Ultrasonics Sonochemistry 21 (2014) 1–14

Contents lists available at ScienceDirect

Ultrasonics Sonochemistry
journal homepage: www.elsevier.com/locate/ultson

Review

Wastewater treatment using hybrid treatment schemes based

on cavitation and Fenton chemistry: A review
Manisha V. Bagal, Parag R. Gogate ⇑
Chemical Engineering Department, Institute of Chemical Technology, Matunga, Mumbai 40019, India

a r t i c l e i n f o a b s t r a c t

Article history: Advanced oxidation processes such as cavitation and Fenton chemistry have shown considerable promise
Received 18 December 2012 for wastewater treatment applications due to the ease of operation and simple reactor design. In this
Received in revised form 13 July 2013 review, hybrid methods based on cavitation coupled with Fenton process for the treatment of wastewater
Accepted 16 July 2013
have been discussed. The basics of individual processes (Acoustic cavitation, Hydrodynamic cavitation,
Available online 25 July 2013
Fenton chemistry) have been discussed initially highlighting the need for combined processes. The differ-
ent types of reactors used for the combined processes have been discussed with some recommendations
Keywords:
for large scale operation. The effects of important operating parameters such as solution temperature, ini-
Acoustic cavitation
Hydrodynamic cavitation
tial pH, initial pollutant concentration and Fenton’s reagent dosage have been discussed with guidelines
Fenton chemistry for selection of optimum parameters. The optimization of power density is necessary for ultrasonic pro-
Advanced Fenton process cesses (US) and combined processes (US/Fenton) whereas the inlet pressure needs to be optimized in the
Hybrid treatment case of Hydrodynamic cavitation (HC) based processes. An overview of different pollutants degraded
under optimized conditions using HC/Fenton and US/Fenton process with comparison with individual
processes have been presented. It has been observed that the main mechanism for the synergy of the
combined process depends on the generation of additional hydroxyl radicals and its proper utilization
for the degradation of the pollutant, which is strongly dependent on the loading of hydrogen peroxide.
Overall, efficient wastewater treatment with high degree of energy efficiency can be achieved using com-
bined process operating under optimized conditions, as compared to the individual process.
Ó 2013 Elsevier B.V. All rights reserved.

1. Introduction and also used as pretreatment to convert pollutants into shorter-

chain compounds that can be treated by conventional or biological
Many industrial processes, and agricultural and domestic activ- methods [1,3,4]. Cavitation, Fenton chemistry and photocatalytic
ities leads to wastewater streams containing recalcitrant organic oxidation are such AOP’s which are based on the generation of
pollutants which need to be disposed off in a proper manner. Also highly reactive hydroxyl radicals having high oxidation potential
the concentration of chemicals in the effluent stream should be as compared to the conventional oxidants like hydrogen peroxide
kept at a certain minimum level in order to comply with the envi- and KMnO4 [1].
ronmental laws, which are becoming more stringent these days The complex and biorefractory organic compounds can be effec-
[1]. The research field of water purification and wastewater treat- tively degraded using cavitation which can be generated either by
ment has been extensively growing in the last decades due to the ultrasonic irradiation or using constrictions such as orifice or ven-
stringent water quality control and regulations against hazardous turi in hydraulic devices [5–9]. Violent collapse of the cavities in
pollutants [2]. The conventional biological methods cannot be used the cavitating systems results in the formation of reactive
for complete treatment of the biorefractory wastewater streams hydrogen atoms and hydroxyl radicals as well as gives rise to ther-
due to high toxicity and carcinogenicity of the pollutants. Newer mal hot spots, which can yield pyrolytic cleavage of chemicals [1].
technologies need to be developed to degrade biorefractory Fenton process is another advanced oxidation process which
molecules into smaller molecules, which can be further oxidized can be effectively used in the destruction of hazardous organic pol-
by biological methods. lutants in water via generation of hydroxyl radicals by catalytic
Advanced oxidation processes (AOPs) have been applied suc- decomposition of hydrogen peroxide using ferrous ion as the cata-
cessfully for the removal or degradation of recalcitrant pollutants, lyst. The advantage of the Fenton method is mineralization of the
organic substances as compared to separation and concentration
of toxic chemicals by physical and mechanical methods such as
⇑ Corresponding author. Tel.: +91 22 3361 2024; fax: +91 22 3361 1020. flocculation, precipitation, adsorption on activated carbon, filtra-
E-mail address: [email protected] (P.R. Gogate). tion etc., which generate secondary pollution [10].

1350-4177/$ - see front matter Ó 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.ultsonch.2013.07.009
2 M.V. Bagal, P.R. Gogate / Ultrasonics Sonochemistry 21 (2014) 1–14

A combination of different AOPs has been found to be more effi- magnitude of the pressure drop and the rate of pressure recovery,
cient for wastewater treatment as compared to individual oxida- has a profound effect on cavitation intensity. Thus the desired
tion process due to the high degree of energy efficiency and intensity of turbulence, in turn the intensity of cavitation can be
generation of higher quantum of free radicals. Various combination achieved using suitable geometry of the constriction and the flow
techniques have been investigated and reported in the literature conditions of the liquid [23,24]. A dimensionless number known
for the wastewater treatment [11–15]. The similarity between as the cavitation number (Cv) has generally been used to relate
the mechanisms of destruction of organic pollutant, common opti- the flow conditions with the cavitation intensity:
mum operating conditions and elimination of some of the draw-
backs of the individual techniques points towards the efficacy of
P2  Pm
Cm ¼ 1
the combined process for the degradation of recalcitrant organic 2
qm2th
pollutants [1]. Also use of intensifying additives and/or catalyst
Where P2 is the fully recovered downstream pressure, Pm is the va-
in combination with cavitation results in significant enhancement
pour pressure of the liquid and vth is the velocity of the liquid at the
in the degradation efficiency, making it suitable technology for the
constriction. Ideally cavitation inception occurs at Cvi lower than
degradation of the pollutants [16].
one where Cvi is the cavitation inception number [25]. The cavita-
Combination of Fenton with acoustic cavitation (Sono-Fenton or
tion inception number (Cvi) is a function of the flow geometry
US/Fenton) and hydrodynamic cavitation (HC/Fenton) can be ap-
and usually increases with an increase in the size of the constriction
plied to increase the mineralization efficiency of the organic com-
or the size of the pipe at comparable fluid velocities [25]. The cav-
pounds. This article also presents an overview of recent work on
itation number in the range of 0.1–1 (which can be obtained by
removal of different kinds of toxic pollutants from wastewater,
adjusting the flow conditions and the geometry) gives maximum
including aromatic compounds, dyes, pharmaceutical compounds
benefits from the reactor as very low operating cavitation numbers
and pesticides using combination of cavitation (acoustic and/or
can lead to super-cavitation resulting in vapor cloud formation and
Hydrodynamic) and Fenton process, giving the details of various
no cavitational collapse [25]. Reactions requiring moderately rigor-
operating parameters and removal effectiveness of the pollutants.
ous conditions can be carried out easily under ambient conditions
using simple and low maintenance reactor used for generating cav-
2. Acoustic cavitation itation with relatively easy scale up prospects [19]. The hydrody-
namic cavitation phenomenon provides substantially lower
Ultrasound-based chemical and physical transformations are intensity of collapse of the individual cavities in terms of tempera-
becoming popular for research investigations because of the wide ture and pressure pulse generated than the acoustic cavitation [26].
range of applications in various fields such as chemical synthesis, The efficiency can be compared on the basis of cavitational yield
wastewater treatment, biotechnology, polymer engineering, micro- which is defined as the ratio of the cavitational effect (moles of pol-
mixing, homogenization, emulsification, crystallization, extraction, lutant degraded) to the total energy input to the system.
filtration, etc. [17–19]. Sonochemical reactors of different types and
scales have been widely used for laboratory/ pilot-scale investiga-
4. Fenton process
tions, though successful industrial-scale exploitation is still lacking
[20]. The physical effects of ultrasound are due to acoustic stream-
The Fenton process is also widely used for the treatment of both
ing which is generated due to the pressure field and continuous
organic and inorganic substances under laboratory conditions
generation and collapse of the cavities in the system [19]. The
using synthetic effluents as well as real effluents from different
generation of highly reactive free radicals due to implosion of
sources like chemical, refinery and fuel terminals, engine and me-
microbubbles leads to a series of different reactions resulting in
tal cleaning etc. [1,27]. Fenton Process is based on the production
chemical effects of ultrasound [20,21]. The reaction mechanism
of highly reactive hydroxyl radicals (OH) under acidic conditions
for the splitting of water molecules in the presence of dissolved
as a result of the reaction between hydrogen peroxide (H2O2)
oxygen in presence of ultrasonic irradiation have been presented
and ferrous ions (Fe2+) which is also called as Fenton’s reagent
by Pang et al. [21]. The effectiveness and the actual site of degrada-
[28]. The oxidation system based on the Fenton’s reagent can be
tion strongly depend on the nature of the pollutant under question
employed to treat a variety of industrial wastes containing a range
(hydrophobic or hydrophilic). Cavitation also gives additional
of organic compounds like phenols, formaldehyde, pesticides,
mechanism for the degradation of pollutants in terms of pyrolysis.
wood preservatives, plastic additives, and rubber chemicals [2].
The pyrolysis mainly takes place inside the cavity but some effects
The wastewater treatment using Fenton process results in reduc-
can also be observed near the interface of cavity due to the very
tion of toxicity, improvement in biodegradability, odour and colour
high temperature and pressure reached during cavitation [22].
removal. The reaction mechanism for the Fenton process has been
reported in the literature [2].
3. Hydrodynamic cavitation Operating pH, ferrous ion concentration, hydrogen peroxide
loading, initial concentration of pollutants, operating temperature
Hydrodynamic cavitation can simply be generated by the pas- are some of the operating parameters that need to be optimized
sage of the liquid through a constriction such as an orifice, valve to maximize the effectiveness of Fenton reaction. The pH of the
or venturi. When the liquid passes through the constriction the solution plays an important role in Fenton process as the form of
velocity of the liquid increases at the expense of the local pressure. iron species and their catalytic activities are affected by solution
If the pressure around the point of vena contracta falls below the pH [29]. An optimum pH range in the homogeneous Fenton reac-
threshold pressure for cavitation (usually vapor pressure of the tion is 2–4, and the process needs a strict pH control, whereas
medium at the operating temperature) due to sufficient throttling, the heterogeneous Fenton process possesses a wider applicable
cavities are generated. At the downstream of the constriction, as pH range [30]. The optimum catalyst (Ferrous salt) to peroxide ra-
the liquid jet expands, the pressure recovers and this results in tio is usually 1:5 wt/wt [1]. An enormous increase in the ferrous
the collapse of the cavities [23,24]. Due to the passage of the liquid ions will lead to an increase in the unutilized quantity of iron salts,
through the constriction, boundary layer separation occurs and a which will contribute to an increase in the TDS content of the efflu-
substantial amount of energy is lost in the form of a permanent ent stream which is not permitted [1]. The large quantities of
pressure drop. The intensity of turbulence, which depends on the hydrogen peroxide act as a scavenger for the generated hydroxyl
 M.V. Bagal, P.R. Gogate / Ultrasonics Sonochemistry 21 (2014) 1–14 3

radicals and also the residual hydrogen peroxide contributes to case of advanced Fenton process, solid particles provide additional
COD and hence excess amount is not recommended. Thus, labora- nuclei for the cavitation phenomena and hence the number of cav-
tory scale studies are required to establish the optimum loading of itation events occurring in the reactor is enhanced resulting in a
ferrous ions and hydrogen peroxide under similar operating condi- subsequent enhancement in the cavitational activity and hence
tions. Usually lower initial concentration of the pollutant is favored the overall extents of degradation [19].
for enhanced degradation of pollutant [1]. Heterogeneous Fenton Homogeneous Fenton systems have been widely studied for
Processes which use solid zero valent iron metal instead of ferrous wastewater treatment. However, the homogeneous Fenton process
salts as in the case of conventional Fenton process have received has major disadvantages such as removal of the sludge contami-
much attention in recent years as it avoids the formation of sludge nated with Fe ions after the treatment, and requirement of acidic
and thus overcomes the disadvantages of Fenton process. The solid pH preferentially between 2.5 and 3.5. A further significant draw-
iron-containing catalysts are first transferred into Fe2+ and Fe3+ back of the use of soluble iron salts is the complexation of the iron
ions in the presence of H2O2 or O2, which then generate oxidizing ions by compounds present in real feeds such as EDTA or possible
species via the conventional Fenton chemistry route [30]. reaction products such as oxalic acid which results in the reduction
of the concentration of free iron ions in solution and also promotion
of an unwanted side reaction, viz. the decomposition of H2O2 to
5. Limitations of individual operations
water and oxygen [10]. The use of solid catalysts in principle elimi-
nates or reduces these drawbacks of homogeneous Fenton process.
Industrial scale operation using acoustic cavitation is difficult
In the case of ultrasound coupled with Fe2+/H2O2, hydrogen per-
due to uneven distribution of cavitating events, its higher cost of
oxide reacts with ferrous ions to generate active hydroxyl radicals,
treatment and problems associated with efficient operation at
which improves the degradation rate of organic pollutant [21]. The
the levels of power dissipation required for large scale treatment,
resulting Fe3+ can react with H2O2 to generate an intermediate
though it is highly successful on laboratory scale operation [31].
complex (Fe–O2H2+) which further dissociates into Fe2+ and HO2
Hydrodynamic cavitation provides substantially lower intensity
under ultrasonic irradiation (symbol used in equation 3, 8 and
of collapse of the individual cavities in terms of temperature and
11). The isolated Fe2+ further reacts with H2O2 to produce OH
pressure than acoustic cavitation [26]. Thus the rates of minerali-
and the cycle continues [21,32]. The reaction mechanism leading
zation can be significantly lower in the case of hydrodynamic cav-
to enhanced OH radical generation from the recovered Fe2+ due
itation. Also poor pressure recovery downstream of the
to the simultaneous action of ultrasound and Fenton chemistry
constriction is also another shortcoming of this process. The appli-
can be given as follows [21]:
cability of hydrodynamic cavitation or in general the cavitational
reactors to actual effluent streams is hardly explored and all the Fe2þ þ H2 O2 ! Fe3þ þ HO þ HO ð1Þ
studies are mostly with the simulated single pollutant solutions,
the results of which may not be applicable for a complex effluent H2 O2 þ Fe3þ ! FeðOOHÞ2þ þ Hþ ð2Þ
stream with large COD values.
Fenton processes are effective in the range of pH 2–4. Hence the
FeðOOHÞ2þ þÞÞÞ ! Fe2þ þ HOO ð3Þ
required acidification of the effluent stream, relatively high cost of
hydrogen peroxide, additional treatment stage for the removal of
the generated iron sludge, risk related to the storage and transpor- Fe3þ þ HOO ! Fe2þ þ Hþ þ O2 ð4Þ
tation of hydrogen peroxide and requirement of neutralization of
the treated solution before disposal are some of the disadvantages Fe2þ þ H2 O2 ! Fe3þ þ HO þ HO ð5Þ
of Fenton process [29]. Fenton chemistry is not a universal solution Advanced Fenton reaction refers to the combination of zero va-
as there are many chemicals refractory towards Fenton’s reagent lent iron (Fe0) and H2O2. In heterogeneous Sono-Fenton process,
such as acetic acid, carbon tetrachloride, methylene chloride etc. De- acoustic cavitation can enhance the mass transfer, dispersion,
gree of oxidation is limited as the oxidant dose cannot be increased and disaggregation of catalyst particles, and increase the surface
beyond a certain limit and hence the applicability of only Fenton defects or active sites on the catalyst surface [33]. The reaction
process to real industrial effluent is still an unanswered question [1]. mechanism due to the simultaneous action of ultrasound and ad-
Overall it can be said that none of the methods operating individ- vanced Fenton chemistry can be given as follows [19,11]
ually are beneficial for the effective destruction of the complex
industrial streams. The combination of these processes may be used Fe0 þ 2Hþ ! Fe2þ þ H2 ð6Þ
to overcome the disadvantages of the individual technique. We now
discuss the different aspects related to the combined process of cav- Fe2þ þ H2 O2 ! Fe3þ þ HO þ HO ð7Þ
itation (Hydrodynamic and acoustic) and Fenton’s reagent with
emphasis on enhancement and proper utilization of the generated H2 O2 þÞÞÞ ! 2HO ð8Þ
hydroxyl radicals under optimized operating conditions.
H2 O2 þ HO ! H2 O þ HO2 ð9Þ
6. Cavitation coupled with Fenton process
Fe3þ þ H2 O2 ! FeðOOHÞ2þ þ Hþ ð10Þ
6.1. Sono-Fenton process
FeðOOHÞ2þ þÞÞÞ ! Fe2þ þ HO2 ð11Þ
Ultrasound coupled with Fenton’s reagent utilizes the advanta-
ges of these two methods to generate more OH radicals and can Fe0 þ 2Fe3þ ! 3Fe2þ ð12Þ
effectively improve the degradation rate of organic pollutants. Also
cavitation gives additional mechanism in terms of pyrolysis in the
Fe3þ þ HO2 ! Fe2þ þ Hþ þ O2 ð13Þ
system, which can help in removing some of the chemicals which
are refractory to hydroxyl radicals. Also, the mass transfer resis- It is hypothesized that initially iron metal is corroded in the
tances associated with the Fenton based processes could be elimi- presence of H2O2 under acidic conditions oxidizing Fe0 to Fe2+,
nated due to the turbulent conditions present in the reactor. In the which then further reacts with H2O2 in a Fenton-like process to
4 M.V. Bagal, P.R. Gogate / Ultrasonics Sonochemistry 21 (2014) 1–14

generate hydroxyl radicals and Fe3+ which further reduces back to Fe(0) loading as 1 g/L, H2O2 loading as 5.15  103 mol/L with
Fe2+ and the cycle continues [34]. In advanced Fenton process ultrasound density of 120 W/L at 60 kHz, 99% decoloration of
(AFP), the propagation of US waves into the media results in two 4.7  105 M DB15 (4130 ADMI) solution was obtained within
effects viz. enhanced dispersion of iron particles in the media 10 min. DB15 decoloration followed first-order decoloration
and enhanced reproduction of Fe (II) in the media. The additional kinetics [42].
advantage of using AFP would be that AFP utilizes zero valent iron To overcome the disadvantages of the homogeneous Fenton
pieces as the catalyst, which considerably reduces the cost of the process for the degradation of BPA in wastewater, Huang et al.
treatment as it is likely that waste iron particles or sheets can be [43] have studied the degradation of Bisphenol-A using reusable
used for the treatment of pollutants [35]. Fe3O4 magnetic nano particles (MNPs) as a heterogeneous Sono-
Table 1 depicts some of the applications of cavitation (Acoustic Fenton catalyst and reported about 95% degradation of BPA. The
and Hydrodynamic) combined with Fenton process for the waste- removal efficiencies of BPA were over 95% and about half total or-
water treatment illustrating the type of pollutant, equipment used, ganic carbon (TOC) in solution was eliminated under neutral con-
optimum operating parameters and the important findings of the dition by Sono-Fenton process. Also the Fe3O4 MNPs gave similar
work. activity over a wide pH range from 3 to 9 and showed good sta-
bility and activity even after five recycles. The rate of degradation
6.2. Overview of the earlier work using Sono-Fenton process for could be further enhanced by modifying or doping of Fe3O4 MNPs
wastewater treatment [43].
Overall it can be said that the addition of Fe2+ can help revert
Ranjit et al. [36] have reported a reduction in the required Fe2+ the loss of oxidation potential of radicals due to recombination of
concentration (50%) and H2O2 concentration (31%) for the Sono- reactive hydroxyl radicals to form less reactive hydrogen peroxide
Fenton method as compared to conventional Fenton process and by regeneration of the radicals with simultaneous oxidation of Fe2+
also established that this method could be applicable even at pH to Fe3+ which in turn enhance the oxidation of pollutant by effec-
5.0 instead of pH 2.5 required for conventional Fenton Process. tive utilization of these hydroxyl radicals. Also the combination
Kinetic studies for the degradation of DCP proved that the degrada- with ultrasound results in reduction in the requirement of the oxi-
tion of DCP tends to follow pseudo first order reaction and the rate dant dosage leading to cost benefits as well as reducing the dis-
constant was found to be 7  104 min1. Ma et al. [37] have stud- posal problems.
ied carbofuran decomposition by ultrasound alone and combina-
tion of ultrasound and Fenton process with initial carbofuran 6.3. Hydrodynamic cavitation coupled with Fenton oxidation
concentration of 20 mg/L at 25 °C and pH 3. It has been reported
that more than 40% of carbofuran was oxidized by ultrasonic pro- Similar to Sono-Fenton process, combination of hydrodynamic
cess in 120 min with less than 15% reduction in TOC, whereas in cavitation and Fenton chemistry can result in enhanced degrada-
the combined ultrasonic process and Fenton reagent, the tion efficiency due to the generation of higher quantum of free rad-
degradation of carbofuran was increased to more than 99% with icals in the presence of Fe2+ ions.
40% mineralization within 30 min. Liang et al. [32] have reported
complete degradation of 2-chlorophenol by combination of ultra- 6.4. Overview of the earlier work using Hydrodynamic cavitation/
sound generated cavitation and Fenton chemistry at pH 3. Song Fenton process for wastewater treatment
et al. [38] have reported that the degradation of Acid Red 88 in-
creased with an increase in the loading of Fe+2 from 0.036 to Hydrodynamic cavitation can be generated by using constric-
0.108 mM at constant H2O2 loading of 1.96 mmol/l. Ioan et al. tion such as orifice, venturi or throttling valve in the liquid flow.
[12] have reported an increase in the degradation rate of BPA with The wastewater treatment studies related to the combination ap-
increasing initial Fe (II) concentration and decreasing initial pH and proach are mainly based on the use of orifice or venturi as a cavi-
also faster rate of degradation for the Sono-Fenton as compared to tating device. Pradhan and Gogate [44] have investigated the
Fenton process. efficacy of combination of hydrodynamic cavitation and Fenton
Li and Song [39] have reported that the combination of ultra- chemistry for the removal of p-nitrophenol for different loading ra-
sound irradiation and Fenton is a more efficient method for degra- tio of FeSO4:H2O2 with venturi as the cavitating device whereas Pa-
dation of AR 97 aqueous solution and the degradation rate constant til and Gogate [45] have investigated the degradation of Methyl
was found to be 4.9  102 min1 (with 0.054 mmol L1 Fe2+ and Parathion with orifice plate as cavitating device. Overview of the
1.57 mmol L1 H2O2) for the combined approach, whereas the earlier work using Hydrodynamic cavitation/Fenton process for
degradation rate constants were only 5.4  104 min1 and wastewater treatment has been presented in details in Table 2
3.1  102 min1 for sonication and Fenton oxidation respectively. [44–49].
Lan et al. [40] have studied the degradation of naproxen (NPX) Joshi and Gogate [46] have reported maximum degradation of
by the combination of Fenton’s reagent and ultrasound (US) at pH dichlorvos as 91.5% at loading of FeSO4:H2O2 as 3:1 with orifice
of 3 and ultrasonic power amplitude of 90%. A degradation effi- as cavitating device in the combined process of Fenton’s reagent
ciency of 100% was achieved within 10 min in Sono-Fenton process and hydrodynamic cavitation, which was significantly higher as
using hydrogen peroxide concentration of 9.98 mmol L1 and fer- compared to that obtained using hydrodynamic cavitation alone.
rous ion concentration of 4.83 mg L1 for NPX initial concentration Patil and Gogate [45] have investigated degradation of methyl
of 20 mg L1. parathion using hydrodynamic cavitation coupled with Fenton
Wu et al. [41] have investigated the decolorization of Reactive oxidation process using orifice as cavitating device at fixed load-
Red 2 using Sono-Fenton process and reported that the higher oxi- ing of H2O2 as 100 mg/L with varying concentration of FeSO4 over
dant and iron concentrations resulted in faster decolorization in the H2O2:FeSO4 ratio as 1:0.5 to 1:4 and reported that as the ra-
Fenton and Fenton-like systems and accelerated decolorization tio of H2O2:FeSO4 increases, the extent of degradation also in-
was obtained in presence of ultrasound (US). Weng et al. [42] creases. Mishra and Gogate [47] have investigated efficacy of
investigated the decolorization of direct azo dye, direct blue 15 combination of hydrodynamic cavitation and Fenton chemistry
(DB15), by an advanced Fenton process using Zero-valent iron for degradation of Rhodamine B using FeSO4:H2O2 for 10 ppm ini-
(ZVI) aggregates as the catalyst, coupled with ultrasonic irradiation tial concentration of the Rhodamine B at pH of 2.5 using venturi
(Fenton/US) and reported that at optimum conditions of pH 3.0, as the cavitating device and reported that near-complete
 M.V. Bagal, P.R. Gogate / Ultrasonics Sonochemistry 21 (2014) 1–14 5

Table 1
Overview of the earlier work using combined Acoustic cavitation/Fenton process for wastewater treatment.

Compound Equipment Details Optimum operating conditions Important results Ref.

Dichlorvos Ultrasonic probe Frequency: pH = 3; Temperature = 25 °C [H2O2]=15 mg/ Sono-Fenton Process results in complete [59]
20 kHz, Power 270 W L optimum FeSO4/H2O2 ratio 3:1 removal of the pesticide Diclorvos.
Alachlor Ultrasonic horn: Frequency: 20 kHz US/Fenton Process pH = 3; Alachlor initial (1) US/Fenton: 100%; Only Fenton:82% [35]
Power:100 W Treatment concentration = 20 ppm; (2)US/advanced Fenton: 100%
Volume = 100 ml Temperature = 28 °C US + 0.07 g/l Only advanced Fenton:70%
FeSO4 + 0.07 g/l H2O2 FeSO4/H2O2 ratio 1:1.
US/Advanced Fenton pH = 3 US + 0.02 g/l
Fe + 0.07 g/l H2O2 Fe/H2O2 ratio 1:3.5
Reaction time: 60 min
Methyl Parathion (1)Ultrasonic horn: US/Fenton Process pH = 3; Methyl (1)Ultrasonic Horn US/Fenton: Degradation: [103]
Frequency:20 kHz; Power:270 W Parathion = 20 ppm H2O2 = 200 ppm FeSO4/ 98.5% TOC removal: 73.7%
Treatment Volume:100 ml H2O2 ratio 3:1. (2)Ultrasonic Bath: US/Fenton: Degradation:
(2)Ultrasonic bath Frequency: 20 Treatment volume = 3.2 L 96.5% TOC removal: 75%
kHzPower: 230 W
Textileazo dye CI Reactive Ultrasonic bath frequency:35 kHz Sono-Fenton process pH = 3, [Fe2+] = 25 mg/ Fenton Process: Color removal: 89.9% US/ [110]
Orange 127 Power = 80 W L and [H2O2] = 5 mg/L; for Fenton process, FentonColour removal:91.8%
pH = 3, [Fe2+] = 20 mg/L, [H2O2] = 15 mg/L Reaction time = 1 h
p-nitrophenol The ultrasonic bath equipped with US/Fenton: For 0.5% p-nitrophenol 1 g/ Treatment time = 90 min [34]
longitudinal transducer Frequency: LFeSO4 + 5 g/L H2O2 For 1% p-nitrophenol US/Fenton:
25 kHz 1 g/L FeSO4 + 7.5 g/L H2O2 US/advanced For 0.5% p-nitrophenol
Power: 1 kW Fenton: For 0.5% p-nitrophenol 1 g/L 57.6%
Fe + 5 g/L H2O2 For 1% p-nitrophenol 1 g/L For 1% p-nitrophenol
Fe + 7.5 g/L H2O2 52.2%
US/advanced Fenton: For 0.5% p-nitrophenol
66.4% For 1% p-nitrophenol 59.2%
Sodium Formate An ultrasonic homogenizer Sodium Formate: 250 ppm, pH = 3 The mineralization extent of approximately [113]
Frequency:20 kHz, power:200 W [Fe2+] = 1.25 mmol/L 81% obtained by classic Fenton process, after
Cylindrical batch reactor made from [H2O2/Fe2+] = 27.5 30 min of reaction, but after only 5 min by
borosilicate glass with the cooling Treatment Volume: 0.75 L applying the ultrasound (US/Fe2+/H2O2)
jacket
Carbofuran Sonicator equipped with sealed Concentration of carbofuran 20 mg/L pH = 3 More than 99% carbofuran degradation [91]
convertor and titanium probe tip. H2O2 = 100 mg/L Fe2+ = 20 mg/L, combined with 46% mineralization was
Frequency: 20 kHz achieved after 30 min reaction time.
Reactive Yellow 16 Sono reactor (DU-MINI-120), Dye Concentration = 50 mg/L Fenton: Removal of COD = 80% Color = 90% [114]
Frequency: 34 kHz; H2O2 = 900 mg/L FeSO4 = 1000 mg/L US/Fenton
Power:120 W Treatment volume = 500 ml Removal of COD = 82% Color = 95%
2,4-dichlorophenoxy acetic acid Ultrasonic horn frequency: 20 kHz Acoustic cavitation: Treatment TOC removal Efficiency: Acoustic cavitation [115]
Power: 45 W (calorimetric volume = 200 ml and advanced Fenton 60% Treatment
measurement); 2,4-D = 0.235 g/l, H2O2 = 1.7 ml, powdered time = 20 min
iron = 0.12 g pH = 3; Temperature = 20 °C
Reactive brilliant red K-BP Ultrasonic probe: Frequency:20 kHz Reactive brilliant red K-BP 10 mg/lit The degradation rate constants are found to [88]
Power:150 W Temperature = 25 °C pH = 3.0. be 6.01  103 min1 with 5 lmol/L Fe2+
and 20 mol/L H2O2 addition, but the
degradation rate constants are only
1.52  103 and 1.12  103 min1 with
sonication and Fenton reagent operated
alone
Azo dye Acid black 1 (AB1) Ultrasonic bath Frequency: 40 kHz. AB1 concentration = 0.081 mM, The degradation of AB1 by US only was not [14]
Power density: 50 W/L H2O2 = 8.0 mM, observed. A degradation of 98.83% was
Fe2+ = 0.025 mM, achieved by US/Fenton within 30 min under
pH = 3.0,Temperature = 20 °C optimum conditions
2,4,Dinitrophenol Ultrasonic horn Frequency: 20 kHz, 2,4,-dinitrophenol: 20 ppm, Reaction Increasing output intensity favors the [63]
Power 200 W, 400 W, 600 W, 800 W volume = 50 ml pH = 4 degradation of DNP. The degradation of DNP
in US, Fe2+/H2O2 and US/Fe2+/H2O2 systems
are 4%, 82%, 98% after 60 min of treatment
Methyl tert-butyl ether (MTBE) Ultrasonic Probe sonicator: The effects of Fe2+/H2O2 and the ultrasonic More than 95% degradation of MTBE along [61]
frequency: 20 kHz vibracell irradiation on the rate of MTBE degradation with its intermediate products has been
operated at 40% power amplitude were investigated at several differential achieved using the coupled ultrasound/Fe2+/
initial H2O2 concentrations (0,0.05, 0.5 and H2O2 method
1 M) with 1.13  101 mM MTBE
and1.08  103 mM Fe2+ ion loadings

degradation of Rhodamine B was obtained with TOC reduction of 7. Reactor designs

57%. Bremner et al. [48] have investigated hydrodynamic cavita-
tion induced by a liquid whistle reactor (LWR) in conjunction 7.1. Sonochemical reactors
with the advanced Fenton process (AFP) for the treatment of real
industrial wastewater and reported that higher pressures, Reactors used for generation of cavities using ultrasound are
sequential addition of hydrogen peroxide at higher loadings and known as Sonochemical reactors. Gogate and Pandit [1] have pre-
lower concentration of the effluent was favorable for a rapid sented schematic representations of different types of sonochemi-
TOC mineralization (about 60–80% removal of TOC under opti- cal reactors in the review article. There are different types of
mized conditions). sonochemical reactors such as Ultrasonic Horn, Ultrasonic Bath,
6 M.V. Bagal, P.R. Gogate / Ultrasonics Sonochemistry 21 (2014) 1–14

Table 2
Overview of the earlier work using combined Hydrodynamic cavitation /Fenton process for wastewater treatment.

Compound Equipment Details Optimum conditions Result Ref.

Dichlorvos Hydrodynamic Cavitation (HC) set up; Dichlorvos initial Maximum degradation HC/Fenton = 91.5%; [46]
Cavitating device:Orifice; Power rating of concentration = 20 ppm inlet HC alone = 16% Treatment time = 60 min
pump = 1.1 kW Orifice plate of diameter pressure = 5 bar; temperature = 31 °C;
25 mm with single hole of 2 mm initial
diameter. pH = 3.0;(dichlorvos:H2O2) = (1:0.8). HC/
Fenton [FeSO4:H2O2 (3:1)]
Methyl Parathion Hydrodynamic Cavitation (HC)set up; Initial Methyl parathion HC/Fenton: Degradation:93.8% TOC [45]
Cavitating device: Orifice; concentration = 20 ppm H2O2 = 100 mg/ removal of 76.6%
Power rating of pump = 1.1 kW L H2O2:FeSO4 ratio 1:4 HC alone
Orifice plate of diameter 25 mm with Degradation = 44%
single hole of 2 mm diameter Treatment time = 120 min
Rhodamine B Hydrodynamic Cavitation (HC)set up; Rhodamine B initial HC/Fenton [48]
Cavitating device: Venturi; concentration = 10 ppm; optimum inlet maximum extent of degradation 99.9%
Power rating of pump = 1.1 kW pressure = 4.8 atm operating TOC removal = 57%
temperature = 35 °C Optimum pH = 2.5 HC alone: degradation = 59.3% TOC
FeSO4:H2O2 ratio of 1:5 removal = 30%
Treatment time = 120 min
p-Nitrophenol Hydrodynamic Cavitation (HC)set up; For initial concentration 5 g/L For 5 g/l initial concentration of p- [44]
Cavitating device: Orifice; Fenton loading: nitrophenol, maximum removal of 63.2%
Power rating of pump = 1.1 kW FeSO4 = 1 g/L, was observed whereas for 10 g/l solution it
Orifice plate of diameter 25 mm with H2O2 = 5 g/L; was 56.2%.
single hole of 2 mm diameter. For initial concentration 10 g/L Treatment time = 90 min
Fenton loading:
FeSO4 = 1 g/L,
H2O2 = 7.5 g/L
Industrial Effluent Hydrocavitator (orifice unit) Triplex Initial pH = 1.7, initial COD = 42,000 mg/ Increased pressures, higher operating [49]
consisting of a plunger pump L TOC = 14,000 mg/L. temperature and the absence of copper
complexmixture Pressure = 4500 psi Fenton loading = 150 g iron windings are more favorable for a rapid
containing Orifice area = 7  102 m2 (100pieces,1 cm  2 cm  0.1 cm) and TOC mineralization. Maximum TOC
substituted phenolic H2O2=1900 mg/L removal of about 60%
compounds Optimum pressure = 1500 psi Treatment time = 150 min
Industrial wastewater Liquid whistle reactor (LWR) (orifice unit) Industrial Effluent 1 Original: pH = 1.7 The novel combination of hydrodynamic [48]
effluent positive displacement pump 5 lit COD = 42,000 mg/l TOC = 14,000 mg/l cavitation with AFP results in higher
Effluent 1: complex capacity; max discharge pressure 2000 psi Industrial Effluent 2 Original pH = 10.4 removal of TOC under optimized conditions
mixture of COD = 17,000 mg/l TOC = 6000 mg/l as compared to HC alone.
substituted phenolic Fenton loading: The highest COD removal was about 85% in
compounds. Two cycles of addition of H2O2(each of both the cases.
Effluent 2: pink 1900 ppm -loading); Iron bed containing Treatment time = 150 min
dyestuff solution. iron pieces(80 g, 50 pieces of 1cmx2 cm
L-shaped having thickness of 0.10 cm
2,4-Dichlorophenoxy Hydrocavitator (orifice unit); Pump with Treatment volume 8 L 2,4-D = 0.235 g/l, TOC removal Efficiency: Hydrodynamic [115]
acetic acid max discharge pressure 4500psi) H2O2 = 46 ml,1.9 g/l, Iron pieces = 150 cavitation and advanced fenton process
gm pH = 2.5 Temperature = 20 °C 70% (volume treated 8 litres) Treatment
time 20 min

and Flow Cells etc. In ultrasonic horn type reactors, the cavitational The dual or triple frequency flow cells should be used which will
effects are observed only close to the vibrating surface. The cavita- also give similar results to a single very high frequency transducer
tional intensity decreases exponentially on moving away from the which is also difficult for efficient design and operation [19]. Dion
horn and vanish at a distance of 2–5 cm, depending on the supplied [53] has presented a new sonoreactor technology which is based
energy to the equipment and the operating frequency [50]. The on cylindrical converging ultrasonic waves producing a powerful
scale up prospects of the horn type system are poor as it cannot concentric and confined, chemically active cavitation zone in a Tef-
effectively transmit the acoustic energy into large process volume lon tube, away from the wall, in such a way that there is no erosion
[51]. In ultrasonic bath type reactor, the bottom of the reactor is avoiding contamination of the products. The processing conditions
irradiated with single or multiple transducers. Thus better energy can be widely varied with pressure, power, temperature, and flow
dissipation in the reactor can be achieved by increasing the irradi- rate and the processing capacity of the largest models may be up to
ating surface which increases the magnitude of pressure pulse due several tons per hour, depending on the required cavitation energy
to decreased ultrasonic intensity defined as power dissipation per per unit volume to produce the desired process enhancement,
unit area of the irradiating surface [51]. using an electric power input of about 50 kW [53].
The magnitude of collapse pressure, temperature as well as the
number of free radicals generated at the end of cavitation events 7.2. Hydrodynamic cavitation reactor
are strongly dependent on the operating parameters of the sono-
chemical reactors namely, intensity and frequency of irradiation In Hydrodynamic cavitation reactors, cavities are generated by
along with the geometrical arrangement of the transducers and the virtue of the fluid energy where the orifice plate, venturi or
the liquid phase physiochemical properties which affect the initial throttling valve can be used as cavitating device. Multiple hole ori-
size of the nuclei and the nucleation process [52]. Sonochemical fice arrangement having different combinations of number and
reactors with multiple frequency as compared with single fre- diameter of holes varying the free area offered for flow helps in
quency operation results in higher intensities of cavitation due to achieving different intensities of cavitation [52]. Thus, these
violent collapse of cavities. Also use of multiple transducers gives reactors present flexibility in terms of the operating parameters
better cavitational effects as compared to single transducer system. (control of inlet pressure, inlet flow rate and temperature) and
 M.V. Bagal, P.R. Gogate / Ultrasonics Sonochemistry 21 (2014) 1–14 7

geometric conditions (different arrangements of holes on the ori- 8. Effect of important operating conditions
fice plates). Following important strategies for the design of hydro-
dynamic cavitation reactors have been reported [53]: 8.1. Effect of power density in ultrasonic treatment

(1) An orifice flow configuration is necessary only for intense Effectiveness of the sonochemical rector depends on the ultra-
oxidation capacity whereas for milder requirements, a ven- sonic power dissipation which is important equipment parameter
turi configuration is more suitable and energy efficient. as it affects the cavitational activity [55]. The effect of power dissipa-
(2) In the case of a venturi flow, the cavitational intensity could tion depends on the range of power dissipation and sometimes opti-
be increased by reducing the length of venturi and by reduc- mum power dissipation might exist depending on the reactor
ing the venturi throat to pipe diameter ratio. configuration and application under question [56–58]. Beyond this
(3) In the case of an orifice flow configuration, the most conve- optimum power dissipation, the cavitational activity is either af-
nient way of controlling the cavitation intensity will be to fected marginally or decreases. Increase in power density below
control the orifice to pipe diameter ratio and to control the the optimum value increases cavitational activity and in turn in-
cross-sectional flow area through the manipulation of the creases the net production of free radicals which enhances the extent
number and diameter of the hole on the orifice plate. of degradation of pollutant [59]. The bubble formation increases
with an increase in the power dissipation rate which may lead to
Sampathkumar and Moholkar [54] have proposed a conceptual cloud formation due to bubble coalescence. Hence reduction in en-
design of a novel hydrodynamic cavitation reactor that uses a con- ergy transfer can be observed at very high power levels as these bub-
verging–diverging nozzle for creating pressure variation in the ble clouds can absorb or scatter the incident sound waves [56].
flow necessary for driving the bubble motion. Different gases can Acoustic decoupling also contributes to the lower energy transfer
be used for the introduction of the bubbles in the water flow exter- efficiency from ultrasound source to the medium [56] and also insuf-
nally, upstream of the nozzle using a sparger. Also, the size of the ficient collapse of cavitation bubbles may result giving reduced cavi-
gas distributor, flow rate of gas and the pressure of gas in the res- tational activity [60]. In the specific case of US /Fenton process more
ervoir from which it is withdrawn can be suitably controlled in or- decomposition of Fe–O2H2+ to Fe2+ and OOH and also improved
der to achieve the desired initial size of the cavitational nuclei, mass transfer rates at higher power density below the optimum re-
which significantly affects the resultant cavitational intensity. sults in enhanced degradation rate of pollutant [14].
The length and diameter of the nozzle are the geometric parame- Neppolian et al. [61] have reported that the rate of sonolytic
ters that can be varied in this reactor. degradation of MTBE increases with an increase in the power den-
sity of system. The degradation of MTBE was 21% at power density
7.3. Reactors used for Fenton processes of 22 W/L, whereas 77% and 84% degradation were obtained when
the power density of the system was 48 and 76 W/L, respectively. It
A batch Fenton reactor consist of non pressurized reactor with is clearly seen that initial increase in power density results in sig-
metering pumps for addition of base, acid, a ferrous sulfate catalyst nificant increase in extent of degradation whereas the second stage
solution and industrial strength hydrogen peroxide [1]. Stirring increase results in a marginal change confirming the existence of
must be provided for the proper mixing of Fenton’s reagents (Fer- optimum power density. Hwang et al. [62] have investigated the
rous salts or iron and hydrogen peroxide) and pollutant. The dis- degradation of diethyl Phthalate by Sonochemical, Fenton and
charge from the Fenton reactor is fed into a neutralizing tank for Sono-Fenton processes and its dependence on the power density
adjusting the pH of the stream followed by a flocculation tank (80, 180 and 330 W/L).It has been reported that the first order deg-
and a solid–liquid separation tank for adjusting the TDS (total dis- radation rate constant increases linearly with increasing power
solved solids) content of the effluent stream. The reactor need to be density in the sonochemical and Sono-Fenton processes. Zhang
coated with acid resistant material as Fenton’s reagent is very et al. [60] have investigated degradation of C.I. Acid Orange 7 by
aggressive and can cause serious problem of corrosion [1]. The US/heterogeneous Fenton process and reported that the rate of
materials of construction for the reactor and holding tank should degradation increases with an increase in the ultrasonic power
be typically 304 or 316 stainless steel, while those for the chemical from 0 to 80 W and further decreases with an increase in ultrasonic
storage systems may be HDPE. power above 80 W. Sun et al. [14] have also reported that the high-
er degradation efficiency of Acid Black 1was achieved at higher
7.4. Reactor designs for the combined process (US/Fenton and HC/ power density. Guo et al. [63] have investigated the sonodegrada-
Fenton) tion of DNP using ultrasound with different power dissipation
(200, 400, 600 and 800 W) and reported that increasing power dis-
The Sonochemical and Hydrodynamic cavitation reactors as de- sipation favors the degradation of DNP and also the rate constant
scribed for the individual operation can be used for the combina- linearly increases with an increase in the ultrasonic output power.
tion process without any modifications by adding Fenton reagent Also similar results are reported in the literature for degradation of
into the reactor. Additional stirring can be provided in the case of dichlorvos [59], Acid Black1 [14] and parathion [64]. It can be
large scale sonochemical reactor for proper mixing of Fenton’s re- established here that optimum power dissipation depends on the
agent, especially in the case of heterogeneous Advanced Fenton reactor type and pollutant under question.
process. Bremner et al. [48] have reported some modifications in
the reactor design for advanced Fenton process in combination
with Hydrodynamic cavitation. The set-up for combined HC/Ad- 8.2. Effect of inlet pressure in hydrodynamic cavitation
vanced Fenton process is depicted in Fig. 1 where Hydrodynamic
cavitation was generated using a liquid whistle reactor (LWR), Inlet pressure is an important operating parameter of Hydrody-
which is coupled to a positive displacement pump and is employed namic cavitation system. The cavitational effects are dependent on
in a comprehensive system containing the motor, variable fre- the inlet fluid pressure to the cavitating device. The number of cav-
quency drives, pressure and flow measuring devices [48]. Waste- ities being generated and the cavitational intensity depends on the
water was circulated through the cavitating device and the inlet pressure [1]. Cavitation number decreases with an increase in
subsequent iron chamber at a fixed flow rate for a desired contact the inlet pressure due to increased liquid flow and velocity which
time so that a measurable amount of degradation occurs [48]. results in an increase in the number density of cavities [65].
8 M.V. Bagal, P.R. Gogate / Ultrasonics Sonochemistry 21 (2014) 1–14

Fig. 1. Schematic representation of the experimental setup with expanded view of the arrangement of orifice and blade [48].

Saharan et al. [65] have done photographic analysis of cavitat- at an operating temperature of 30 °C using conventional Fenton
ing device and reported that till an optimum inlet pressure, the chemistry. In cavitation, the change in operating temperature af-
number density of cavities are low and these cavities behave as fects the cavitational intensity due to alteration in the physio-
individual cavities and they collapse as soon as they come out of chemical properties of the liquid medium [59]. As the
the cavitating device. The significant increase in the number of cav- temperature of the liquid increases, its viscosity and/or surface
ities beyond the optimum operating pressure results in choked tension decreases but vapor pressure increases substantially [71].
cavitation where the entire downstream area is filled with the In general, for an application where chemical reactions are occur-
vaporous cavities reducing the cavitational effects. It is also re- ring, an optimum temperature might exist. On one side, higher
ported that choked cavitation occurs when the minimum pressure rated are expected as the higher concentration of chemical species
approaches the vapour pressure and vaporization of the liquid be- is present in cavitating bubble due to higher vapor pressure which
comes dominant at choked cavitation. Saharan et al. [65] have re- generates higher amount of free radicals. This is counteracted by
ported optimum inlet pressure of 5 bar beyond which drop in the fact that at higher operating temperatures, increase in the va-
degradation of reactive red 120 was observed. Similar results have pour content in the bubble decreases the collapse pressure result-
been reported in the literature for the degradation of dichlorvos ing in a net decrease in the energy being released at the collapse
[46] where optima exists at 5 bar pressure using orifice plate as and thus reduces the generation of reactive hydroxyl radicals in
cavitating device in hydrodynamic cavitation. On the other hand, the system [5,59,72]. The growth of cavity and total lifetime of
Wang and Zhang [66] have reported a continuous increase in the the cavity remains unaffected by the increase in the operating tem-
degradation rate of alachlor with increasing inlet pressure using perature. Thus it is important to establish the optimum operating
swirling jet cavitation over the range of operating pressure from temperature for the degradation of pollutant under investigation
0.2 to 0.6 MPa. The existence of the optimum inlet pressure may as the kinetic rates will be strongly dependent on reactivity of
be dependent on the type of pollutant, type of cavitating device the pollutant with the generated hydroxyl radicals [46]. Chiha
and the reactivity of these pollutants with generated hydroxyl rad- et al. [73] have observed optima at 30 °C for the degradation of
icals. The effect of operating pressure is strongly dependent on the 4-cumylphenol using ultrasonic irradiation over the temperature
geometry of the cavitation chamber as well as the pollutant to be range of 20–50 °C. The existence of the optimum temperature
treated. Hence the optimization of the inlet pressure is necessary (25 °C) has been reported in the literature for the sonochemical
to obtain maximum cavitational effects and to avoid choked cavi- degradation of dichlorvos [59]. Also for Chlorpyrifos and diazinon
tating conditions in hydrodynamic cavitation. pesticides [74], increase in degradation was observed over the
range of temperatures from 15 to 25 °C and beyond this optimum,
8.3. Effect of operating temperature decrease in degradation was observed. The effect of the bulk tem-
perature might be dependent on the ultrasonic frequency. Son
Temperature plays an important role in the degradation of pol- et al. [75] have observed a decrease in degradation efficiency for
lutant using cavitation (Hydrodynamic and acoustic) process as 1, 4-dioxane at 35 kHz and 170 kHz ultrasonic frequency with an
well as the Fenton process. In Fenton process, the rate of reaction increase in bulk temperature but this decrease in degradation
between H2O2 and Fe2+ increases with an increase in temperature was lower at higher frequency (170 kHz) than at 35 kHz. This
leading to formation of more number of hydroxyl radicals, which in was attributed to the enhanced generation of hydroxyl and HO2
turn results in enhanced degradation efficiency [49,67–70]. Sun radicals at higher frequency which results in higher rate of degra-
et al. [67] have reported that the rate constant for degradation of dation whereas genearation of large number of cavitation bubbles
p-nitroaniline increased by almost 100% with a rise in temperature at low frequency results in loss of activity due to coalescence of the
from 20 to 30 °C whereas Kavitha and Palanivelu [68] have re- bubbles. Many researchers have reported enhancement in the deg-
ported that the maximum extent of degradation of cresols occured radation rate with an increase in temperature using the combined
 M.V. Bagal, P.R. Gogate / Ultrasonics Sonochemistry 21 (2014) 1–14 9

US/Fenton process. Sun et al. [14] have reported that degradation levels of initial dye concentration (50, 125 and 250 mg/L respec-
efficiency of acid black 1 increases from 92.39% to 99.14% as a con- tively). The increase in C0 resulted in a decrease in the color re-
sequence of increasing the temperature from 20 to 40 °C within moval for both processes, since the oxidizing agent concentration
10 min whereas for 2,4 dichlorophenol [76], the degradation rate produced by Fenton and Sono-Fenton processes is insufficient at
increased from 0.0494 min1 to 0.11 min1 with increased in tem- 125 and 250 mg/L RY 145. It was also observed that 95% of the
perature from 10 to 50 °C using combination of ultrasound and decoloration was achieved by Sono-Fenton process for RY 145 at
Fenton like system based on the use of Fe/EDTA complex. initial loading of 50 mg/L and the decolorization rate was higher
The effect of temperature on degradation of various pollutants in Sono-Fenton process, compared to Fenton process. Babuponnus-
using Hydrodynamic cavitation operated individually and in com- ami and Muthukumar [90] have reported similar decrease in the
bination with Fenton’s reagent has also been reported in the liter- extent of phenol degradation with an increase in the initial phenol
ature. The existence of the optimum operating temperature have concentration over the range of 100–400 mg/L by Fenton, Sono-
been reported for alachlor degradation [66] using Hydrodynamic Fenton and Sono-photo-Fenton Methods. Wang et al. [88] have
cavitation which can be attributed to counteracting effects of the also investigated the effect of initial dye concentration on the deg-
kinetic mechanism and dampened cavitational activity [66] radation of reactive brilliant red (K-BP) in aqueous solution by
whereas no existence of optima have been reported for dichlorvos ultrasonic cavitation and observed that by increasing initial con-
degradation [46] over the selected range of temperatures. It has centration from 10 to 100 mg/L, the degradation rate constant de-
been reported that the degradation of methyl parathion [45] and creased from 10.3  104 min1 to 4.35  104 min1. Sun et al.
rhodamine B [47] using hydrodynamic cavitation increased with [14] have reported about 18% reduction in the degradation ratio
an increase in temperature over the range of 30–40 °C. Chakinala of Azo dye acid black 1(AB1) on increasing the initial concentration
et al. [49] have reported about 50% higher extent of mineralization of AB1 from 0.041 to 0.164 mM. Ma et al. [91] have reported more
of indusrial wastewater at 30 °C as compared to that at 20 °C using than 99% carbofuran degradation by combined ultrasound/Fenton
hydrodynamic cavitation and heterogeneous advanced Fenton pro- process for initial carbofuran concentration of 50 mg/L with rate
cess which has been attributed to the controlling contribution from constant 102.7  103 min1. As the initial carbofuran concentra-
the advanced Fenton process compared to hydrodynamic cavita- tion increased from 100 to 200 mg/L, the rate constant dropped
tion at higher operating temperatures. Wang et al. [77] have stud- from 41.3  103 min1 to 37.1  103 min1. Patil and Gogate
ied the effect of temperature on degradation of reactive brilliant [45] have reported similar results for Methyl Parathion degrada-
red K-2BP in aqueous solution using swirling jet-induced cavita- tion using Hydrodynamic cavitation.
tion and reported that the effect of temperature was more signifi- Though higher degradation efficiency can be achieved using
cant when temperature varied from 303 to 323 K, and this effect lower pollutant concentration, the problems associated with treat-
was substantially weakened with further increase in temperature, ment of large processing volumes needs to be analyzed before fix-
from 323 to 333 K for instance and hence 323 K was chosen as ing the dilution ratio.
optimum temperature.
Thus, in general, lower operating temperature is recommended
8.5. Effect of initial pH
for an application where cavitational collapse is the primary cause
of the activation whereas an optimum operating temperature
The efficacy of the degradation of pollutant using cavitational
might exist where radical formation from the pollutants is also sig-
reactors either operated alone or in combination with hydrogen
nificantly contributing to the overall extent of degradation.
peroxide or Fenton’s chemistry has been found to be enhanced un-
der acidic conditions. In Fenton process and its modifications, pH
8.4. Effect of initial concentration
has an important influence on the oxidation potential by directly
affecting the concentration of Fe2+ in the solution and the amount
The initial concentration of the pollutant is another significant
of OH radicals produced by Fenton’s reagent. It is well known that
parameter affecting the efficiency of degradation of pollutant. In-
Fenton’s processes are efficient in the acidic range from pH 3–4
crease in pollutant concentration results in a decrease in the deg-
[79]. At lower pH (pH-2.5), the formation of (Fe(II) (H2O))2+ occurs,
radation efficiency of pollutant. This may be due to the decreased
which reacts more slowly with hydrogen peroxide and, therefore,
cavitational effects at higher pollutant load and also the amount
produces less amount of reactive hydroxyl radicals thereby reduc-
of hydroxyl radicals produced may not be sufficient to destruct
ing the degradation efficiency [1]. Also at pH < 2.5, hydroxyl radi-
the organics completely [78]. The limited diffusion of hydroxyl rad-
cals could be consumed by the scavenging effects of H+ which
icals out of the interfacial regions of the collapsing cavitation bub-
will limit the degradation rate [92]. Hydrogen peroxide could cap-
bles [61] may result in a decrease in the degradation rate with
ture a proton to form an oxonium ion (H3 Oþ 2 ) at very low pH value
increasing pollutant concentration. Thus the better efficacy of Fen-
and H3O2+ will make hydrogen peroxide to be electrophilic and en-
ton chemistry and cavitation either operated individually or in
hance its stability, which presumably reduces the reactivity of
combination, has been generally observed at lower initial concen-
hydrogen peroxide with ferrous ion [79].
trations [45,61,79–88]. Neppolian et al. [61] have reported a de-
crease in the reaction rate constant with an increase in initial OH þ Hþ þ e ! H2 O ð14Þ
concentration of MTBE over the range of 2.84  102–
2.84  101 mM using ultrasound with fixed ultrasonic frequency
H2 O2 þ Hþ ! H3 Oþ2 ð15Þ
of 20 kHz. Ozdemir et al. [89] have investigated the effect of the
initial concentration of RY 145 on the decoloration at 50, 125, Also at pH > 4, the formation of Fe (II) complexes reduces the
and 250 mg/L RY 145 concentrations by both Fenton and Sono- generation of free radicals and also regeneration of ferrous ion gets
Fenton processes under the determined optimum conditions at inhibited by the precipitation of ferric oxyhydroxides thereby
room temperature. Approximately 95% of the decolorization by decreasing the rate of degradation of the pollutant [1,79]. Also at
Sono-Fenton process was achieved at initial concentration (C0) of higher pH, a decrease in the oxidation potential of hydroxyl radi-
50 mg/L. When C0 was increased to 125 mg/L, the extent of color cals results in decrease in the rate of degradation of pollutant
removal significantly decreased to 71% for an initial concentration [14]. Under acidic conditions (pH around 3), generation of hydroxyl
of 250 mg/L. Color removal efficiencies were 92, 74, and 70% for radicals due to decomposition of hydrogen peroxide is favored i.e.,
Fenton process alone after the reaction time of 60 min, for similar recombination reaction between the free radicals is hampered
10 M.V. Bagal, P.R. Gogate / Ultrasonics Sonochemistry 21 (2014) 1–14

thereby increasing the availability of the free radicals for the de- efficacy of the degradation process especially for Fenton chemistry.
sired reaction of oxidation of the pollutant [47]. Iron powder used Usually the loading of hydrogen peroxide should be adjusted in
in advanced Fenton process can be easily dissolved in under acidic such a way that the entire amount is utilized in the process as
conditions producing ferrous ion [32] which further react with the residual hydrogen peroxide contributes to COD and also is
hydrogen peroxide to generate hydroxyl radicals [93]. Also decom- harmful to micro-organisms (important if the technique is used
position of hydrogen peroxide at metal surface produces hydroxyl as a pre-treatment strategy for conventional biological oxidation)
radicals thereby increasing the rate of degradation in advanced [15]. Hydrogen peroxide is known to dissociate into hydroxyl rad-
Fenton process as well as combined US/Advanced Fenton process. icals in the presence of ultrasonic irradiations and hence can be
used as an intensifying agent to enhance the extent of degradation
M þ H2 O2 ! Mþ þ OH þ OH ð16Þ of pollutants [101].

where M is metal. H2 O2 ! OH þ OH ð17Þ

Wang et al. [88] have investigated the effect of the initial pH on
On one side where hydrogen peroxide acts as a source of free
the sonochemical degradation of reactive brilliant red K-BP at dif-
radicals by the dissociation process, it also acts as the scavenger
ferent pH in the range of 2.0–12.0 with initial concentration as
of the generated free radicals, as indicated by the following reac-
10 mg/L and temperature of 25 °C. It has been observed that the
tion scheme [4]:
ultrasonic degradation rate constants in acidic conditions (pH
2.0–3.0) are higher than those obtained in near neutral solutions H2 O2 þ OH !  HO2 þ H2 O ð18Þ
(pH 5.0–8.0), and also that observed in basic medium (10.0–
Optimization of hydrogen peroxide loading plays an important
12.0). Many researchers have reported that acidic conditions fa-
role in deciding the efficiency of US/H2O2, HC/H2O2, Fenton process
vours the sonodegradation of phenol [94], p-nitrophenol [95], 2-
and combined processes such as US/Fenton and HC/Fenton. The
chlorophenol [96], 4-chlorophenol [97], trichlorophenol [98,100]
efficacy of the combined process is dependent on the utilization
and 2, 4 dinitrophenol [63,66]. Lu et al. [99] have reported a high
of free radicals which are generated due to the cavitating condi-
rate constant for the degradation of dichlorvos when the initial
tions and its reactivity with the pollutant molecules [102]. Thus
pH was set to 3 as compared to higher pH using Fenton process.
the optimum loading of hydrogen peroxide is based on the type
Ranjit et al. [36] have reported that Sono-Fenton process is more
of pollutant, operating conditions (ultrasonic frequency and
efficient as compared to Fenton process for the degradation of
power) as well as the type of the sonochemical reactor [102]. Since
2,4 dichlorophenol at various ranges of pH and acidic pH favors
the main cost associated with Fenton process is due to H2O2, the
the degradation. Similarly Ozdemir et al. [89] have also investi-
treatment cost also goes up with an increase in H2O2 dosage
gated color removal from synthetic textile wastewater by Sono-
[89]. The addition of hydrogen peroxide as external oxidizing agent
Fenton process over the range of 2–4.5 and reported maximum col-
affects the degradation of non volatile compounds as compared to
or and COD removals at pH 3.
volatile compounds as the degradation of volatile organic com-
Similar results have also been reported in the literature for the
pounds takes place either in the interior of bubble or in the bubble
degradation of various pollutants using hydrodynamic cavitation
water interfacial region and that of non volatile compounds takes
alone and/or combined with Fenton process using orifice plate or
place in the bulk solution [21]. Many researchers
venturi as cavitating device. It has been reported that the degrada-
[102,89,59,103,104] have reported that an optimum concentration
tion efficiency of Rhodamine B [47] and acid Red 88 [100] with
of H2O2 exists where maximum degradation of organic pollutants
venturi as cavitating device and degradation of Dichlorvos [46]
is observed and excessive amounts of H2O2 could reduce the deg-
and Methyl Parathion [45] with orifice plate as cavitating device
radation rate.
increases at acidic pH. Also the degradation using HC combined
Drijvers et al. [105] investigated the degradation of 2-chloro-
with Fenton process was favoured at low pH. Pradhan and Gogate
phenol using ultrasonic irradiation and observed that the degrada-
[44] have investigated the effect of pH on removal of p-nitrophenol
tion efficiency increases with an increase in hydrogen peroxide
at three different pH values of 2.0, 3.75 and 8.0 using venturi at
loading till an optimum of 300 mg/L. Guo et al. [63] have studied
optimum FeSO4 and H2O2 concentration. Maximum removal of
the influence of the addition of H2O2 on the ultrasonic degradation
63.2% was observed at pH value of 3.75. At pH 8.0 (alkaline condi-
of 2,4-dinitrophenol (DNP) and reported an existence of optimum
tions), the extent of removal was 5.7% which is considerably lower
concentration for the degradation of 2, 4-dinitrophenol where
than that obtained under acidic conditions.
H2O2 concentration was varied from 100 to 800 mg/l. Similar re-
Acidic pH is favorable for the degradation of pollutant using
sults have been reported in the literature for sonodegradation of
Fenton’s reagent. In cavitation process, the effect of pH on the rates
methyl parathion [103], 2-chlorophenol [101] and p-chlorophenol
of degradation is dependent on the state of the pollutant molecule
[106].
i.e., whether the pollutant is present as ionic species or as a mole-
Also, similar existence of optimum loading of hydrogen perox-
cule. Thus it can be said that the pollutant must in the molecular
ide using Hydrodynamic cavitation have been reported in the liter-
state and the operating pH must be kept lower than the pKa value
ature for the degradation of dichlorvos [46], methyl parathion
for the specific pollutant in question for both the pyrolytic and free
[45]and Rhodamine B [47]. Wang et al. [107] have reported that
radical attack to take place [16]. Overall it can be said that the effi-
the extent of degradation of Rhodamine B in a hydrodynamic cav-
cacy of combined process (US/Fenton and HC/Fenton) for the deg-
itation reactor based on swirling jet increases with an increase in
radation of pollutant is high at acidic pH. It is also recommended
the hydrogen peroxide concentration over the range 0–150 mg/l.
that a comparative analysis needs to be done using laboratory scale
In combined US/Fenton processes, Sun et al. [14] have reported
studies to quantify the extent of degradation at natural pH and
an increase in the decoloration efficiency of Acid Black 1(AB1) from
optimum pH (2.5–3.5) and weigh the extent of intensification
67% to 92.39% as a consequence of increasing H2O2 dosage from 0.5
against the cost of chemicals required for pH adjustment.
to 8.0 mM in 10 min of treatment. The further increase of the H2O2
dosage from 8.0 to 32.0 mM resulted in a decrease in the degrada-
8.6. Effect of initial H2O2 concentration tion rate of AB1.
Bremner et al. [15] have investigated the effect of hydrogen per-
Hydrogen peroxide is a strong oxidizing agent. The loading of oxide concentration on the extent of degradation of phenol in a
hydrogen peroxide plays a crucial role in determining the overall combined hydrodynamic cavitation and heterogeneous advanced
 M.V. Bagal, P.R. Gogate / Ultrasonics Sonochemistry 21 (2014) 1–14 11

Fenton process and reported that the extent of degradation in- electric-energy-driven systems) or collector area (for solar-en-
creases with the hydrogen peroxide concentration over the range ergy-driven systems) are proposed for the comparison and evalua-
500–2000 mg/L. Similar trend has been reported by other research- tion of various wastewater treatment technologies. These standard
ers [108,109]. figures-of-merit provide a direct link to the electric or solar-energy
Overall it can be said that the concentration of hydrogen perox- efficiency (lower values mean higher efficiency) of an advanced
ide must be kept at optimum levels in order to achieve a high deg- oxidation technology (AOT), independent of the nature of the sys-
radation efficiency of pollutant in HC/Fenton or ultrasound/Fenton tem, and therefore allow for direct comparison of widely disparate
process. Also optimum value of hydrogen peroxide loading de- AOTs [112]. We now present remarks on the economics of the
pends on the type of pollutant to be degraded. treatment processes based on the combined operation of cavitation
and Fenton based processes. The operating cost of ultrasonic treat-
ment processes is high due to the poor efficiency of conversion of
8.7. Effect of ferrous ion concentration
electrical energy into cavitation energy. The scaled up versions of
these reactors requires huge amount of energy which in turn re-
The loading of ferrous ion is also an important parameter in
sults in high capital cost of equipment and higher operating and
deciding the efficacy of the Fenton process alone and also the com-
maintenance costs [22]. However, the treatment costs can be effec-
bined cavitation (HC and US)/Fenton process. The hydroxyl radicals
tively decreased by using a combination of ultrasonic reactors with
are generated by the catalytic decomposition of hydrogen peroxide
Fenton based processes. Mahamuni and Adewuyi [22] have re-
by ferrous ion and hence the treatment yield and operating cost are
ported that the cost of phenol degradation using US and US/Fenton
very much dependent on the loading of ferrous ion [110]. The opti-
process is $15536.59/1000gallon and $137.626/1000 gallon
mization of Fe2+ is necessary as overdose of iron would produce too
respectively, which clearly shows that the cost of ultrasonic waste-
many ferrous ion, which would scavenge hydroxyl radicals result-
water treatment reduced more than 100 times when it is combined
ing in reduced degradation efficiency [89]. Also treatment cost will
with Fenton. Mahamuni and Adewuyi [22] have also reported that
increase by using an excess amount of iron salts as the amount of
the costs of treatment of hydrophilic pollutants are relatively high-
sludge increases introducing enhanced treatment costs [110].
er than that of hydrophobic contaminants. The hydrophobic pollu-
Again the use of zero valent iron could reduce the overdose of iron
tants degrade inside the cavitation bubbles whereas hydrophilic
and enhance the degradation rate significantly [89].
compounds degrade outside the cavitation bubble.
Ozdemir et al. [89] have reported enhanced COD and color re-
Hydrodynamic cavitational reactors are more energy efficient as
moval of CI reactive Yellow 145 using Fenton and Sono-Fenton
compared to the ultrasonic reactors and the scale up of these reac-
process over the Fe2+ loading in the range of 5–20 mg/L for fixed
tors is also easy. The efficient design of reactors helps in reducing
20 mg/L loading of hydrogen peroxide and further increase in Fe2+
the treatment cost. In the case of combined operation, the optimi-
loading to 30 mg/L resulted in a decrease in COD and color re-
zation of operating parameters such as flow rates/inlet pressures
moval for both Fenton and Sono-Fenton process. Hence 20 mg/L
and loadings of Fenton’s reagent may help in reducing the overall
of Fe2+ loading was chosen as optimum concentration. Zhang
treatment cost as it reduces the electrical cost and cost of chemi-
et al. [111] have reported optimum loading of iron as 0.25 g/L
cals. Overall, the use of hydrodynamic cavitation based processes
for the degradation of CI Acid Orange 7 by the advanced Fenton
with additives at optimum loadings looks promising and econom-
Process in combination with ultrasonic irradiation and scavenging
ical as compared to ultrasound based process.
of hydroxyl radicals at higher loadings of ferrous ion resulted in a
decrease in the degradation beyond the optimum loading. Similar
results are reported in the literature using US/Fenton process
10. Suggestions for future work
for carbofuran degradation [91] where TOC removal increased
from 8% to 43% for an increase in the Fe2+ loading from 1 to
Following are some of the suggestions for future work.
20 mg/L.
The efficacy of combined HC/Fenton is also dependent on the
(1) Generalized correlations relating the obtained yield with the
loading of ferrous ion in the similar way as that of Fenton process
operating parameters need to be developed for a variety of
and US/Fenton attributed to enhanced generation of more number
equipments.
of free radicals due to the presence of Fe2+ ion. In the combined HC/
(2) The frequency of the sonochemical reactor need to be opti-
Fenton process the effect of Fe2+ loading on the degradation of
mized for the energy efficient operation depending on the
dichlorvos [46] and methyl parathion [45] have been reported in
type of pollutant.
the literature. Joshi and Gogate [46] have reported that the extent
(3) In case of conventional ultrasonic horn cavitationally active
of degradation of dichlorvos increased from 39% to 91.5% in 1 h
zone is restricted to a small zone around the irradiating sur-
treatment time in combined HC/Fenton process with increasing
face. Hence active zones can be increased by modifying the
concentration of Fe2+ at fixed loading of H2O2 over the range of
position of transducers and using multiple transducers for
FeSO4:H2O2 ratio as 0.5:1, 1:1, 2:1 and 3:1. Patil and Gogate [45]
large scale operation. Thus the newer designs must be devel-
have investigated degradation of methyl parathion in combined
oped for the large scale operation to enhance the ultrasonic
HC/Fenton process at fixed H2O2 concentration (100 mg/L) with
activity.
varying Fe2+ loading over the range of 50–400 mg/L and reported
(4) Study of newer materials of construction for ultrasonic
that the extent of degradation increases from 78.5% to 93.8% in
transducers operating efficiently at large scale.
2 h of treatment time.
(5) Development of suitable design strategies relating the theo-
retically available information with experimental results.
9. Some remarks on the economics of the treatment process (6) In case of hydrodynamic reactors, the development of the
Modern CFD codes to get the flow field information which
The development of a cost effective technology for the waste- affects cavity dynamics and hence cavitational activity is
water treatment is very important for achieving successful opera- necessary.
tion for the treatment of wastewater in the actual industrial (7) The cavitating devices with different geometric consider-
scale operation. In IUPAC technical report [112], standard ations must be designed to alter the flow conditions and
figures-of-merit based on electric-energy consumption (for hence cavitational activity.
12 M.V. Bagal, P.R. Gogate / Ultrasonics Sonochemistry 21 (2014) 1–14

(8) The role of sequential addition of Fenton’s reagent on the optimization of hydrogen peroxide is very important for bet-
extent of degradation of pollutant using combined process ter efficacy of the process. Also overdose of hydrogen perox-
of cavitation and Fenton must be established in order to ide leads to the additional pollution and it is harmful for the
optimize the loadings of Fenton’s reagent. microorganisms, severely affecting the efficacy of biological
(9) Heterogeneous Fenton like processes must be developed on oxidation.
the pilot scale in order to reduce/eliminate the sludge forma- (7) Iron salt loadings also play an important role in Fenton pro-
tion during homogeneous Fenton process. cess, HC/Fenton and US/Fenton process. Sludge formation
can be eliminated using iron particles in place of ferrous salt.
11. Conclusions The heterogeneous Sono-Fenton process can enhance mass
transfer, dispersion and disaggregation of catalyst particles
Cavitation and Fenton processes have been widely used for the and increase the surface defects or active sites on the cata-
destruction of recalcitrant organic pollutants at laboratory scale lyst surface. Optimum loadings of iron ion must be estab-
and combination technique (Cavitation/Fenton) can prove to be lished as the unutilized iron salts contribute to an increase
more energy efficient as compared to individual techniques as it in the TDS content of the effluent stream which is not per-
utilizes the advantages of these two techniques to generate more missible and also saturation of iron salts undergo self

OH radicals and improves the degradation rate of organic pollu- quenching of hydroxyl radicals resulting in decrease in the
tants. The present work has highlighted the different aspects of degradation efficiency.
cavitation (Hydrodynamic and acoustic) coupled with Fenton’s re- (8) Combined US/Fenton or HC/Fenton is very cost effective as
agent for the treatment of wastewater. It has been observed that compared to individual technique to treat the wastewater.
the operating parameters such as pH, temperature, initial concen- (9) Overall it can be concluded that the combined treatment
tration of effluent stream and reactor design plays an important strategy is energy efficient and economical as compared to
role in deciding the efficacy of cavitation (US and HC) and Fenton individual processes of cavitation (hydrodynamic and acous-
process operated individually or in combination (US/Fenton, HC/ tic) and Fenton process under optimized conditions of
Fenton) for the degradation of pollutant. Also operating parameters operation.
such as power density in US process and inlet pressure in the case
of HC affects the rate of degradation of pollutant. Some of the
important guidelines as established in the present work are as
follows:
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