. --- 0.0 n.d. ---
Vib io ische i Inhibi ion 15 min (%) 46.7 n.d. --- 23.1 n.d. --- 0.0 n.d. ---
Vib io ische i Inhibi ion 30 min (%) 49.2 n.d. --- 26.7 n.d. --- 0.0 n.d. ---
n.d. – no de e mined.
* calcula ed om he abso bance a 520 nm o aw was ewa e a pH 3.5 (0.6805 abs. uni s).
** calcula ed om he abso bance a 520 nm o was ewa e a e Fen on a pH 7.0 ( 0.0415, 0.0397 and 0.0390 abs. uni s in un #1, #2 and #3, espec i ely).
*** . O dinance No. 423/97 o 25 June.
Pa IV
275
As shown in Figu e 11.5, he ope a ing cos s associa ed wi h he consump ion o
chemicals and ene gy inc ease wi h he amoun o chemicals used in he chemical
ea men , i.e, un #3 (2.4 €/m
3
) > un #2 (2.1 €/m
3
) > un #1 (1.8 €/m
3
). Howe e , only
uns #2 and #3 allowed ob aining e luen s ha mee he discha ge s anda ds, namely in
e ms o COD (see Table 4). As he cos s a e sligh ly smalle , condi ions used in un #2
a e p oposed o p ac ical applica ions. The o e all e iciencies achie ed by he
combina ion o Fen on’s oxida ion and biological deg ada ion in SBR unde such
condi ions a e 63.0, 49.5, 64.6, 12.7, 11.9 and 96.5% o COD, BOD
5
, DOC, o al ni ogen,
o al phospho us and colo , espec i ely. I is no ewo hy ha such in eg a ed p ocess is
mo e expensi e han Fen on’s oxida ion pe se (c . Figu e 11.5), which is due o ene gy
consump ion in he SBR, al hough doses o chemicals we e minimized in he chemical
oxida ion s age.
Figu e 11.5 - Ope a ing cos s o Fen on alone and Fen on plus SBR o ea men o a eal co on
dyeing was ewa e .
11.5 Conclusions
A combina ion o coagula ion/ loccula ion and Fen on’s oxida ion, Fen on’s oxida ion
alone, and in eg a ed p ocesses o Fen on´s oxida ion wi h coagula ion/ loccula ion o
biological deg ada ion in SBR was applied o a eal co on dyeing was ewa e aiming a
0
1
2
3
Fen on Run #1 Run #2 Run #3
Ope a ing Cos (€/m3)
Fen on plus SBR

Chap e 11
–
Co on Dyeing Was ewa e T ea men
276
o ganic ma e mine aliza ion, colo emo al and oxici y educ ion while ob aining an
e luen ha mee s he legisla ed discha ge limi s a he lowe ope a ing cos .
All he ea men p ocesses es ed allowed ob aining an e luen ha comply wi h he
discha ge limi s, bu he cheapes al e na i es a e he applica ion o
coagula ion/ loccula ion ollowed by Fen on’s oxida ion o , in e sely, he combina ion o
Fen on’s oxida ion wi h subsequen coagula ion/ loccula ion p ocess. The ope a ing cos s
associa ed o he consump ion o chemicals a e 0.83 and 0.87 €/m
3
, espec i ely. This is
in pa explained by ini ially using a cheape ea men ha pe mi s a educ ion o he
amoun s o chemicals employed in he second p ocess, hen dec easing he o al cos s
(App oach 1) and by aking ad an age o dissol ed i on esul ing om Fen on’s eac ion,
as coagulan in he coagula ion/ loccula ion s ep (App oach 3). Global emo al e iciencies
o 99.5, 70.8, 66.1, 47.6% and 96.6, 62.6, 64.4 and 47.5 % we e ob ained o colo , COD,
DOC and BOD
5
, espec i ely, in he i s and second in eg a ed ea men p ocesses
(App oaches 1 and 3).
11.6 Re e ences
Ala on, I.A.; Teksoy, S. (2007). Acid Dyeba h E luen P e ea men Using Fen on’s Reagen :
P ocess Op imiza ion, Reac ion Kine ics and E ec s on Acu e Toxici y. Dyes Pigmen s, 73, 31-39.
Azba , N.; Yona , T.; Kes ioglu, K. (2004). Compa ison o a ious ad anced oxida ion p ocesses
and chemical ea men me hods o COD and colo emo al om a polyes e and ace a e ibe
dyeing e luen . Chemosphe e, 55, 35-43.
Bali, U.; Ka agözoglu, B. (2007). Pe o mance compa ison o Fen on p ocess, e ic coagula ion
and H2O2/py idine/Cu (II) sys em o decolou iza ion os Remazol Tu quoise Blue G-133. Dyes
Pigmen s, 74, 73-80.
Blanco, J.; To ades, F.; Va ga, M. de la; Ga cía-Mon año, J. (2012). Fen on and biological-Fen on
coupled p ocesses o ex ile was ewa e ea amen and euse. Desalina ion, 286, 394-399.
Elmolla, E.S.; Chaudhu i, M. (2012). The easibili y o using combined Fen on-SBR o an ibio ic
was ewa e ea men . Desalina ion, 285, 14-21.
Li, J.; Luan, Z.; Yu, L.; Ji, Z. (2012). P e ea men o ac ylic ibe manu ac u ing was ewa e by he
Fen on p ocess. Desalina ion, 284, 62-65.
Me iç, S.; Selçuk, H.; Belgio no, V. (2005). Acu e oxici y emo al in ex ile inishing was ewa e by
Fen on’s oxida ion, ozone and coagula ion- loccula ion p ocesses. Wa e Resea ch, 39 (6), 1147-
1153.
Pa IV
277
Olle , I.; Mala o, S.; Sánchez-Pé ez, J.A. (2011). Combina ion o ad anced oxida ion p ocess and
biological ea men s o was ewa e decon amina ion – A e iew. Science o he To al
En i onmen al, 409, 4141-4156.
Papadopoulos, A.E.; Fa a, D.; Loizidou, M. (2007). De elopmen and op imiza ion o da k Fen on
oxida ion o ea men o ex ile was ewae s wi h high o ganic load. Jou nal o Haza dous Ma e ial,
146, 558-563.
Pe digon-Melon, J.A.; Ca bajo, J.B.; Pe e, A.L.; Rosal, R.; Ga cia-Cal o, E. (2010). Coagula ion-
Fen on coupled ea men o eco oxici y educ ion in highly pollu ed indus ial was ewa e . Jou nal
o Haza dous Ma e ials, 181, 127-132.
Pe es, J.A.; He edia, J.B. de; Domínguez, J.R. (2004). In eg a ed Fen on’s eagen –
coagula ion/ loccula ion p ocess o he ea men o co k p ocessing was ewa e s. Jou nal o
Haza dous Ma e ials, 107 (3), 15-121.
Rami ez, J.H.; Cos a, C.A.; Madei a, L.M. (2005). Expe imen al design o op imize he deg ada ion
o he syn he ic dye o ange II using Fen on’s eagen . Ca alysis Today, 107-108, 68-76.
Rod igues, C.S.D.; Madei a, L.M.; Boa en u a, R.A.R. (2009 a)). T ea men o ex ile e luen by
chemical (Fen on’s Reagen ) and biological (Sequencing ba ch eac o ) oxida ion. Jou nal o
Haza dous Ma e ials, 172, 1551-1559.
Rod igues, C.S.D.; Madei a, L.M.; Boa en u a, R.A.R. (2009 b)). Op imiza ion o he azo dye
P ocion Red H-EXL deg ada ion by Fen on’s eagen using expe imen al design. Jou nal o
Haza dous Ma e ials, 164, 987-994.
Sanchis, S.; Polo, A.M.; Tobaja, M.; Rod iguez, J.J.; Mohedano, A.F. (2013). Deg ada ion o
clo ophenoxy he bicides by coupled Fen on and biological oxida ion. Chemosphe e, in p ess.
DOI:10.1016/j.chemosphe e.2013.04.097.
Wu, D.-L.; Wang, W.; Guo, Q.-W.; Shen, Y.-H. (2013). Combined Fen on-SBR p ocess o bamboo
indus y was ewa e ea men . Chemical Enginee ing Jou nal, 214, 278-284.
Wu, H.; Wang, S. (2012). Impac s o ope a ing pa ame e s on oxida ion- educ ion po en ial and
p e ea men e icacy in he p e ea men o p in ing and dyeing was ewa e by Fen on p ocess.
Jou nal o Haza dous Ma e ials, 243, 86-94.
Xing, Z.-P.; Sun, D.-Z. (2009). T ea men o an ibio ic e men a ion was ewa e by combined
poly e ic sul a e coagula ion, Fen on and sedimen a ion p ocess. Jou nal o Haza dous Ma e ials,
168, 1264-1268.
Pa V
Conclusions and Sugges ions o Fu u e Wo k
Chap e 12
–
Concluding Rema ks and Fo hcoming Wo k
286
Table 12.1 – T ea men app oaches es ed, analysis o compliance wi h maximum allowable alues and ope a ing cos s o each simula ed e luen and
eal was ewa e es ed. In bold a e highligh ed he cheapes s a egies o each e luen ha complie wi h legal limi s o discha ge.
T ea men
App oach
*
Simula ed E luen s Real Was ewa e
Ac ylic Dyeing Co on Dyeing Polyes e Dyeing Co on Dyeing
Compliance
wi h Discha ge
S anda ds
**
Ope a ing
Cos (€/m
3
)
Compliance wi h
Discha ge
S anda ds
**
Ope a ing
Cos (€/m
3
)
Compliance wi h
Discha ge
S anda ds
**
Ope a ing
Cos (€/m
3
)
Compliance wi h
Discha ge
S anda ds
**
Ope a ing
Cos (€/m
3
)
C/F No 3.7 No 0.25 No 2.0 No 0.25
C/F + FR Yes 7.0 Yes 0.83 Yes 3.1 Yes 0.83
FR No 18.1 No 9.2 Yes 2.7 Yes 1.2
FR + C/F Yes 9.1 Yes 4.6 Yes 1.3 Yes 0.87
PhFR Yes 5.8 Yes 3.5 Yes 1.0 --- ---
SBR --- --- No 1.2 No 1.2 --- ---
FR + SBR Yes 14.8 Yes 5.8 Yes 2.6 Yes 2.1
* C/F – coagula ion/ loccula ion; FR – Fen on’s eac ion: PhFR – pho o-Fen on’s eac ion wi h sola adia ion; SBR – sequencing ba ch eac o .
** Acco ding o Po uguese legisla ion – O dinance No. 423/97 o 25 June.

Pa V
287
12.2 Fo hcoming Wo k
Fo u u e wo k i is sugges ed o s udy he possibili y o ecycling he i on sludge esul ing
om he Fen on p ocess as ca alys in he same oxida ion p ocess o as coagulan , hus
dec easing he ea men cos s and a oiding he sludge deposi ion. Such app oach could
also be es ed in eac o s ope a ing in con inuous a he han discon inuous mode.
When applying he combina ion o Fen on’s oxida ion plus coagula ion/ loccula ion o SBR
i was possible o educe he doses o chemicals in he oxida ion s age while main aining
he compliance wi h he discha ge limi s. Such app oach could also be es ed in eac o s
ope a ing in con inuous a he han discon inuous mode.
Wi h espec o he biological p ocess i wouldl be in e es ing o in es iga e he in luence
o he du a ion o each cycle and he du a ion o each phase o he cycle, as well as he
e ec o he empe a u e and o he condi ions on he e iciency o he biological
deg ada ion.
The ea men o indus ial ex ile dyeing was ewa e s by he pho o-Fen on p ocess using
na u al sunligh ins ead o simula ed sunligh should be u he s udied and op imized.
The ea abili y s udy o he eal co on (and o he ) dyeing was ewa e could include he
op imiza ion o each p ocess o combina ion o p ocesses, namely by using mul i a ia e
s a is ical ools.
Gi en he high ea men e iciency esul ing om he applica ion o he in eg a ed p ocess
o coagula ion/ loccula ion ollowed by Fen on’s eac ion and ice e sa, and pa icula ly o
he eal co on dyeing was ewa e , allowing ob aining an e luen ha mee s he discha ge
s anda ds a low ope a ing cos , he s udy should p oceed in con inuous mode ope a ion
o simila and o he ypes o e luen s.
Finally, his s udy could be ex ended by applying he elec o-Fen on o elec o-pho o-
Fen on p ocesses o eal ex ile dyeing e luen s.
Appendix
Suppo ing In o ma ion
Appendix
291
A.1 Suppo ing In o ma ion o Chap e 4
This appendix shows he expe imen al esul s ob ained in he e alua ion o he e ec o
he s i ing speed and ime o coagula ion (Figu es A.1 and A.2) and loccula ion (Figu es
A.3 and A.4) on he syn he ic co on and polyes e was ewa e s ea men by
coagula ion/ loccula ion using Fe
2+
as coagulan and Magna loc 155 as locculan .
Figu e A.1 – In luence o he s i ing a e on he coagula ion s age o DOC (a) and colo (b)
emo al om polyes e and co on simula ed e luen s (
coagula ion
=3 min, T=T
ambien
=23-25 ºC,
[Fe
2+
]=200 mg/L and pH=8.3).
Figu e A.2 – E ec o he coagula ion ime on DOC (a) and colo (b) emo al om polyes e and
co on simula ed e luen s (
coagula ion
=150 pm, T=T
ambien
=22-24 ºC, [Fe
2+
]=200 mg/L and pH=8.3).
0
10
20
30
40
50
60
100 150 200
DOC emo al (%)
coagula ion
( pm)
Polyes e
Co on
a)
0
20
40
60
80
100
100 150 200
Colo emo al (%)
coagula ion
( pm)
Co on
b)
0
10
20
30
40
50
60
1 2 3 5
DOC emo al (%)
coagula ion
(min)
Polyes e
Co on
a)
0
20
40
60
80
100
1
2
3
5
Colo emo al (%)
coagula ion
(min)
Co on b)

292
Figu e A.3 - Va ia ion o DOC (a) and colo (b) emo al wi h he s i ing speed in he loccula ion
s age o polyes e and co on simula ed e luen s (
coagula ion
=150 pm,
coagula ion
=3 min,
T=T
ambien
=22-28 ºC, pH
polyes e
=8.3, pH
co on
=9.4, [Fe
2+
]
polyes e
=[Fe
2+
]
co on
=200 mg/L,
loccula ion
=15 min
and [Magna loc 155]=2.5 mg/L).
Figu e A.4 – In luence o he loccula ion ime on DOC (a) and colo (b) emo al om polyes e and
co on simula ed e luen s (
coagula ion
=150 pm,
coagula ion
=3 min, T=T
ambien
=22-28 ºC, pH
polyes e
=8.3,
pH
co on
=9.4, [Fe
2+
]
polyes e
=[Fe
2+
]
co on
=200 mg/L,
loccula ion
=20 pm and [Magna loc 155]=2.5 mg/L).
0
10
20
30
40
50
60
20 30 50
DOC emo al (%)
loccula ion
( pm)
Polyes e Co on
a)
0
20
40
60
80
100
20 30 50
Colo emo al (%)
loccula ion
( pm)
Co on
b)
0
10
20
30
40
50
60
15 30 45
DOC emo al (%)
loccula ion (min)
Polyes e Co on a)
0
20
40
60
80
100
15 30 45
Colo emo al (%)
loccula ion
(min)
Co on
b)
Appendix
293
A.2 Suppo ing In o ma ion o Chap e 9
Some expe imen al esul s ob ained in he ea men o he simula ed e luen s by he
pho o-Fen on p ocess a e p esen ed below.
a)
b)
c)
Figu e A.5 – E ec o adia ion in ensi y on DOC and colo emo al om he co on e luen du ing
he pho o-Fen on p ocess wi h a i icial adia ion o 3.75 g/L (a), 5 g/L (b) and 10 g/L (c) o
hyd ogen pe oxide (T=50 ºC, Fe
2+
:H
2
O
2
=1:33 and pH=3.5).
0
20
40
60
80
100
0 20 40 60 80 100 120
DOC emo al (%)
I adia ion ime (min)
0
20
40
60
80
100
0 20 40 60 80 100 120
Colo emo al (%)
I adia ion ime (min)
253 W/m2
500 W/m2
0
20
40
60
80
100
0 20 40 60 80 100 120
DOC emo al (%)
I adia ion ime (min)
0
20
40
60
80
100
0 20 40 60 80 100 120
Colo emo al (%)
I adia ion ime (min)
7 W/m2
107 W/m2
220 W/m2
253 W/m2
500 W/m2
0
20
40
60
80
100
0 20 40 60 80 100 120
DOC emo al (%)
I adia ion ime (min)
0
20
40
60
80
100
0 20 40 60 80 100 120
Colo emo al (%)
I adia ion ime (min)
7 W/m2
107 W/m2
253 W/m2
500 W/m2
294
a)
b)
c)
Figu e A.6 – E ec o he adia ion in ensi y on DOC emo al om he polyes e e luen du ing he
pho o-Fen on p ocess o 0.938 g/L (a), 1.25 g/L (b) and 2.5 g/L (c) o hyd ogen pe oxide (T=50 ºC,
Fe
2+
:H
2
O
2
=1:7 and pH=3.5).
0
20
40
60
80
100
0 20 40 60 80 100 120
DOC emo al (%)
I adia ion ime (min)
253 W/m2
500 W/m2
0
20
40
60
80
100
0 20 40 60 80 100 120
DOC emo al (%)
I adia ion ime (min)
7 W/m2 107 W/m2
220 W/m2 253W/m2
500 W/m2
0
20
40
60
80
100
0 20 40 60 80 100 120
DOC emo al (%)
I adia ion ime (min)
7 W/m2
107 W/m2
253 W/m2
500 W/m2
Appendix
295
a)
b)
c)
Figu e A.7 – E ec o H
2
O
2
dose on DOC and colo emo al om he ac ylic (a), co on (b) and
polyes e (c) e luen s using pho o-Fen on’s oxida ion wi h simula ed sunligh ( adia ion in ensi y =
500 W/m
2
, T=50 ºC, Fe
2+
:H
2
O
2 ac ylic
=1:57, Fe
2+
:H
2
O
2 co on
=1:33 Fe
2+
:H
2
O
2 polyes e
=1:7, pH=3.5).
0
20
40
60
80
100
0 20 40 60 80 100 120
DOC emo al (%)
I adia ion ime (min)
0
20
40
60
80
100
0 20 40 60 80 100 120
Colo emo al (%)
I adia ion ime (min)
6.5 g/L H2O2
10 g/L H2O2
20 g/L H2O2
0
20
40
60
80
100
0 20 40 60 80 100 120
DOC emo al (%)
I adia ion ime (min)
0
20
40
60
80
100
0 20 40 60 80 100 120
Colo emo al (%)
I adia ion ime (min)
3.75 g/L H2O2
5 g/L H2O2
10 g/L H2O2
0
20
40
60
80
100
0 20 40 60 80 100 120
DOC emo al (%)
I adia ion ime (min)
0.938 g/L H2O2
1.25 g/L H2O2
2.5g/L H2O2