water
Article
Study on the Mechanism and Control Strategy of Advanced
Treatment of Yeast Wastewater by Ozone Catalytic Oxidation
Xianglong Jing 1,2,3 , Shikun Cheng 1 , Cong Men 1, *, Huimin Zhu 2,3 , Mei Luo 2,3 and Zifu Li 1, *
Citation: Jing, X.; Cheng, S.; Men, C.;
Zhu, H.; Luo, M.; Li, Z. Study on the
Mechanism and Control Strategy of
Advanced Treatment of Yeast
Wastewater by Ozone Catalytic
Oxidation. Water 2023, 15, 274.
https://doi.org/10.3390/w15020274
Academic Editor: Weihua Zhao
Received: 15 November 2022
Revised: 5 January 2023
Accepted: 6 January 2023
Published: 9 January 2023
Copyright: © 2023 by the authors.
Licensee MDPI, Basel, Switzerland.
This article is an open access article
distributed under the terms and
conditions of the Creative Commons
Attribution (CC BY) license (https://
creativecommons.org/licenses/by/
4.0/).
Water 2023, 15, 274. https://doi.org/10.3390/w15020274
1 School of Energy & Environmental Engineering, Beijing Key Laboratory of Resource-Oriented Treatment of
Industrial Pollutants, University of Science & Technology Beijing, Beijing 100083, China
2 Beijing Municipal Research Institute of Eco-Environmental Protection, Beijing 100037, China
3 Chinese National Engineering Research Center of Urban Environmental Pollution Control,
Beijing 100037, China
* Correspondence: mencong@ustb.edu.cn (C.M.); zifuli@ustb.edu.cn (Z.L.)
Abstract: In this paper, the yeast wastewater secondary treatment effluent using catalytic odor oxida-
tion treatment, using an orthogonal reaction experiment to determine the best reaction conditions, and
the online monitoring of the pH, oxidation-reduction potential (ORP), and liquid ozone concentration
monitoring, to the catalytic odor oxidation reaction, chemical oxygen demand (COD), and color re-
moval effect were analyzed. The results showed that the optimal reaction condition for the advanced
treatment of yeast wastewater by catalytic ozonation was accomplished with manganese dioxide
used as the catalyst and a catalyst dose of 6 g·L−1 , pH of 12, and catalytic ozonation reaction time
of 20 min. The COD was effectively reduced from 880 mg·L−1 to 387 mg·L−1 under this condition,
the chroma was reduced from 700 times to 40 times, and these two parameters of the effluent could
meet the standard of GB25462-2010. The real-time monitoring system showed that the whole reaction
can be divided into two processes. The first 14 min was the indirect reaction of ozone and then the
direct oxidation reaction of ozone. This process was further verified by the change trend of COD
and the amount of ozone depletion by COD removal. The average ozone consumption levels of the
two stages were 1.97 and 4.91 mgO3 ·mgCOD−1 . This system can effectively monitor the reaction of
the catalytic odor oxidation in the complex system to guide the effective use of ozone in practical
engineering applications.
Keywords: yeast wastewater; heterogeneous catalytic ozonation; advanced treatment; calcium
hydroxide; catalyst
1. Introduction
The production of yeast mainly uses molasses waste liquid in sugar production
as a growth carbon source and sodium chloride, magnesium sulfate, and ammonium
phosphate as nutrients to produce yeast. Residual organic matter and new organic matter
produced in the growth and metabolism enter the wastewater, resulting in a large amount
of high-concentration organic wastewater because yeast cannot fully utilize organic matter
in waste molasses. Yeast wastewater is characterized by complex water quality, high
pollutant concentration, high chromaticity, difficult-to-biodegrade substances, and high salt
content. There are various methods of wastewater treatment [1–3], but yeast wastewater is
usually treated by the secondary biological treatment process of “anaerobic + aerobic” and
supplemented by chemical precipitation as an advanced treatment [4–6]. However, after
the biological treatment with a hydraulic retention time of 5–7 days, the effluent chemical
oxygen demand (COD) is still as high as 800–900 mg·L−1 , and after the coagulation and
precipitation treatment with iron or aluminum salts, with a coagulant dosage as high as
1 g·L−1 , the effluent COD is still higher than 500 mg·L−1 , which cannot reach the standard
for water pollutant discharge in the yeast industry (GB25462-2010). The COD is less than
400 mg·L−1 [7,8]. The chroma in yeast wastewater is gradually accumulated by the chroma
https://www.mdpi.com/journal/water
Water 2023, 15, 274 2 of 14

in the waste molasses in the process of sugar production and yeast fermentation [9,10]. It
mainly consists of phenols and amino nitrogen compounds. The polyphenols are oxidized
into brown pigment under the action of enzymes, and the polymer brown melanin is
synthesized by the decomposition of the reducing sugar base [11,12]. Yeast wastewater
is brown and black, with a chromaticity of about 6000 times when combined with the
pigment of the above substances, such as the thermal decomposition of sugar into dark
brown caramel pigment and the reaction of phenols with iron to produce dark compounds.
In the biological treatment of yeast wastewater, the anaerobic process has a good chroma
removal effect on the wastewater, the influent chroma is about 3000 times, the anaerobic
effluent can generally reach 400–600 times, and the chroma removal rate is more than
80%. However, after the aerobic treatment, the chroma increases, and the aerobic effluent
chroma is generally 600–800 times because at the anaerobic stage, and the chromogenic
groups of some polyphenolic compounds are reduced but not completely decomposed
into small molecules, which temporarily do not show color. At the aerobic stage, after
the oxidation of these chromogenic groups, they restore the former chromogenic groups
and show color again. Such polyphenolic compounds are biodegradable substances but
are difficult to be completely decomposed and removed in the process of the biological
system. Finally, it is discharged from the biological system with an aerobic effluent [13]. At
present, the advanced treatment method of yeast wastewater is mainly a chemical method,
which uses a flocculant for COD removal and decolorization treatment. Given the chemical
precipitation method, the large amount of coagulant dosing and its resulting chemical
sludge substantially increase the cost of yeast wastewater treatment [14].
Ozone is a strong oxidant, and its application in the field of wastewater treatment has
been extensively studied. Ozone can change the structure of refractory substances in water
and convert them into biodegradable substances, thus improving the biochemical prop-
erties of wastewater [15–19]. Using metal oxides as catalysts to form catalytic ozonation
systems [20–23] or homogeneous catalytic ozonation systems formed by combining UV and
hydrogen peroxide with ozone, respectively [24–28], both systems enhance ozonation by
catalytic methods to produce hydroxyl radicals and other radicals with stronger oxidizing
properties, thus improving the removal of refractory substances and chromaticity [29–31].
Ozone can destabilize particulate matter in water, and the use of ozone as a micro floccula-
tion technique for pretreatment processes can achieve the goal of reducing the amounts
of pharmaceuticals added to coagulation processes and sludge treatment and increasing
the removal rate of coagulation processes [14,32,33]. Ozone or the use of free radicals with
strong oxidizing properties generated by ozone can also directly react with toxic substances
to remove or reduce the toxicity of wastewater [34–37], thus allowing biological treatment.
Several scholars have conducted studies on the kinetics of ozone oxidation for various
characteristic pollutants [38–40]. However, the above studies focus on wastewater with
a relatively simple composition, which greatly reduces the efficiency of ozone oxidation
due to the complex water quality of actual production wastewater and the complicated
reaction processes between ozone and pollutants and intermediates. Exploring the ozone
oxidation reaction in complex water quality systems and controlling it are important to
achieve the efficient treatment of complex water quality systems. Although ozone can play
an evident role in the treatment of all kinds of wastewater, the investment and operation
costs of ozone equipment are very high. In China, except for disinfection with ozone, other
fields of wastewater treatment are still in the research stage.
In this paper, the COD in the secondary treatment effluent of yeast wastewater is used
as the targeted parameter, the optimal catalytic ozonation conditions are determined by
orthogonal tests, and the ozonation monitoring system is established to study the catalytic
ozonation reaction. The change law in the complex system and the reaction process is
evaluated by the ozone utilization rate and other indicators. The chroma removal of
wastewater during catalytic ozonation is also investigated, the catalytic ozonation reaction
control strategy is proposed for the catalytic ozonation-based theoretical basis, and the
Water 2023, 15, 274 3 of 14

control method for effective ozone addition for the industrial application of advanced
treatment of yeast wastewater based on catalytic ozonation is provided.

2. Materials and Methods

2.1. Materials
Industrial-grade oxygen with a purity of 99.2%, aluminum trioxide, nickel trioxide,
manganese dioxide, titanium dioxide, and analytical purity were obtained from Sinopharm
Chemical Reagent Co., Ltd. (Shanghai, China). All solutions were prepared with deionized
water, and the pH was adjusted with dilute sulfuric acid and sodium hydroxide solutions.
The COD testing agent was Hash reagent 21259-25, with a range of 20–1500 mg·L−1 . Yeast
wastewater was taken from the effluent of the secondary sedimentation tank of a yeast
plant in Hebei (referred to as wastewater later), which has the characteristics of high
concentration of organic pollutants, high salinity, high chromaticity, and complex water
quality, and can be used as a representative of a complex system water quality. The main
water quality indices are detailed in Table 1.

Table 1. Composition of wastewater.

Num. Parameter Numerical Value Unit

1 COD 880 mg·L−1
2 Biochemical oxygen demand (BOD5 ) 41 mg·L−1
3 Bicarbonate 182 mg·L−1
4 Carbonate <0.10 mg·L−1
5 Total dissolved solids (TDS) (TDS) 13,300 mg·L−1
6 pH 8.10 -
7 Chroma 700 times

2.2. Main Reaction Device and Online Monitoring System

The experiment uses the device shown in Figure 1 for the catalytic ozonation of yeast
wastewater. All experiments were carried out under normal temperature and pressure. The
catalytic ozonation is completed in the ozone contact oxidation tower, which is a bubbling
reactor with a height of 120 cm, an inner diameter of 5 cm, and a maximum volume of 2 L.
The material is organic glass. The ozone in the experiment uses oxygen as the air source
and is produced by an ozone generator. The ozone enters through the microporous aeration
plate at the bottom of the ozone contact oxidation tower, and the exhaust gas is collected
at the top of the ozone contact oxidation tower and discharged into a tail gas absorption
bottle containing potassium iodide solution.
The catalyst used in the experimental process was in powder form, which can be
mixed with the wastewater and pumped into the reactor to be mixed with the wastewater
fully during the ozone aeration. The catalysts used in the experiments were chemically
pure grade, and the details are shown in Table 2.

Table 2. List of catalyst characteristics.

Catalyst Type Molecular Weight Purity Quotient

MnO2 86.94 ≥85.0
Ni2 O3 165.39 70.0–75.0
Al2 O3 101.96 ≥90.0
TiO2 79.87 ≥98.0
Water 2023, 15, x FOR PEER REVIEW 4 of 14
Water 2023, 15, 274 4 of 14

exhaust gas 11 exhaust gas emission

7
legend 6 9
trial water 12
gas
signal acquisition and transmission
14
13
oxygen 3 4 7 8
10
1 raw water
2 5 catalyst
ozone 7

Figure 1.
Figure Ozonation experiment
1. Ozonation experiment equipment
equipmentonline
onlinemonitoring
monitoringsystem
systemdiagram
diagram(1—oxygen
(1—oxygen cylinder;
cylin-
2—gas flow meter; 3—ozone generator; 4—gas phase ozone concentration meter
der; 2—gas flow meter; 3—ozone generator; 4—gas phase ozone concentration meter (in); (in); 5—microporous
aeration plate; 6—ozone
5—microporous aeration contact oxidation contact
plate; 6—ozone tower; 7—pump;
oxidation 8—constant flow meter;
tower; 7—pump; 9—pH, flow
8—constant ORP,
liquid phase
meter; 9—pH, ozone
ORP,sensor; 10—pH,
liquid phase ORP,
ozoneliquid phase
sensor; ozone transmitter;
10—pH, ORP, liquid11—gas
phase phase
ozoneozone concen-
transmitter;
11—gas phase(out);
tration meter ozone concentration
12—KI meter (out);
tail gas absorption 12—KI
bottle; tail gas
13—data absorption
acquisition bottle; 14—computer).
module; 13—data acqui-
sition module; 14—computer).
In this paper, an online monitoring system is designed to monitor the parameters such
as gas phase
The ozone
catalyst concentration,
used pH, ORP, process
in the experimental and liquidwasphase ozone concentration
in powder form, which canin and
be
out of the contact oxidation tower during the reaction in real
mixed with the wastewater and pumped into the reactor to be mixed with the time at the second level and
uploaded tofully
wastewater the data acquisition
during the ozonesystem through
aeration. signal conversion.
The catalysts used in theIn the reaction,
experiments the
were
mixed liquid
chemically is pumped
pure grade, and from
the the upper
details are part
shown of in
theTable
contact
2. tower into the constantator
and the pH, ORP, and liquid phase ozone concentration are measured. At the same time,
the other
Table end
2. List of the constantator
of catalyst characteristics.is pumped back to the bottom of the contact oxidation
tower. Through the circulation, the online monitoring is realized, and the mixing effect
Catalyst Type Molecular Weight Purity Quotient
is enhanced.
MnO2 86.94 − 1 ≥85.0
The ozone output of the ozone generator is 7 g·h at the oxygen source input, and
Ni2O3 165.39 70.0–75.0
the maximum ozone concentration is 25~50 g·m−3 , with an adjustable ozone production
Al2O3 101.96 ≥90.0
concentration.
TiO2 79.87 ≥98.0
2.3. Analysis and Test Instruments
In this paper, an online monitoring system is designed to monitor the parameters
In this research, a UV–visible spectrophotometer (DR6000, HACH, Loveland, CO,
such as gas phase ozone concentration, pH, ORP, and liquid phase ozone concentration
USA) was used to analyze the COD concentration. Gas phase ozone concentration me-
in and out of the contact oxidation tower during the reaction in real time at the second
ter (Ozone Monitors UV-500, Guangzhou Limei, Guangzhou, China) online monitoring
level and uploaded to the data acquisition system through signal conversion. In the re-
of ozone concentration in the contact tower was performed using liquid phase ozone
action, the mixed liquid is pumped from the upper part of the contact tower into the
concentration meter (CL7685, B&C Electronics Srl, Carnate, Italy) to monitor the ozone
constantator and the pH, ORP, and liquid phase ozone concentration are measured. At
concentration in wastewater online. A pH/ORP instrument (PH7685, B&C Electronics
the same time, the other end of the constantator is pumped back to the bottom of the
Srl, Carnate, Italy) was used for online pH monitoring. Real-time water samples were
contact oxidation tower. Through the circulation, the online monitoring is realized, and
collected with an SZ7263 three-hole constant-current device for the pH, ORP, and liquid
the mixing effect is enhanced.
phase ozone concentration, and a data acquisition module (FS-1208, MAC DAQ) was used
The ozone
for real-time output
data of the ozone
acquisition. Chroma generator is 7 g·
was detected h−1the
by at water-quality
the oxygen source input, and
determination of
the maximum ozone concentration is 25~50
colority dilution level method (HJ 1182-2021). g·m −3, with an adjustable ozone production

concentration.
2.4. Data Acquisition Conversion
2.3. Analysis and monitoring
The online Test Instruments
system configures the meter signal output as 4–20 mA current
Inand
signal thisthe
research, a UV–visible
data acquisition modulespectrophotometer
FS-1208 signal input(DR6000, HACH, Loveland,
as −10V/+10V. Therefore,CO,
one
500 Ωwas
USA) usedis to
resistor analyze in
connected theseries
CODatconcentration.
each group of Gas
meter phase ozone
output concentration
to convert meter
the current sig-
(Ozone Monitors
nal to voltage UV-500,
signal. Guangzhou
The voltage Limei,collected
data values Guangzhou,
by theChina)
moduleonline monitoring
at different moments of
ozone concentration in the contact tower was performed using liquid phase
and the data values measured by the meter are counted. Five groups of data are randomly ozone con-
centration meter
selected, the (CL7685,
following B&C Electronics
functional Srl,can
relationship Carnate, Italy) toThe
be obtained. monitor therelationship
function ozone con-
centration
between pH inand
wastewater
voltage isonline. A pH/ORP
y = 1.7792x (R2 = 1). The
− 3.7441instrument (PH7685,
functionB&C Electronics
relationship Srl,
between
Carnate,
ORP andItaly)
voltagewasis yused
= 124.94x − 253.5
for online pH(R 2 = 1). The function
monitoring. Real-time water samples
relationship wereliquid
between col-
phase ozone
lected with an concentration and voltage
SZ7263 three-hole is y = 2.55x −
constant-current device (R2 the
5.168 for = 0.9990).
pH, ORP,The and
function
liquidof
Water 2023, 15, 274 5 of 14

inlet ozone concentration and voltage is y = 21.684x − 31.352 (R2 = 0.9995). The function of
outlet ozone concentration and voltage is y = 25.661x − 53.295 (R2 = 0.9998). The sampling
time interval of the module is 3 s, and the Trace DAQ software version 6.0 stores the
voltage values collected during the measurement time period in the computer, which can
be transformed by calculation to derive the values of the process parameters.
The calculation method of instantaneous ozone depletion is shown in Equation (1):

(cG1 − cG2 ) × QG − c L × VL
C= (1)
VL

where C is the instantaneous ozone depletion, mg·L−1 ; cG1 is the ozone concentration at the
inlet end, mg·L−1 ; cG2 is the ozone concentration at the outlet, mg·L−1 ; QG is the gas flow
rate, L·min−1 ; cL is the liquid phase ozone concentration, mg·L−1 ; and VL is the volume of
liquid involved in the reaction, L.

3. Results and Discussions

3.1. Orthogonal Test Results and Optimization
To determine the best catalytic ozonation reaction conditions, the orthogonal test
method is used. Given that ozone is spilled or dissolved in water during the reaction,
the reaction process cannot precisely control the amount of ozone participating, and the
reaction time is selected as the investigating factor instead of the ozone dosage in the test.
The ozone reactor is charged with a mass concentration of 60 mg·L−1 and a gas volume
of 2 L·min−1 . The test setup considers four factors, namely, the type of catalyst, the ozone
dosage, the pH of the reaction environment, and the catalyst dosage, and four levels of
each factor are selected. The orthogonal test setup and its results are shown in Table 3.

Table 3. Results of orthogonal experiment.

Catalyst Reaction Time Catalyst Dosage COD Value

pH Value
Type (mg·L−1 ) (g·L−1 ) (mg·L−1 )
1 MnO2 200 5 3 807
2 MnO2 300 8 6 682
3 MnO2 400 10 9 465
4 MnO2 500 12 12 387
5 Al2 O3 200 8 9 703
6 Al2 O3 300 5 12 763
7 Al2 O3 400 12 3 508
8 Al2 O3 500 10 6 467
9 Ni2 O3 200 10 12 680
10 Ni2 O3 300 12 9 647
11 Ni2 O3 400 8 6 708
12 Ni2 O3 500 5 3 743
13 TiO2 200 12 6 735
14 TiO2 300 10 3 689
15 TiO2 400 8 12 723
16 TiO2 500 5 9 730
K1 2341 2925 3043 2747 10,437
K2 2441 2781 2816 2592 -
K3 2778 2404 2301 2545 -
K4 2877 2327 2277 2553 -
k1 585 731 761 687 -
k2 610 695 704 648 -
k3 695 601 575 636 -
k4 719 582 569 638 -
R 134 130 192 51 -

Table 3 shows the factors affecting the COD removal efficiency in the advanced
treatment of catalytic ozonation of yeast wastewater are ranked as pH > catalyst type >
 k2 610 695 704 648 -
k3 695 601 575 636 -
k4 719 582 569 638 -
R 134 130 192 51 -

Water 2023, 15, 274 Table 3 shows the factors affecting the COD removal efficiency in the advanced 6 of 14
treatment of catalytic ozonation of yeast wastewater are ranked as pH > catalyst type >
reaction time > catalyst dosage. Therefore, the optimal reaction conditions for catalytic
ozonation in yeast
reaction time wastewater
> catalyst dosage.advanced
Therefore,treatment are manganese
the optimal dioxide as
reaction conditions forcatalyst,
catalytic
catalyst dosage
ozonation of 6 g·
in yeast L−1, pH of 12,advanced
wastewater and catalytic ozonation
treatment reaction time
are manganese of 20 min.
dioxide as catalyst,
catalyst dosage of 6 g·L−1 , pH of 12, and catalytic ozonation reaction time of 20 min.
3.2. Catalytic Ozonation Reaction Parameter Study
3.2. Catalytic Ozonation Reaction Parameter Study
To observe the optimal catalytic ozonation determined by orthogonal experiment
To observethe
and determine themost
optimal catalytic ozonation
economical and effectivedetermined
ozonationby dosage,
orthogonal
theexperiment
comparative and
determine
study of thethe most economical
experimental processandis effective
carried outozonation dosage,
based on the comparative
the reaction conditions study
pre-of
the experimental process is carried out based on the reaction conditions preferred
ferred by the orthogonal test, using deionized water as a control group to react with the by the
variation of catalytic ozonation parameters. The monitored parameters are pH, ORP, andof
orthogonal test, using deionized water as a control group to react with the variation
catalytic
liquid ozonation
phase parameters. The monitored parameters are pH, ORP, and liquid phase
ozone concentration.
ozone concentration.
3.2.1. pH
3.2.1. pH
The initial pH of the reaction system with deionized water is 6.50, and as the reac-
The initial pH of the reaction system with deionized water is 6.50, and as the reaction
tion proceeds as the pH slowly increases to close to 7.00, after which it remains stable, as
proceeds as the pH slowly increases to close to 7.00, after which it remains stable, as shown
shown in Figure 2. This result may be because the deionized water dissolves some carbon
in Figure 2. This result may be because the deionized water dissolves some carbon dioxide
dioxide in the air during the injection of the reaction tower, so a weakly acidic environ-
in the air during the injection of the reaction tower, so a weakly acidic environment is
ment is formed
formed in the water,
in the water, which lowers
which lowers the pH the pHdeionized
of the of the deionized water. However,
water. However, with the with
ozone
the ozone injection, the carbon dioxide in the water is blown off during the
injection, the carbon dioxide in the water is blown off during the aeration, which aeration,
leads to
which leads tointhe
the increase pHincrease
[41]. in pH [41].

Figure
Figure2. 2.
pHpHcurve under
curve thethe
under combined action
combined of ozone
action (25 g·
of ozone m−3
(25 g)·m
and
−3 )manganese dioxide
and manganese as cat-as
dioxide
alysts (6 g·L−1). −1
catalysts (6 g·L ).

For the wastewater-based reaction system, NaOH is used to adjust the pH from 8.10
to 11.85 at the beginning of the experiment. In the first 16 min, pH decreases rapidly
as the reaction proceeds until it decreases to 7.60 and then stabilizes. As the reaction
proceeds, hydroxide ions trigger the decomposition of ozone, and the reaction is shown in
Equation (2).
O3 + OH− → ·O2 − + ·HO2 (2)
The hydroxide ion in the water causes the decomposition of ozone, but the water also
contains HCO3 − alkalinity, which can capture ·OH. The reaction is shown in Equation (3):

HCO3− + ·HO2 → ·H2 O2 + CO3− (3)

In the initial process of the reaction, the pollutants in the water and the alkalinity of
HCO3 − consume the hydroxyl radicals produced continuously, accelerate the decomposi-
tion of ozone, and continuously consume the hydroxide ions in the water, which may be
the main reason for the rapid decline of pH. From the change in pH, the whole reaction can
be divided into two stages from the 16th min, the change in pH in the first stage decreases
substantially from 11.85 to 7.60, and the latter stage stabilizes at 7.60. The main reason is
that under the condition of this reaction, the hydroxide in the solution is largely consumed
by the dissolved ozone, and the reaction should be mainly the indirect reaction of ozone.
Water 2023, 15, 274 7 of 14

The pH of the reaction after 16 min does not change, so the reaction should be dominated
by the direct reaction of ozone.

3.2.2. ORP
ORP is a comprehensive reflection of the concentration of various oxidizing substances
and reducing substances that can have oxidation-reduction reactions in water and can be
considered an ORP energy in water. The higher the concentration of oxidizing substances
in water is, the higher the ORP [42].
The initial ORP of deionized water is 367 mV, which rapidly increases to the upper
Water 2023, 15, x FOR PEER REVIEWlimit of measurement of 1000 mV with the addition of ozone, as shown in Figure 3. This
8 of 14
result is probably due to the continuous production of hydroxyl radicals and dissolved
ozone in the water [32].

Figure 3. ORP curve under the combined action of ozone (25 g·−3m−3 ) and manganese dioxide as
Figure 3. ORP curve under the combined action of ozone (25 g·m ) and manganese dioxide as cat-
catalysts (6 g·L−1 ).
alysts (6 g·L−1).
No remarkable change is observed in the ORP during the first two minutes, which is
The wastewater comes from the secondary effluent with an initial ORP of −132 mV,
probably due to the hydraulic delay from the beginning of the reaction to the data detected
and the increase in ORP is stable in the first 14 min. At this stage, the decomposition re-
in the cross flower. Although the ORP increases at the fastest rate from the second minute
action of ozone and the direct reaction of pollutants coexist. Under the effect of hydroxyl
to the sixth minute of the reaction, the delay is substantial compared with the reaction
and manganese dioxide catalytic ozonation, the hydroxyl free radical chain reaction of
rate. The main reason may be that the water condition of the reactor is not good enough,
ozone dissolves
resulting in poorinmass the water.
transferA effect
part ofofthe direct
ozone in reaction
water. Inofaddition,
ozone and thethe pollutants
maximum ORPin
the water are in the water reducing agents, and the oxidizing substance
that can be reached in the deionized water system cannot be determined for the time being increases. The
system
due to theORP increases
limitation of gradually
measuringafter 14 minconditions.
instrument of rapid ascension, and then the change
flattens. The maximum ORP during the
The wastewater comes from the secondary effluent reaction is 857 mV. The
with anORP of ORP
initial the system
of −132in mV,
the
whole
and the reaction
increase caninbeORPconsidered
is stablethe result
in the of 14
first themin.
superposition of oxidizing
At this stage, substances
the decomposition
and
reaction of ozone and the direct reaction of pollutants coexist. Under the effect ofdeionized
reducing substances. The failure to reach the maximum value as in the hydroxyl
water comparison
and manganese test indicates
dioxide catalytic that substances
ozonation, theinhydroxyl
the system freeatradical
this stage
chaincannot be ox-
reaction of
idized by ozone and hydroxyl radicals.
ozone dissolves in the water. A part of the direct reaction of ozone and the pollutants in the
water are in the water reducing agents, and the oxidizing substance increases. The system
3.2.3. Liquid Phase
ORP increases Ozoneafter
gradually Concentration
14 min of rapid ascension, and then the change flattens. The
The change
maximum in ozone
ORP during thedissolved
reaction isin857 water
mV. isTheshown
ORP ofin the
Figure 4. When
system in theozone
wholeisreaction
added
candeionized
to be considered
water,the theresult of the superposition
concentration of ozone in water of oxidizing
rapidlysubstances
increases fromand reducing
0 to 8.20
substances.
mg· L−1. In theThe failure
first 6 min, tothe
reach the maximum
liquid phase ozone value as in the deionized
concentration increaseswater
rapidlycomparison
and then
test indicates
reaches a stablethat substances
state. in the
This result system at with
is consistent this stage cannot
the trend be oxidized by ozone and
of ORP.
hydroxyl radicals.
However, in the catalytic ozonation of wastewater, no dissolved ozone is in the early
stage of the reaction, indicating that the ozone dissolved in wastewater reacts rapidly
3.2.3. pollutants,
with Liquid Phase Ozone Concentration
catalysts, and hydroxide. After 12 min of reaction, liquid phase ozone
concentrations begin ozone
The change in to appeardissolved
and slowly in water
increase,is shown
levelinginoffFigure
at about4. 1.50
When mg·ozone
L−1 fromis
added
the 16thtominute.
deionized As thewater,
levelthe
of concentration
liquid ozone does of ozone in water
not reach 8 mg· rapidly
L in the
−1 increases from
comparison
test, substances that consume liquid ozone still exist in the system. The reaction enters a
slow process, which may be due to the decrease in the concentration of pollutants that
can react directly with ozone in the system; the hydroxyl radical is produced by ozone
and the catalyst, and the reaction between hydroxyl radical and pollutant plays a major
role [43,44].
Water 2023, 15, 274 8 of 14

Water 2023, 15, x FOR PEER REVIEW 9 of 14

0 to 8.20 mg·L−1 . In the first 6 min, the liquid phase ozone concentration increases rapidly
and then reaches a stable state. This result is consistent with the trend of ORP.

Figure4.4.Ozone
Figure Ozoneconcentration
concentration(liquid)
(liquid)curve
curveunder
underthe
thecombined
combinedaction
actionofofozone
ozone(25
(25g·g·
mm−3−3)) and
and
manganese dioxide as catalysts (6 g·L
manganese dioxide as catalysts (6 g·L ).−−1
1 ).

3.3. Study
However,on Ozone
in theConsumption and COD
catalytic ozonation ofRemoval
wastewater,Effectno dissolved ozone is in the early
stage The
of the reaction,
online indicating
monitoring that conversion
and data the ozone dissolved
system caninbewastewater
used to obtainreacts
therapidly
change
with pollutants,
in ozone catalysts,
consumption in and hydroxide.
the reaction AfterEquation
through 12 min of(1),
reaction, liquid
as shown phase ozone
in Figure 5. The
concentrations begin to appear and slowly increase, leveling off at about 1.50 mg · L −1 from
overall change trends of COD and ozone consumption in the reaction are similar, and the
the 16thtrend
overall minute. As the
shows level ofdecline
a gradual liquid ozone
with thedoes not reach
reaction. 8 mg
At the ·L−1 in the
beginning of comparison
the catalytic
test,
ozonation reaction, the ozone consumption increases sharply, with a maximum enters
substances that consume liquid ozone still exist in the system. The reaction a
value of
slow process, which may be due to the decrease in the concentration
69 mg·L , and gradually decreases with the progress of the reaction, with a minimum
−1 of pollutants that can
react
valuedirectly with
of 36 mg· L−1ozone in early
. At the the system;
stage ofthethe
hydroxyl
reaction, radical is produced
the direct reactionby ozone
and and the
decomposi-
catalyst, and the reaction between hydroxyl radical and pollutant plays
tion reaction of ozone with pollutants are carried out synchronously, and the consump-a major role [43,44].
tion of ozone is large. At the later stage of the reaction, the direct reaction of ozone and
3.3. Study on Ozone Consumption and COD Removal Effect
the decomposition reaction with hydroxide are weakened, and the ozone consumed by
The online
the catalytic monitoring
reaction is the and
maindata conversion
ozone systemThe
consumption. canCOD
be used to obtain
in the the change
wastewater grad-
in ozone consumption in the reaction through Equation (1), as shown
ually decreases, the decrease trend becomes smooth after 14 min, and the minimum in Figure 5. The
overall
value ischange trends
387 mg· of COD
L−1, which andthe
meet ozone consumption
requirement in the
of the Yeast reaction are Water
Industry similar,Pollutant
and the
overall trend
Discharge shows a(GB25462-2010)
Standard gradual declinethat
with
thethe reaction.
COD is lessAt the400
than beginning
mg·L−1. of the catalytic
ozonation reaction, the ozone consumption increases sharply, with a maximum value of
69 mg·L−1 , and gradually decreases with the progress of the reaction, with a minimum
value of 36 mg·L−1 . At the early stage of the reaction, the direct reaction and decomposition
reaction of ozone with pollutants are carried out synchronously, and the consumption
of ozone is large. At the later stage of the reaction, the direct reaction of ozone and the
decomposition reaction with hydroxide are weakened, and the ozone consumed by the
catalytic reaction is the main ozone consumption. The COD in the wastewater gradually
decreases, the decrease trend becomes smooth after 14 min, and the minimum value is
387 mg·L−1 , which meet the requirement of the Yeast Industry Water Pollutant Discharge
Standard (GB25462-2010) that the COD is less than 400 mg·L−1 .
Every 2 min in the reaction is taken as a statistical stage, and the catalytic ozonation
is divided into 10 stages on average. The utilization rate of ozone in each stage is shown
in Figure 6. When the reaction time is less than 15 min, the utilization rate of ozone in the
catalytic ozonation is very high. The average value of the ozone consumed by removing
COD per unit mass is 1.97 mgO3 ·mgCOD−1 . In the last five minutes of the reaction, the
average value of ozone consumed by COD degradation is 4.91 mgO3 ·mgCOD−1 .
Figure 5. Ozone consumption curve and COD degradation under the combined action of ozone (25
g·m−3) and manganese dioxide as catalysts (6 g·L−1).

Every 2 min in the reaction is taken as a statistical stage, and the catalytic ozonation
is divided into 10 stages on average. The utilization rate of ozone in each stage is shown
in Figure 6. When the reaction time is less than 15 min, the utilization rate of ozone in the
catalytic ozonation is very high. The average value of the ozone consumed by removing
 tion reaction of ozone with pollutants are carried out synchronously, and the consump-
tion of ozone is large. At the later stage of the reaction, the direct reaction of ozone and
the decomposition reaction with hydroxide are weakened, and the ozone consumed by
the catalytic reaction is the main ozone consumption. The COD in the wastewater grad-
ually decreases, the decrease trend becomes smooth after 14 min, and the minimum
Water 2023, 15, 274 9 of 14
value is 387 mg·L−1, which meet the requirement of the Yeast Industry Water Pollutant
Discharge Standard (GB25462-2010) that the COD is less than 400 mg·L−1.

Water 2023, 15, x FOR PEER REVIEW 10 of 14

Figureper
COD
Figure 5.5.Ozone
Ozone consumption
unit mass curve
is 1.97 mgO
consumption and
curve3· COD
mgCOD
and COD−1 degradation under
. In the last
degradation five the
under thecombined
minutes action
of the
combined of of
ozone
reaction,
action (25
the
ozone
g·m −3) and manganese dioxide as catalysts (6 g·L−1).
average − 3value of ozone consumed by COD −
degradation
(25 g·m ) and manganese dioxide as catalysts (6 g·L ). 1 is 4.91 mgO 3 ·
mgCOD −1.

Every 2 min in the reaction is taken as a statistical stage, and the catalytic ozonation
reduce the mass of O3 required by COD per unit mass
is divided into 10 stages on average. The utilization rate of ozone in each stage is shown
in Figure
6 6. When the reaction time is less than 15 min, the utilization rate of ozone in the
O3 comsuption (mg)

catalytic ozonation is very high. The average value of the ozone consumed by removing
5
4
3
2
1
0
1 3 5 7 9 11 13 15 17 19
reaction time(min)

Figure 6. Ozone
Figure 6. Ozone utilization
utilization change
changeunder
underthe
thecombined
combinedaction
actionofofozone
ozone(25 ·mm−−33 ) and manganese
(25gg· manganese
dioxide as
dioxide as catalysts
catalysts (6
(6 gg· − 1
·L ).).
−1

3.4.
3.4. Study
Study onon Ozone
Ozone Consumption
Consumption andand Color
Color Removal
Removal Effect
Effect
The orthogonal test finds that each catalytic ozonation
The orthogonal test finds that each catalytic ozonation test has a very
test has evident
a very chroma
evident
removal
chroma removal effect, the effluent chroma can reach less than 100 times, and theremoval
effect, the effluent chroma can reach less than 100 times, and the chroma chroma
rate can reach
removal rate can85%.
reachAmong them, the
85%. Among them,three
the groups numbered
three groups 3, 4, and
numbered 3, 4, 10
andhave the
10 have
best effluent color effect, which can reach 40 times, which is better than the
the best effluent color effect, which can reach 40 times, which is better than the discharge discharge
requirement of 50 times in “Discharge Standard of Water Pollutants for Yeast Industry”
requirement of 50 times in “Discharge Standard of Water Pollutants for Yeast Industry”
GB25462-2010. The pigment formed by saccharine reaction (Maillard reaction) during
GB25462-2010. The pigment formed by saccharine reaction (Maillard reaction) during
yeast fermentation and caramel pigment added artificially during product preparation are
yeast fermentation and caramel pigment added artificially during product preparation
the main reasons for the high color of yeast wastewater. Both substances are mixtures of
are the main reasons for the high color of yeast wastewater. Both substances are mixtures
complex macromolecular compounds with conjugated double bonds. Ozone can react with
of complex macromolecular compounds with conjugated double bonds. Ozone can react
benzene rings, double bonds, and co-yoked carbonyl groups in the chromogenic group.
with benzene rings, double bonds, and co-yoked carbonyl groups in the chromogenic
Moreover, due to the excellent properties of dehydrogenation, oxidation, and isomerization
group. Moreover, due to the excellent properties of dehydrogenation, oxidation, and
of transition metals, under the synergistic action of ozone, the chromogenic group can be
isomerization of transition metals, under the synergistic action of ozone, the chromogenic
destroyed to achieve the decolorization effect.
group can be destroyed to achieve the decolorization effect.
Figure 7 shows that the removal effect of chroma is clearly better than that of COD, but
Figure 7 shows that the removal effect of chroma is clearly better than that of COD,
their change trends are the same. Moreover, the substance causing the chroma contributes
but their change trends
to the measurement are theHowever,
of COD. same. Moreover, the substance
the degradation causing
of pigment the chroma
substances con-
is only
tributes to the measurement of COD. However, the degradation of pigment
the change in molecular structure and has not been completely removed from the water substances is
only the change
as pollutants. in molecular structure and has not been completely removed from the
water as pollutants.

chroma removal rate COD removal rate

100
rate（%）

ate（%）

60
50
95
40
 isomerization of transition metals, under the synergistic action of ozone, the chromogenic
group can be destroyed to achieve the decolorization effect.
Figure 7 shows that the removal effect of chroma is clearly better than that of COD,
but their change trends are the same. Moreover, the substance causing the chroma con-
tributes to the measurement of COD. However, the degradation of pigment substances is
Water 2023, 15, 274 only the change in molecular structure and has not been completely removed from 10 ofthe
14

water as pollutants.

chroma removal rate COD removal rate

100

chroma removal rate（%）

COD removal rate（%）

60
50
95
40
90 30
20
85 10
0
80
1 3 5 7 9 11 13 15 17 19
reaction time(min)
Figure7.7.Chroma
Figure Chromaand
andCOD
CODremoval
removalrate
ratecurves
curvesunder
underthe
thecombined
combined action
action ofof ozone
ozone g·m
(25(25 −3−3) )and
g·m and
manganese dioxide as catalysts (6
manganese dioxide as catalysts (6 g·Lg·
L− 1
−1 ).

3.5. Comprehensive Analysis of Control Strategy for Process Monitoring Data

The whole reaction is divided into two stages from the 14th minute. At the first stage,
the COD removal is 450 mg·L−1 , accounting for 91.28% of the total removal rate. No
liquid phase ozone is in the system all the time, the pH decreases, and the reoxidation
potential increases gradually. The average ozone consumption is about 1.97 mg·L−1 . At this
stage, the pH decreases steadily, and ORP gradually increases, but no liquid phase ozone
appears. According to Equation (3), dissolved ozone continuously reacts with hydroxide
ions and generates hydroxyl radicals. Hydroxyl radicals constantly react with pollutants.
At this stage, the gradual increase in ORP can imply that reducing substances are constantly
removed by oxidizing groups such as hydroxyl radicals generated in the system.
In the second stage, the most apparent sign is the emergence of liquid phase ozone,
and the ORP value substantially increases. The main reason for liquid phase ozone is that
the hydroxide ions added to the system are consumed. At this stage, the reaction of the
system is mainly the direct reaction of ozone, and the removal effect of COD decreases,
which also leads to the decrease in the utilization rate of ozone. The reason why liquid
phase ozone cannot reach higher levels as in deionized water is that most ozone is still
directly reacting with pollutants. At the 18th minute, the liquid phase ozone concentration
in the wastewater system is about 1.41 mg·L−1 . Compared with the deionized water
system, the corresponding time point of this liquid phase ozone concentration is 30 s at
the second minute. The ORP values corresponding to these two moments are 790 and
481 mV. Therefore, the ORP at this time is only 1.5 mg·L−1 liquid phase ozone and part of
the oxidizing-free group.

3.6. Analysis of Control Strategy for Catalytic Ozonation

Compared with direct oxidation of ozone, catalytic ozonation has noticeable advan-
tages in the COD removal effect [45]. The effect of indirect catalytic ozonation is more
evident under the experimental conditions determined by orthogonal reaction. The real-
time monitoring of pH, ORP, and dissolved ozone in the process finds that with the change
in COD, the process parameters also change regularly. From the point of view of the change
in reaction parameters, the whole reaction can be divided into two stages, the rapid change
stage and stationary stage. At the rapid change stage, the pH decreases gradually, and the
system ORP and the liquid phase ozone concentration are low. At the stationary phase, pH
is low, and the ORP and liquid phase ozone concentration are high. From the perspective
of time points, the pH is flat at the 16th minute, the ORP reaches the maximum at the
16th minute, and the liquid phase ozone concentration approaches the maximum at the
16th minute. Therefore, the 16th minute can be used as the cut-off point of the reaction.
In terms of the removal effect, for the catalytic ozonation reaction, the reaction be-
tween ozone and wastewater can also be divided into two stages of high efficiency and
Water 2023, 15, 274 11 of 14

low efficiency. The 15th minute is the cut-off point. Before the cut-off point, the ozone
utilization rate is high, and the COD removal effect is apparent. After the cut-off point, the
ozone utilization rate decreases, and the COD removal is slow, only from 436 mg·L−1 to
387 mg·L−1 .
In the catalytic ozonation, the efficient period of COD degradation is mainly composed
of the direct and indirect reaction of ozone. The indirect process includes metal oxide
catalyst and hydroxy joint action, and the reaction pH change is most evident. During this
period, liquid ozone concentration is not detected, which suggests that the process is the
quick response of ozone. In the second stage, the removal of COD is mainly via the indirect
reaction of ozone, and the concentration of liquid phase ozone appears, which is in line
with the characteristics of a slow reaction of ozone oxidation. During this period, the ORP
and liquid phase ozone concentration reach the maximum value, whereas the pH reaches
the minimum value.
In the advanced treatment of yeast wastewater by catalytic ozonation technology,
the online monitoring system is used to monitor the pH, ORP, and liquid phase ozone
concentration in the reaction in real time. The liquid phase ozone concentration can
be used as a marker to judge the rapid reaction stage and slow reaction stage of the
ozonation reaction. The ORP can assist in characterizing the degree of wastewater COD
degradation. The change in pH fluctuates greatly in this experiment, reflecting the degree
of ozonation reaction from one aspect. However, in the reaction without regulating the pH,
the fluctuation range is relatively small.
In the catalytic ozonation reaction with pH adjustment, when the changes in these
three process parameters are flat, the efficient period of ozone reaction has ended, and
the continued addition of ozone is not conducive to the economic efficiency of yeast
wastewater treatment.
The catalytic ozonation has a clear chroma removal effect. When the experimental
conditions achieve the best COD removal effect, the effluent chroma can also achieve the
standard discharge. Therefore, it is not a focus of research.

4. Conclusions
In this experiment, the effect of heterogeneous catalytic ozonation is strengthened by
adjusting the pH. Manganese dioxide is used as a solid catalyst to treat yeast wastewa-
ter effectively and deeply. The effluent COD decreases from 880 mg·L−1 to 387 mg·L−1 ,
and the removal rate reaches 56%. Under the same test conditions, the chroma is re-
duced from 700 times to 40 times. The effluent COD can meet the requirement of COD
less than 400 mg·L−1 , and the effluent chroma can achieve 40 times in current industry
discharge standards.
The online monitoring system designed in the experiment can reflect the changes in
process parameters such as pH, ORP, and liquid phase ozone concentration in time. The
catalytic ozonation can be marked as a high-efficiency stage and low-efficiency stage by
using the changes in process parameters above. The high-efficiency stage lasts for 15 min.
The COD removal rate is 50.50%, and the average ozone consumed by removing the unit
mass of the COD is 1.97 mgO3 ·mgCOD−1 . The low-efficiency stage lasts for 5 min, the
COD removal rate is 11.20%, and the average ozone consumption of removing the unit
mass of the COD is 4.91 mgO3 ·mgCOD−1 .
Under the synergistic action of the catalyst, regulating the system pH can effectively
promote the indirect ozone oxidation reaction. The device inside the constant current
parameter change slightly lags behind the actual data of the contact oxidation tower
internal instant levels, but the overall trend is consistent with the reactor internals. During
the indirect reaction, the decreasing trend in pH and the redox potential are stable. When
comparing the reaction conditions of catalytic odor, the treatment effect of catalytic odor in
a complex system can be investigated by the rate of change in these two indices, which can
be verified by the removal of pollutants. In practical application, the economy of ozone
use can be maintained by the index of liquid phase ozone concentration. The process
Water 2023, 15, 274 12 of 14

determined in this experiment is better than the current coagulation and precipitation
in terms of hydraulic residence time, agent injection cost, and subsequent treatment of
waste. In practical engineering, the operation cost of ozone equipment investment and
construction and the use of ozone is higher than the cost of coagulation and precipitation,
but through advanced, effective monitoring means and optimized reaction conditions, it is
bound to improve the effective utilization and continuous promotion of ozone.

Author Contributions: Conceptualization, C.M. and Z.L.; methodology, X.J.; validation, S.C.; formal
analysis, S.C.; investigation, S.C.; resources, H.Z. and M.L.; writing—original draft preparation, X.J.;
writing—review and editing, S.C., H.Z. and M.L.; visualization, X.J.; supervision, C.M. and Z.L.;
funding acquisition, Z.L. All authors have read and agreed to the published version of the manuscript.
Funding: This research was funded by National Key Research and Development Plan (2019YFC0408700).
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Data Availability Statement: Not applicable.
Acknowledgments: We would like to thank the editors and the anonymous reviewers for their
long-term guidance and constructive comments.
Conflicts of Interest: The authors declare no conflict of interest.

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