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Flocculation, Ozonation, and Fenton’s Process in the Treatment of Distillery

Effluents

Article  in  Journal of Environmental Engineering · January 2013

DOI: 10.1061/(ASCE)EE.1943-7870.0000527

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1 1 Flocculation, Ozonation, and Fenton’s Process
in the Treatment of Distillery Effluents

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2 2
3

3 Rui C. Martins1; Fábio L. Pinto2; Sérgio Castro-Silva3; and Rosa M. Quinta-Ferreira4

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4 Abstract: This paper reports the application of flocculation, Fenton’s process, and ozonation on the depuration of distillery wastewaters.
5 The treatment processes were analyzed separately; nevertheless, integration schemes were also considered. The commercial flocculant
64 923PWG led to up to 84% of total suspended solids (TSS) removal even if a very low chemical oxygen demand (COD) abatement
7 was observed (<2%). The effect of hydrogen peroxide concentration and ½H2 O2
=½Fe2þ
molar ratio were tested on the Fenton’s process
8 efficiency. Moreover, the H2 O2 injection mode was still analyzed. Gathering up both COD degradation and biodegradability enhancement,

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9 it was possible to select the following operating conditions: ½H2 O2
¼ 0.5 M and ½H2 O2
=½Fe2þ
¼ 10 ðmol=molÞ, being the oxidant totally
10 introduced at the beginning of the reaction. Ozonation showed poor results regarding organic matter removal; however, it seems to be an
11 interesting methodology raising the effluent’s biochemical oxygen demand ðBOD5 Þ=COD ratio. In fact, in the strategies involving the
12 integration of ozonation with Fenton’s process, it was possible to conclude that ozone oxidation did not improve COD degradation; none-
13 5 theless, it was essential to improve biodegradability, particularly when conducting ozonation (at pH ¼ 3) after Fenton’s process was revealed

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14 to be an interesting approach leading to an effluent amenable to further biodegradation. DOI: 10.1061/(ASCE)EE.1943-7870.0000527.
15 © 2013 American Society of Civil Engineers.
16 CE Database subject headings: Wastewater management; Ozonization; Biological processes; Water treatment.
17 Author keywords: Distilleries wastewater; Ozonation; Fenton’s process; Flocculation; Processes integration; Biodegradability.

18 Introduction industrial wastewater toward the water bodies has been forcing 27
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governments to strike environmental legislation compelling com- 28
19 In modern society of extreme consumers, which is continuously panies to be responsible for their effluents. 29
20 growing, and in which the assets that support their existence are Distilleries produce high-strength wastewaters characterized by 30
21 becoming more in number and larger in quantities, the global large amounts of organic matter (Beltran de Heredia et al. 2005). 6 31
22 industry has a strong and decisive role as the main piece in the con- Some management approaches for such streams encompass their 32
23 sequent ecological puzzle by managing wherewithal as a supplier disposal throughout the sewage or evaporation ponds, which is
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33
24 of final products, and being also the principal cause of pollution. environmentally dangerous with possible contamination of under- 34
25 The increasing concern with the depletion of the natural resources ground waters (Beltran de Heredia et al. 2005). Several treatment 35
26 allied with the health issues caused by the uncontrolled release of technologies were tested and are reported in specialized literature 36
dealing with this type of stream, which were reviewed by Pant and 37
1 Adholeya (2007) and Satyawali and Balakrishnan (2008). Thanikal 38
CIEPQPF—Centro de Investigação em Engenharia dos Processos
et al. (2007) successfully tested an anaerobic fixed-bed reactor that 39
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Químicos e Produtos da Floresta, GERSE—Group on Environment,

Reaction and Separation Engineering, Dept. of Chemical Engineering, was able to remove up to 80% of a distillery vinasse chemical 40
Faculty of Science and Engineering, Univ. of Coimbra, 3030–790 Coimbra, oxygen demand (COD). Due to its high amount of COD allied with 41
Portugal. E-mail: martins@eq.uc.pt a huge quantity of phenolic compounds and suspended solids, 42
2
CIEPQPF—Centro de Investigação em Engenharia dos Processos Amarula distillery wastewater can harmfully affect the traditional 43
Químicos e Produtos da Floresta, GERSE—Group on Environment, biological systems. In this ambit, Strong (2010) identified the white 44
Reaction and Separation Engineering, Dept. of Chemical Engineering, rot fungi Tramates pubenscens as a suitable microorganism able to 45
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Faculty of Science and Engineering, Univ. of Coimbra, 3030–790 Coimbra,

depurate this effluent. In regard to chemical oxidation technologies, 46
Portugal. E-mail: fbiopinto@hotmail.com
3
Adventech-Advanced Environmental Technologies, Centro
Beltran de Heredia et al. (2005) tested an integrated Fenton- 47
Empresarial e Tecnológico, São João da Madeira, Portugal. E-mail: coagulation/flocculation process reaching a maximum COD 48
sergio.silva@adventech.pt removal of 74% on the treatment of wine distillery wastewaters. 49
4 Hadavifar et al. (2010) detected an increase of COD abatement 50
Associate Professor, CIEPQPF—Centro de Investigação em
from 47% to 73% when applying photo-Fenton rather than Fenton
P

Engenharia dos Processos Químicos e Produtos da Floresta, GERSE— 51

Group on Environment, Reaction and Separation Engineering, Dept. of process on the remediation of vinasse. The use of ozonation also 52
Chemical Engineering, Faculty of Science and Engineering, Univ. of proved to be an interesting strategy to improve the biodegradability 53
Coimbra, 3030–790 Coimbra, Portugal (corresponding author). E-mail: of this kind of wastewater (Beltrán et al. 1999, 2001; Santos et al. 54
rosaqf@eq.uc.pt
2003; Álvarez et al. 2005; Sigge et al. 2007). 55
Note. This manuscript was submitted on May 12, 2011; approved on
December 19, 2011; published online on December 23, 2011. Discussion According to Instituto Nacional de Estatística (INE) in 2008, 56
period open until June 1, 2013; separate discussions must be submitted for 2 × 106 L of liqueurs were produced in Portugal, anise, milk, 7 57
individual papers. This paper is part of the Journal of Environmental En- and coffee being the most popular ones. In this context, the high 58
gineering, Vol. 139, No. 1, January 1, 2013. © ASCE, ISSN 0733-9372/ amount of liquid effluents discharged by this industry constitutes an 59
2013/1-0-0/$25.00. important ecological threat being thus necessary to study treatment 60

JOURNAL OF ENVIRONMENTAL ENGINEERING © ASCE / JANUARY 2013 / 1

 61 approaches able to at least improve their biodegradability before biodegradability and inhibitory effect over activated sludge through 119
62 their release into the sewage. Among the advanced oxidation Eqs. (1) and (2), respectively. 120
63 processes (AOPs), those based on ozone (ozonation) and hydrogen  
64 peroxide (Fenton’s process) operating at room conditions of OURAcetic Acid I − OURSample
%Biodegradability ¼ × 100 ð1Þ
65 pressure and temperature are of special industrial interest. In this OURAcetic Acid I
66 ambit, the main objective of this research carried out in straight

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67 cooperation with the authors’ spin-off company ADVENTECH,  
68 which is devoted to effluents depuration, is the treatment of a liquor OURAcetic Acid I − OURAcetic Acid II
%Toxicity ¼ × 100 ð2Þ
69 industry wastewater by optimizing and integrating flocculation/ OURAcetic Acid I
70 coagulation with Fenton’s and ozonation processes.
Ecotoxicity was determined by luminescence in a LUMIStox 121
(Dr. Lange, Berlin) based on the ISO DIS 11348 method, which 122

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71 Experimental leads to the effluents dilution to be able to restrain light production 123
of 20% and 50% of the Vibrio fischeri population (EC20 and EC50 , 124
72 Wastewater Treatment Procedures respectively). 125
The samples were run at least in duplicate and the maximum 126
73 8 Flocculation deviations between analyses were 8% (COD), 2% (TOC), 20% 127

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74 The flocculation procedure applied was the one proposed by (BOD5 ), 9% (TPh), 5% (TSS), 10% (VSS), 8% (respirometry), 128
75 Eckenfelder (1989) and already described previously (Martins et al. and 2% (luminescence). 129
76 2009). Basically, the flocculant (0.1 mg) was added to 200 cm3 of
77 9 effluent in a 500 cm3 reactor stirred by baffle paddles at 300 rev- Effluents’ Characterization 130
78 olutions per minute (rpm) during 5 min; after this time, the rotation
79 speed was decreased during 25 min to permit the formation of the The raw wastewater was collected from a distillery located in 131

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80 flocks. The anionic flocculant used (923PWG, Polyacrilamide) was Portugal that produces different kinds of liqueurs, namely coffee, 132
81 provided by AMBIENTAGUA, S.A. (Portugal). anise, and milk. The stream presented an opaque white color with 133
many particles in suspension. A strong alcohol and milk smell was 134
82 Fenton’s Process detected; Table 1 summarizes its main physicochemical character- 135
83 Fenton’s process was carried out in a magnetically stirred glass re- istics. As seen by COD and TOC loads, the effluent has a high 136
84 actor (500 cm3 ). A volume of 200 cm3 of effluent and the ferrous organic matter, above the values described in specialized literature 137
85 sulphate (Fisher Scientific, United Kingdom, 99%) were first intro- dealing with this type of wastewater (Beltran de Heredia et al. 138
86 duced, and the reaction started when hydrogen peroxide (industrial, 2005). Also a high BOD5 was measured (8; 745 mgO2 =L), which 139
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87 50%) was slowly added. Samples were withdrawn at predetermined leads to a BOD5 =COD ratio of 0.44, which is within the threshold 140
88 times and immediately alkalinized (NaOH, 3 M, Panreac, Spain, to be considered as biodegradable (Esplugas et al. 2004). In addi- 141
89 98%) in order to promote iron precipitation as FeðOHÞ3 and to tion, 27% of instantaneous biodegradability was determined by 142
90 eliminate the remaining hydrogen peroxide. respirometry. Nevertheless, the aerobic digestion of such stream 143
can be compromised by the presence of toxic organic matter such 144
91 Ozonation
as phenolic compounds (TPh ¼ 90 mg=L); in fact, it was verified
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145
92 The ozonation process was carried out in a semibatch stirred reactor
respirometrically that the contact with the effluent inhibited bacte- 146
93 (500 cm3 ). The effluent was introduced at the beginning of the
ria to process acetic acid (corresponding to almost 100% of inhib- 147
94 experiment, whereas ozone (produced in a BMT 802N ozone
ition). Moreover, the seasonal character of this wastewater, with 148
95 generator, BMT, Berlin) was continuously supplied by a gaseous
composition changing along the year, would require the activated 149
96 stream (500 cm3 = min with an ozone concentration of 40 g=m3 ,
sludge to permanently adapt, which reduces aerobic treatment 150
97 measured in a BMT 963vent ozone analyzer, BMT, Berlin) bubbled
efficiency. These facts reinforce the necessity of implementing a 151
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98 in the liquid bulk throughout a gas diffuser.

chemical oxidation process. 152
99 Analytical Techniques Furthermore, a high amount of solids (2,200 and 800 mg=L in 153
100 Measurements of pH were carried out with a Crison micropH 2002 TSS and VSS, respectively) was identified as proving the necessity 154
101 (Barcelona, Spain). COD, biochemical oxygen demand (BOD), of a preliminary flocculation system as a pretreatment stage. 155
102 total suspended solids (TSS), and volatile suspended solids
(VSS) were determined by the methods stipulated in the Standard
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103
104 Methods 5220D (Greenberg et al. 1985). Total phenolic content Table 1. Raw Effluent Characteristics
105 (TPh) was obtained by the Folin-Ciocalteau method referred to Parameter Value T1:1
106 elsewhere (Silva et al. 2007). Respirometry was performed using
107 a WTW InoLab 740 sensor equipped with a stirrOX (WTW, COD (mgO2 =L) 19,833  160 T1:2
TOC (mgO2 =L) 9,320  20 T1:3
108 Weilleim, Germany) to monitor the dissolved oxygen along the
BOD5 (mgO2 =L) 8,745  1,750 T1:4
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109 time of activated sludge coming from a winery wastewater treat- TPh (mg=L) 90  18 T1:5
110 ment plant (3;000–4;000 mg=L of volatile suspend solids) to TSS (mg=L) 2,200  110 T1:6
111 determine the oxygen uptake rate (OUR) in four situations: absence VSS (mg=L) 800  80 T1:7
112 of nutrients (OURendogeneous ); when in the presence of acetic acid BOD5 =COD 0.44 T1:8
113 (Riedel-deHaën, Germany, 99.8%), which is a biodegradable Biodegradability (%) 27  8 T1:9
114 compound used as reference (OURacetic acid I ); after feeding the Toxicity (%) 100  8 T1:10
115 pollutants sample (OURsample ); and finally, when acetic acid is EC20 (%) 1.5  2 T1:11
116 introduced a second time subsequent to microorganisms being EC50 (%) 4.5  2 T1:12
117 in contact with the potentially toxic substances (OURacetic acid II ). pH 3.0 T1:13
Temperature (°C) 25 T1:14
118 This procedure allows inferring about the effluents ready

2 / JOURNAL OF ENVIRONMENTAL ENGINEERING © ASCE / JANUARY 2013

156 Results and Discussion Fenton’s Process 195

157 This section first addresses the results regarding flocculation, There are several operational parameters governing the effective- 196
158 the Fenton process, and ozonation. Aiming to optimize these ness of Fenton’s process, namely, pH, iron salt type and con- 197
159 technologies, the effect of the main operational parameters was centration, besides hydrogen peroxide load. It is commonly 198
160 checked. Finally, the different treatment integration schemes are accepted in literature (Peres et al. 2004) that this system works 199
more efficiently at pH values within the range 3–4. In fact, for more 200

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161 discussed.
acidic conditions, an inhibition on the formation of iron (III) 201
peroxocomplexes occurs, reducing the ability for catalyst regener- 202
162 Flocculation Process ation (Neyens and Baeyens 2003). Besides, for higher pH, hydro- 203
gen peroxide decomposition into useless water and oxygen is 204
163 Flocculation promotes the aggregation of colloidal particles in enhanced without significant generation of hydroxyl radicals 205
164 suspension by the addition of chemical agents. This phenomenon

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(Gogate and Pandit 2004). In this context, pH was maintained at 206
165 can be explained by several mechanisms such as neutralization of the effluents raw value (3), being thus analyzed on the effect of hy- 207
166 surface electrical charges of formation of bridges, which allows drogen peroxide concentration and the ½H2 O2
=½Fe2þ
molar ratio. 208
167 the flocks growth (Eckenfelder 1989). The pH highly affects the The influence of temperature was not studied because, aiming 209
168 particles surface charge, being, this way, a key parameter regard- an integration methodology, it will be important to run off the pro- 210
169 10 ing this process (Sarika et al. 2005). In this respect, the effect of cess under ambient operation, because otherwise the costs associ- 211

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170 this variable was studied in a wide range (pH ¼ 2–9) and ated with an increase in temperature could jeopardize the in situ 212
171 0.5 mg=L of 923PWG were used. This concentration corresponds installation. In fact, even though temperature has some effect on 213
172 to four times the optimal value found in a previous research the degradation efficiency, the main advantage of this technology, 214
173 concerning the depuration of winery wastewater (Martins et al. when compared with other AOPs requiring the reactor heating up, 215
174 2009). is that it can occur at room conditions. 216
175 According to the TSS removal data depicted in Fig. 1, an

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176 increase on TSS elimination when pH raises from 2 to 3 (from Effect of Hydrogen Peroxide Concentration 217
177 75% to 84%) can be observed; however, a decrease of the efficiency The effect of hydrogen peroxide load on the flocculated effluent 218
178 is detected for higher pH values with only 57%, 48%, and 61% of COD abatement was checked within a range from 0.25 to 1.5 M. 219
179 TSS depleted for pH ¼ 4, 7, and 9. In fact, pH is reported to be the In fact, Beltran de Heredia et al. (2005) indicate 0.5 M as the 220
180 most important factor influencing flocculation and the optimal optimum concentration for the Fenton’s peroxidation of a distillery 221
181 range depends on the characteristics of the flocculant and the effluent. Moreover, the stoichiometric [H2 O2 ] theoretically 222
182 specific effluent (Sarika et al. 2005). In this particular case, alkaline required to totally oxidize the wastewater is 1.2 M (Eckenfelder 223
183 conditions are unfavorable for solids separation. 1989), which is within the chosen interval. 224
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184 With these results, it seems interesting to operate at pH ¼ 3, Beltran de Heredia et al. (2005) studied a similar effluent and 225
185 which is also economically preferable because this is the effluent’s referred a best ½H2 O2
=½Fe2þ
molar ratio of 15 among the tested 226
186 raw pH, thus not requiring additional costs for pH adjustments. ones (5, 10, 15, 20, 50, and 100), so that this value was maintained 227
187 These conditions lead to an effluent with slightly the same organic in these experiments concerning the study of the effect of hydrogen 228
188 charge (19; 650 mgO2 =L), even if with a much lower content in peroxide concentration. Regarding the results shown in Fig. 2, it is 229
solids (350 and 50 mg=L in TSS and VSS, respectively). In fact,
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189 possible to conclude that an increase of hydrogen peroxide load 230

190 less than 2% of COD was removed by this process, which means promotes a higher removal of COD. In fact, while a ½H2 O2
¼ 231
191 that most organic matter is dissolved in the liquid and the solids 0.25 M led to barely 10% of COD drop off in 60 min of reaction, 232
192 contribution to the effluents’ global COD is negligible. The high the augment in the oxidant concentration to 1.5 M promoted 233
193 COD load reveals the necessity of implementing an oxidation approximately 50% depletion. It should be referred that the 234
194 treatment after flocculation. well-known radical scavenger capacity attributed to hydrogen 235
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Fig. 2. Effect of hydrogen peroxide concentration on COD abate- F2:1

F1:1 Fig. 1. Effect of pH in flocculation process with 923PWG (0.5 mg=L ment during Fenton’s peroxidation (pH ¼ 3; ½H2 O2
=½Fe2þ
¼ 15; F2:2
F1:2 of flocculant) ½H2 O2
¼ 0.25–15 M) F2:3

JOURNAL OF ENVIRONMENTAL ENGINEERING © ASCE / JANUARY 2013 / 3

236 peroxide reducing Fenton’s process efficiency (De Laat and Le
237 2006) was not detected within the range of [H2 O2 ] tested.
238 All the tests had a similar behavior, a strong initial COD removal
239 after an apparent stabilization with low reaction rates. It should be
240 referred that the oscillations detected in COD=COD0 during the
241 treatment are within the experimental error associated to COD

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242 determination (8%), which means that a plateau with no significant
243 COD abatement is attained after 10 min of reaction. This is the
244 typical profile of Fenton’s process (Guedes et al. 2003; Malik
245 and Saha 2003), a first phase with a very fast COD decay attributed
246 to the initial high amount of hydroxyl radicals produced by the
247 reaction between hydrogen peroxide and Fe2þ (Fe2þ stage) fol-

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248 lowed by a slower degradation due to the formation of Fe3þ , which
249 leads to the less reactive hydroperoxil radicals (Fe3þ stage).
250 Table 2 shows the BOD5 values after each Fenton’s test. Once
251 again, the augment in hydrogen peroxide concentration improved
252 BOD5 depletion in 25% for ½H2 O2
¼ 0.25 M when compared with

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253 almost 80% for ½H2 O2
¼ 1.5 M. Fig. 3. Effect of ½H2 O2
=½Fe2þ
on COD abatement during Fenton’s F3:1
254 Even though high efficiency is attributed to this chemical oxida- peroxidation (pH ¼ 3; ½H2 O2
¼ 0.5 M; ½H2 O2
=½Fe2þ
¼ 10–30) F3:2
255 tion process, the COD and BOD5 values are still far from the legal
256 thresholds required for a safe discharge throughout the natural water
257 courses (150 and 40 mgO2 =L, respectively). In this context, it is
time is a function of the by-products formed and their ability to be 291
258 important to infer about the applicability of a costless biological

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bioprocessed. Taking into account the complexity of the wastewater 292
259 posttreatment by analyzing the final BOD5 =COD ratio (Table 2).
and the wide range of possible intermediates that can be formed 293
260 The experiment involving 1.5 M of hydrogen peroxide had depending on the operating conditions applied, it is natural that 294
261 the best COD removal, and a higher BOD5 decrease, yet resulted this parameter does not follow the trends of COD abatement. It 295
262 in an effluent characterized by a low biodegradability (BOD5 = seems thus that low ½H2 O2
=½Fe2þ
molar ratios promote the partial 296
263 COD ¼ 0.22) even below the initial value (0.44), which makes oxidation of the parent compounds (removing COD), leading to 297
264 the effluent untreatable by biological processes (<0.4). Also with more biodegradable intermediates. 298
265 this high amount of [H2 O2 ], it was difficult to control the reactor’s In the analysis of this process, it is important to rely on the bio- 299
266 temperature because hydrogen peroxide decomposition catalyzed degradability achieved because a posterior biological treatment will 300
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267 by iron is an extremely exothermic reaction, which can compro- be required to refine the effluent until fulfilling the legal thresholds 301
268 mise the industrial implementation of Fenton’s process under those for discharge throughout the natural water courses. As Table 3 302
269 severe operational conditions. The remaining tests had smaller shows, higher iron content (lower ½H2 O2
=½Fe2þ
) promotes BOD5 = 303
270 COD degradation, but the biodegradability was maintained above COD values. In fact, while a BOD5 =COD ¼ 0.68 is attained for 304
271 0.4. Moreover, almost 30% of COD was degraded when ½H2 O2
¼ ½H2 O2
=½Fe2þ
¼ 10, a BOD5 =COD ¼ 0.37 is detected for 305
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272 0.5 M (compared with barely 10% for ½H2 O2
¼ 0.25 M). There- ½H2 O2
=½Fe2þ
¼ 30, which is even below the value determined 306
273 fore, this value was selected to proceed with the experiments. for the raw effluent (0.44). In this context, the use of a 307
½H2 O2
=½Fe2þ
proportion of 10 allows a high COD removal and 308
274 Effect of
H2 O2 =
Fe2  still leads to a BOD5 =COD ratio suitable for a subsequent 309
275 The effect of the ½H2 O2
=½Fe2þ
molar ratio was tested within biological treatment. 310
276 the range of 10–30, which encompasses the optimum value of
15 reported by Beltran de Heredia et al. (2005) for this kind of
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277 Effect of the Mode of Hydrogen Peroxide Addition 311

278 effluent. Hydrogen peroxide can act as a radical scavenger if present in 312
279 The results show (Fig. 3) that the COD removal is potentiated by excess. This way, a preceding work (Martins et al. 2010) revealed 313
280 diminishing ½H2 O2
=½Fe2þ
ðmol=molÞ, which means that the a slight improvement in the process efficiency when this reactant 314
281 increase of iron load promotes the depuration reaction. Regarding was gradually added to the reactor rather than totally introduced at 315
282 60 min of reaction, it can be clearly observed that a ratio of 10 led to the beginning of the reaction. The study of the best mode of 316
283 almost 45% of COD abatement, while a significant decrease in the hydrogen peroxide addition was then carried out using the previ- 317
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284 efficiency was detected when ½H2 O2
=½Fe2þ
ðmol=molÞ reaches 30 ously selected conditions: hydrogen peroxide concentration of 318
285 with only 15% of degradation. 0.5 mol=L and a ratio of ½H2 O2
=½Fe2þ
equal to 10. Fig. 4 shows 319
286 Table 3 reveals BOD5 as a function of ½H2 O2
=½Fe2þ
, and it is COD depletion trends in two situations: when H2 O2 was totally 320
287 possible to point out that BOD5 removal increases from 15% to added at the beginning of the experiment and when its global 321
288 41% for ½H2 O2
=½Fe2þ
¼ 10 and 30, respectively. This is the volume was divided in two aliquots injected at 0 min and 20 min. 322
289 reverse of what was found in COD abatement, which increased As it can be observed, COD removal rate decreases when H2 O2 is 323
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290 to lower ½H2 O2
=½Fe2þ
ratios. The effluents’ BOD5 profile along added in two separated samples rather than in only one addition. 324

Table 2. BOD5 Removal and BOD5 =COD Ratio after Fenton’s Process Table 3. BOD5 Removal and BOD5 =COD Ratio after Fenton’s Process
T2:1 [H2 O2 ] (M) BOD5 (mgO2 =L) BOD5 removal (%) BOD5 =COD ½H2 O2
=½Fe2þ
BOD5 (mgO2 =L) BOD5 removal (%) BOD5 =COD T3:1
T2:2 0.25 7,660 25 0.44 10 7,530 15 0.68 T3:2
T2:3 0.5 7,035 20 0.45 15 7,035 20 0.45 T3:3
T2:4 1.5 2,130 79 0.22 30 5,265 41 0.37 T3:4

4 / JOURNAL OF ENVIRONMENTAL ENGINEERING © ASCE / JANUARY 2013

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F4:1 Fig. 4. Effect of H2 O2 injection mode on COD abatement during Fig. 5. Effect of pH on single ozonation efficiency for the depuration of F5:1
F4:2 Fenton’s peroxidation (pH ¼ 3; ½H2 O2
¼ 0.5 M; ½H2 O2
=½Fe2þ
¼ 10) distilleries wastewater (40 gO3 =m3 ) F5:2

325 In fact, while 45% of COD is degraded in 60 min of Fenton’s Integration between Single Ozonation 365

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326 oxidation with hydrogen peroxide totally available on the begin- and Fenton’s Process 366
327 ning of the process, only 33% of COD are depurated for the same In this step, it was intended to study the effect of implementing 367
328 time when the H2 O2 quantity is divided in two. Also with regard integration schemes using single ozonation and Fenton’s process 368
329 to BOD5 =COD ratio, it seems favorable to perform only one to chemically depurate the flocculated distillery effluent. Fenton’s 369
330 addition of the oxidant because BOD5 =COD decays from 0.68 peroxidation was carried out using the operating conditions 370
331 (one addition) to 0.55 (two addition). previously selected (½H2 O2
¼ 0.5 M, ½H2 O2
=½Fe2þ
¼ 10, and 371
332 Actually, within the range of hydrogen peroxide concentrations pH ¼ 3). In regard to ozonation, ozone inlet concentration was kept 372
333 tested, the H2 O2 radical scavenger effect was still not detected. This at 40 g=m3 and both pH ¼ 3 and 10 were tested. For the sequences 373
334 means that, for a concentration of 0.5 mol=L, this reactant is not yet
F
involving Fenton’s process followed by ozone oxidation, iron 374
335 in excess and no improvement is gained by dividing its feed to the was not precipitated because this metal can act as catalyst in 375
336 reactor in small amounts as in previous work. The loss in efficiency ozonation. 376
337 is probably due to the lack of H2 O2 at the beginning of the reaction. Fig. 6 reveals the COD abatement trends during the several 377
integration strategies. As can be observed, the COD removed is 378
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338 Single Ozonation slightly the same (approximately 45%) whichever approach is 379
applied. Moreover, it is possible to conclude that Fenton’s process 380
339 At this stage, the flocculated effluent oxidation by single ozonation is much more effective in COD reducing than ozonation. In fact, 381
340 was tested at room temperature under the experimental conditions COD instantaneously drops whenever Fenton’s process starts. Even 382
341 previously described. though iron is present in the solution when ozonation is preceded 383
342 The pH is a key parameter in ozone chemistry; in fact, this by Fenton’s process, which could catalyze ozone decomposition 384
343 oxidant presents two possible reaction pathways depending on
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344 the medium pH value. If for acidic conditions, molecular ozone

345 selectively attacks pollutants comprising high electronic density
346 sites, for high pH values, the hydroxide anions promote its decom-
347 position into the highly reactive hydroxyl radicals, which, generally
348 speaking, improve the process efficiency (Pera-Titus et al. 2004).
349 The effect of this parameter was checked and the results regard-
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350 ing COD abatement are depicted in Fig. 5. Ozonation carried out at
351 the effluents’ raw pH (3) led to a small COD removal (≈10%). The
352 pH increasing to 10 did not improve ozonation efficiency; even a
353 slight decrease of COD degradation was detected. This may indi-
354 cate the existence of radical scavengers in the effluent (such as
carbonates and bicarbonates) that compete by the hydroxyl radi-
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355
356 cals, ending up with the chain oxidation reactions inhibiting thus
357 the effluents treatment.
358 Even though this low efficiency concerns the organic charge
359 abatement, a high increase on the effluent’s biodegradable character
360 was detected with BOD5 =COD ratios of 0.81 and 0.75 when ozo-
361 nation was carried out at pH ¼ 3 and 10, respectively. In fact,
Fig. 6. COD abatement during ozonation and Fenton’s processes in- F6:1
362 ozone is able to decompose complex organic molecules into small
tegration (ozonation: pH ¼ 3, 40 gO3 =m3 ; Fentons’ process: pH ¼ 3; F6:2
363 aldehydes or organic acids that, even if no further reactive with O3 ,
½H2 O2
¼ 0.5 M; ½H2 O2
=½Fe2þ
¼ 10) F6:3
364 are more amenable to biodegradation.

JOURNAL OF ENVIRONMENTAL ENGINEERING © ASCE / JANUARY 2013 / 5

385 into more reactive species such as hydroxyl radicals, this process by respirometry (≈100%), which leads to some quite good per- 405
386 shows an insignificant role in COD abatement. spectives for a subsequent efficient biological treatment; this 406
387 Because none of the treatments were able to fulfil the environ- was strengthened by the null toxicity over activated sludge attained 407
388 mental legislation for the direct discharge into the water bodies, it by respirometric analysis. 408
389 will be necessary to implement a subsequent biological treatment.
390 In fact, as Fig. 7(a) reveals, the maximum COD abatement attained

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391 was 45% for Fenton’s process or its integration with ozonation at Conclusions 409
392 pH ¼ 10. In this sense, Fig. 7(b) compares the final BOD5 =COD
393 ratios attained with the several approaches with the initial value The depuration of high-strength wastewater coming from a distill- 410
394 determined for the flocculated effluent before oxidation. As can ery was studied in this article. The high amount of solids present 411
395 be observed, even if ozonation is not suitable to remove organic justified the need of a flocculation step to pretreat the stream. The 412
396 matter, it is an important step if the aim is to promote an augment flocculant 923PWG led to a fast flock formation with up to 85% of 413

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397 in the wastewater biodegradability, especially when pH ¼ 3 is TSS depleted. At this stage, low COD (below 2%) was removed, 414
398 used. According to these results, a highly biodegradable stream which means that organic matter is essentially dissolved in the 415
399 is reached using Fenton’s peroxidation followed by ozonation at liquid. 416
400 pH ¼ 3 (BOD5 =COD ¼ 0.98). Hydrogen peroxide and the ½H2 O2
=½Fe2þ
ratio were revealed 417
401 Under those conditions, an effluent still containing a COD ¼ to be key parameters in Fenton’s peroxidation efficiency. The 418

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402 11; 170 mgO2 =L is achieved. However, the remaining organic increase in [H2 O2 ] improved COD abatement; nevertheless, for 419
403 matter is practically all biodegradable, as revealed by the high [H2 O2 ] higher than 0.5 M, the effluent’s biodegradability de- 420
404 BOD5 =COD ratio (0.98) and the biodegradability level attained creased, which can compromise a posterior biological process. 421
Additionally, at those high concentrations it was difficult to control 422
the reactor’s temperature. The decrease of ½H2 O2
=½Fe2þ
propor- 423
tion was favorable to both COD abatement and BOD5 =COD 424

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augment. 425
Ozonation led to low COD removal (below 10%); furthermore, 426
at alkaline conditions, a slight inhibition was detected, which may 427
indicate the presence of radical scavengers on the wastewater 428
composition. Even so, this process truly improves the flow 429
biodegradability. 430
In regard to the several integration strategies involving Fenton’s 431
process and ozonation, it was possible to conclude that ozone ox- 432
F
idation does not improve COD abatement, yet it is an essential step 433
concerning BOD5 =COD raise. Particularly, the scheme Fenton + 434
ozonation (pH ¼ 3) leads to a wastewater with characteristics 435
enabling a successful further activated sludge treatment. 436
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Acknowledgments 437

Rui C. Martins gratefully acknowledges the Fundação para a 438

Ciência e Tecnologia, Portugal, for the financial support under 439
the post-doctoral grant (SFRH/BPD/72200/2010). This work was 440
financially supported by FCT-MCTES under the contract PTDC/ 441
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EQU-ERQ/113308/2009. 442

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