3370 Ind. Eng. Chem. Res.

2002, 41, 3370-3378

A Sonophotochemical Reactor for the Removal of Formic Acid from

Wastewater
Parag R. Gogate, Sukti Mujumdar, and Aniruddha B. Pandit*
Chemical Engineering Section, U.I.C.T., Matunga, Mumbai 400 019, India

The efficacy of a sonophotochemical reactor coupling ultrasonic irradiation with photocatalytic

oxidation has been evaluated using formic acid degradation as the model reaction. The reactor
used in the present work is a hexagonal flow cell irradiated with multiple-frequency transducers
placed at the wall of the reactor and by ultraviolet radiation positioned at the center of the
reactor. The various operating parameters studied in the present work include the concentration
of the photocatalyst, initial concentration of the pollutant, and effect of aeration for the case of
photocatalytic oxidation. The sonophotochemical operation has been studied in two ways:
simultaneous irradiation and sequential irradiation with the aim of understanding the expected
synergism between the two modes of energy transmission. The effect of the addition of hydrogen
peroxide on the extent of degradation has also been studied. The hybrid technique of
sonophotochemical degradation in the presence of aeration and hydrogen peroxide has been
compared with the individual techniques of photocatalysis, ultrasonic irradiation, and addition
of hydrogen peroxide alone, and recommendations about the effective techniques have been made
for wastewater treatment applications.

1. Introduction power input of 900 W and frequencies of 20, 30, and 50

kHz operating in multiple combinations and was used
Pollution is the contamination of water, air, and land for the degradation of formic acid. It was observed that,
with materials that distract from their ability to support although the equipment was able to destroy formic acid
the ecosystem or provide some human need. Human
at a reactor capacity of 7 L, the rate of degradation was
activities, industrial processes, and agricultural usage
quite less (only 6-7% destruction was observed in 2 h
are the big contributors to the pollution problem. With
new developments in almost all of the fields and the of time) and, hence, the time spans required for achiev-
invention of new molecules which can withstand bio- ing complete degradation of chemical contaminants will
logical degradation, it is important to invent and apply be quite large (the rate of degradation will be further
new treatment procedures to keep the balance of the reduced for complex real effluents where a large variety
ecosystem intact. One of the new generation technolo- of chemicals will be present that would interfere with
gies, quite well established on a laboratory scale, is the main reaction pathways). Further, it is also impor-
acoustic cavitation, i.e., cavitation generated using tant to consider the cost of using US irradiation for the
ultrasound. During the cavitation phenomenon, very destruction process on an industrial scale. The current
large magnitudes of temperature and pressure are costs for the cleaning of contaminated groundwater with
generated locally, also releasing large amounts of free ultrasound are an order of magnitude higher than those
radicals by the dissociation of water, which are capable by an air stripping/active carbon process.7 Thus, it is
of oxidizing/degrading a variety of organic and inorganic important to either find an alternative means for using
compounds, specifically biorefractory chemicals. The use cavitation energy efficiently or use acoustic cavitation
of sonochemical reactors for wastewater treatment (generated by US irradiation) in combination with other
applications is not new to researchers.1-10 Excellent methods, e.g., photocatalytic oxidation, etc., with the
reviews are also available on the use of sonochemical aim of enhancing the rates of degradation.
reactors depicting in detail the mechanism of generation
A promising aspect of photocatalysis with semicon-
of cavitation as well as its action, the types of reactors
ductor materials is the near-complete mineralization of
used, the optimum operating conditions, and different
applications.11-15 It should be noted here that the environmental pollutants in the waste stream under
majority of the studies are on a laboratory scale, with ambient conditions. Various chalcogenides (oxides such
the capacity of the reactor on the order of a few as TiO2, ZnO, ZrO2, CeO2, etc., or sulfides such as CdS,
milliliters. It is very unreliable to use this knowledge ZnS, etc.) can been used as photocatalysts; however, it
to design large-scale reactors for wastewater treatment should be noted that the best photocatalytic perfor-
applications because of very high scale-up ratios and mances with maximum quantum yields have always
also nonsuitability of ultrasonic (US) transducers to been reported with titania (Degussa P-25 type, which
operate at high frequencies and high power dissipation is a combination of rutile and anatase grade). There has
rates efficiently. In an earlier work,5 a triple-frequency been extensive literature on the application of photo-
flow cell was designed with operating conditions of a catalysis to wastewater treatment,16-25 and excellent
reviews are also available on this subject.26-30 In the
* To whom correspondence should be addressed. E-mail: case of photocatalytic oxidation, the most common
abp@udct.ernet.in. Phone: 91-22-414 5616. Fax: 91-22- problem is the reduced efficiency of the photocatalyst
4145614. with continuous operation possibly due to the adsorption
10.1021/ie010711l CCC: $22.00 2002 American Chemical Society
Published on Web 06/07/2002
 Ind. Eng. Chem. Res., Vol. 41, No. 14, 2002 3371

of contaminants on the catalyst surface and blocking of

the sites, which makes them unavailable for the de-
struction. Thus, the aim should be to devise a technique
for proper cleaning of the catalyst surface during the
photocatalytic operation. US irradiation can be one such
technique, and it also provides an additional surface
area for the reaction due to fragmentation or deagglom-
eration of the catalyst particles. Ultrasound will play a
profound role in the situations where the adsorption of
pollutants at the specific sites is the rate-controlling
step. Moreover, photocatalytic oxidation is also affected
by severe mass-transfer limitations especially in the
supported catalyst types of reactors, which are generally
preferred over slurry reactors to avoid separation prob-
lems. Turbulence created by the acoustic streaming
produced by ultrasound should eliminate or decrease
the mass-transfer resistance considerably. One more
factor suggesting that the two techniques will give Figure 1. Experimental setup used for studying synergism
better results when operated in combination is the fact between the US and UV irradiations.
that, for both of the techniques, the basic reaction
mechanism is the generation of free radicals and The effect of the addition of hydrogen peroxide (it is
subsequent attack of these on the pollutant species. If an additional source of free radicals) has not been
the two irradiations are operated in combination, a studied in the literature (except for some papers by the
larger number of free radicals will be available for the Fung group33,34,37 at an operating capacity of 4.5 L) for
reaction, thereby increasing the rates of reaction, as well the combination technique of US and UV irradiation,
as the degree of oxidation conditions will be compara- and hence some experiments with the addition of
tively higher and hence the hybrid method should be hydrogen peroxide have been performed in the present
able to degrade a wider range of pollutants. work at enhanced capacities.
There have been many studies depicting the observed
synergism and the enhanced rates of degradation for 2. Experimental Section
the combinatorial operation of sonochemical reactors The experiments were performed in a hexagonal flow
and photocatalytic oxidation.31-42 Recently, Toma et al.43 cell depicted schematically in Figure 1. The reactor has
have given a brief overview of different studies pertain- a total capacity of 7.5 L and can be operated in either
ing to the effect of ultrasound on photochemical reac- batch or continuous mode. In the present work, 7 L of
tions concentrating on the chemistry aspects, i.e., aqueous formic acid has been used and the operation
mechanisms and pathways of different chemical reac- was in batch mode.
tions. It has also been observed that the majority of Each side of the hexagonal flow cell is provided with
studies are restricted to volumes of less than 1 L, and three transducers, each with a power dissipation of 150
hence the scale-up of these reactors for actual waste- W/side. The opposite faces of the hexagon have trans-
water treatment application will be extremely difficult ducers with irradiating frequencies of 20, 30, and 50
because the scale-up ratio required is very high. With kHz and can be operated either individually or in
a view of moving one step ahead in this direction, it was combinations. The total maximum power that can be
thought desirable to study the synergism between dissipated in the system is 900 W when all of the
sonochemical and photocatalytic reactors at a large scale transducers (a combination of 20 + 30 + 50 kHz) are
of operation (7 L) in a triple-frequency hexagonal operated.
sonophotochemical flow cell. The system chosen was the In the annular space provided at the center of the
destruction of formic acid because in the majority of the reactor, one tube of UV light was used with a power
degradation schemes of organic compounds the end dissipation of 8 W. The UV light source was fitted in a
products are usually lower acids which control the quartz tube placed inside the reactor, and the entire
overall rate of reduction of total organic carbon (TOC) volume of the reactant is enclosed in an annular space
or chemical oxygen demand. It should be also noted that surrounding the quartz tube and enclosed by the
the destruction of formic acid leads to a complete hexagonal faces. A stirrer was fitted in the reaction zone
mineralization if operated for longer times (oxalic acid to ensure a good dispersion of TiO2 catalyst along with
and hydrogen peroxide, which may be formed in the continuous renewal of the film of the reactants around
course of the reaction, are also susceptible to both US the quartz tube for UV irradiation as well as around
and ultraviolet (UV) irradiation and hence should be the wall of the reactor for US irradiation.
degraded; the other oxidation products can be carbon Different concentrations of formic acid, in the range
dioxide, water, CO, and H2). Because the main aim of 100-1000 ppm, have been used to study the effect of
the present work is to highlight the engineering aspects the initial concentration on the extent of degradation.
of the large-scale operation of sonophotochemical reac- Anatase-grade TiO2 was used as the photocatalyst, and
tors, not much effort was put forward to perform a its concentration was also varied in the range 100-1000
detailed kinetic analysis. Much of the information is ppm to check for optimum concentration of the same.
available regarding the kinetic studies in the open The temperature of the reaction mixture was always
literature,33,34,36,37,41 and all of the studies have reported maintained in the range of 28-30 C, and continuous
that the degradation using the combination of US and aeration using a sintered multipoint sparger, at a rate
UV irradiation follows first-order kinetics with respect of 1.02 cm3/s, was carried out in all of the experiments.
to the pollutant, irrespective of its type. Some experiments were done in the presence of H2O2
3372 Ind. Eng. Chem. Res., Vol. 41, No. 14, 2002

Figure 3. Variation of percentage degradation of formic acid with

Figure 2. Degradation of formic acid using US irradiation alone. initial concentration during an irradiation time of 90 min at a
catalyst concentration of 500 ppm.
(concentration in the range 0.1-0.5 mL/L of formic acid)
alone and also in the combination of UV/US/H2O2 to individual sonochemical degradation of formic acid can
examine the extent of enhancement observed due to be obtained in the earlier work.5 Moreover, the presence
hydrogen peroxide. of air increases the extent of irradiation. The enhance-
The amount of the formic acid remaining in the ment in the presence of air was observed for all of the
solution was determined using titration with the stan- seven combinations studied in terms of frequency;
dard alkali (NaOH). The concentration of the standard results are only shown for the multiple-frequency opera-
alkali (NaOH) was so adjusted that the readings of tion to avoid repetition.
titration were in the range of 20-25 mL with the least 3.2. Photocatalytic Oxidation. The experiments for
count of the buret used as 0.1 mL. Moreover, the individual photocatalytic oxidation studies were per-
titration was repeated two to three times to get accurate formed in two different sets for investigating the effect
readings, and hence attempts have been made to keep of the initial concentration of formic acid and the
the errors below 0.1%. The experiments were continued concentration of photocatalyst TiO2. Aeration was found
for up to 2 h of irradiation time, and analysis was done to be essential for the photocatalytic oxidation, and
at intervals of 30 min. hence in all of the experiments aeration was used.
3.2.1. Effect of the Initial Concentration of For-
3. Results and Discussion mic Acid. Figure 3 shows the variation in the percent-
The experiments with degradation of formic acid age reduction in the concentration of formic acid with
consisted of three parts: US irradiation alone, photo- time for different initial concentrations. It can be seen
catalytic oxidation alone, and a combination of US and that the percentage degradation of formic acid is found
UV irradiation (in two parts: sequential operation, i.e., to be inversely proportional to the initial concentration
US irradiation followed by UV irradiation and simul- of formic acid (in the range of 100-1000 ppm at a
taneous irradiation of US and UV irradiation). The aim catalyst loading of 500 ppm). Topalov et al.16 have also
of comparing the simultaneous and sequential opera- reported that the rate of degradation of metalaxyl (a
tions was to check whether any synergism exists typical fungicide) decreases with an increase in the
between the two processes or only the individual effects initial pollutant concentration although the total volume
are contributing to the overall effect. The sequential treated was only 20 mL. Sakthivel et al.,24 with experi-
operation of UV irradiation followed by US irradiation ments on a leather dye, acid green 16, in a reactor with
was not considered in the present work. This can be a capacity of 90 mL, have obtained similar results. In
attributed to the fact that the most important contribu- the present case, the total volume treated was 7 L, and
tion of US irradiation is to regenerate the deactivated thus it can be said that the total volume to be treated
catalyst as well as to increase the surface area of the does not have much effect on the trends observed for
catalyst particles available for the adsorption of the the variation in rate constants with the initial concen-
pollutant and subsequent reaction due to the photo- tration of the pollutant.
catalytic oxidation. If UV irradiations were to be used Further, it was also shown in the earlier work5 that
first, with fresh or the recycled catalyst in the actual the rate of sonochemical destruction of formic acid also
operation, this contribution would not be there and may shows similar trends, a fact that is very much important
result in an even lesser extent of degradation as and essential when designing reactors with the combi-
compared to the operation of US irradiation followed nation of the two modes of irradiation. One must have
by UV irradiation. similarities in terms of the variation with respect to the
3.1. US Irradiation. The results with only US different operating parameters, when the combination
irradiation of formic acid have been discussed in detail of two techniques has to be used for synergism.
in the earlier work,5 and only important findings have It should be, however, also noted that, even if the
been depicted here to give readers better insight into percentage degradation of formic acid is found to be
optimum parameters. Figure 2 gives the variation of inversely proportional to the initial concentration of
percentage degradation with time of irradiation for the formic acid, the net number of moles degraded (calcu-
different combinations studied in the work. It can be lated as percentage degradation multiplied by the initial
seen from the figure that the extent of degradation concentration of the pollutant) is greater for the higher
increases with an increase in the frequency of operation; initial concentrations. This may be attributed to the fact
further, multiple frequencies give better degradation as that the variation in the rate of degradation is perhaps
compared to single frequencies. The detailed explana- little hampered by the effect of pH of the solution. As
tion for this observation and also more studies with the initial concentration of acid increases, the pH
 Ind. Eng. Chem. Res., Vol. 41, No. 14, 2002 3373

Figure 5. Parity plot for the model equation.

of the system (affecting in terms of blockage of the light)

and the operating conditions viz., incident intensity of
UV light and concentration and type of the pollutant
Figure 4. Variation of the percentage degradation of formic acid (deciding the optimization in terms of relative rates of
with catalyst concentration during 90 min of irradiation and at generation and recombination of the electron-hole
100 ppm initial concentration of acid. pairs). Thus, it is of utmost importance to perform
laboratory-scale experiments for the pollutant in ques-
decreases, thereby causing an increase in the expected tion unless data are available in the existing literature
rates of degradation (acidic conditions are always with similarity in the operating conditions and geometry
preferred for the photocatalytic oxidation of the pollut- of the reactor.
ants as observed by Tanaka et al.21 and Andreozzi et 3.2.3. Modeling Approach Required for Design.
al.23). Thus, the observed degradation in the present The data obtained should be modeled to study the effect
case will be somewhat lower as compared to the one of various parameters, and the fitted equation should
observed with constant pH. Thus, one should always give the net degradation of the pollutant. To give an
aim at having a lower initial concentration of the indication about the type of equations to be developed,
pollutant for having higher rates of degradation; no the variation of the extent of degradation with the
doubt some compromise will have to be done because of catalyst concentration (only until the optimum value)
the problems associated with the treatment of higher and the initial concentration of the acid for 30 min of
volumes of pollutant. irradiation has been modeled using regression analysis
3.2.2. Effect of the Catalyst Concentration. The and the resulting equation is given as
effect of the catalyst concentration on the extent of
degradation is shown in Figure 4 (the experimental Ct/C0 ) 0.6631(catalyst concentration)-0.0474
conditions are a formic acid initial concentration of 100 (initial concentration of acid)0.0955 (1)
ppm and a total time of irradiation of 90 min). It can be
seen from the graph that the percentage degradation where Ct is the concentration remaining after time t and
increases with an increase in the catalyst concentration C0 is the initial concentration of acid. The equation
until an optimum value of 500 ppm, beyond which the requires that the catalyst as well as the initial concen-
degradation is observed to decrease. The initial increase tration of acids be in units of ppm and is valid in the
in the rate of degradation can be attributed to the fact range of catalyst concentration of 0-500 ppm (500 ppm
that a greater number of electron-hole pairs are formed is the optimum concentration found in the present work)
because of the large amount of the photocatalyst, and in the range of acid concentration of 100-1000 ppm.
resulting in a greater number of free radicals that attack The constant 0.6631 will be a strong function of the time
the pollutant molecules. Above 500 ppm, however, it is of irradiation, whereas the exponents may or may not
the opacity of the solution due to the presence of solid be dependent on the time of operation. The resultant
particles which inhibits the transmission of UV light model should be checked for accuracy by comparison
as well as results in the scattering of the incident UV with the experimental data, and parity plots (graph of
light and the enhanced rate of electron-hole pair predicted Ct/C0 against experimentally observed Ct/C0)
recombination which results in reduced rates of degra- as shown in the Figure 5 should be made. It must be
dation. Another factor affecting the degradation might noted at this stage that the present equation has been
be the poor dispersion characteristics of the solid pho- developed only to give an indication about the design
tocatalyst at higher concentrations though the contribu- strategy and is valid only in a small range of operating
tion of this might be quite low as compared to the earlier parameters. The generalized equations to be used for
two factors. design procedures must be developed considering the
Similar results have been obtained in the past with entire range of operating parameters and must contain
respect to variation of percentage degradation with the a large number of data points to enhance the confidence
catalyst concentration although for different operating in the design.
and geometric conditions. Sakthivel et al.24 have also 3.3. Combination of US and UV Irradiation. As
reported an optimum value of 250 000 ppm for the was said earlier, two sets, viz., sequential and simul-
catalyst concentration in the destruction of acid green taneous irradiation, were performed in order to inves-
16 dye, whereas Andreozzi et al.23 have shown that the tigate the mechanism of the synergism for the two
photocatalytic degradation of 4-nitrophenol increases techniques under consideration. The simultaneous ir-
with an increase in the catalyst concentration until an radiation technique was studied under different condi-
optimum value of 40 000 ppm. It can be seen that, tions of catalyst concentration and frequencies of irra-
although the trends in the observed variation are same, diation.
the optimum values of the catalyst concentration are 3.3.1. Comparison of Sequential and Simulta-
2-3 orders of magnitude different. This can be at- neous Operation. In sequential operation, the photo-
tributed to the fact that the optimum catalyst concen- catalyst was predispersed using ultrasound, resulting
tration value will be a strong function of the geometry in an increase in the catalyst surface area by fragmen-
3374 Ind. Eng. Chem. Res., Vol. 41, No. 14, 2002

the comparison with photocatalytic oxidation alone

follows a somewhat complex nature. The percentage
degradation initially appears to be reduced in the
presence of ultrasound, which can be explained on the
basis of relative contributions of the different factors
underlying the expected synergism between the two
techniques. Initially, fragmentation of the catalyst is the
dominant factor due to large catalyst size as compared
to cleaning as well as enhancement in the formation of
free radicals. The formation of a large number of solid
particles increases the available surface area, but, on
the other hand, it also causes scattering of the UV light
as well as the ultrasound and also inhibits efficient
Figure 6. Comparison of sequential and simultaneous irradiation transmission of both through the medium. This was also
techniques for sonophotochemical reactors. observed visually by way of the appearance of high
turbidity in the initial periods of irradiation. As the time
progresses, a greater number of free radicals are gener-
ated because of the combined action (UV + US), result-
ing in the enhancement, and also continuous cleaning
of the catalyst particle takes place which is absent in
the case of photocatalytic oxidation alone, resulting in
a higher extent of degradation for the combination.
Moreover, as the catalyst size reaches a certain lower
limit (an equilibrium value), further fragmentation does
not take place. It appears that fouling of the catalyst
surface is the controlling factor in the later stages of
the degradation of formic acid by UV light alone as the
extent of degradation almost reaches a constant value
Figure 7. Comparison of the combination method with the within 2 h of irradiation. In contrast, the extent of
individual techniques for degradation of formic acid. degradation increases continuously in the presence of
ultrasound possibly because of the continuous cleaning
tation/deagglomeration and also cleaning of the catalyst, of the catalyst surface.
and the resultant solution was irradiated by UV light. To validate the above hypothesis of relative contribu-
The experimental conditions were 100 ppm initial tions of different effects of ultrasound, the experiments
concentration of the formic acid and 500 ppm catalyst were repeated with a catalyst concentration of 300 ppm.
concentration. In the simultaneous irradiation tech- For this set, the percentage degradation for the combi-
nique, as the name suggests, both ultrasound and UV nation was 12.24%, whereas for photocatalytic oxidation
light were put on simultaneously. The results for these
alone, it was 14.23% in the first 30 min of irradiation
two techniques are shown in Figure 6. It can be seen
time. Thus, the combination technique gives 14% less
from the graph that the simultaneous irradiation tech-
degradation as compared to only photocatalytic oxida-
nique gives better results as compared to the sequential
tion. However, for the case of 500 ppm catalyst concen-
technique, confirming the fact that not only an increase
in the surface area and precleaning of catalyst are the tration, the same technique gives 28% less degradation
important factors but also production of an additional as compared to the photocatalytic oxidation. This can
number of hydroxyl radicals as well as continuous be attributed to the fact that the negative contribution
cleaning of the catalyst surface during the process of due to the fragmentation of photocatalyst will be less
photoactivation under the continuous action of ultra- in the case of 300 ppm concentration as compared to
sound are equally contributing to the expected enhance- 500 ppm catalyst concentration. In other words, the time
ment using the combination. To give a quantitative idea, required for the combination to give better results as
the extent of degradation of formic acid by the simul- compared to photocatalytic oxidation alone is less as
taneous technique is 30% more as compared to that of soon as the fragmentation is reduced. Further confirma-
the sequential technique. Similar results have also been tion of this fact was obtained when the US irradiation
obtained by Stock et al.36 for the degradation of an azo was restricted to 20 kHz alone instead of a 20 + 30 +
dye, naphthol blue black (NBB). In their work (640 kHz 50 kHz combination for the 300 ppm catalyst concentra-
sonoreactor with a power input of 240 W and a capacity tion. The percentage degradations were found to be
of 600 mL has been used), the simultaneous technique 12.24% (for a combination of UV light and 20 + 30 +
resulted in a decrease of TOC by 75% as compared to 50 kHz ultrasound), 15.75% (for a combination of UV
only 50% with the sequential technique. Thus, simul- light and 20 kHz ultrasound), and 14.23% (for UV light
taneous use of UV irradiation and ultrasound is recom- alone) in the first 30 min of irradiation time. In this
mended for getting better results in terms of the extent case, the combination technique shows better results for
of degradation. 30 min of irradiation time as the extent of fragmen-
3.3.2. Comparison of Combination with the In- tation in the case of 20 kHz ultrasound is considerably
dividual Techniques. The results for experimentation lowered (because of a lower intensity of cavitation and
with 100 ppm initial concentration of formic acid in the hence the turbulence for the 20 kHz irradiating fre-
presence of air for different techniques are shown in quency as compared to a combination of 20 + 30 + 50
Figure 7. The combination gives about 4 times more kHz ultrasound). It must also be noted at this stage that
degradation as compared to sonication alone, whereas all of these results are only at initial stages and
 Ind. Eng. Chem. Res., Vol. 41, No. 14, 2002 3375

indeed a 20 + 30 + 50 kHz combination gives better

results than 20 kHz alone over extended time periods.
The negative contribution resulting from the scatter-
ing of the waves due to solid particles makes a certain
contribution throughout the irradiation time. This is
evident also from the fact that, in 90 min of irradiation,
a combination gives 15% more degradation as compared
to photocatalytic oxidation for 300 ppm concentration,
whereas for 500 ppm concentration of catalyst, the
enhancement is just 10%, indicating a higher contribu-
tion of fragmentation at higher solid loadings.
It was also observed in the study that 300 ppm Figure 8. Results for the combination of hydrogen peroxide and
concentration of catalyst in the presence of ultrasound US irradiation.
gives almost the same amount of degradation as com-
pared to 500 ppm catalyst in the absence of ultrasound. but are still quite lower considering the final aim of
Thus, it can be said that the presence of ultrasound designing reactors for effluent treatment.
decreases the required catalyst loading to achieve the 3.4.2. Combination of Hydrogen Peroxide and
same degradation, which is likely to reduce separation US Irradiation. The results of experiments with the
problems and give some cost benefits. It should also be combination of US irradiation (20 + 30 + 50 kHz
noted that the optimum value of the catalyst concentra- operating simultaneously; power input of 900 W) and
tion (500 ppm for photocatalytic oxidation as observed hydrogen peroxide (loading of 0.5 mL/L) are shown in
in this case) will be different for the combination of US Figure 8. The degradation for the combination is almost
and UV irradiation because the relative contributions double as compared to both individual techniques of US
of different factors (fragmentation, cleaning, and pro- irradiation and the addition of hydrogen peroxide with
duction of free radicals) will be strongly dependent on the catalyst. Thus, it is now confirmed that, in the
the catalyst concentration. presence of US irradiation, hydrogen peroxide does
dissociate, forming highly reactive hydroxyl radicals and
3.4. Effect of the Addition of Hydrogen Peroxide.
resulting in an expected enhancement in the overall rate
It can be seen from the above results that the production
of degradation. Moreover, the acoustic streaming pro-
of the free radicals and further enhancement in the rate
duced by US-induced cavitation phenomena50 also helps
of generation of the same in the presence of ultrasound
in decreasing the effect of mass-transfer limitations
make a crucial impact on the overall rates of degrada-
which otherwise severely affect the processes for treat-
tion. Thus, with the aim to increase the extent of
ment with hydrogen peroxide alone. Teo et al.8 have also
degradation further, it was thought of supplying an reported that the initial rate of degradation of a 0.4 mM
additional source for the free radicals in the form of p-chlorophenol aqueous solution increases substantially
hydrogen peroxide. It is well-known that hydrogen (by about 3 times for a concentration of hydrogen
peroxide in the presence of US as well as UV irradiation peroxide of 15 mM as compared to that in the absence
undergoes a dissociation reaction, forming free hydroxyl of hydrogen peroxide) but observed that the addition of
radicals which are strong oxidizing agents.44-48 It must hydrogen peroxide is only facilitated until an optimum
also be noted here that if one tries to estimate the concentration of hydrogen peroxide (40 mM for the
dissociation rates alone in the presence of US irradia- initial concentration of pollutant as 0.4 mM).
tion, it may not be possible to get measurable rates
It can also be seen from the figure that the extent of
because the recombination of the formed free radicals degradation is marginally higher for the catalyst loading
to form hydrogen peroxide will be the dominant mech- of 500 ppm as compared to 300 ppm, which can be
anism.49 attributed to the enhanced contribution of surface
The loading of hydrogen peroxide was restricted in cavitation at the surface of solid particles.51 Shirgaonkar
the range of 0.1-0.5 mL/L of formic acid to be treated. and Pandit32 have also reported that the presence of
This can be attributed to the fact that if the concentra- TiO2 increases the extent of degradation of 2,4,6-
tion of H2O2 is increased beyond certain limits, ad- trichlorophenol for the operation with 22 kHz frequency
ditional hydrogen peroxide usually recombines with the and a power input range of 0.4-0.12 W/mL. In the
dissociated hydroxyl radicals, decreasing the availability present case, the operating power density is 0.13 W/mL
for the pullutant degradation, and it also acts as an and the reactor is irradiated by 20 + 30 + 50 kHz
additional pollutant if present in large quantities. frequencies operating simultaneously.
3.4.1. Addition of Hydrogen Peroxide Alone. To 3.4.3. Hybrid Technique of UV/US/Hydrogen
see the contribution of hydrogen peroxide as an oxidiz- Peroxide. Figure 9 shows the extent of degradation of
ing agent, experiments were performed with the addi- formic acid for different catalyst loadings at different
tion of 0.5 mL/L of hydrogen peroxide to 7 L of a 100 times of operation. It can be seen that the presence of
ppm formic acid solution. It was, however, observed that hydrogen peroxide significantly enhances the extent of
the hydrogen peroxide has almost no effect on the degradation (an almost 120% increase is observed for
removal of formic acid with a percentage removal of just hydrogen peroxide loading of 0.5 mL/L over the UV/US
1.65% in 90 min of treatment time. Thus, it can be said combination). This can be very well explained on the
that hydrogen peroxide alone is ineffective in the basis of enhanced formation of free radicals from the
treatment of formic acid. Further addition of 500 ppm dissociation of hydrogen peroxide under the combined
catalyst (TiO2) with 0.5 mL/L of hydrogen peroxide with action of US as well as UV irradiation.
continuous stirring increases this degradation to 6.3% Fung et al.37 have also shown that the extent of
in the same time of operation. Thus, the rates of degradation of CI reactive red 120 dye increases with
degradation are comparable with US irradiation alone5 an addition of hydrogen peroxide until loading of 0.2
3376 Ind. Eng. Chem. Res., Vol. 41, No. 14, 2002

Table 1. Comparison of the Results Obtained for Different Approaches Used in the Present Work
approach experimental conditions results and comments
US irradiation seven different combinations of multiple frequencies are better as compared
frequencies, experiment with the to single frequencies; the presence of air
presence of air also increases the extent of degradation by
providing additional nuclei; the maximum
degradation achieved by US alone in the
presence of air is around 6.5%
hydrogen peroxide concentration of 0.5 mL/L, additional hydrogen peroxide does not oxidize formic acid
experiment with TiO2 catalyst (1.65% destruction in 90 min); stirring in
and stirring the presence of TiO2 (500 ppm concentration)
increases degradation to 6.3%
US irradiation + all of the frequencies operating and a percentage degradation is almost double as
hydrogen peroxide hydrogen peroxide loading of 0.5 mL/L compared to individual techniques,
confirming the release of free radicals due
to dissociation of hydrogen peroxide
photocatalytic different initial concentrations of acid rate decreases with an increase in the initial
oxidation and catalyst TiO2 in the range of concentration of pollutant and shows optima
100-1000 ppm with respect to the catalyst concentration
at 500 ppm; maximum percentage degradation
is observed at 500 ppm catalyst loading and
100 ppm acid initial concentration
US irradiation + 100 ppm acid concentration, 500 ppm results better than the individual techniques
UV irradiation of catalyst, all frequencies operating for larger treatment periods; simultaneous
for US irradiation and UV irradiation; irradiation gives better results as compared
two different methods of sequential to sequential operation (30% more degradation);
and simultaneous irradiations dependency of synergism between the two
techniques on time of operation, more synergistic
at higher treatment times
US + UV + 100 ppm acid concentration, 500 ppm best treatment approach with maximum
hydrogen peroxide of catalyst, all frequencies operating percentage degradation achieved as 55%
for US irradiation and UV irradiation in 90 min of treatment time; more enhanced
(simultaneous way); addition of generation of free radicals due to faster
hydrogen peroxide in the range of dissociation of hydrogen peroxide under the
0.1-0.5 mL/L) combined action of ultrasound and UV light

is a strong function of the pollutant studied and also of

the reaction conditions.
Thus, it has been conclusively established that the
hybrid technique of sonophotochemical destruction along
with the addition of hydrogen peroxide as a source of
hydroxyl radicals gives excellent results as compared
to individual techniques. Table 1 gives at a glance a look
at the various results obtained in the work and helps
the comparison of the different approaches used in the
study.

5. Conclusions
Destruction of formic acid was found to be more for
Figure 9. Results for the hybrid technique of UV/US/hydrogen
peroxide.
the operation with multiple frequencies for US irradia-
tion alone as compared to operation with a single
mL/L, whereas for the degradation of Cuprophenyl frequency and was further enhanced by aeration.
Yellow RL, the optimum loading of hydrogen peroxide Photocatalytic oxidation of formic acid was observed
was reported to be 0.1 mL/L.33 The operating conditions to increase with an increase in the catalyst concentra-
used in the experimentation of Poon et al.33 and Fung tion until an optimum value of 500 ppm, whereas a
et al.37 are US transducers operating at 340 kHz lower initial concentration of formic acid gives better
frequency and UV radiations with a power input of 66 results. It must be kept in mind that this optimum
W (six tubes of 11 W each), whereas in the present case, concentration will be different for the hybrid technique.
the frequencies of operation are 20 + 30 + 50 kHz and Net degradation (Ct/C0) has been correlated with these
a power input of 8 W for UV light. Thus, the rate as two parameters, indicating the type of correlations to
well as the number of formation of hydroxyl radicals be developed using the data available in laboratory-scale
will be much higher in the case of Poon et al.33 and Fung studies, which will then be used in the design of large-
et al.37 because of more severe conditions as compared scale reactors.
to the present case, and hence the optimum concentra- The common optimum conditions for the two tech-
tion of hydrogen peroxide (beyond which the scavenging niques of US irradiation and photocatalytic oxidation
action of hydrogen peroxide and the recombination of coupled with the similarity in the mechanism of de-
free radicals are dominant52) will be lower. In the struction and cleaning of photocatalyst due to the
present case, we have found no decrease in the extent turbulence generated by acoustic streaming make way
of degradation with an increase in the hydrogen per- for the development of sonophotochemical reactors.
oxide loading in the range of 0.1-0.5 mL/L. Thus, it can Three important factors, viz., fragmentation of the
be said that the optimum loading of hydrogen peroxide catalyst under the action of ultrasound leading to an
 Ind. Eng. Chem. Res., Vol. 41, No. 14, 2002 3377

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