Chemical Engineering Journal Advances 3 (2020) 100031

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Chemical Engineering Journal Advances

journal homepage: www.elsevier.com/locate/ceja

Recent advances in ozone-based advanced oxidation processes for

treatment of wastewater- A review
Chhaya V. Rekhate∗, J.K. Srivastava
Chemical Engineering Department, Ujjain Engineering College, Ujjain 456006, India

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

Keywords: The wastewater reclamation is the need of today’s world. Advanced oxidation processes (AOPs) are considered
Ozonation as a good option for removing recalcitrant organic materials in wastewater by oxidation reactions with powerful,
Advance oxidation process non-selective hydroxyl radical (OH•). Ozone alone does not cause complete oxidation of some refractory organic
Photocatalytic ozonation
compounds and has a low reaction rate. The ozone is combined with H2 O2 , UV light, catalyst, ultrasound to
O3 /Fenton
enhance the generation of hydroxyl radicals to increase the efficiency of the treatment process. The ozone-based
Heterogeneous catalytic ozonation
O3 /Fe (II) AOPs have been proved to be effective in detoxifying an ample range of industrial effluents containing recalcitrant
organics, pharmaceutical products, pesticides, phenols, dyes, etc. Ozone based AOP processes such as O3 /UV,
O3 /H2 O2 , O3 /Fe (II), O3 /metal oxide catalyst, O3 /activated carbon, O3 /ultrasound, O3 /Fenton, photocatalytic
ozonation were discussed. A review of ozone-based AOP processes as a combination of ozonation with other
techniques for the degradation and mineralization of recalcitrant organics present in the industrial/municipal
wastewater based on the recently published work were reported.

1. Introduction alyst, ultrasound to advance the oxidation process. AOPs may be

The entire world is dealing with water crises and effective treat-
ment for wastewater reclamation is the need of the present world. In-
dustrial doings releases about 300–400 million tons of waste compris-
ing of heavy metals, solvents, recalcitrant organics, toxic sludge, and
micro-pollutant into the global waters each year, posing a great threat
to human beings [1]. The conventional municipal wastewater treatment
plants are designed based on organic load and removal of recalcitrant
organics, personal care products, pesticides, pharmaceuticals, and toxic
heavy metals from wastewater remains a huge challenge for municipal
wastewater treatment plants.
Advanced oxidation processes (AOPs) are a set of chemical treat-
ment procedures that are able to remove recalcitrant organic materials
in wastewater by oxidation reactions with a powerful, non-selective hy-
droxyl radical (OH•) which oxidize recalcitrant organic pollutants re-
sistant to conventional approaches and can also enhance the biodegrad-
ability of wastewater. Theoretically, AOPs could fully mineralize organic
compounds to carbon dioxide and water according to Eq. (1)
𝑅 − 𝐻 + OH∙ → H2 𝑂 + R ∙
Advanced oxidation processes use Fenton’s reagent, hydrogen per-
oxide, ozone, photocatalyst to produce highly reactive hydroxyl rad-
icals. These reagents may be used in the presence of UV light, cat-
classified broadly into four groups: photocatalytic process (H2 O2 /UV,
O3 /H2 O2 /UV, UV/TiO2 , H2 O2 /TiO2 /UV, O3 /TiO2 /UV); the Fenton
reaction-based processes (Fe2+ /H2 O2 , Fe2+ /H2 O2 /UV, Electro -Fenton),
and ozone-based processes (O3 /UV, O3 /H2 O2 , O3 /Fe++ , O3 /metal oxide
catalyst, O3 /activated carbon, O3 /ultrasound); Other processes which
may include processes such as activated persulfate, ionizing radiation
or electron beam technology. Table 1 lists typical AOP systems. Ozone
has been widely used in water treatment since the late 19th century.
Ozone is a bluish gas with a pungent smell and is an extremely reactive
and unstable allotrope of oxygen (O2 ). The physical properties of ozone
are listed in Table 2 (compiled from [2]).
The increasing popularity in recent years concerning ozone appli-
cations are mainly due to two factors (i) costs associated with ozone
production considerably decreased in the last decade and (ii) ozone
presents environmental advantages over chlorine. Ozonation is an ef-
ficient alternative to the treatment of wastewater containing organic
complexed metals [3]. Ozone is an unstable gas; therefore its generation
should be carried out in situ. The commercially available technology
for ozone generation is based on the corona discharge process, which
(1)
involves the application of a high voltage discharge in a cooled/dried
gaseous phase containing oxygen (O2 or air). The fundamental processes
leading to ozone generation during the silent electric discharge are de-
picted in the scheme presented in Fig. 1. The discharge gas reaction is

∗
Corresponding author.
E-mail address: chhayaprafulla@gmail.com (C.V. Rekhate).

https://doi.org/10.1016/j.ceja.2020.100031
Received 16 June 2020; Received in revised form 28 September 2020; Accepted 29 September 2020
2666-8211/© 2020 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/by-nc-nd/4.0/)
C.V. Rekhate and J.K. Srivastava Chemical Engineering Journal Advances 3 (2020) 100031

Fig. 1. Scheme describing the corona processes for ozone generation.

Table 1
Typical Advanced Oxidation Processes (AOP).

H2 O2 /UV Fe2+ /H2 O2 (Fenton System) O3 /H2 O2

2+
O3 /H2 O2 /UV Fe /H2 O2 /UV(Photo-Fenton) O3 /Ultrasound
UV/TiO2 Electro -Fenton O3 /Activated Carbon
H2 O2 /TiO2 /UV O3 /Fenton O3 /Metal oxide
O3/ Fe2+
O3 /TiO2 /UV O3 /UV

Table 2
Physical properties of ozone (compiled from
[2]).

Parameter Value

Molecular weight 48
Density(Kg/m3 ) 2.14
Boiling point( °C) −111.9
Melting point ( °C) −192.6
Critical temperature ( °C) −12.1
Critical pressure (Atm) 54.6
Oxidation potential(V) −2.07
Solubility in water at 0 °C (L/L) 0.64
Solubility in water at 15 °C (L/L) 0.456
Fig. 2. Ozone based AOP.
Solubility in water at 40 °C (L/L) 0.112
Solubility in water at 60 °C (L/L) 0
The benefits of ozonation in wastewater treatment plants include
sludge reduction and removal of recalcitrant organic contaminants from
given as: wastewater. It is seen that ozonation leads to sludge solubilization, re-
ducing overall biomass yield [7]. The ozone mass transfer is influenced
𝑂2 + 𝑒𝑙𝑒𝑐𝑡𝑟𝑖𝑐 𝑠𝑝𝑎𝑟𝑘 → 2𝑂∙ (2) by many factors, which can be divided into hydrodynamic and physic-
ochemical effects. Ozone itself is unstable and can quickly decompose
𝑂2 + 𝑂 → 𝑂3
∙
(3)
into molecular oxygen leading to a low utilization rate [8]. Further,
Ozone being the powerful oxidants (2.07 V) can degrade organic pol- ozone alone does not cause complete oxidation of some refractory or-
lutants using two mechanisms: (1) direct electrophilic attack by molec- ganic compounds, has a low reaction rate. The ozone is combined with
ular ozone; (2) indirect attack by OH• radicals produced through the H2 O2 , UV light, catalyst, photocatalyst, ultrasound to enhance the pro-
ozone decomposition process. It was observed that raising the ozone duction of hydroxyl radicals which increases the treatment efficiency.
concentration promotes the degradation rate of some pollutants but has The scope of the present review is to address the ozone-based AOP
no obvious effect on the degradation of some other pollutants. This may processes for the treatment of industrial wastewater. Recent reviews
be because ozone molecules directly react with pollutants according to published on the application of AOP for recalcitrant pollutant removal
four categories: (i) The oxidation-–reduction reaction such as the reac- by various methods are reported in Table 3. The search was conducted
tions between O3 and HO− ∙−
2 (or O2 ) mostly proceed through the electron in the ScienceDirect database using the keyword ozone-based advanced
transfer process [4]. (ii) The ozone reacts with pollute via cycloaddi- oxidation process from period time 2016–2020. Most articles focus on
tion reaction by forming a five-member ring ozonide structure [5]. (iii) the efficiency of AOP whereas some of them studied the pollutant degra-
Ozone being an electrophilic agent can attack the nucleophilic position dation by AOPs in combination with other processes such as membrane
of the organic substances and the group in the aromatic molecule, such filtration. The present paper reports the detailed review of ozone-based
as -OH− , -NO−
2
and –Cl has a significant influence on the reactivity of the AOP processes (Fig. 2) exclusively as a combination of ozonation with
aromatic ring with ozone. (iv) Ozone demonstrates nucleophilic prop- other techniques to increase the generation of hydroxyl radical thereby
erty and nucleophilic reaction occur with molecules especially, when enhancing the treatment efficiency. The present paper reviewed the
the compound contains carbonyl or double and triple nitrogen carbon mechanism and application of the ozone-based AOP processes for degra-
bonds [6]. dation and mineralization of recalcitrant organics found in the industrial
C.V. Rekhate and J.K. Srivastava Chemical Engineering Journal Advances 3 (2020) 100031

Table 3
Recent reviews published on application of AOP.

Title of review paper Contaminants/wastewater Process used References

Nanomaterials based Advanced Oxidation Processes for Waste Wastewater Nano material based AOP Bethi et al. [9]
Water Treatment
Catalytic ozonation for water and wastewater treatment: Recent Wastewater Catalytic ozonation Wang et al. [10]
advances and perspective
Consolidated vs new advanced treatment methods for the Wastewater Adsorption, NF and RO membrane Rizzo et al. [11]
removal of contaminants of emerging concern from urban filtration
wastewater
Wastewater treatment by means of Advanced Oxidation Wastewater AOP at basic pH Boczkaj and Fernandes
Processes at basic pH conditions [12]
Oxidation byproducts from the degradation of dissolved organic Wastewater Ozone based AOP; H2 O2 based AOP; Ike et al. [13]
matter by advanced oxidation processes Sulphate based AOP
Sonolytic ozonation for water treatment: efficiency, recent Wastewater/dissolved Sonolytic ozonation Merouani and Hamdaoui
developments, and challenges organic matter [14]
Catalytic ozonation for the treatment of synthetic and industrial Synthetic and industrial Catalytic ozonation Ghuge and Saroha, [15]
effluents - Application of mesoporous materials effluents
Hybrid ozonation process for industrial wastewater treatment: Industrial wastewater O3 /H2 O2 ; O3 /UV; Malik et al. [16]
Principles and applications O3 /Electrocoagulation; Catalytic
ozonation; Nano catalyzed
ozonation
Coupling catalytic ozonation and membrane separation Wastewater Catalytic ozonation coupled with nano Manas et al. [17]
filtration, ultra filtration
Detoxification of water and wastewater by advanced oxidation Arsenic AOP Babu et al. [18]
processes,

and municipal wastewater along with a summary of experimental results control of the relative pressure within the reactor, ozone addition ratio,
reported so far. and intensity of UV radiation.

2. Ozone based AOP 2.2. O3 /H2 O2

2.1. Ozonation and UV radiation (O3 /UV) The ozonation combined with H2 O2 is an efficient catalytic system
for the degradation of refractory pollutants in wastewater. The O3 /H2 O2
The ozonation combined with UV-radiation (O3 /UV) is an efficient process commonly known as peroxone AOP involves a radical chain
catalytic system for the degradation of refractory pollutants in wastew- mechanism based on the ozone decomposition initiated by the hydroper-
ater. The process is initiated by the photolysis of ozone and followed by oxide anion HO− 2
. The synergistic effect of O3 with H2 O2 promotes the
the production of OH• radicals by the reaction of O• with water [19]. production of OH• radicals.
The synergistic effect of O3 with UV radiation promotes ozone decompo-
H2 O2 → HO−
2 +H
+
(9)
sition by direct Eq. (4)–(6) and indirect production of hydroxyl radicals
Eqs. (7) and (8).
2 + O3 → HO2 + O3
HO− ∙ ∙−
The hydroxyl radicals generated in aqueous solution attack the aro- (10)
matic ring in dye molecule resulting in the formation of smaller aliphatic O3 likely reacts with excess HO− formed from Eq. (9)- (10) and generates
2
molecules such as organic acid, aldehydes, ketones, etc. [20]. UV pro- OH• through Eq. (11-13).
motes the degradation of recalcitrant dyes by yielding more free OH•
radicals thereby increasing the decolorization rate [21]. Illustration of
3 + H → HO3
O∙− + ∙−
(11)
hydroxyl radical formation can be described by Eq. (4) to (8).
HO3∙ − → O2 + OH∙ (12)
O3 + uv → O2 + O∙ (4)

OH∙ + H2 O2 → HO∙2 + H2 O (13)

O∙ + H2 O → 2OH∙ (5)
However excess H2 O2 leads to OH• scavenging and formation of
2O + H2 → OH + 𝑂 H → H2 O2
∙ ∙ ∙
(6) hydroperoxide ion (HO∙2 ) as shown in Eq. (13). Neither a hydrogen per-
oxide concentration that is too low is desirable because H2 O2 competes
The indirect production of OH• by the following reaction is also pos- successfully for hydroxyl radicals (Eq. (13)) and decomposes without
sible. oxidizing the pollutants as shown in Eq. (14) [25]

O3 + H2 O → O2 + H2 O2 (7) 1
H2 O2 → H2 𝑂 + O (14)
2 2

H2 O2 → 2 OH∙
Combining O3 with UV enhances the degradation of azo dye at all
pH [22]. Wu et al.[23] found that the decolorization rate constant of
the O3 /UV process exceeded that of the O3 system.
A pilot study was carried out by Yang et al. [24] on the biochem-
ical tailwater of industrial park sewage treatment plant. The authors
reported that the key factors affecting the economically efficient oper-
ation of the UV/O3 process were the efficient O3 distribution mode,
(8) There exists an “ozone dose threshold” below which the addition of
H2 O2 yielded no noticeable increase in the rate of OH• production [26].
H2 O2 (initiators/promoters) react with ozone until they no longer im-
pact ozone degradation. Barry et al. [26] termed the ozone dose that ex-
hausts reactions with the initiators/promoters compounds as the ozone
dose threshold, above which the addition of H2 O2 increases the rate of
HO• production. The authors observed that regardless of H2 O2 addition,
ozonation has little impact on HO• exposure until doses greater than the
threshold ozone doses were applied.
C.V. Rekhate and J.K. Srivastava
It was observed that the use of a homogeneous reactor enables fast
and high production of the radical species directly in the bulk liquid
with no transport and mass-transfer limitations compared to a tradi-
tional gas-liquid reactor in which the oxidation of the pollutants by hy-
droxyl radicals might be limited by their transport from the liquid bulk
to the interface as these radicals are very reactive and do not diffuse in
solution [27].
H2 O2 can be generated in-situ from cathodic O2 reduction during
ozonation, called as an E-peroxone process. Wang et al. [28] reported
enhanced the kinetics and OH• yields from O3 decomposition in a water
matrix that has high ozone stability than those with low stability. Au-
thors found that at specific ozone doses of 0.5–1.5 mg O3/mg dissolved
organic carbon, the abatement efficiencies of ozone-resistant pharma-
ceuticals (ibuprofen and clofibric acid) increased up to ~14–18% in
Groundwater, moderately up to 6–10% in surface water, and negligibly
in secondary effluent during the O3/H2O2 and E-peroxone treatment
compared to conventional ozonation.
2.3. Catalytic ozonation
2.3.1. O3 /Homogeneous catalyst
Catalytic ozonation employs catalysts to enhance the decomposition
of ozone which leads to the production of hydroxyl radicals. Adding
catalysts may increase the degradation rates of non-biodegradable com-
ponents [29]. Transition metal ions (Fe2+ , Cu2+ , Cr2+ , Mn2+ , Ni2+ , Co2+ ,
Cd2+ , Ag+ , Zn2+ ) are usually used as the catalysts in the homogeneous
catalytic procedure, to degrade the recalcitrant organic pollutants in
wastewater [30]. The metal ions influence the rate of reaction, the se-
lectivity of ozone oxidation, and the efficiency of ozone utilization. Two
major mechanisms of homogeneous catalytic ozonation can be found
[31]
1 Decomposition of ozone by metal ion resulting in the production of
free radicals.
2 Formation of a complex between the catalyst and organic molecule
following oxidation of the complex.
The ozonation of oxalic acid in the presence of Co (II) proceeds with
the formation of Co-oxalic acid complex and then ozone attacks the com-
plex [32]. Beltran et al. [5] studied the ozonation of oxalic acid in water
using an iron catalyst. It was observed that the mechanism of ozona-
tion likely develops through the formation of iron-oxalate complexes
that further react with ozone without the participation of hydroxyl rad-
icals following first-order kinetics with respect to ozone and oxalic acid.
Sauleda et al. [33] studied the mechanism for mineralization of aniline
in acidic solution by ozonation catalyzed with Fe2+ and observed that
process is initiated by the attack of O3 and/or OH• on aniline to yield
either benzoquinone or nitrobenzene.
Fe (II) enhances ozonation efficiency considerably [34]. In the O3 /Fe
(II) process, the ferrous ion can promote the breakdown of ozone leading
to the formation of hydroxyl radicals according to Eq. (15) to (17)
Fe2+ + O3 → FeO2+ + O∙ (15)
FeO2+ + H2 O → Fe3+ + OH∙ + OH− (16)
FeO2+ + Fe2+ + 2H+ → 2Fe3+ + H2 O (17)
Metals promote the ozonation of organics by oxidation–reduction
reaction [23]. In the O3 /Fe (II) process, ozone decomposes to hydroxyl
radicals at alkaline pH. Ozone reacts with Fe (II) to form FeO2+ . The
synergistic effect of adding Fe (II) to O3 is observed at all pH [22].
2.3.2. O3 /heterogeneous catalysts
The heterogeneous catalytic ozonation process is a promising process
due to its ability to improve the ozonation of refractory organic pol-
lutants in the presence of a solid catalyst. Catalysts used in ozonation
Chemical Engineering Journal Advances 3 (2020) 100031
mainly include metal oxides (e.g., MnO2 [35], Fe2 O3 , MgFe2 O4 [36],
CuFe2 O4 [37], ZnFe2 O4 [38], MgO [39]); supported metal oxides (e.g.
Fe-SBA-15 [40], MnOx/SBA-15 [41], Fe/MCM41 [42], Mg-Ce-MCM41
[43], Fe3 O4 /Co3 O4 [44]); and some porous materials (e.g. activated
carbon, carbon nanotube, zeolites [45] I are used as possible catalysts
for ozonation process. These solid catalysts are primarily attributed to
the active d-electronic structure of the metal oxides which enhance the
probability of electron transfer between the catalyst and target com-
pound, lowering the activation energy of catalytic ozonation [46]. For
instance, the various porous materials such as active carbon, zeolite,
honeycomb ceramics, etc. were developed as supports to improve the
mechanical strength and the stability of transition metal oxides [46].
These catalysts were reported to enhance the removal efficiencies of
pollutants by O3 . Among these catalysts, iron oxides and manganese
oxides are the most widely explored. Manganese oxides exhibit high
catalytic activity but manganese ions prone to leaching resulting in the
second pollution [47]. Formation of a complex between the catalyst and
organic molecule is necessary to observe the catalytic activity of MnO2
(Nawrocki et al., 2013) whereas the Fe based catalyst exhibit various
mechanism.
The metal-catalyzed ozonation enhances the removal efficiency of
organic compounds such as oxalic acid, formic acid, and humic acids
in water [48]. In heterogeneous catalytic ozonation, the solid catalyst
is combined with ozone to advance the effective use of ozone. The
heterogeneous catalytic ozonation may involve three phases, including
gaseous, liquid, and solid. The catalytic process efficiency depends on
the kinds of catalysts, the target pollutants, and the pH value of the so-
lution. There are two representative mechanisms for the heterogeneous
catalytic ozonation: (1) Interfacial reaction mechanism. (2) OH• mech-
anism:
In the Interfacial reaction mechanism, the main function of cata-
lysts is to act as adsorptive material using its large surface to adsorb the
organic pollutants and combine with target molecules to form active
complexes with lower activation energy. Further, the ozone or hydroxyl
radical would oxidize the surface complex to give oxidation by-products
either desorbed in solution or still adsorbed at the surface of the cata-
lyst [30,49]. This mechanism can explain the catalytic ozonation system
with good adsorptive properties.
The OH• mechanism proposes that the metal oxide catalysts can in-
crease the solubility of ozone and initiates the ozone decomposition [1].
The reaction of ozone on reduced metal could produce OH• radical. Sol-
uble ozone in aqueous solution is adsorbed to the surface of the catalyst,
a series of radical chain transfer are occurred to produce more OH• hav-
ing a high oxidation potential to oxide the organic pollutants in wastew-
ater. The catalytic ozonation system with poor adsorptive ability can be
explained by this mechanism [30]. Ikhlaq et al. [50] found that catalytic
ozonation of recalcitrant organics on alumina includes the reactions of
hydroxyl radicals with pollutants adsorbed on the surface of alumina
and the reaction proceeds via a radical mechanism.
2.3.2.1. Fe based catalyst. Fe-based catalysts are most popular as they
are abundant in nature, nontoxic, can be easily synthesized, and some
Fe-based catalysts own special characteristics, for example, Fe3 O4 own
magnetic properties, and iron oxyhydroxides (FeOOH) has a high den-
sity of hydroxyl group. Fe based catalysts are prepared by precipitation,
wet impregnation, sol-gel method, thermal decomposition, hydrother-
mal method, electrochemical method, and biomineralization [8].
Many iron-based catalysts have shown promising results for catalytic
ozonation, namely iron silicate doped hydroxylation iron (IS-FeOOH) to
remove p-chloronitrobenzene by promoting ozone decomposition into
hydroxyl radicals (OH•), iron silicate-loaded pumice (FSO/PMC) for
mineralization of diclofenac [46] by enhancing the mass transfer of
aqueous ozone, boosting the solubility of aqueous ozone, and hastening
the production of OH• radicals; CuFe2 O4 to improve the degradation of
phenacetin [51]; Fe-MCM-41 to enhance diclofenac mineralization [42];
reused spent fluid catalytic cracking catalysts for a significant increase
C.V. Rekhate and J.K. Srivastava
on the COD removal efficiency of petrochemical wastewater [52]; Ce
substituted goethite (Ce0.1Fe0.9OOH) catalyst to improve the mineral-
ization of sulfamethazine [53,54].
Catalytic oxidation with nanomagnetic catalysts has the advantages
of easy recovery, good stability, and high activity. Spinel ferrites with
the general formula MeFe2 O4 (Me = Mg, Mn, Ni, Cu, etc.) are a kind of
important soft magnetic materials with excellent structural stability. The
magnetic property provides a convenient method to remove and recy-
cle the nanoparticles from the treated water under an external magnetic
field. It is found that magnetically separable nanoparticles of NiFe2 O4 ,
MnFe2 O4 , and CuFe2 O4 are catalytically active in the ozonation of re-
fractory organic pollutants [36]. However, nickel, manganese, and cop-
per are toxic and may cause the second pollution to the treated water.
On the contrary, magnesium is nontoxic and abundant. Additionally,
the electron transfer between catalyst and ozone governs ozone decom-
position into active radicals on the surface of solid catalysts. The ozone
decomposition mechanism onto metal oxide surfaces is shown below
≡ 𝑂𝑀 + 𝑂3 →≡ 𝑂𝑀 − 𝑂 − 𝑂 − 𝑂∙ (18)
≡ 𝑂𝑀 − 𝑂 − 𝑂 − 𝑂∙ → 𝑂2 + ≡ 𝑂𝑀 − 𝑂∙ (19)
The lower electronegativity or the higher metallicity of M (metal ion)
would lead to the higher electron density of 𝑂2− bond to M and conse-
quentially favor the catalytic decomposition of ozone into radicals due
to the electrophilic property of ozone molecules [36]. Since magnesium
has stronger metallicity than nickel, manganese, and copper the oxygen
bond to magnesium in MgFe2 O4 possibly possesses the highest electron
cloud density among these four spinel ferrites. Hence, it is reasonable to
believe that MgFe2 O4 may exhibit superior catalytic activity due to the
electrophilic property of ozone molecules [36].
2.3.2.2. Mn-based catalyst. Manganese dioxide (MnO2 ) is more attrac-
tive for practical applications due to their low cost, natural abundance
and was widely recognized as active heterogeneous catalysts in catalytic
ozonation for degrading refractory organics [35,55]. The multiple oxi-
dation states of Mn can enhance electron transfer. Manganese dioxide
exhibits a net negative surface charge within the pH range (5–11) of
principal interest for natural waters for water treatment operations [56].
Ozone reacts readily with the negatively charged surface because of its
electrophilic characteristics [56]. Various methods have been developed
for the synthesis of nano MnO2 including hydrothermal, sol-gel, thermal
decomposition, reflux, sonication, electrodeposition, and precipitation
methods. Surfactants are used to control the surface area and morphol-
ogy of MnO2 [35,57].
2.3.2.3. Zn-based catalyst. The zinc oxide has been usually used as an
ozonation catalyst due to its stable structure and high density of surface
hydroxyl groups [58]. ZnO-catalytic ozonation follows a radical-type
mechanism [58]. When the ozone molecules entered the liquid phase, a
five-member ring structure was formed by the dispersion force between
ozone molecules and the surface hydroxyl groups, facilitating electron
transfer [59]. Zn ions would get the electrons to form to Zn+ , then Zn+
delivered electrons to the unstable five-member ring structure and the
bonds would be broken to produce O.2− or HO.2− . Zhao et al. [59] observed
that the ability to transmit electrons was various for different states of
zinc ions, causing distinct di-n‑butyl phthalate removal efficiency.
Liu et al. [60] synthesized zinc copper silicate polymer by using Zn
(NO3 )2 , Cu (NO3 )2 , and Na2 SiO3 as precursors. The authors found that
it is an effective catalyst for the ozonation of p-chloronitrobenzene hav-
ing good reusability and stability. Zhao et al. [61] found that nanocrys-
talline ZnAl2 O4 prepared by a hydrothermal method is a promising
ozonation catalyst with improved catalytic activity in the removal of
phenol (300mgL−1 ) in a wide pH range from 3.3 to 9.3.
2.3.2.4. Mg-based catalyst. MgO has high surface activity and reactiv-
ity, high stability in water, and less toxicity [39]. Mashayekh-Salehi
Chemical Engineering Journal Advances 3 (2020) 100031
et al. [39] found that MgO prepared with magnesium acetate as Mg
source leads to complete degradation and 94% mineralization of ac-
etaminophen. The reaction with OH• was the main mechanism involved
using mesoporous nanocrystalline MgO nanoparticle [39]. Chen et al.
[47] concluded that the catalytic activity can be tailored by preferring
the surface orientation except increasing the surface area. Aghapour
et al. [62] found that catalytic ozonation using MgO/granular activated
carbon composite is effective in the degradation of catechol.
2.3.2.5. Other. Ikhlaq et al. [50] found that catalytic ozonation on alu-
mina has higher ibuprofen and acetic acid removal efficiency as com-
pared with ozonation alone. Ikhlaq et al. [45] studied the catalytic
ozonation of chlorinated volatile organic chemicals (VOCs) removal on
𝛾-alumina and ZSM-5 zeolites. The authors observed that zeolites pro-
moted the decomposition of VOCs as opposed to alumina.
Xu et al. [63] found that cerium-modified red mud catalysts exhibit
enhanced catalytic activity in bezafibrate degradation and detoxifica-
tion. Xu et al. [64] found that surface cobalt loading developed meso-
pores which lead to enhance the specific surface area thereby increas-
ing the catalytic activity. OH• generation was enhanced by the surface
hydroxyl groups which were considered as main active sites of cata-
lyst [65]. Martins et al. [66] found that ceramic catalyst Mn-Ce-O had
a significant impact on COD removal while no significant impact on
the degradation of pharmaceutical pollutant sulfamethoxazole. The tita-
nium silicate ETS-4 as a novel class of zeolite materials containing metal
Ti has received attention for its great potential to remove chemicals and
has an excellent catalytic capability for the ozonation of recalcitrant or-
ganic contaminants in wastewater [67]. Gomes et al. [68] studied the
catalytic ozonation of parabens using volcanic rock. Authors found that
catalytic ozonation treated samples are more toxic as single ozonation
allowed the elimination of toxic by-products such as hydroquinone and
1, 4-benzoquinone.
The microbubbles are used to enhance the dissolution of ozone in
water as ozone has low solubility in water. It is observed that decreasing
the bubble size increases the mass transfer coefficient due to the higher
gas-liquid interfacial area thus increasing the ozonation efficiency. It
was found that ozone microbubbles increase the rate of the degradation
of the Congo red dye [69]. Quan et al. [70] studied O3 /Ca (OH)2 system
in microbubbles gas-liquid reactor for the degradation of Acid red 18
and obtained 100% TOC removal. Table 4 represents the application of
catalytic ozonation for the degradation of organics. Table 5 represents
the review of various catalysts used in the catalytic ozonation process
2.3.2.6. O3 /activated carbon based-catalyst. In the last decade, a huge
amount of different carbon-based materials have been applied. Ac-
tivated carbon has high adsorption capability but low mechanical
strength and is easily oxidized during the reaction. The active carbon
surface can act as an initiator/promoter of ozone decomposition since
ozonation modifies its surface chemical properties. There are various
mechanisms proposed to explain the catalytic activity of active carbons
e.g. O3 decomposes on the surface of active carbons, OH• are formed,
and react with organics in bulk solution [32]. In another mechanism
adsorbed O3 decomposes on activated carbon with a formation of O•,
and OH• active oxygen species, which react with both adsorbed and
dissolved organics. Nawrocki et al. [32] proposed two routes for ozone
decomposition: (i) Activated carbon acts as an initiator of O3 decompo-
sition into hydroxyl radicals and (ii) ozone reacts with surface groups,
generates adsorbed H2 O2 and it reacts with ozone in bulk solution yield-
ing OH• radicals.
Hu et al. [101] found that mesoporous carbon aerogel and its sup-
ported cobalt oxide nanoparticles catalyst could improve both decol-
orization and COD removal for the treatment of textile dyeing efflu-
ents. Restivo et al. [102] found that N-doped carbon nanofibers en-
hanced catalytic activity for the ozonation of organic pollutants. Mous-
savi et al. [103] found that the rates of degradation and mineralization
of amoxicillin for carbon activated with NH4 Cl were 3.2 and 1.8 times
Table 4
Application of catalytic ozonation for degradation of organics.

C.V. Rekhate and J.K. Srivastava

Sr No Target pollutant Catalyst Treatment Efficiency Condition References

1 Herbicide Alachlor Cu/Al2 O3 75% TOC removal pH 4.4 Li et al. [48]

2 Acid Orange II MgFe2 O4 90% Degradation efficiency pH 4.6–9.6 Lu et al. [36]
3 Sulfamethoxazole Mn-Ce-O 69% COD removal Ozone dose 120 mg/hr; pH 6.9 Martins et al. [66]
4 Methylene blue Fe-Mn 100% decolorization; 65–78%TOC Ozone dosage 1.92 mg/min; Catalyst dosage 0.5 g Liu et al. [71]
removal
5 Fulvic acid CeO2 /Activated Carbon 83% Fulvic acid removal 5% Ce loading Qin et al. [29]
6 Diclofenac Iron silicate-loaded pumice 73.3% mineralization; 21.17% TOC Ozone dosage 5052 mg/L; O2 flow rate 1.0 L/min; Catalyst dose 8000 mg/L, pH Gao et al.[46]
removal 5; Reaction time 30 min
7 p-Chloronitro benzene Iron silicate doped 61.3% TOC removal Ozone dose 0.6 mg/L; Catalyst dosage 500 g/L; pH 7.0; Reaction time 15 min Liu et al. [72]
hydroxylation iron
8 Sulphametha- zine antibiotic Ce 1.0 Fe 0.9 OOH 41.2% mineralization efficiency Ozone dose 15 mg/L; Catalyst dose 0.2 g/L; pH 7.3; Reaction time 15 min Bai et al. [53,54]
9 Phenacetin CuFe2 O4 95% of degradation Ozone dose 3058 mg/L; pH 7; Reaction time 5 min Qi et al. [37,51]
10 Diclofenac Fe-MCM-41 76.3% mineralization; 70% TOC Ozone dose 100 mg/hr; Catalyst dose 1 g/L; pH 7; Reaction time 30 min Chen et al. [42]
reduction
11 Oxalic acid Fe-MCM-41 94% degradation efficiency; 6% Ozone dose 21.8 mg/L; Catalyst Conc. 0.4 g; Reaction time 30 min Jeirani and Soltan [43,73]
reduction of TOC/TOCo
12 Oxalic acid Fe-SBA-15 86.6% removal efficiency pH 3; Reaction time 60 min Yan et al. [40]
13 Oxalic acid MnOx-0.013/KCC-1 86% TOC removal Ozone dose 20 mg/L; O3 flow rate 4 mg/min; Catalyst Conc. 0.25 g/L; pH 3.8; T Afzal et al. [74]
25 °C
14 Phenol Mn/ᵧ-Al2 O3 62.76% degradation efficiency Ozone dose 8 mg/min; Catalyst Conc. 4%; T 15 °C Wang et al. [55]
15 4-Nitrophenol 𝛼-MnO2 96.7% degradation efficiency; 79.5% Ozone dose 20 mg/L; pH 3.5–5.9 Nawaz et al. [35]
TOC removal
16 Sulfosalicylic acid MnO2 /CeO2 97% TOC removal pH 6.5; Reaction time 30 min Xing et al. [56]
17 Norfloxacin MnOx/SBA-15 54% mineralization efficiency pH 5; Catalyst loading 2%; T 298 K; Reaction time 60 min Chen et al. [41]
18 Clofibric acid MnOx/SBA-15 43.8% TOC removal Ozone dose 1.0 mg/L; Catalyst 0.2 g/L; pH 3.85; T 293 K; Reaction time 15 min Sun et al. [49]
19 Acetamino-phen MgO 100% degradation; 94% mineralization Ozone dose 50 mg/L; pH 5.4; Reaction time 10 min Mashayekh-Salehi et al. [39]
20 Methylene blue MgO 50% COD removal Ozone dose 5 mg/L; Reaction time 60 min Kong et al. [75]
21 4-Chloro phenol MgO 99.5% removal efficiency Ozone dose 2.5 mg/min; Catalyst 1.0 g/L; pH 6.2 Chen et al. [47]
22 Oxalic acid MnOx /sewage sludge derived 92.2% removal efficiency pH 3.5; Catalyst loading 30%; Reaction time 60 min Huang et al. [76]
activated carbon
23 p-Chloronitro benzene Mn oxide incorporated 68% removal efficiency – Cheng et al. [77]
ceramic membrane
24 Reactive black-5 Ce deposited magnetic pyrite Increase in 42.12% mineralization Reactive black 200 mg/L; Catalyst Conc. 2.5 g/L; Ozone dose 5.6 mg/min; pH 5.5 Wu et al. [78]
cinder efficiency compare to O3 alone
25 Phenacetin CuFe2 O4 95% removal efficiency pH 7.72; O3 Conc. 0.36 mg/L; Catalyst Conc. 2.0 g/L Qi et al. [37]
26 Phenol 𝛾-Al2 O3 46% TOC; 75% COD removal T 25 °C; O3 flow rate 40 L/Hr; O3 Conc. 2 gN/m3 , Phenol 50 mg/L Vittenet et al. [79]
27 4- Chloro phenol 𝛽-FeOOH 99% removal efficiency Catalyst 0.1 g/100 ml; pH 3.5; Reaction time 40 min Oputu et al. [80]
28 Bisphenol-A 𝛼-MnO2 93.5% removal efficiency O3 dosage 4.47 mmol/min; T 20 °C; pH 6.25; Catalyst 0.1 mg/L Li et al. [71]
29 Oxadine dye Plasma treated Natural 93.47% degradation efficiency O3 0.3 g/L; pH 6.7; Catalyst Conc. 600 mg/L Taseidifar et al. [81]
magnetite

Chemical Engineering Journal Advances 3 (2020) 100031

30 Crystal violet dye Fe/activated carbon >96% decolorization; 57% COD O3 dosage 4.44 mg/min; O3 flow rate 300 ml/min; Catalyst dosage 2.5 g/L; pH 7 Wu et al. [82]
removal efficiency
31 Chlorophyll Activated carbon 76% DOC removal O3 1.0 mg/L Mousavi et al. [83]
32 Orange (II) Alumino Silicate Montanit 100% Decolorization; 91% TOC removal Inchaurrondo et al. [84]
33 Ciprofloxacin 𝛾-Al2 O3 93% removal efficiency pH 9.5; Reaction time 60 min Sani et al. [85]
34 Formate Iron oxide/AC – pH 3 Yuan et al. [86]
35 Chlorobenzene Mn/Al2 O3 82.92% conversion efficiency – Chen et al. [87]
36 Naphthenic acid Carbon Xerogel 65% removal efficiency Catalyst Conc. 0.5 g/L; O3 Conc. 30 mg/L; pH 8; Reaction time 15 min Messele et al. [88]
37 Isoniazid Mg doped ZnO 76.3% removal efficiency Catalyst Conc. 0.1 g/L; pH 7.2; Reaction time 9 min Shen et al. [89]
38 Sulfamethoxazole (SMX) Fe3 O4 /Co3 O4 60% TOC SMX 20 mg/L; O3 Conc. 6.0 mg/L; pH 5.1; T 25 °C; Catalyst Conc.0.1 g/L Chen and Wang [44]
39 Nitrobenzene Si doped 𝛼-Fe2 O3 – – Yan et al. [90]
40 Phenol CeO2 on oxidized carbon Phenol mineralization is 2–3 times of – Wang et al. [6]
nanotube (OCNT) pure CeO2 and OCNT
41 Ƿ-CBA Co(II) 95.5% degradation efficiency Catalyst Conc.1 mg/L; O3 Conc. 2 mg/L; pH 8 Psaltou et al. [91]
42 Ƿ-CBA Fe(II) 92.5% degradation efficiency Catalyst Conc. 1 mg/L; O3 Conc. 2 mg/L; pH 8 Psaltou et al. [91]
43 Rhodamine Iron based metal organic TOC removal is 4 times higher than – Yu et al. [92]
framework O3 alone
44 Bisphenol-A MgO/Graphite felt 88.2% removal efficiency; 42.1% COD – Zhang et al. [93]
removal efficiency
Table 5

C.V. Rekhate and J.K. Srivastava

Review of various catalysts used in catalytic ozonation process.

Sr No Catalyst condition efficiency Synthesis method Characterization techniques Application References

1 FE-Mn Calcination Temp. 650oC 100% decolorization Co-precipitation method XRD Methylene blue Lu et al. [36]
2 MnCe-O pH 4.8; Calcination Temp. 300 °C 69% COD removal Co-precipitation method BET Sulfamethoxazole Martins et al. [66]
3 Cu/Al2 O3 Calcination Temp. 873 K; Catalyst 75.3% TOC removal Impregnation method BET, XRD Alachlor Li et al. [48]
loading 110 g/L
4 MgFe2 O4 Catalyst dose 50 mg/L 90% degradation efficiency Sol-Gel Process XRD, BET, SEM, XPS Acid orange II Lu et al. [36]
5 Ce1.0 Fe0.9 OOH Catalyst dose 0.2 g/L 41.2% mineralization Isomorphous substitution method SEM, TEM, XRD, EDS, FTIR Sulfamethazine Bai et al. [53]
6 Fe-SBA-15 Weak acid condition 86.6% Oxalic acid removal Hydrothermal method XRD, BET Oxalic acid Yan et [40]
7 Mg-Ce-MCM41 Calcined at 540 °C for 5 hr 90.3% TOC removal Hydrothermal method XRD, BET, TEM Oxalic acid Jeirani et al. [43]
8 MnO2 porous Calcined at 400 °C for 4 hr 90% degradation efficiency By self template (MnCO3 microsphere) XRD, SEM, TEM, XPS Bisphenol A Tan et al. [94]
hollow process at room Temp.
microspheres
9 𝛼-MnO2 Calcined at 250 °C for 3 hrs 96.7% degradation efficiency Using surfactant Cetyl trimethyl XRD, TEM, ICP-OES 4- Nitro phenol Nawaz et al. [35]
ammoium bromide and Sodium
dodecyl benzene sulfate
10 MnO2 /CeO2 CeO2 synthesized by reflux method; 97% TOC removal Impregnation method XRD, TEM, XPS TGA, FTIR Sulfosalicylic acid Xing et al. [56]
Calcined at 400 °C for 4 hr
11 MnOx/SBA-15 Calcined at 823 K for 3 hr 54% mineralization efficiency Wet impregnation method using XRD Norfloxacin Chen et al. [41]
Manganese acetate tetrahydrate as
precursor
12 MgO Calcined at 500 °C Complete degradation; 94% Sol-Gel method BET, XRD, FTIR, SEM, XPS Acetamino-phen Mashayekh-Salehi
mineralization et al. [39]
13 Granular MgO 3 mm pellets thermally treated at 50% COD removal Precipitation method XRD, FTIR, SEM Methylene blue Kong et al. [75]
–porous sludge 500 °C
derived char
14 IS-FeOOH Incubated at 313 K for 24 hr; pH 12 99.8%degradation efficiency Precipitation method TEM, XRD, EPR Ƿ-chloronitro Liu et al. [72]
benzene
15 FSO-PMC (Iron Incubated at 60 °C for 24 hr 73.3% mineralization efficiency Polymerization method BET diclofenac Gao et al. [46]
silicate loaded
pumice)
16 MnO2 porous Prepared at room temp 90% degradation efficiency Self template process XRD, SEM, TEM, XPS, BET Bisphenol -A Tan et al. [94]
hollow micro
sphere
17 Zinc copper silicate 99.3% degradation Polymerization method XRD, SEM, EDX p-chloronitro Liu et al. [60]
polymer benzene
18 CuFe2 O4 CuO (79%) Fe2 O3 (70%); Calcined at 83% removal Hydrothermal method XRD, SEM, TEM NOx Zhao et al. [95]
600 °C for 3 hr
19 Ce 0.1 Fe 0.9 OOH 42.1% mineralization efficiency Isomorphous substitution method XRD, SEM, TEM, EDS, FTIR Sulfametha-zine Bai et al. [53]
20 Fe doped SBA-15 86.6% degradation efficiency Hydrothermal method XRD, BET Oxalic acid Yan et al. [40]
21 Cerium doped Red 96.5% removal efficiency Precipitation method XRD, XPS Benzafibrate Xu et al. [63]

Chemical Engineering Journal Advances 3 (2020) 100031

mud
22 Ce/SiO2@Fe2O4 Calcined at 600 °C for 2 hr 97.6% removal efficiency Chemical precipitation XRD, XPS, EDX, TEM Diethyl phthalate Wang et al. [96]
23 Zn Fe2 O4 Annealed at 550 °C for 5 hr 92.6% removal efficiency Hydrothermal XRD, SEM, XPS, FTIR phenol Zhang et al. [38]
24 Cobalt modified – – Wet impregnation XRD, XPS, FTIR Benzafibrate Xu et al. [64]
Red mud
25 WO3 Calcined at 450 °C for 5 min 100% removal efficiency; 87% TOC Thermo decomposition TGA, XRD, XPS Ibuprofen Rey et al. [97]
removal
26 MgO/AC – 88.5% Phenol removal; 83.5% COD Impregnation method ICP-MS, IR, XRD, SEM, TEM; Phenol Zhou et al.
removal efficiency BET, XPS [98,199]
27 CuO/C3 N4 – 97.9% removal efficiency Reflux condensation method BET, FTIR.; HRSEM, TEM Oxalic acid Liu et al. [99]
28 Co loaded on Fe – – Co-precipitation method BET, SEM 2–4–6 Gounden et al.
Tribromophenol [100]
29 Mn doped ZnFe2 O4 Calcined at 500 °C First order kinetic constant is 5.73 Sol Gel method – di-n-butyl Zhao et al. [59]
times than that in ozone alone phthalate
XRD: X-ray Powder Diffraction; SEM: Scanning Electron Microscopy; TEM: Transmission Electron Microscope; XPS: X-ray Photoelectron Spectroscopy; BET: Brunauer–Emmett–Teller
FTIR: Fourier Transform Infrared Spectroscopy; HRSEM: High resolution Scanning Electron Microscopy; ICP-MS: Inductively Coupled Plasma-Mass Spectroscopy; IR: Infra Red Spectroscopy
EDX: Energy Dispersive Spectroscopy; EPR: Electron paramagnetic resonance; TGA: Thermal Gravimetric Analysis; EDS: Energy Dispersive X-Ray Spectroscopy; ICP-OES: Inductively Coupled Plasma Optical Emission Spectrometry.
C.V. Rekhate and J.K. Srivastava
respectively those for analytical grade activated carbon. Rezaei et al.
[104] found that MgO/GAC composite is an efficient catalyst for the
ozonation of hydrocarbon vapors. Jalali et al.[105] found that catalytic
ozonation of antibiotic ciprofloxacin using a carbon nano-tube loaded
with MnO2 is effective in increasing the reactivity of ozone and drug on
the surface of the carbon nano-tube.
2.4. Photocatalytic ozonation
Photocatalytic ozonation processes are less ozone consuming tech-
nologies [106] and cost-effective than ozonation and photocatalysis
[107]. Titanium dioxide (TiO2 ) is widely used as photocatalyst but it
is photoactive in UV radiation whereas. WO3 , Fe2 O3 , In2 O3 , and BiVO4
functioned as visible-light-responsive photocatalysts and WO3 is an ef-
fective catalyst for the solar photocatalytic ozonation system due to its
activity in the wavelength range of solar energy [108].
The combination of photocatalysis and ozonation for water treat-
ment reported having enhanced oxidation efficiencies (synergy) com-
pared to the sum oxidation efficiencies of ozonation and photocatalysis
separately [109,110,107,111]. The positive synergistic effect of photo-
catalytic ozonation results in the generation of hydroxyl (OH•) radi-
cals which enhances the degradation of organic pollutants [1]. Quiñones
et al. [112] reported that solar photocatalytic ozonation for the treat-
ment of municipal secondary effluent was cost-effective over the solar
photo-Fenton system.
Further another advantage of photocatalytic ozonation is that it
could be used for disinfection of municipal wastewater as many studies
have been reporting bacterial inactivation [113,114,115] and reported
no post-treatment regrowth of E. coli in the dark after 24 and 48 h.
However, some studies reported that after inactivation, some bacteria
are able to recover and regrow [116,117]. This may be due to fact that
the injured bacteria were able to use the available carbon and energy
sources in the treated water as substrates thereby enabling them to me-
tabolize and reproduce [118].
Bacterial inactivation using photocatalytic ozonation is achieved
through disrupting normal cellular functions by the •OH radicals re-
sulting in oxidative damage to cellular components, thereby leading to
the death of the microorganisms [115]. Mecha et al. [119] analyzed the
cytotoxicity of the municipal wastewater and observed that after photo-
catalytic ozonation treatment water was less toxic than before treatment
and hence suitable for reuse. The coupling of photocatalysis to ozona-
tion not only enhances the oxidation rate but also controls the ozonation
by-product of the main concern (bromate) [120].
Semiconductor particles absorb a photon of energy equal to or
greater than its bandgap and electrons get excited from the valence band
(VB) to the conduction band (CB), thus leaving electron deficiencies or
holes in the VB. This contributes to the generation of electron-hole pairs
to transfer into the particle surface, in turn, to trigger a series of oxida-
tion/reduction reactions of the adsorbed substrates. The photocatalytic
ozonation occurs through a series of complex reactions. Ozone generates
OH• radicals on the TiO2 surface through the formation of 𝑜∙− 3
radical in
a series of steps [99,100]. Fig. 3 demonstrates the photocatalytic ozona-
tion reaction mechanism. When light falls on the surface of photocat-
alyst (T), the photogenerated holes and electrons travel to the surface
of the photocatalyst, participating in the redox reactions with adsorbed
species resulting in the formation of superoxide radical anion (O∙− ) and
2
hydroxyl radical (OH•) respectively, as illustrated by Eq. (20-25).
𝑇 + hγ → h+ + 𝑒− (20)
O3 + e− → O∙−
3
(21)
O∙−
3
+ H+ → HO∙−
3 (22)
3 → O2 + OH
HO∙− ∙
(23)
Chemical Engineering Journal Advances 3 (2020) 100031
O3 + H2 O → H2 O2 (24)
H2 O2 → HO− +
2 +H (25)
The synergistic performance of photocatalytic and ozonation is caused
by competent trapping of photogenerated electrons by ozone
e− + O2 → O∙− (26)
2
O∙− + O3 → O∙− + O2 (27)
2 3
Solís et al. [121] studied the photocatalytic ozonation of three pyri-
dine herbicides (Clopyralid, Triclopyr, and Picloram) in water using
nitrogen-doped titania and found that nitrogen doping improves tita-
nia photoactivity. Ling et al. [122] studied the photocatalytic ozonation
of Atenolol by Ag-TiO2 micro-tube prepared using cotton fiber as a tem-
plate and found that Ag-TiO2 is more efficient than TiO2 . Ag acts as the
electron acceptor for photocatalysis and decomposition center for O3 .
Table 6 represents the application of photocatalytic ozonation for the
degradation of organics.
2.5. Sonolytic ozonation
The sonolytic systems with the addition of ozone increased the re-
moval rate of recalcitrant organics significantly compared to ozonation
alone. The synergic enhancement is accredited to the improved O3 de-
composition in collapsing bubbles producing further free radicals [134].
The ultrasonic wave increased the O3 decomposition in solution because
of ultrasonic dispersion which results in the synergetic phenomenon
[135]. High-power ultrasound at frequencies between 20 and 100 kHz
is used for the formation of high-intensity bubbles which are propagated
by the alternation of compression (high pressure) and rarefaction (low
pressure). Furthermore, high shearing phenomena are generated in the
liquid phase, while radicals including OH• and H• may be formed which
oxidize the organic pollutants in the bulk of the solution.
During acoustic cavitation, water is pyrolytically decomposed into
hydroxyl and hydroperoxyl radicals as follows:
H2 O → H∙ + 𝐻 O∙ (28)
H∙ + O2 → HO∙2 (29)
The coupling of sonolysis with ozonolysis increases OH• because of
thermolytic ozone decomposition which occurs in the vapor phase of a
cavitation bubble as follows:
O3 → O2 + O∙ (30)
O∙ + H2 O → 2HO∙ (31)
2HO∙ → H2 O2 (32)
Ziylan and Ince [136] investigated a total degradation and miner-
alization of ibuprofen using ozonation combined with high-frequency
ultrasound and nanoparticles of zero-valent iron at pH 3. Yavaş and
Ince [137] studied the impact of ultrasound on catalytic ozonation of
paracetamol using Pt-supported nanocomposites of Al2 O3 . It was ob-
served that the addition of ultrasound accelerates mineralization. The
increase in mineralization was explained by the shift of the reaction site
from the bulk solution (poor adsorption on catalyst surfaces) to the solid
surface and the gaseous cavity bubbles (via enhanced hydrophobicity),
both being considerably more active reaction media. High efficiency in
sonolytic ozonation results due to a higher mass transfer effect. Also
coupling sonolysis with ozonolysis may exclude the formation of poi-
sonous intermediates by the active species that provided an additional
mineralization route [135].
C.V. Rekhate and J.K. Srivastava Chemical Engineering Journal Advances 3 (2020) 100031

Fig. 3. Mechanism of photocatalytic

ozonation.

Table 6
Application of photocatalytic ozonation for degradation of organics.

System Target % efficiency References

O3 /UVA- TiO2 Diclofenac 80% TOC removal García-Araya et al. [123]

UV/TiO2 /O3 Malathion, parathion 99% decomposition in 10 min Beduk et al. [124]
O3 /UV/WO3 N-diethyl meta toluamide 60% mineralization Mena et al. [125]
O3 /UV/TiO2 -reduced grapheme oxide Bisphenol -A 98.4% TOC removal efficiency Liao et al. [126]
O3 /UV/TiO2 -multiwalled carbon nanotube Aniline 70% TOC removal in 15 min; Ozone dose 50 g/m3 Orge et al. [127]
UV/TiO2 /O3 Perflurooctanoic acid 99.1% degradation efficiency Huang et al. [128]
UV/O3 /g-C3 N4 Oxalic acid 98.0% degradation efficiency Xiao et al. [129]
UV/TiO2 /O3 Amoxicillin, Diclofenac 68% TOC removal Moreira et al. [130]
UV/Boron doped TiO2 /O3 Pesticide 75% mineralization efficiency Quiñones et al. [131]
O3 /UV/TiO2 coated on ceramic plates Phenazopyridine 85% removal efficiency in 35 min Fathinia and Khataee [132]
O3 /UV/TiO2 Acetamiprid 100% degradation efficiency Silva et al. [133]

2.6. O3 /Fenton process

H2 O2 → HO−
2 +H
+
(37)
In the recent past, the Fenton process such as electro-Fenton,
Ozone itself has higher oxidation potential and selectivity towards or-
photo-Fenton, sono-Fenton, sono- photo-Fenton, sono-electro-Fenton,
ganic pollutants and generates OH• through the following Eq. (38)-(40)
and photo-electro-Fenton was efficiently utilized in the wastewater
treatment process for the removal of many hazardous organics from O3 + e− → O∙3 − (38)
wastewater [8,138]. There exists a synergetic effect in the combined
ozonation/Fenton reagent process as ozonation could accelerate Fenton
3 + H → HO3
O∙− + ∙−
(39)
reagents to enhance hydroxyl radical generation which leads to higher
oxidation rates [139,140,141] and removed COD, color at reduced treat-
ment time [142]. Fe (II) might also play an important role in catalyz- HO3∙ − → O2 + OH∙ (40)
ing ozone. Fe (II) reacts with excess H2 O2 to form highly reactive OH
O3 likely reacts with excess HO−
2 formed from Eq. (37) according to
through electron transfer as shown in Eq. (33)
Eq (41)
Fe(II) + H2 O2 → Fe(III) + 𝑂H∙ + 𝑂H− (33)
2 + O3 → HO2 + O3
HO− ∙ ∙−
(41)
• •
OH are scavenged by higher Fe (II) concentration as shown in Eq. (34) And generates OH through Eq. (39-40). Thus the combination of
ozonation and Fenton process results in the enhanced generation of OH•
Fe(II) + 𝑂H∙ → Fe(III) + 𝑂H− (34) thereby increasing treatment efficiency.

Excess H2 O2 leads to OH• scavenging and formation of hydroperoxide

3. Influencing factors in catalytic ozonation
ion (HO−
2
) and hydroperoxide radical (HO∙2 ) as shown in Eq. (35) – (37)
3.1. pH values
OH∙ + H2 O2 → HO∙2 + H2 O (35)
The pH of the solution plays an important role in catalytic ozona-
HO∙2 + Fe(II) → HO−
2 + Fe(III) (36) tion as it controlled the mass transfer and decomposition of O3 . At a
C.V. Rekhate and J.K. Srivastava
higher pH, the reaction mechanism follows a radical pathway and gen-
erates more OH• while at a lower pH, it follows a selective direct reac-
tion pathway. Therefore, a higher pH of the solution is suggested to in-
crease the decomposition of ozone into OH• which enhances the degra-
dation of refractory organics [48] also results in higher TOC removal at
higher pH levels [49]. The pH is also an important factor determining
the charge property of surface hydroxyl groups at the catalyst/solution
interface [8]. Higher pH of the solution could increase the efficiency
of the Cu/Al2 O3 -honeycomb catalyst during the ozonation of alachlor
[48]. It was observed that higher pH promote the OH• reaction route
for Methylene Blue decolorization [25,34]
The effect of pH on the catalytic ozonation is different from the non-
catalytic system. The O3 /Fe (III) system was effective at alkaline pH,
whereas O3 /Fe (II), O3 /Mn (II), and O3 /Cu (II) were effective at acidic
pH. Yang et al. [143] found that the COD removal efficiencies increased
gradually from 34% to 56% with pH increased from 4.0 to 12.0. The
higher oxidation efficiency under the higher solution pH could be due
to elevated ozone utilization ratio at higher pH. It was observed that
during the ozonation reaction the solution pH was a little declined.
The ozone solubility depends on the pH, presence of radical scav-
engers, and temperature [144]. The production of hydroxyl radicals as
a result of ozone decomposition is significant at neutral pH for ozonation
only [145]. At increased pH, more hydroxyl radicals would be generated
by ozone decomposition due to the presence of a large quantity of hy-
droxide ions for homogeneous catalytic ozonation [34]. During ozona-
tion, it was observed that the pH of the solution decreased gradually
when the initial pH is 10 while the solution became acidic rapidly at
lower initial pH [146]. An increase in pH (that is, a higher concentra-
tion of hydroxide anion) also promotes the decomposition of O3 into
OH• radicals [4]. At pH 10, it is most likely all the ozone decomposes,
with no or little dissolved ozone in the medium [4].
The pH of the solution is a key factor in the Fenton process be-
cause it controls the production of the hydroxyl radical and ferrous ions
concentration [147]. Fenton reaction proceeds with higher rates at the
higher initial concentration of H2 O2 , and more acidic conditions (pH
3), whereas ozonation reaction requires a higher ozone dose, and basic
conditions (pH 11) for rapid rates [148]. It has been observed that at
high pH a decrease in ozone transfer efficiency is observed because the
increase in reaction rate is compensated by greater ozone requirement
due to the loss of oxidant by self decomposition [149]. At high pH, the
formation of ferric hydroxide may deactivate the ferrous catalyst [150].
It was found that the efficiency of oxidation depends on the point
of zero charge (PZC) of the catalyst [12]. It was observed that below
the PZC the surface of the catalyst is positively charged, making in-
teractions with anionic pollutants/oxidants. Above the PCZ the surface
is negatively charged promoting the interactions with cationic pollu-
tants/oxidants. Most of the catalysts used had higher performances at
neutral/acidic pH values, due to their PCZ [12]
3.2. Ozone dosage and/ozone flow rate
The selection of suitable ozone flow rate for the degradation of tar-
get pollutant is very important for the optimization of ozone utilization.
The increase in ozone dose enhances the driving force for the transfer
of ozone to the effluent, thereby, increasing the generation of hydroxyl
radicals which ultimately enhances degradation efficiency and miner-
alization rate for organics [15]. Nawaz et al. [35] found that the TOC
removal rates were 50.6%, 79.5%, and 85.2% with 10, 20, and 50 mg/L
of ozone dosage respectively. Further increase in ozone dosage slightly
increased the removal rate of pollutants, but the effect was very limited.
It could be stated that TOC removal rates increased with the increase of
ozone dosage but that did not mean the total mineralization of the pol-
lutant [35].
An excess of ozone dose lowered the utilization efficiency of ozone.
The increase of the COD removal rate was insignificant when the ozone
dose of >1.86 mg/min was introduced [67]. Huang et al. [128] found
Chemical Engineering Journal Advances 3 (2020) 100031
that when the ozone dosage increased from15 mg/hr to 25 mg/hr, the
defluorination of perfluorooctanoic acid improved rapidly from 16.7%
to 39.4%. On the other hand, as the ozone dosage enhanced from
25 mg/hr to 100 mg/hr by a large margin, the defluorination of perflu-
orooctanoic acid increased only slightly by 4.9%. This may be because
the ozone utilization efficiency was limited when excessive ozone was
bubbled in the solution as the amounts of active sites were definite on
the surface of the catalyst.
The variation in ozone flow rates could influence the gas-liquid mass
transfer thereby, the effective ozone utilization ratio. The higher ozone
flow rate was corresponding to the higher ozone mass rate; accelerated
agitation thereafter increased its contact probability with the pollutants.
Yang et al. [143] found that the COD removal efficiency increased with
the ozone flow rate initially thereafter it reduced. This may be due to
excessive turbulence under the high flow rate may lead to exorbitant
hydro-mechanical shear stress which has a negative effect on pollutant
removal.
3.3. Catalyst loading
Chemisorption of the organic compounds on the surface of the cata-
lyst was widely suggested to be one of the essential steps for the catalytic
reaction. The adsorbed organics were then degraded by ozone or OH• .
Basiri and Rafiee [58] observed that by increasing the dosage of ZnO
nanocatalyst, the rate of 2–4–6 Trichlorophenol ozonation increased. It
is shown that the rate of ozone decomposition and thus the production
of hydroxyl radicals were accelerated on the ZnO surface during cat-
alytic ozonation. The increase in catalyst concentration increased the
number of reactive sites and enhanced the light absorption for photo-
catalysis [151]. The higher concentrations of the catalyst may result in
light-scattering and screening effects due to high opacity caused by an
excess catalyst which compromised light penetration thus counteracting
the effect of increasing catalyst surface area. Furthermore, the tendency
toward particle agglomeration was also enhanced at high catalyst con-
centration, resulting in a reduction in surface area available for light
absorption and hence a drop in photocatalytic degradation rate [149].
3.4. Temperature
The catalytic ozonation process involving the aqueous-gaseous-solid
phase is largely influenced by temperature. It was observed that TOC re-
moval efficiency increased with temperature. However, ozone solubility
decreases with an increase in temperature, which reduces the reaction
efficiency at higher temperatures [67]. The combined result of these two
opposite effects determines the outcome of temperature variation. Most
of the research articles reported higher degradation efficiency at room
temperature [46,128,60,35].
3.5. Reaction time
The decolorization efficiency for the degradation of azo dyes in-
creases with reaction time[22]. With an increase in initial dye concen-
tration, the time required for complete decolorization increases gradu-
ally [152]. It was observed that with an increase in ozone concentration,
degradation of azo dyes increases with reaction time [22]. It is found
that wastewater biodegradability increases with ozonation time.
4. Application of ozonation to various industries
4.1. Dairy industry
The dairy industry wastewaters are mainly produced from the clean-
ing and washing operations in the milk processing plants. The charac-
teristics of a dairy effluent contain temperature, color, pH (6.5–8.0),
DO, BOD (80–95,000), COD (40–48,000), dissolved solids, suspended
solids, nutrients, oil, and grease [153]. Ozonation is an effective method
C.V. Rekhate and J.K. Srivastava
for COD and odor removal of dairy wastewater [154]. Sivrioglu et al.
[155]obtained the highest COD removal efficiency (71%) at pH 12 for
ozonation of dairy wastewater due to accelerated ozone decomposition
at elevated pH. Ozone is a highly effective disinfectant. It decomposes
to nontoxic products thereby reducing the environmental impacts and
costs of the company. Another advantage of the application of ozone in
food-processing operations is that ozone can be generated on-site and
as opposed to conventional chemical sanitizers, it requires neither trans-
portation nor storage.
4.2. Hospital wastewater
Hospital wastewater includes a complex high percentage of recal-
citrant micropollutants and there are no specific treatments have been
investigated for the removal of these pollutants. Ozone as a disinfectant
can also effectively kill pathogens and viruses in hospital wastewater.
This is also a major advantage of ozone technology used in hospital
wastewater.
Aracil et al. [156] concluded that the direct ozonation of raw hos-
pital wastewater is a technically and economically feasible treatment
process for the chemical abatement of particular cytostatic compounds,
antibiotics, and other dissolved organics present in hospital waters. It
was found that the elimination yield for the cyclophosphamide (a cy-
tostatic compound) is 97%. The micropollutants present in the hospi-
tal wastewater effluent such as phenols, aniline, thioethers, aromatics,
amines, pharmaceuticals could be efficiently (93%) eliminated at spe-
cific ozone doses [157]. Kern et al. [158] studied photocatalytic ozona-
tion (UV/O3 /Fe2+ ) with Fe2+ concentration of 150 mg L − 1 for the
toxicity removal of hospital laundry wastewaters and found that pho-
tocatalytic ozonation using Fe2+ catalyst was efficient in reducing COD
(59.1%), BOD5 (50.3%) and TKN (86.8%). Khan et al. [159] observed
that the degradation of pharmaceuticals present in hospital wastewater
was comparatively low for the O3 /H2 O2 process as compared to ozona-
tion alone so the addition of hydrogen peroxide along with the ozone
for the removal of pharmaceuticals is not efficient as compared to the
ozone alone treatment.
4.3. Petrochemical wastewater
Petrochemical wastewater includes significant amounts of recalci-
trant contaminants like aliphatic and aromatic hydrocarbons, inorganic
dissolved salts, phenolic substances, nutrients, and solids which are usu-
ally environmentally toxic. Ozonation decomposes or mineralize the
refractory organic contaminants and improved the biodegradability of
petrochemical wastewater. It was observed that the ozonation of petro-
chemical wastewater declined the concentration of heavy metals such as
Pb As, Cd, and Cr existed in the petrochemical wastewater. It was most
possible that these heavy metals were oxidized into insoluble oxides pre-
cipitate by ozone [160]. Huang et al. [160] studied the catalytic ozona-
tion of petrochemical wastewater using a nickel-iron foam catalyst. They
found 61% DOC removal and 96% TOC removal at 110 gL−1 catalyst
dosage, 10.2 mgL−1 ozone concentration after 120 min reaction time in
wide pH range (4–10). Ahmadi et al. [161] studied catalytic ozonation
of petrochemical wastewater using carbon-impregnated by iron oxide
(PAC@Fe3 O4 ) catalyst. Authors found 75.3% COD, 50.3% TOC removal
using 0.45 g L − 1 catalyst dosage, pH 5 and 0.1 gh−1 ozone dosage af-
ter 120 min catalytic ozonation. It is well known that ozone breakdown
large molecules into smaller ones. It was observed that ozonation can
change organics molecular size [162]. Wu et al. [162] treated petro-
chemical wastewater using ozonation and biological aerated filter. Au-
thors found that after ozonation the organics with large molecular size
(>30k) decreased to 12% while the percentage of small molecular size
(<1k) organics increased to 67%.
Chemical Engineering Journal Advances 3 (2020) 100031
4.4. Piggery wastewater
Kim et al. [163] studied the feasibility of ozonation as pretreatment
for better performance of microalgae-based wastewater remediation of
highly colored piggery effluent. It was found that ozonation is efficient
in the decolorization of colored piggery effluent and it also increases
biodegradability by producing a large amount of low molecular and eas-
ily degradable organics. Lee et al. [164] investigated the simultaneous
removal of antibiotics and antibiotic-resistant bacteria by ozone-based
advanced oxidation technology for the treatment of piggery wastewa-
ter. The performance of four different combinations of oxidation agents
was investigated, showing the order of removal rate as O3 < O3 /H2 O2
< O3 /UV < O3/UV/H2 O2 for wastewater. It was found that the com-
bination of ozone/H2 O2 did not contribute significantly to antibiotics
degradation, whereas the application of O3 /UV enhanced the disinfec-
tion performance compared to UV alone.
4.5. Pharmaceuticals wastewater
Almomani et al. [165] found that the ozonation process is more ef-
fective than other conventional oxidation processes (Cl2 and ClO2 ) in
eliminating pharmaceuticals (antibiotics, estrogens, and neutral) and
detoxification of the effluent wastewater. García-Araya et al. [123] con-
cluded that the O3 /UV-A/TiO2 oxidation system at pH 7 is effective for
the diclofenac, a popular nonsteroidal anti-inflammatory pharmaceuti-
cal drug removal from water. Martins et al. [66] studied the effect of
catalytic systems on the degradation of pharmaceutical contaminants
like diclofenac and sulfamethoxazole. Authors observed that the use of
ceramic catalyst Mn-Ce-O enhances COD removal but it had no signif-
icant impact on pharmaceutical removal when compared with single
ozonation.
Kidak and Dog˘an [166] observed that ozonation alone in the degra-
dation of amoxicillin, a common antibiotic drug resulted in 32% miner-
alization but the final solution contained intermediates with high toxi-
city. Ozonation coupled with ultrasound resulted in a high degradation
rate, high mineralization (45%), and lower toxicity by less toxic interme-
diates [166]. Liu et al. [167] explored visible light photocatalytic ozona-
tion using bismuth vanadate (BiVO4 ) as a catalyst for the degradation of
penicillin, a representative contaminant in pharmaceutical wastewater.
The authors found a TOC removal rate over 71.4% and obtained a syn-
ergy index of 2.8 indicating a better positive synergistic effect between
ozonation and photocatalysis. Yang et al. [168] used WO3 materials as
catalysts in visible light photocatalytic ozonation for the mineralization
of cephalexin, an extensively used macromolecular antibiotic, widely
found in pharmaceutical wastewater. Authors concluded that O3 effi-
ciently traps the photoelectron upon WO3 , and consequently more holes
with higher oxidizing ability are released in photocatalytic ozonation.
4.6. Municipal wastewater
Conventional aerobic treatment methods are inadequate for the re-
moval of recalcitrant organics present in municipal wastewater. The
application of ozonation for municipal wastewater treatment has been
demonstrated as a promising technology for the removal of a large
number of trace organic compounds such as pharmaceuticals, personal
care products, and endocrine disruptors present in secondary wastewa-
ter effluents and the improvement of water quality [169]. Vatankhah
et al. [170] found enhanced removal of micropollutants in munici-
pal wastewater effluent using simultaneous ozone and granular acti-
vated carbon (O3 /GAC) process. Ozonation was economically competi-
tive with photo-Fenton as the investment cost of the solar field is offset
by the operating cost of ozonation [171]. Farzaneh et al. [172] stud-
ied the removal of ibuprofen and gemfibrozil from treated sewage ef-
fluent by ozonation and ozone/hydrogen peroxide (O3 /H2 O2 ). It was
found that 100% removal of gemfibrozil and 80% ibuprofen removal
C.V. Rekhate and J.K. Srivastava
were achieved using an ozone dosage of 1.5 mg/L with an O3 :H2 O2 ra-
tio of 1:0.25 in the O3 /H2 O2 process. King et al. [173] concluded that
ozonation was an effective process for the removal of pesticides, heavy
metals, and viruses from reverse osmosis concentrate generated during
potable reuse of municipal wastewaters.
Tang et al. [174] found that ozonation with a dose of 10 mg/l com-
pletely removed genotoxicity. Ozonation was found to change chemical
aliphatic carbon and C–O of dissolved organic matter which might be
the reason for a significant decrease of specific ultraviolet absorbance
and genotoxicity. It can be concluded from the literature that the toxi-
city of municipal wastewater is reduced significantly during photocat-
alytic ozonation [115,119]. The photocatalytic ozonation is effective in
reducing recalcitrant pollutants to meet the set standard for wastewater
discharge (COD). However further tests on microbiological quality and
toxicity studies may be required to make water fit for human consump-
tion [119].
4.7. Surfactant wastewater
The surfactants are used in the formulation of detergents and are
recalcitrant. The effectiveness of ozonation depended on the chemical
structure of the surfactant molecule. Ozonation attack the aromatic ring
present in surfactants thus improving the biodegradation of surfactant
[175].
Utrilla et al. [176] found that 55% of surfactant dodecyl benzene
sulfonate was removed by consecutive use of ozonation and biodegra-
dation. Ozonation did not significantly mineralize the organic matter
however the performance of the system can be increased by consecutive
use of ozonation and biodegradation as ozonation generates a molecule
with lower molecular weight favoring metabolism of the organic species
present by microorganism and their removal from the medium.
Patil et al. [177] studied the intensification of ozonation by the addi-
tion of solid ZnO and CuO catalysts for the treatment of laundry wastew-
ater containing surfactants. The authors observed that the extent of
degradation was increased with catalytic ozonation as compared to non-
catalytic ozonation and obtained COD degradation of 89.3% at initial pH
of 9 and 0.1 g L − 1 of ZnO loading. Lechuga et al. [175] observed that
the ozonation of aqueous solution of non-ionic amine oxide-based sur-
factant causes the decrease of TOC but the mineralization degree is slow.
Arslan et al. [178] studied the removal of anionic surfactant sodium do-
decyl sulfate (SDS) from aqueous solutions by the O3 /UV/H2 O2 process.
The authors found that an increase in the H2 O2 concentration resulted
in a decrease in SDS removal. Further SDS removal increased as pH in-
creased.
4.8. Textile industry wastewater
Dyes are widely used in the textile industry to color their prod-
ucts. Textile wastewaters contain variable compositions of colored dyes,
surfactants, and toxic chemicals. Discharge of textile wastewater to
the environment is very harmful to ecosystems as it is highly col-
ored. Due to low biodegradability of synthetic dyes, conventional bi-
ological method such as activated sludge is ineffective to degrade
dyes satisfactorily [179]. Ozone was very effective for color removal
[180,20,181]. Nakhate et al. [182] investigated catalytic ozonation us-
ing copper-doped zinc oxide for the treatment of real textile wastewa-
ter. The authors found that Cu-doped ZnO removed 89% of COD within
30 min. Shokouhi et al. [183] obtained enhanced color and COD re-
moval for activated carbon catalyzed ozonation of Reactive Blue azo
dye in aqueous saline solution against single ozonation. Bilińska et al.
[184] compared several ozone-based AOPs (e.g. O3 , O3 /UV, O3 /H2 O2 ,
and O3 /UV/H2 O2 ) processes in terms of their effectiveness in remov-
ing Reactive Black 5 industrial textile wastewater. Authors found that
O3 or O3 combined with a moderate concentration of H2 O2 (below
0.005 M) were cost-effective processes and exhibited good color and
Chemical Engineering Journal Advances 3 (2020) 100031
toxicity reduction of Reactive Black 5, with increased mineralization
and biodegradability.
Ozonation in combination with aerobic biological treatment resulted
in a more feasible system for color removal, total organic carbon, chem-
ical oxygen demand, and toxicity reduction. Also, it was found that the
combined approach not only allowed the better achievement of decol-
orization and biodegradability efficiency but also contributed towards
reducing treatment costs. Castro et al. [185] studied the feasibility of ad-
vanced oxidation processes and biological treatment for cotton textile
effluent containing benzidine-derived azo dyes. It was observed that the
ozonation technique is probably better for decolorization than the other
advanced oxidation processes such as Fenton, photo-Fenton, UV/TiO2
[185]. However, Cardoso et al. [110] observed that the bubbling reactor
with an ozone system resulted in reduced energy consumption compared
to a combination of ozone with photocatalysis or photo-electrocatalysis
[110].
Eldein et al. [186] observed that H2 O2 /UV can compete with ozona-
tion when the treatment goal was decolorization textile dye effluent
only; however ozonation was more cost-effective when mineralization
was desired. O3 /Fe (II) process was found to be more effective compared
with O3 and O3 /UV processes in the decolorization of azo dyes [22].
4.9. Tannery wastewater
Tannery wastewaters may contain considerable amounts of bio re-
fractory organics, so that applying biological treatment alone may
not yield adequate COD removal efficiencies to meet discharge stan-
dards. Such cases necessitate the use of an advanced chemical oxida-
tion method such as ozonation along with biological treatment for re-
moving color and the residual COD present in the wastewater [187].
Sivagami et al. [187] concluded that a three-step process of coagula-
tion, aeration followed by ozonation as the best method of treatment of
tannery wastewater exhibiting 80–90% COD reduction. Kalyanaraman
et al. [188] studied the biodegradation of tannins by ozonation. The au-
thors found that ozonation as pre-treatment increased the BOD5 /COD
ratio to 0.298 and resulted in 20% COD and 49% of total phenol removal
due to mineralization.
Table 7 represents the application of the ozone-based AOP for the
treatment of various wastewaters.
4.10. Gas station wastewater
Gas-stations usually consume large volumes of water in many activ-
ities such as car washing, floor cleaning, toilet, cafeteria use, etc. The
conventional biological treatment processes do not completely remove
dissolved solids, detergents, and heavy metals of gas-station wastewa-
ter. Emam [19] found that 91% of dissolved organic carbon removal
was achieved by the photocatalytic ozonation.
5. Economic aspect of the combined process
Treatment cost based on electric energy consumption plays an im-
portant role in process economics. The cost for catalytic ozonation
mainly depends on the power consumption for ozone generation. The
ozone consumption was normalized by the COD removal efficiency as
Eq. (42) [143]
ΔCO3 ⋅ Q ⋅ T
𝐴= (42)
ΔCCOD ⋅ V
where A is the normalized ozone consumption (mg O3 /mg COD); ΔCO3
is the difference between inlet and outlet ozone concentrations (mg/L);
Q is the ozone flow rate (L/min); T is the reaction time(min); ΔCCOD is
the difference between inlet and outlet COD concentrations (mg/L); V
is the volume of the reactor (L).
Yang et al. [143] calculated unit cost for ozonation based on the fol-
lowing data. The inlet and outlet ozone concentration was 53.9mgL−1
C.V. Rekhate and J.K. Srivastava Chemical Engineering Journal Advances 3 (2020) 100031

and 50.3mgL−1 respectively. The COD concentration (reactor vol. 0.5 L)

was reduced by ~20 mgL−1 after 5 min reaction at an ozone flow rate

García-Araya et al. [123]

of 2 Lmin−1 . The normalized ozone consumption of 3.6 mgO3/ mg COD

Shahmahdi et al. [193]

Shanthakumar. [196]
was obtained. The power consumption of the ozone generator is around

Li and Zhou, [192]

Beduk et al. [124]

Asgari et al. [191]

Aracil et al. [156]
16 kWh/kgO3 . Therefore, the unit cost for ozonation was around 0.14

Kim et al. [163]

Wu et al. [162]

Wu et al. [189]
Hu et al. [101]
Hu et al. [190]

Li et al. [194]

Li et al. [195]
USD/m3 assuming a 90% ozone utilization rate, and the local electric

Saranya and
Emam [19]
Emam [19]
References

charge as 0.10 USD/kWh. Malik et al. [16] concluded that combined

ozonation processes such as catalytic ozonation, photocatalytic ozona-
tion require less energy compared to O3 alone at the same pollutant
abatement levels due to the higher energy efficiency of ozonation and
Ozone dosage 2.2 mg/min; Catalyst Conc. 3 g; T 24 °C the synergism of combined treatment Nakhate et al. [197] concluded
that the O3 /Fenton process has higher treatment efficiency based on

Catalyst Conc. 200 g/L; O3 dosage 5 mg/min; pH 6.81

electrical energy consumption. The authors calculated the treatment
cost for Fenton, ozonation alone, and combined the O3 /Fenton process
Ozone 55.3 g/m3 ; pH 8; Reaction time 20 min
Ozone 1.5 mg/L; pH 9; Reaction time 30 min

based on energy cost involved to reduce undesired components (e.g.

Ozone 25 mg/L; Fe++ dosage 0.08 mmol/L

COD) and time to reduce the same. The authors reported that the re-
TiO2 Cons. 1.5 g/L; pH 7; Ozone 1 mg/L
Ozone 15 mg/L; Catalyst Conc. 0.3 g/L
Ozone 15 mg/L; Catalyst Conc. 0.3 g/L

Ozone 10 mg/L; Reaction time 4 min

quired energy for degradation of COD in landfill leachate was 0.525 kWh
for O3 /H2 O2 and 0.111 kWh for the O3 /Fenton process whereas for
ozonation alone it was 0.15 kWh. Although treatment cost required
1.5 g of O3 /g of COD; pH 7.6

based on power dissipation was found to be less in the case of the ozona-
tion process, the COD reduction capacity is found to be limited. Pillai
et al. [198] have shown that specific energy consumption for the treat-
ment of terephthalic acid wastewater using O3 , O3 /UV, O3 /H2 O2 /UV,
Ozone 1.1 mg/L

and O3 /Fe2+ was 31.3 kWhm−3 , 58.6 kWhm−3 , 32.1 kWhm−3 , and 21.3
kWhm−3 respectively where the COD removal efficiency was 43%, 53%,
Condition

45%, and 47% respectively which demonstrates the cost-effectiveness of

O3 /Fe2+ . Further O3 /Fe (II) process was found to be more cost-effective
–
–
–
–
–

compared with O3 and O3 /UV processes [22]. UV promotes degradation

by ozone, but it adds to the initial cost.
1.36 times greater COD removal efficiency than
99% decomposition of malathion & parathion

50% increase in light transmittance of liquid

100% diclofenac removal& 90% TOC removal

85.2% removal of pollutants with molecular

Conclusion and future perspective

100% removal of cytostatic compound

weight 10–20 KDa; 78% TOC removal

The ozone-based AOPs have been proved to be effective in detox-

ifying a wide range of industrial effluents, pharmaceutical products,
pesticide, and recalcitrant organics. The various ozone-based AOP
processes such as O3 /UV, O3 /H2 O2 , O3 /Fe(II), O3 /metal oxide cat-
68.37% TSS removal

86.6% TOC removal

78.7% TOC removal

Treatment efficiency

91% DOC removed

88% DOC removed

37% DOC removal

alyst, O3 /activated carbon, O3 /ultrasound, photocatalytic ozonation,

46% COD removal

60% COD removal

80% COD removal

sonolytic ozonation, O3 /Fenton are discussed and recent research based

on these AOPs is compiled. Future studies should be focused on the iden-
tification of reaction intermediates, development of rate expressions,
and identification of scale-up parameters.
O3
–

The identification of reaction intermediates should be assisted by

Application of ozone based AOP for the treatment of various wastewaters.

chromatographic techniques such as GC and HPLC. With the use of

these techniques detailed description of reactions taking place during
Carbon aerogel supported copper oxide
Carbon aerogel supported cobalt oxide

the treatment process may be explored in detail. Sometimes interme-

diate/transformation products found to be more toxic than the parent
compounds, toxicity tests should be employed at various stages of treat-
MgO/CNT/Graphite composite

ment to check the toxicity effects of these compounds. Future studies

O3+ hydrogen peroxide
UV/O3 /activated carbon

should be focused on the cost-effectiveness of ozone-based AOP and

should explore the actual amount of energy consumed by using ozone-
Iron Shaving (Feo )

Fe based catalyst

based AOP over the other conventional treatment methods. It is neces-

Catalyst/Process

O3 /TiO2 /UV-A

sary to carry out the more pilot-plant scale experiments with real indus-
Iron scrapes
TiO2 /O3 /UV
UV/O3 /TiO2

Fe shaving

trial wastewater for the identification of scale-up parameters.

Fe++ -BAF

The efficacious systems for the detection and destruction of ozone

are required for the safety of personnel in various processing plants as
O3
O3

O3

exposure to ozone may cause irritation to the eyes, nose, and throat
whereas high ozone levels (up to 95 mg/L) can even have fatal effects
Pesticide ww (Atrizine)

on humans [2].
Pharmaceutical ww

Hybrid methods are economically viable techniques for the treat-

Petrochemical ww

Petrochemical ww
Textile dyeing ww

ww- wastewater.

ment of a wide range of industrial effluents. Also, the capital cost for
Gas Station ww
Gas Station ww

Municipal ww

Industrial ww
Pesticide ww

Pesticide ww

reactors and other accessories can be reduced because of the use of one
Hospital ww

Tannery ww
Piggery ww

Coking ww
Textile ww
wastewater

reactor for simultaneous Fenton/UV/photocatalytic oxidation process

Table 7

and ozonation instead of two separate reactors. The use combined pro-
cess decreases the operational cost based on energy consumption, en-
hances OH• availability, and enhances treatment efficiency. The high
∗
C.V. Rekhate and J.K. Srivastava
effectiveness and low energy consumption make the ozone-based AOP
process an attractive process for wastewater remediation.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
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