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Review 1

Yuequn Tao1,2
Application of Hydrodynamic Cavitation
Jun Cai1
Xiulan Huai1 to Wastewater Treatment
Bin Liu1,2
Zhixiong Guo3 Hydrodynamic cavitation is a promising application in wastewater treatment due
to its simple reactor design and capacity in large-scale operation. Theoretical stud-
1
Institute of Engineering ies including the basic mechanism of pollutant degradation, modeling of pressure
Thermophysics, Chinese distribution in the cavitation reactor, and bubble dynamics models coupled with
Academy of Sciences, Beijing, chemical reactions are evaluated. Experimental setups with different cavitation
China. reactors and operation parameters are compared for degrading specific kinds of
2
University of Chinese Academy pollutants. The effort directions for both theoretical and experimental investiga-
of Sciences, Beijing, China. tions are suggested on the basis of the reviewed contents. Easy large-scale opera-
3
tion, effective combination with intensified strategies, and capability to deal with
Department of Mechanical biorefractory or toxic compounds contribute to the great potential of hydrody-
and Aerospace Engineering,
namic cavitation.
Rutgers, The State University
of New Jersey, Piscataway, NJ, Keywords: Hydrodynamic cavitation, Pollutant degradation, Ultrasonic cavitation,
USA. Wastewater treatment
Received: August 13, 2015; revised: January 31, 2016; accepted: April 13, 2016
DOI: 10.1002/ceat.201500362

1 Introduction Subsequently, in the downstream region of constriction, the


pressure is subjected to recovery because of the sectional
Water pollution has become a serious problem due to large expansion and cavitation bubbles collapse. Due to the collapse,
amounts of domestic sewage and industrial effluent discharged an extreme environment with high temperatures of 1000–
into the water body. Wastewater coming from industries like 10 000 K, high pressures between 100 and 5000 bar, and high-
textile, pharmacy, pesticide, and petrochemical processing con- speed microjet (102 m s–1 magnitude) can be formed [10]. As a
tains large amounts of organic compounds such as textile dyes, consequence, some highly reactive free radicals, such as HO.,
aromatic compounds, chlorinated hydrocarbons, and phenolic H., HOO., HO2., and H2O2 generate. All above-mentioned
compounds. These compounds are biorefractory or toxic to the factors favor the degradation reactions [11]. Therefore, hydro-
microorganisms and thus, conventional biochemical processes dynamic cavitation has been considered as an effective means
are not able to completely degrade them [1]. In the past decade, to destruct contaminants in wastewater.
many researchers have tried different methods for the degrada- Recently, Gogate and Pandit [6–8, 11–16] published a series
tion of organic pollutants [2–5], among which a new technolo- of excellent reviews on cavitation from reactor design to its ap-
gy called hydrodynamic cavitation has drawn significant atten- plication, while Adewuyi et al. [4, 17, 18] covered the subject of
tion. Compared with acoustic cavitation, it allows for easier wastewater treatment using acoustic cavitation. In this review,
realization of scale-up applications [6–8]. more attention is paid to the application of hydrodynamic cavi-
Cavitation is a pressure-related process and occurs when the tation to wastewater treatment. Different aspects of hydro-
local pressure falls below the vapor pressure corresponding to dynamic cavitation used for wastewater treatment are
the liquid temperature. In case of acoustic cavitation, the local addressed. The emphasis is focused on both the related theoret-
pressure fluctuation caused by acoustic waves is responsible for ical development and the experimental setups applied in the
the cavitation phenomenon [9], while the hydrodynamic cavi- experiments. Some important contributions are incorporated,
tation occurs when liquid passes through a constriction-diverg- and their advantages and disadvantages are also compared.
ing device, such as throttling valve, orifice plate, and venturi Energy efficiency and economy are assessed and finally, some
[10]. In the constriction region, the fluid velocity increases at useful recommendations and effort directions are provided to
the expense of pressure drop and then cavitation bubbles form. enable efficient large-scale operations for hydrodynamic cavita-
tion technology.

Correspondence: Dr. Jun Cai (caijun@mail.etp.ac.cn), Institute of
2 Theoretical Development
Engineering Thermophysics, Chinese Academy of Sciences, No. 11,
North 4th Ring West Road, Haidian District, Beijing 100190, China; 2.1 Degradation Mechanism
Prof. Zhixiong Guo (guo@jove.rutgers.edu), Department of Mechanical
and Aerospace Engineering, Rutgers, The State University of New The degradation of contaminants is usually interpreted as the
Jersey, 98 Brett Road, Piscataway, NJ 08854, USA. physical and chemical effects induced by the bubble collapse.

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2 Review

There are a number of illustrations in the literature dealing the reported approaches, the liner pressure recovery approach
with the mechanism of cavitation-induced chemical transfor- is the simplest, but is especially adequate to a geometry gener-
mations. These studies have shown that wastewater treatment ating relatively low turbulence intensity, e.g., a venturi tube.
due to cavitation should be attributed to the mechanical (e.g., Yan et al. [27] used this kind of method to consider the behav-
shear stress), chemical (e.g., free radicals), and thermal effects ior of a single bubble in the orifice-plate reactor (Fig. 1).
(e.g., hot spots) induced by bubble collapse. The strong shear
stress, generated during bubble collapse [19], can break down
the carbon-carbon bond and thus enable the direct decomposi-
tion of organic macromolecules into low-molecular organic
compounds. Besides, local hot spots are generated as the bub-
ble radius contracts violently. Under high-temperature condi-
tions of the gas inside the bubble or at the gas-liquid interface,
the organic molecules can be directly decomposed into inor-
ganic or low-molecular organic compounds during bubble col-
lapse. This process, which takes place in the solution, is similar
to a combustion reaction process and is called liquid-phase
combustion. Moreover, water molecules trapped inside the
bubble will be decomposed into free radicals [20]. These free
radicals will participate in oxidation reactions taking place at
the gas-liquid interface or in the bulk liquid.
The specific degradation process is determined by the prop-
erties of pollutants. For example, rhodamine B is destructed by
hydroxyl radicals at the bubble interface or within the bulk
solution because of the low vapor pressure [21]. With the effect
of hydroxyl radicals, polyaromatic rings are first separated
Figure 1. Schematic of the flow and pressure distribution down-
from the chromophore at the initial stage and then degraded stream of the orifice plate.
[5, 22]. The degradation of Red K-2B is mainly due to the
cleavage of the conjugate structures in the molecule, and the
Through time and space conversion [28], the local pressure
aromatic groups are just destroyed partly [23]. For the degrada-
at any position downstream is expressed as:
tion of chitosan solution, there is no obvious modification of
the chemical structure of degraded chitosan, and the reaction P2  Pv
only causes the cleavage of b-(1,4)-glycosidic linkages [24]. P ¼ Pv þ t (3)
t
It should be noted that the total amount of degradation
depends on the cavitation intensity and the number of cavita- where P is the axial pressure, t is the specific moment corre-
tion events. Two important parameters known as cavitation sponding to the geometrical position, and t is the total time for
number Cv1) [25] and cavitation event rate J [26] have been the pressure recovery. By means of this method, the bubble will
introduced to characterize these two aspects: experience a stable oscillation and produce pressure pulses with
P2  Pv extremely low amplitude. Such nonviolent oscillation is not
Cv ¼ 1 (1) able to bring about the observed chemical effects. Thus, this
rv02 approach certainly loses its validity in modeling the cavitation
2
flow with chemical reactions.
and Moholkar and Pandit [29] proposed a more realistic ap-
J ¼ J0 expðGÞ (2) proach by incorporating the turbulent fluctuation effect. The
bubbles oscillate in the form of transient state instead of stable
where P2 is the fully recovered pressure downstream, Pv is the state in a nonturbulent model. In comparison with the nontur-
saturated vapor pressure of the liquid, v0 is the velocity of the bulent condition, the bubble has larger growth rates as well as
liquid at the constriction position, J0 is the normalized pre- higher amplitude of pressure pulse. Cai et al. [30, 31] used the
exponential factor, and G denotes the normalized Gibbs activa- turbulence model to investigate the bubble behavior and the
tion energy. resultant temperature evolution inside the bubble. They found
that both collapse pressure and temperature increased after
considering the effect of turbulence. Gogate and Pandit [13]
2.2 Pressure Driving the Motion of Bubbles applied the turbulence model to determine the magnitude of
pressure pulse during the bubble collapse in an orifice flow,
Adequate quantification of both the pressure and velocity dis- and also found a significant increase in the magnitude of pres-
tribution in a cavitation reactor is critical to quantitatively ana- sure pulse. All these are attributed to the violent collapses of
lyze the bubble dynamics and the related chemistry. Among all cavities caused by the turbulence action. It should be noted that
the pressure profile consists of two parts in Moholkar and
– Pandit’s model, i.e., linear recovery pressure and turbulent fluc-
1) List of symbols at the end of the paper. tuating pressure. Nevertheless, it can still not reflect the real

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Review 3

pressure distribution in a cavitation reactor. With the develop- sion-limited model based on boundary layer approximation.
ment of computational fluid dynamics (CFD) technology, it is According to this boundary layer approximation, the regions
possible to obtain more realistic pressure distributions in the inside the bubble are divided into two sections, i.e., core and
reactor. The key is to legitimately substitute the discrete CFD boundary layer. The spatial distribution of species concentra-
simulation results into the bubble dynamics calculation. tion is uniform in the core region, but changes sharply inside
the boundary layer. The boundary layer thickness is calculated
throughout the lifetime of cavity, and two regions are treated
2.3 Bubble Dynamics Models Coupled separately. This kind of approach reduces the solving difficulty,
with Chemical Reactions but still preserves the accuracy. Most of the later theoretical
studies were based on these models. A brief overview about
Various models have been proposed to study the link between these studies is given in Tab. 1.
bubble dynamics and formation of free radicals. Among these, It should be noted that the acceptability of a model and its
the investigations conducted by Storey and Szeri [20, 32], Yasui solution schemes strongly depend on the assumptions em-
et al. [33, 34], and Toegel et al. [35] are regarded to be a land- ployed in its derivation. Most of the previous investigations
mark paving the way for the related studies. were based on the uniform cavity interior model, while Mishra
Yasui [33] developed a model of single-bubble sonochemis- et al. [36] introduced a model based on the multiphase lattice
try. By considering the compressibility of liquid and the effect Boltzmann method that allowed for the couple of reaction
of evaporation and condensation of water vapor, a new formu- kinetics and hydrodynamics in a collapsing cavity. This kind of
lation of bubble dynamic equation is included. The conserva- couple can lead to highly inhomogeneous concentration of sol-
tions of mass, momentum, and energy are analytically calcu- utes, and thus bring about the enhancement of concentration-
lated and the effects of the thermal conduction both inside and dependent reaction rates.
outside the bubble, the kinetic energy of gas, and the chemical
reactions under high-temperature conditions during bubble
collapse are all analyzed. The number of HO. radicals dissolv- 2.4 Deficiency of the Theoretical Investigation
ing into the surrounding liquid from the interior of the bubble
is further calculated [34]. There are three regions where chemical reactions occur in a
By considering mass transfer, nonequilibrium vapor conden- cavitation bubble: the interior of the bubble, the interface
sation and evaporation, and chemical reactions, Storey and between bubble and liquid, and the bulk liquid field. Although
Szeri [20] firstly presented a general method solving the partial there already exist some numerical calculations of the chemical
differential equations for bubble dynamics. Undoubtedly, the reaction rate inside a collapsing bubble, the lifetime of different
most precise treatment method is the full-depth numerical sim- radicals and the main reaction region are not yet understood
ulation, but the calculation process is very complicated to solve clearly, and there is a lack of quantitative description of the
these mutual coupling equations. Later, they developed a reactions between free radicals and contaminants from the per-
reduced model consisting of only ordinary differential equa- spective of chemical reaction kinetics. Since the previous inves-
tions [32]. Toegel et al. [35] proposed a relatively simple diffu- tigations are based on the single spherical bubble assumption

Table 1. Bubble dynamics models considering chemical reactions.

Researchers Important features of the models

Yasui et al. [34] Nonequilibrium evaporation and condensation of water vapor at the bubble wall, chemical reactions and the dissolution
of chemical products into the surrounding liquid, thermal conduction and diffusion of gases and vapor are taken into
account.

Capocelli et al. [81] Simulations of single-bubble dynamics with chemical reactions were conducted. The radical production rate that varies
with initial bubble size was obtained.

Kumar et al. [82] In addition to incorporation of heat transfer and solvent vapor transport across a bubble during radial motion, this
cavitation model also considered the bubble-flow and bubble-bubble interactions. Flow regime maps were presented
according to the combinations of design and process parameters.

Kumar and Moholkar [83] The diffusion-limited model of cavitation bubble dynamics was coupled to hydrodynamic characteristics of the flow
through an orifice.

Mishra et al. [36] A model based on the multiphase lattice Boltzmann method (LBM) considering inhomogeneous concentrations of the
solute was presented.

Sharma et al. [65] An empirical correlation for predicting the pressure was established as a function of operating parameters. The Weber
number criterion for the stability of the growing bubble was used.

Krishnan et al. [84] Both the bubble dynamics model and the associated heat and mass transfer model for the orifice flow were established
based on the following approximations: (i) only turbulent velocity fluctuation along the flow direction was concerned;
(ii) thermodynamic equilibrium was constituted during the bubble collapse.

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4 Review

when studying the degradation effect of hydrodynamic cavi-


tation, it is difficult to quantitatively compare the calculation
results with the experimental data. A key step to solve this
problem is to develop reasonable theoretical correlations to
quantify the cavitation event number in different cavitation re-
actors under various operating conditions. Hence, more refined
models which relax previous assumptions need to be developed
further. Furthermore, the pressure profiles used in previous
studies are still not the real pressure distribution of liquids in a
cavitation reactor. More accurate pressure achieved by CFD
method should be introduced into refined cavitation models.

3 Experimental Studies
3.1 Typical Scheme of the Experimental System

Among available experimental studies [8, 14, 37–39], the most


common system is illustrated in Fig. 2. It consists of a closed
circulation loop comprising a reservoir, a pump, control valves, Figure 2. Typical experimental system.
a cavitation reactor, and measurement gauges. Water is
pumped from the reservoir branches into two lines, i.e., a main Recently, another device which can generate shear cavitation
line where hydrodynamic cavitation takes place and a by-pass was proposed by Petkovšek et al. [43], as displayed in Fig. 5. An
line that is used to control the pressure and flow rate. As tem- outstanding feature of this device is that it works not only as
perature has a significant effect on cavitation, a cooling system cavitation generator, but also as driving pump. Such structure
is provided to control the liquid temperature. avoids additional pressure drop. The results indicate that this
kind of device can bring about better disintegration of the
sludge and higher biogas production for the pretreatment of
3.2 Hydrodynamic Cavitation Reactors the waste-activated sludge.
Based on a rotor and a stator, Badve et al. [44, 45] proposed
3.2.1 Rotating Device another kind of cavitation reactor, as demonstrated in Fig. 6.
The rotor is presented in the form of a solid cylinder with
When liquid swirls rapidly around the axis of a rotating device indentations on its surface, and the cavitation is formed on the
in a chamber, the local pressure near the central region will de- surface of the rotor as well as within the indentations due to
crease. If it falls below the vapor pressure of the liquid, vortex high-speed rotation. Testing the wastewater in the papermak-
cavitation occurs. Subsequently, as water moves towards the ing industry, almost 90 % chemical oxygen demand (COD)
bottom surface of the chamber where the pressure rises rapidly, reduction was achieved.
cavitation bubbles collapse. Wang et al. [21, 40] carried out
degradation experiments of rhodamine B and alachlor by using
the reactor shown in Fig. 3. A pseudo-first-order degradation
reaction was detected in all experimental
cases. The operating conditions, such as
pressure, temperature, initial concentration
of pollutant, pH, and H2O2 concentration,
were found to have significant effects on
the degradation rate.
Considering that the opposite move-
ments of two shear layers can generate
shear cavitation, Petkovšek et al. [41, 42]
used a novel rotation cavitation generator
to remove pharmaceuticals in water. The
generator is based on two facing rotors
with special radial grooves spinning in the
opposite direction, as indicated in Fig. 4.
This kind of cavitation generator has
advantages such as large cavitation volume,
rapid pressure recovery, low pressure loss,
and easy installation. Figure 3. Rotating cavitation reactor.

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Review 5

Figure 7. Liquid whistle reactor.

3.2.3 Orifice Plate Reactor

Compared with other cavitation generators, a multiple-hole


Figure 4. Cavitation reactor based on two rotors. orifice plate offers maximum flexibility over the design param-

Figure 8. Typical arrangements of orifice plates.


Figure 5. Shear cavitation generator and pump.
eters, making it extensively applied [24, 47–49]. This kind of
3.2.2 Liquid Whistle Reactor reactor may have different arrangement of holes to achieve the
desired cavitation intensity and cavitation event number. Some
A typical liquid whistle reactor consists of an orifice tube and a typical arrangements of holes are illustrated in Fig. 8.
blade, as presented in Fig. 7. With real industrial wastewater, Two parameters are used to characterize the orifice plate, i.e.,
Chakinala et al. [46] conducted an experimental study using a and b, which are defined as:
this kind of reactor. Wastewater flows through the orifice tube
and generates hydrodynamic cavitation in a high-speed liquid npdh
a¼  2 (4)
jet. Then, the jet is projected over the edge of the adjacent d
np h
2
blade, creating pressure fluctuation and bubble collapse. The
main advantage of this reactor lies in the highly efficient mix- !2
ing. When combined with the Fenton process, such cavitation dh
b¼n (5)
structure can achieve 60–80 % removal of total organic carbon dp
(TOC).
where n is the total number of holes, dh is
the hole diameter, and dp is the pipe diame-
ter. It has been qualitatively demonstrated
that the degradation rate of pollutants in-
creases with higher a and lower b for a cer-
tain flow area. Differences just exist in
quantitative aspect [50], which is due to
varying cavitation intensities required for
the desired chemical transformations. For
example, the cavitation intensity necessary
for the decomposition of rhodamine B is
much higher than that for KI decomposi-
tion [5]. Therefore, varying a and b will
lead to a more obvious change for KI de-
composition.
Figure 6. Cavitation reactor based on a rotor and a stator.

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6 Review

3.2.4 Venturi Tube Reactor obtained by considering the comprehensive effects of all the
parameters.
Compared with an orifice plate, the venturi tube reactor can Since the operating and geometrical parameters of cavitation
generate much lower turbulence intensity since the smooth reactors used in the studies are diverse, it is very difficult to
variation of its cross-sectional flow area leads to much less conclusively evaluate different cavitation reactors. Due to the
pressure loss. A typical venturi-type constriction is presented mutual coupling of these parameters, the way how the hydrau-
in Fig. 9. For a venturi reactor, cavitation intensity is seriously lic characteristics of a reactor influence the degradation rate
affected by its length and the ratio of throat diameter to pipe still needs to be further explored. Besides, the physicochemical
diameter. properties also have to be determined as the key consideration
Saharan et al. [38] conducted the degradation of Reactive for the selection of optimum cavitation reactors.
Red 120 dye with a venturi reactor. According to their obser-
vation, cavitation bubbles formed at the throat and gathered
downstream. Subsequently, these bubbles collapsed at the 3.3 Optimization of Operating Parameters
outlet of the venturi tube. In case of the local cavitation state,
the degradation rate rises with increasing the inlet pressure. 3.3.1 Effect of Inlet Pressure
However, as the number density of cavities becomes high
enough, the entire areas downstream are filled with cavities. Increasing the inlet pressure can enhance the fluctuation of tur-
Then, these cavities coalesce with each other and form a bulence pressure, rise the recovered pressure at downstream
cavity cloud, which is called choked cavitation [51]. Once regions of the constriction [54], and bring about the promotion
choked cavitation occurs, the degradation rate decreases with of cavitation intensity and cavitation event number. More
increasing the inlet pressure. The maximum degradation rate water molecules trapped in the cavity will undergo dissociation,
of the organic pollutant was up to 84 % under optimized resulting in higher concentration of hydroxyl radicals and deg-
conditions. radation rate. However, an excessive increase of inlet pressure
will make the number density of cavities become so high that
these cavities coalesce to form much larger cavitation bubbles.
3.2.5 Comparison of Hydrodynamic Cavitation Reactors These large bubbles escape from the liquid without collapse or
suffer from incomplete collapse, reducing the degradation rate.
Early efforts made by Moholkar and Pandit [52, 53] to address The optimum inlet pressure depends on the geometry and con-
the effects of design parameters can be treated as a basis for figuration of the cavitation reactor. Meanwhile, different pollu-
optimization of a cavitation reactor. In case of a venturi tube, tants require various optimum conditions due to diverse
the radical motion of the bubble is of stable oscillatory type due removal mechanisms. Thus, the optimum inlet pressure should
to a linear pressure recovery, whereas the bubble motion in the be adjusted individually for a specific pollutant. The degrada-
orifice flow is a combination of stable oscillation with a tran- tion experiment of Orange 4 dye using a venturi reactor
sient one due to an additional pulsating pressure. Besides, the demonstrated that the maximum discoloration rate was
pressure drop of the orifice plate is much higher than that of a 4.94 ·10–3 min–1 at an optimum inlet pressure of 5 bar [55].
venturi tube, thus cavitation intensity of the former is of much However, the maximum degradation rate of methyl parathion,
higher magnitude than that of the latter. On this basis, Mohol- 2.37 ·10–3 min–1, was achieved at an optimum inlet pressure of
kar and Pandit suggested some important strategies for the 4 bar in an orifice reactor [56].
design of a hydrodynamic cavitation reactor. For more details,
see [52].
Using different cavitation devices, i.e., orifice plate, circular 3.3.2 Effect of Bulk Liquid Temperature
venturi, and slit venturi, Saharan et al. [39] studied the degra-
dation of orange-G dye and discussed the effects of the geomet- The investigation on bubble dynamics reveals that, as the tem-
rical and operating parameters on the degradation rate. The perature of liquid increases, liquid properties such as viscosity,
degradation rate of the slit venturi configuration was almost surface tension, and gas solubility decrease, and thus both the
50 % higher than those of the other two structures. They also cavitation intensity and the number of cavity nuclei are
pointed out that the maximum cavitation yield could only be reduced [57]. An increase of temperature also promotes the
vapor pressure inside the bubble and leads to a
cushioning effect making the bubble collapse less
violently. However, since more free radicals will al-
so be generated in a cavitation bubble at higher
temperature, the overall effect is sometimes unpre-
dictable. The discoloration experiments of Orange
acid-II [58] and Orange 7 [59] showed that low
temperature is favorable for enhancing the dis-
coloration. But, the degradation experiment of
2,4-dinitrophenol indicated that the extent of deg-
radation increased with higher temperature and
Figure 9. Typical venturi tube. then marginally decreased after 35 C [60]. A simi-

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Review 7

lar trend was also observed in the degradation of alachlor 3.3.6 Effect of Physicochemical Properties of the Liquid
[40]. The degradation rate increased with rising the tempera-
ture in the range of 30–40 C and decreased when the temper- According to [28, 51, 57, 67], the favorable conditions for
ature exceeded 40 C. enhancing cavitation effects are low liquid vapor pressure, low
viscosity, and high surface tension. An increase of the vapor
pressure will enhance the vapor content inside the cavity. As
3.3.3 Effect of pH a consequence, the intensity of bubble collapse decreases due
to the cushioning effect caused by the continuous condensa-
Usually, an acid condition is recommended for pollutant degra- tion of vapor. Therefore, liquids with lower vapor pressure
dation by hydrodynamic cavitation [22, 54, 55, 61–63]. Such will generate higher cavitation intensity. Increasing the vis-
condition favors the generation of hydroxyl radicals due to the cosity will raise the threshold pressure of the cavitation event
decomposition of hydrogen peroxide and impedes the recom- since it has to overcome a stronger natural cohesive force.
bination reaction among free radicals. The effect of solution Hence, there is a better cavitation effect in those fluids with
pH on the extent of degradation of diclofenac sodium was lower viscosity. The pressure caused by surface tension can
investigated by varying the initial pH in the range of 4–7.5 be expressed as [68]:
[61]. The degradation rate was raised from 14.7 to 26.8 % when 2s
changing the pH from 7.5 to 4. Similarly, the degradation Ps ¼ (8)
R
experiment of imidacloprid demonstrated that the maximum
rate of degradation was obtained at an optimum pH of 3. where s is the surface tension coefficient. The pressure caused
Under alkaline conditions, the extent of degradation was much by surface tension will accelerate the bubble contraction pro-
lower than that under acidic conditions [62]. cess. Hence, the bubbles collapse more violently as the surface
tension increases and the resultant final collapse temperature
and pressure are marginally higher as well.
3.3.4 Effect of Initial Pollutant Concentration

For the pseudo-first-order degradation reaction induced by 3.4 Deficiency of the Experimental Investigations
cavitation, the reaction process can be described as [40]:
Experiments have proved that hydrodynamic cavitation can
C ¼ C0 e kt
(6) degrade many organic pollutants. Nevertheless, most of them
are conducted in laboratory scale with single-component solu-
or tion and very few studies deal with multicomponent solution
and actual industrial wastewater [42, 44, 49, 69]. Overall, based
k ¼  lnðC=C0 Þ=t (7) on these experiments, some coherent rules of chemical reaction
dynamics and influencing factors have been obtained from the
where C is the pollutant concentration at time t, C0 is the initial qualitative perspective, but some problems still exist in view of
concentration, and k is the degradation rate constant. quantitative analysis.
It can be seen from Eq. (7) that increasing the initial pollu- Considering the cavitation reactor, there is a lack of compari-
tant concentration will decrease the degradation rate [40]. If son and validation of the results since various self-made devices
cavitation conditions keep unchanged, the amount of HO. rad- were used in different research groups. To solve this problem,
icals in the system would be constant. But, the total pollutant standardized devices which only consist of commercially avail-
amount in the solution increases with higher initial pollutant able parts would be helpful. These standardized cavitation devi-
concentration. Therefore, the degradation rate is reduced. ces with different flow fields, turbulence characteristics, and
Nevertheless, the increase of the initial pollutant concentration geometrical parameters are demanded to investigate the effects
will also make more pollutants captured by HO., thereby the of such factors on degradation characteristics. Besides, experi-
total decomposition amount becomes higher [64]. The degra- ments with different scales should be carried out to address
dation experiment of imidacloprid using the slit venturi proved scale-up issues, such as the alteration of flow field and turbu-
that the pseudo-first-order rate constant increased from lence characteristics in large scale.
0.79 ·10–3 to 1.27 ·10–3 min–1 with decreasing the initial con- In terms of properties of pollutant substrates, there are still
centration from 60 to 20 ppm [62]. no clear correlations between physicochemical parameters
and degradation conversion. On the one hand, the number
of substrates in some experiments is probably too small to
3.3.5 Effect of Initial Radius of the Nuclei draw the generalized statements. On the other hand, it is of
great difficulty to compare these data from different experi-
Cavities with lower initial size will grow to a larger extent and ments due to the discrepancy of cavitation devices and oper-
give rise to more violent collapse [65]. Hence, decreasing the ating conditions. Moreover, some recent studies have used
initial radius will promote the pressure pulse caused by the synthetically made effluents. As the actual industrial waste-
bubble collapse and enhance the overall effect of hydrodynamic water contains variable amounts of other compounds, the
cavitation [13, 66]. results achieved under these conditions may not be repro-
duced with actual wastewater.

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8 Review

4 Hydrodynamic Cavitation Fe3þ þH2 O2 fi ½FeOOH2þ þHþ (14)


with Intensified Strategies
Hydrodynamic cavitation has application potential in waste- ½FeOOH2þ fi Fe2þ þHOO (15)
water treatment, but sometimes it is also difficult to obtain
satisfactory treatment efficiency by using hydrodynamic cavita- Fe3þ þHOO fi Fe2þ þO2 þHþ (16)
tion alone. In these situations, the process could be supple-
mented by other advanced oxidation processes (AOPs) to gen- To maximize the effectiveness of AFP, such factors as solu-
erate more oxidizing agents. tion pH, ferrous ion concentration, hydrogen peroxide loading,
and operating temperature should be optimized. By using dif-
ferent additives like hydrogen peroxide, carbon tetrachloride,
4.1 Effect of H2O2 Addition and Fenton’s reagent, Joshi and Gogate [72] conducted a study
on dichlorvos degradation. Effects of different ratios of FeSO4/
Hydrogen peroxide and water molecules can be dissociated H2O2 were investigated. The results indicate that at a fixed con-
forming radicals: centration of H2O2 both the degradation rate constant and the
extent of removal rise significantly with increasing the FeSO4
H2 O fi HO þH (9)
loading. Similar results were reported by Patil and Gogate [56]
for degradation of methyl parathion using the same device.
H2 O2 fi HO þHO (10) The initial concentration and pH of the solution play an im-
portant role in the Fenton process. Pradhan and Gogate [54]
H2 O2 þHO fi H2 O þ HO2  (11) investigated the removal of p-nitrophenol with 5 and 10 g L–1
initial concentrations. In case of using hydrodynamic cavita-
In the presence of cavitation, hydrogen peroxide will show a tion alone, the removal for 5 g L–1 initial concentration of
synergetic effect due to the supply of additional hydroxyl radi- p-nitrophenol was 53.4 % whereas it was 44.8 % for 10 g L–1 ini-
cals, but in case of excessive addition, it can also scavenge the tial concentration under the same conditions. After combina-
generated hydroxyl radicals. Thus, the use of hydrogen perox- tion with AFP, the maximum extent of degradation increased.
ide is favored only in optimum concentrations. The synergetic For 5 g L–1 initial concentration, a maximum removal of 63.2 %
effect of hydrogen peroxide on hydrodynamic cavitation was was obtained at 1 g L–1 FeSO4 and 5 g L–1 H2O2 loadings. For
investigated for the degradation of Reactive Red 120 dye and 10 g L–1 initial concentration, the maximum removal of 56.2 %
Red 88 Dye [38, 63]. Compared with only 60 % reduction of was observed at 1 g L–1 FeSO4 and 7.5 g L–1 H2O2 loadings. For
color and 28 % reduction of TOC in case of only hydrodynamic the higher pollutant concentration, higher loading of hydrogen
cavitation, almost 100 % decolonization and 60 % reduction of peroxide is required to yield more oxidizing agents. The maxi-
TOC were obtained when the molar ratio of added H2O2 to mum removal was obtained at pH 3.75 because the generation
dye concentrations was 1:60. There was only 13.15 % reduction of hydroxyl radicals and their oxidation capacity were favored
of color using the same amount of H2O2 addition without under acidic condition. When the solution was in alkaline con-
hydrodynamic cavitation. dition (pH 8.0), the extent of removal decreased considerably
On the one hand, the addition of H2O2 provides supplemen- since both the formation of iron species and their catalytic
tary oxidizing agents. On the other hand, hydrodynamic cavi- activities were suppressed by the pH of the solution.
tation enhances the decomposing of H2O2 and also the micro-
mixing of reactants. Thus, the combination of hydrodynamic
cavitation and H2O2 could have a better effect as compared to 4.3 Combination with Acoustic Cavitation
the single application of these processes. However, there was
no further increase in color and TOC reduction when exceed- Compared with acoustic cavitation, hydrodynamic cavitation
ing this addition concentration. provides a better scale-up possibility [16], higher bubble num-
ber densities, and lower investment cost [73]. However, the col-
lapse intensity of bubbles in hydrodynamic cavitation is rela-
4.2 Combination with Advanced Fenton Process tively low [15]. Therefore, a combination of both techniques
(AFP) was introduced into one system. Franke et al. [74] investigated
the degradation of chloroform by using ultrasonic cavitation,
AFP is one of the AOPs, in which highly reactive hydroxyls are hydrodynamic cavitation, and their combination. The combi-
produced by decomposition of hydrogen peroxide with ferrous nation of acoustic cavitation with hydrodynamic cavitation
ion (Fe2+) as catalyst in an acidic milieu. The exact reaction gave the best conversion of 90 %, while the conversions were
mechanism leading to enhanced HO generation is given as fol- only 70 and 7 % for individual ultrasonic and hydrodynamic cav-
lows [70, 71]: itation, respectively. This demonstrates that both acoustic cavita-
tion and hydrodynamic cavitation can promote each other.
Fe2þ þH2 O2 fi Fe3þ þHO þOH (12) Jyoti and Pandit [37] compared the efficiencies of acoustic
cavitation, hydrodynamic cavitation, hydrogen peroxide, and
Fe2þ þHO fi Fe3þ þOH (13) their combinations for bacterial disinfection. The results

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Review 9

showed that, though the cavitation yield was not as high as that of cavitation bubbles increases at lower cavitation threshold,
of single acoustic cavitation, the extent of killed bacteriae was the introduction of photocatalysts into the cavitation reaction
much higher in case of the combination of hydrodynamic cavi- system can enhance the cavitation yield. With TiO2 as photo-
tation with acoustic cavitation. A bacterial removal of 99.9 % catalyst, the combination of photocatalytic oxidation with
was achieved by combining hydrodynamic cavitation, acoustic water-jet cavitation was applied to investigate the degradation
cavitation, and hydrogen peroxide. of Reactive Red 2. The results showed that the simultaneous
usage of photocatalyst and jet cavitation could provide 60.5 %
degradation rate. However, this rate is only 25.6 and 3.1 %
4.4 Use of Ozone with Hydrodynamic Cavitation when photocatalytic oxidation and jet cavitation are applied
separately [78].
Ozone is a powerful oxidant widely used in wastewater treat-
ment. But there are some toxic by-products during ozonation
such as aldehydes and other compounds that can’t be ruled
4.6 Patented and Commercialized Oxidation
out. Employing hydrodynamic cavitation during ozonation can
Process Involving Hydrodynamic Cavitation
diminish or eliminate these toxic by-products by reducing the
usage of ozone. Besides, as compared to individual treatment
4.6.1 CAV-OX Process
techniques, the combination of hydrodynamic cavitation with
ozone is proved to be more efficient due to the following reac-
The CAV-OX process, which combines hydrodynamic cavita-
tion mechanism [75]:
tion, ultraviolet radiation, and hydrogen peroxide to oxidize
O3 fi O2 þO (17) organic compounds in water, was developed by Magnum Water
Technology (El Segundo, CA) [79]. A schematic of the process
is illustrated in Fig. 10. The CAV-OX process can treat a num-
OþH2 O fi 2HO (18) ber of contaminants such as pentachlorophenol, benzene, tolu-
ene, ethyl benzene, xylenes, cyanide, phenol, and atrazine. A
In combination with ozone treatment, the removal of blue- variety of cases in pilot-plant scale demonstrates that the pro-
green algae by hydrodynamic cavitation was explored and syn- cess is highly effective. The synergistic work of cavitation, UV
ergetic effects were detected. The destruction of algae individu- radiation, and hydrogen peroxide can reduce contaminant con-
ally using hydrodynamic cavitation and ozone was 15 and centrations by 95 to 99.99 % under optimum conditions.
35 %, respectively, but significantly increased to 91 % when
using the combined method under optimized conditions [76].
4.6.2 Hybrid Advanced Oxidation Reactor: Ozonix

4.5 Use of Photocatalyst with Hydrodynamic Gogate et al. [80] developed a hybrid advanced oxidation reac-
Cavitation tor using a combination of hydrodynamic cavitation, acoustic
cavitation, ozone injection, and electrochemical oxidation/
Heterogeneous photocatalytic oxidation is another AOP for precipitation, which is called Ozonix (see Fig. 11). This chemi-
wastewater treatment. Semiconductor photocatalysts, such as cal reactor was tested, deployed, and commercialized in the
TiO2, ZnO, CeO2 etc., can absorb radiation. If they come into USA and the effectiveness was demonstrated in bacteria dis-
contact with water and oxygen, highly reactive hydroxyl radi- infection over a three-year period. The 776 bacteria samples
cals and superoxide anion (O2–) would be generated [77]. The were taken from 282 wells in the Fayetteville Shale. The results
practical application of photocatalytic oxi-
dation is limited due to the reduced effi-
ciency of photocatalysts caused by the
adsorption of contaminants on its surface
[8]. The microjets, shear stress, and turbu-
lence generating during bubble collapse
can refresh and disperse the catalyst par-
ticles and enable full contact with the reac-
tants. Therefore, cavitation can eliminate
the disadvantages associated with photocat-
alytic oxidation.
In addition, extra hydroxyl radicals gen-
erating in the cavitation can also aid the
degradation process. Besides, because of
the effect of particle surface roughness, the
addition of photocatalysts can also decrease
the cavitation threshold due to their poten-
tial as cavitation nuclei. Since the number Figure 10. CAV-OX process.

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10 Review

ing the wide application of AOPs to Rhodamine degradation,


some experimental data about Rhodamine B degradation were
collected as a starting step to assess the energy efficiency of dif-
ferent cavitation reactors, as summarized in Tab. 2.
The comparison of cavitation yields is depicted in Fig. 12. To
reduce the complexity, only maximum cavitation yields
achieved under optimum conditions are considered. The cavi-
tation yield of unit energy input is initially expressed as
Eq. (19). Then, by taking the pollutant volume into considera-
tion, the cavitation yield of per volume density energy input
Figure 11. Schematic representation of the Ozonix reactor. can be evaluated through Eq. (20):

showed that the removal of bacteria was up to 96.5 % for acid-   amount of pollutant degradated
cavitation yield mg J1 ¼
producing bacteria samples and 97.5 % for sulfate-reducing Pm t
bacteria samples. This kind of reactor behaves also superior in (19)
promoting the flow ability and chemical compatibility of treat-
ed water.
  amount of pollutant degradated
cavitation yield mg L J1 ¼
ðPm t Þ=V
5 Energy Efficiency and Economics (20)
Assessment
where Pm is the power of the pump, t is the operation time,
5.1 Energy Efficiency of Cavitation Technique and V is the volume of pollutant solution.
It can be seen from Fig. 12 that the maximum cavitation
The energy efficiency of cavitation reactors should be evaluated yield of unit energy input is achieved with the combination of
based on the concentration and type of the pollutant. Consider- ultrasonic cavitation and H2O2. However, if the effect of water

Table 2. Results obtained by different cavitation-based techniques (AC = acoustic cavitation, HC = hydrodynamic cavitation) dealing
with Rhodamine B.

Cavitation apparatus Technique Water Electricity Time of Pollutant Maximum Maximum


volume [L] power operation removed cavitation yield of cavitation yield of
input [W] [min] [mg] unit energy input unit volume density
[mg L–1] energy input
[mg L J–1]

Swirling jet reactor [21] HC 20 3500 180 187.2 4.95 ·10–6 9.90 ·10–5

Orifice plate [5] 50 5500 60 43.7 2.21 ·10–6 1.10 ·10–4

Orifice plate [22] 4 1100 120 9.2 1.16 ·10–6 4.64 ·10–6

Venturi [22] 4 1100 120 10.4 1.31 ·10–6 5.25 ·10–6

300-kHz ultrasonic AC 0.3 60 140 1.5 2.97 ·10–6 8.93 ·10–7


generator [85]

Multiple frequency 7.5 900 30 2.2 1.36 ·10–6 1.04 ·10–4


(20 + 30 + 50 kHz)
hexagonal cell [86]

Swirling jet reactor [64] HC and H2O2 25 2500 180 247.8 9.18 ·10–6 2.29 ·10–4

Venturi [22] 4 1100 120 40.0 1.01 ·10–6 2.02 ·10–5

Orifice plate [87] HC and Fe 30 5500 120 45.0 1.14 ·10–6 3.41 ·10–5

Venturi [22] HC and Fenton 4 1100 45 40.0 1.35 ·10–5 5.40 ·10–5

Venturi [22] HC and CCl4 4 1100 120 32.8 4.14 ·10–6 1.65 ·10–5

24-kHz ultrasonic AC and H2O2 0.2 400 210 95.88 1.90 ·10–5 3.80 ·10–5
generator [88]

300-kHz ultrasonic AC and CCl4 0.3 60 40 1.5 1.04 ·10–5 3.13 ·10–6
generator [85]

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Review 11

radation kinetics of hydrodynamic cavitation obeys the first-


order law, given as:

C
ln ¼ kt (21)
C0

where C is the concentration of pollutant solution at time t, C0


is the initial concentration of pollutant solution, and k is the
rate constant. The time for 95 % degradation in the cavitation
reaction zone is:

2:996
t95 ðminÞ ¼ (22)
k

The electric energy in kWh required for 95 % degradation is


Figure 12. Comparison of cavitation yield achieved by different calculated as:
cavitation-based techniques.
Pm t95
EðkWhÞ ¼ (23)
60 · 1000
volume is considered, swirling jet cavitation with H2O2 addi-
tion stands out. Due to a low electricity power input to gen- If the price of electricity is P* ($ kWh–1), the operation cost
erate ultrasonic waves, acoustic cavitation has relatively high of the hydrodynamic cavitation system would be:
energy efficiency in small-volume operation in comparison to
hydrodynamic cavitation. Because the energy is concentrated C1 ¼ EP* (24)
to induce local pressure disturbance, the intensity of bubble
collapse is higher in acoustic cavitation. However, the energy It should be noted that Pm and k are related with the volume
distribution in the hydrodynamic cavitation reactor is rela- of the pollutant as well as with geometry and operation condi-
tively homogeneous. Besides, hydrodynamic cavitation allows tions of the system. Generally speaking, the operating cost of
continuous operation and the volume of treated liquid is the cavitation reactor, especially acoustic cavitation reactor, is
larger. Overall, hydrodynamic cavitation shows certain advan- higher as compared to the conventional biochemical method,
tages in large-scale operation and is more likely to realize but the optimization of operating parameters will help to
industrial operation. In order to further enhance the efficien- obtain better overall benefits. The treatment cost of a unit vol-
cy, hydrodynamic cavitation should be combined with AOPs ume wastewater using hydrodynamic cavitation will reduce in
or additives. large-scale operation. Besides, such advantages as no additional
by-products, easy operation, and ability of decomposing bio-
refractory pollutant should also be weighed against the process-
5.2 Economics Assessment of Hydrodynamic ing cost.
Cavitation Compared with Traditional Method

A general economic method dealing with organic compound 6 Recommendations for Future Work
degradation is the biochemical method. However, some com-
ponents, such as poly(ethylene terephthalate) (PET), poly(vinyl According to the above-mentioned aspects about hydrodynam-
alcohol) (PVA), and some dispersed dyes, are biorefractory or ic cavitation, the following theoretical and experimental work
toxic. Such kind of industrial water has a low BOD/COD value is suggested to establish pathways for transferring the funda-
and an unsuitable pH for biochemical degradation. In this case, mental technique into practice. Efforts needed in terms of theo-
utilization of AOPs is necessary. Mahamuni and Adewuyi [18] retical studies are as follows:
made a cost estimation of acoustic cavitation for wastewater – Most of the existing investigations dealing with the degrada-
treatment. The results showed that the cost of the process using tion effect of hydrodynamic cavitation are based on the as-
acoustic cavitation is higher than AOPs such as ozonation, sumption of a single spherical bubble, which is not identical
O3/H2O2, and UV/H2O2 but the combination of ultrasonic to the real situation. Realistic models considering the bub-
cavitation with AOPs is economically more attractive. ble-bubble/bubble-liquid interface and the nonspherical
So far, the economics assessment of hydrodynamic cavitation bubble collapse are urgently needed. Meanwhile, more accu-
has not been reported. Such factors as wastewater amount, rate pressure distribution should be adopted in new models.
quality of wastewater from different industrial processes, and – Chemical effects of hydrodynamic cavitation in terms of
effluent standards affect the process cost. A simple method to hydroxyl radical generation have been studied massively, yet
evaluate the economics of hydrodynamic cavitation in waste- there is a lack of direct simulation of the degradation process
water treatment is to calculate its operation cost. First of all, on the basis of chemical reaction kinetics. In other words,
the discharge standard is assumed as 95 % of pollutant degra- the existing investigations are insufficient in direct and
dation. According to the most previous investigations, the deg- quantitative descriptions to the free radicals reaction with
the contaminants. Besides, both the lifetimes of different

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12 Review

radicals and the position where the reaction mainly occurs selection of operating parameters plus the use of intensification
need to be studied further. techniques will help to obtain more overall advantages. In sum, it
– Theoretical models that are flexible for the design of a cavi- can be stated that hydrodynamic cavitation is a well-established
tation reactor and the optimization of operating parameters technology at laboratory scale and more efforts are required to ef-
should be established. The effects of geometric and operating fectively promote this technology for industrial operation.
parameters on the cavitation intensity and the number of
cavitation events should be studied in detail. In order to have
a full control over the process, the generalized correlation Acknowledgment
which relates hydroxyl radical generation with operating
parameters and characteristic time scale needs to be devel- This work is financially supported by the National Natural
oped for various cavitation reactors. Science Foundation of China (51376181), the National Basic
– Based on the CFD technique, simulations considering the Research Program of China (2011CB710705), and the Youth
chemical reactions should be conducted to analyze the degrada- Innovation Promotion Association, CAS (2012129).
tion process either in a single bubble or in the cavitation field.
Efforts required on the experimental front are as follows: The authors have declared no conflict of interest.
– Standardized devices that only consist of commercially avail-
able parts should be used to generate comparable results.
The design and fabrication of such devices with different Symbols used
flow fields, turbulence characteristics, and geometrical
parameters are required to study the effects of these factors C [mg L–1] concentration of pollutant solution
on bubble dynamics and degradation characteristics. C0 [mg L–1] initial concentration of pollutant solution
– More experiments with different operation scales should be C1 $ operation cost of the hydrodynamic
conducted to help to understand and address scale-up issues, cavitation system
such as alterations in the flow field and turbulence character- Cv [–] cavitation number
istics due to the scales of operation. dh [m] diameter of orifice holes
– The design of reactors for degrading pollutants with similar dp [m] diameter of pipe
chemical structure should be presented. Experiments dealing E [kWh] electric energy
with multicomponent solutions need to be carried out, and G [J mol–1] Gibbs activation energy
the reaction rate and products should be detected to charac- J [–] cavitation event rate
terize and optimize the degradation process. The interaction J0 [–] normalized pre-exponential factor of
between different components should be considered to give cavitation rate
reproducible results. k [min–1] chemical rate constant
– A large number of substrates should be employed to evaluate n [–] total number of holes
the effect of physicochemical properties on the degradation P [Pa] axial pressure at downstream
process. Properties such as vapor pressure, solubility, viscosi- P2 [Pa] fully recovered pressure at downstream
ty, and density should be correlated with the conversion. Pm [W] power of pump
– Intensified strategies should be optimized to bring maxi- Pv [Pa] saturated vapor pressure
mum chemical effects of hydrodynamic cavitation. Ps [Pa] surface tension pressure
P* [$ kWh–1] electric price
R [m] bubble radius
7 Conclusions R0 [m] initial radius of cavitation bubble
v0 [m s–1] liquid velocity at the constriction
The theoretical and experimental aspects of hydrodynamic cav- t [s] instantaneous time
itation applied to wastewater treatment are overviewed. Hydro- t95 [min] time needed for 95 % pollutant
dynamic cavitation can generate high-temperature and high- degradation
pressure conditions which leads to the dissociation of water V [L] pollutant solution volume
molecules and the release of active radicals. Many of the chemi-
cal transformations take place under these conditions. Both the Greek letters
magnitudes of pressure and temperature and the number of a [m–1] area-to-perimeter ratio of orifice holes
free radicals are affected by the geometrical and operating b [–] flow area ratio of the pipe to orifice plate
parameters. Optimization of these parameters using theoretical r [kg m–3] liquid density
analysis as well as laboratory-scale study is always recom- s [N m–1] surface tension coefficient
mended before putting the new technology into practice. t [s] total time for the pressure recovery
The future of hydrodynamic cavitation in wastewater treat-
ment depends on the design of energy-efficient and economic Abbreviations
reactors, and so the combination with AOPs is necessary. It
should be noted that the operating cost of a cavitation reactor, AC acoustic cavitation
especially an acoustic cavitation reactor, are higher as com- AFP advanced Fenton process
pared to the conventional reactor. Nevertheless, the optimum AOP advanced oxidation process

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Review 13

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These are not the final page numbers! ((

Review 15

Review: Theoretical and experimental Application of Hydrodynamic


aspects of hydrodynamic cavitation Cavitation to Wastewater Treatment
applied to wastewater treatment are
reviewed. Experimental setups, Y. Tao, J. Cai*, X. Huai, B. Liu, Z. Guo*
theoretical models, and research results
are compared and promising synergetic Chem. Eng. Technol. 2016, 39 (XX),
approaches are described. The future XXX K XXX
potential of hydrodynamic cavitation in
wastewater treatment depends on the DOI: 10.1002/ceat.201500362
design of energy-efficient and
economic reactors.

Chem. Eng. Technol. 2016, 39, No. 00, 1–15 ª 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim www.cet-journal.com

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