TITLE OF DISSERTATION

Wastewater Treatment Using Integrated Advanced Oxidation and

Biodegradation Processes

Research Proposal submitted in fulfillment of the requirements for the degree of

xxxxxxx

In the Faculty of xxxxxxxxxxxxxx

Student name: xxxxxxx xxxx xxxx

Highest Qualification: xxxxxxxxxx

Supervisor: xxxx xxxx xxx

Co-supervisor: xxxxxxxx

Date: xxxxxxxx
Table of Contents
Table of Contents.......................................................................................................................1
1. Introduction........................................................................................................................2
1.1. Study background........................................................................................................2
1.2. Problem statement.......................................................................................................3
1.3. General research objective..........................................................................................4
1.4. Specific objectives.......................................................................................................4
2. Literature review................................................................................................................5
2.1. Water pollution............................................................................................................5
2.2. Wastewater treatment technologies.............................................................................5
2.2.1. Anaerobic digestion.............................................................................................6
2.2.2. Ozonation.............................................................................................................6
2.2.3. Photodegradation..................................................................................................7
2.3. Integrated anaerobic digestion and advanced oxidation processes.............................8
3. Methodology......................................................................................................................9
3.1. Equipment and materials.............................................................................................9
3.2. Experimental procedure...............................................................................................9
3.2.1. Ozonation.............................................................................................................9
3.2.2. Anaerobic digestion...........................................................................................10
3.2.3. Catalyst preparation and photodegradation........................................................10
3.3. Catalyst characterization and chemical analyses, and determination of reaction
mechanisms..........................................................................................................................10
3.4. Toxicity analyses.......................................................................................................11
3.5. Experimental design, statistical, data and error analyses..........................................11
3.6. Work plan..................................................................................................................12
3.7. Budget........................................................................................................................12
References................................................................................................................................13

1
1. Introduction
1.1. Study background
Pollution by industrial activities, is one of the major threats to air and water quality.
Continued industrialisation in the recent past has deteriorated various ecological systems on
which human life is dependent. Many industrial processes generate large amount of wastes,
of which approximately 90% comprise wastewaters. The industrial processes generate
pollutants such as dyes, solvents, heavy metals and endocrine disrupting compounds. These
pollutants enter aquatic systems through direct dumping, as industrial discharge or from
dysfunctional wastewater treatment facilities. On direct discharge, the industrial wastewaters
contain high levels of organic and inorganic pollutants and may as high as 10 000 mg/L as
observed in Ji et al. (2016). Industrial wastewater can affect receiving water systems in
several ways including altering the pH, increasing the number of nutrients leading to
eutrophication, altering the colour or increasing turbidity. Highly turbid and coloured water
can affect the aquatic flora and fauna by blocking sunlight penetration thus hindering
photosynthesis, or by providing suspended solid particles that can host and transport disease
causing bacteria and viruses. The increasing environmental hazardous effects associated with
the discharge of the recalcitrant compounds contained in industrial effluents, has led to more
stringent discharge standards set by governments and regulating bodies, thus calling for
appropriate treatment methods (Mantzavinos et al., 1999; Oller et al., 2011).

Anaerobic digestion (AD), is a treatment method can be used to reduce the high organic load
of industrial wastes and sludge, and in the process achieve waste utilisation through biogas
recovery (Roy et al., 2016). Moreover, to mitigate against climate change, brought about by
the over reliance on fossil fuels, anaerobic treatment has found new application as a source of
renewable energy in the form of the recovered valuable biogas. Most of the modern
municipal facilities for wastewater treatment are meant for domestic wastewater remediation.
The industrial wastewaters due to their contents, should be pre-treated before discharge to
municipal collection systems. If not, a disruption may occur at the receiving municipal
wastewater treatment plants due to the presence of toxic organic and inorganic compounds in
the industrial effluents (Shivaraju, 2011). Moreover, the problem of sludge disposal from the
municipal wastewater treatment (WWT) plants is escalating given the rising and high costs
for sludge storage, dewatering, transport and landfilling. The AD treatment presents a
feasible sludge disposal route with ability to reduce the final sludge solids for disposal, and
achieve biogas production in the process. AD is nowadays considered an integral part of

2
modern wastewater treatment as it can reduce the disposal cost and environmental footprint
of the treatment plants (Strong et al., 2011). Anaerobic treatment alone, however, is not
sufficient in meeting the stringent discharge requirements for total suspended solid (TSS) and
chemical oxygen demand (COD) thus calling for its integration with other treatment methods
(Kim et al., 2010).

To enhance the anaerobic digestion of industrial wastewater and municipal waste such as
waste activated sludge (WAS), the integration of AD with other treatment technologies is
required (Oller et al., 2011). Pre-treatment methods have been developed to accelerate the
rate of digestion and enhance biogas production during AD. The pre-treatment can improve
the biodegradability of WAS by rupturing cell walls and making the intracellular substances
available for microorganisms. Also, the biorecalcitrant and toxic organic compounds found in
industrial wastewater, can be converted into easily biodegradable organic compounds through
pre-treatment (Zhen et al., 2017). Of the pre-treatment techniques, currently being employed,
ozonation which is an advanced oxidation process (AOP), is very effective in yielding a
higher degree of organic solids disintegration and improved substrate biodegradability. It also
improves sludge settling properties as well as reducing scum formation and bulking (Chu et
al., 2009). Another route for improving the AD treatment is by integrating it with a post-
treatment AOP such as photodegradation. Photodegradation can achieve complete
mineralization of recalcitrant organic pollutants that are likely to remain after AD. Moreover,
since the pre-treatment is usually intended to lead to partial mineralization, some non-
biodegradable compounds will escape into the subsequent AD and finally to the AD effluent
thus necessitating the need for a post-treatment (Oller et al., 2011).

1.2. Problem statement

Anaerobic digestion, widely used for wastewater treatment, cannot reduce biorecalcitrant
organic compounds such as phenols, which inhibit the much important rate determining
hydrolysis step. Introduction of pre-treatment methods that can reduce the biorecalcitrants, is
therefore important in overcoming the inhibition. As a pre-treatment method, photocatalysis
(an AOP), can reduce the biorecalcitrants, but is majorly limited by light penetration and high
energy requirement associated with the use of UVC lamps. Ozonation, also an AOP, can be
used as a pre-treatment process to reduce the biorecalcitrants into biodegradable compounds,
and avoid the light penetration problem associated with photocatalysis. However, the
determination of the not well understood mechanisms and intermediate compounds formed

3
during ozonolysis, is important for achieving effective and optimised pre-treatment.
Moreover, ozonolysis pre-treatment in some instances does not lead to complete reduction of
the biorecalcitrants into biodegradable compounds. The unreduced biorecalcitrant compounds
escape into the AD process and later into the AD effluent. The AD effluent despite having
reduced light inhibition, therefore still contains the unreduced biorecalcitrants. Photocatalysis
can be introduced as a post-treatment to AD to remove the remaining biorecalcitrants. Since
the threshold will be low in concentration, energy requirement for the photocatalytic process
will be low as well.

1.3. General research objective

To integrate ozonation, anaerobic digestion and photodegradation for effective treatment of
molasses and distillery wastewaters using an ozone reactor, a bioreactor and photoreactor.

1.4. Specific objectives

i. To carry out ozonation of wastewater substrate, analyse sludge solubilisation
mechanism and identify the ozonolysis products

ii. To determine the methane potential of pre-ozonized and non-ozonized wastewater,

and determine ozonation effect on anaerobic digestion

iii. To support commercial titanium dioxide (TiO 2) please check this ? onto zeolite and
characterise the resultant TiO2/Zeolite photocatalyst

iv. To carry out photodegradation using TiO2/Zeolite photocatalyst

v. To determine the mineralization extent of matrix components and study product

formation during photodegradation

vi. To determine the toxicity effect of products formed at each stage of the integrated
treatment system

4
2. Literature review
2.1. Water pollution
Among the natural resources, water is the most important, and is critical for food production,
economic activities, and survival of all living things including humans. Water quality
(including surface and groundwater) and availability influences the environment,
development and economic growth. Human activities, increased urbanisation,
industrialisation, population increase and climate change have all created a decline in water
quality. Industrial processes such as alcohol distillation, leather tanning and textiles generate
copious amount of wastewater (Halder and Islam, 2015). Such industries use large volumes
of water in the production processes, where the water meets toxic chemicals, heavy metals,
organic sludge and even radioactive wastes. The pollutants are then dumped into receiving
streams leading to massive pollution of rivers, lakes and other aquatic systems. Also,
increased population and urbanisation, and expanded sewer coverage has led to the
generation of large amounts of municipal wastewater, which is conveyed as sewage for
treatment at municipal wastewater treatment plants (WWTP). The conventional municipal
WWTP are not effective in removing emerging persistent recalcitrant pollutants such as
pharmaceuticals, detergents and endocrine disrupting substances. These pollutants when
discharged in the treated effluent into water systems can bioaccumulate in organisms and
adversely affect endocrine systems (Bechambi et al., 2015; Shivaraju, 2011).

2.2. Wastewater treatment technologies

One of the major aims for treating wastewater is to remove the high organic carbon. This can
be achieved through several conventional treatment steps such as primary settling, biological
adsorption, biological degradation, and finally sludge removal through secondary settling
(Valerie, 1999). The conventional treatment systems can effectively reduce the high organic
load of most wastewaters, but have been found to be ineffective in removing biorecalcitrant
organic compounds (Achisa et al., 2016). The increased industrial activities and population
has led to generation of wastewaters with varied characteristics and emergence of organic
pollutants not amenable to the conventional biodegradation. There is therefore, an increasing
concern for development effective treatment technologies to remove the low biodegradable
and chemically stable pollutants. Advanced oxidation processes (AOPs) such as ozonation
and photodegradation are highly competitive techniques that can remove the recalcitrant
pollutants. These AOPs are usually high cost, but their application alongside the widely used
anaerobic digestion can significantly reduce the cost of operation (Oller et al., 2011).

5
Anaerobic digestion is widely applied as a first step treatment technique for several industrial
wastewaters such as distillery wastewater (DWW), and forms an integral part in most modern
municipal wastewater (MWW) treatment plants (Van Zyl et al., 2008; Apollo and Aoyi, 2016).

2.2.1. Anaerobic digestion

Anaerobic digestion consists of a series of biological steps, in which biodegradable organic

matter is broken down by microorganisms in the absence of oxygen. The biological steps
include hydrolysis, acidogenesis, acetogenesis and methanogenesis (Braguglia et al., 2015).
Insoluble organic matter such as carbohydrates are broken down in the rate determining
hydrolysis step and readily availed for bacteria. The hydrolysis products consisting of amino
acids and sugars are then converted into organic acids, hydrogen (H 2), carbon dioxide (CO2)
and ammonia (NH3), in the acidogenic step. In the subsequent acetogenesis step, the organic
acids are further converted into acetic acid alongside additional H 2, CO2 and NH3. In the last
step, methanogenic bacteria convert the products from acetogenesis to CO 2 and methane
(CH4).

Hydrolysis of polymers such as cellulose, which are not easily decomposed, is the step that
limits the rate of anaerobic digestion. The waste activated sludge (WAS) generated from most
MWW treatment plants consist of heterotrophic bacteria not easily biodegradable, complex
floc structure, hard cell wall and large organic molecules which cannot be absorbed by
microorganisms. The hard cell wall consisting of microbial cells inside extracellular
polymers, is a physical barrier that does not allow intracellular organic compounds to be
biodegraded easily. A large amount of energy is therefore required for the rupturing of the
bacterial cell envelope (Bougrier et al., 2006). The hydrolysis step is also limited by the
presence of melanoidins mostly found in DWW and other high molecular weight (HMW)
biorecalcitrant organic compounds such as pharmaceuticals, phenolic acids and polyphenols
(Chaiprapat and Laklam, 2011). To improve the AD process, implementation of pre-
treatment methods that would enhance the hydrolysis step is necessary.

2.2.2. Ozonation
Ozonation, which is a chemical pre-treatment and considered most effective for sludge
disintegration, does not lead to an increase in salt concentration and has no chemical residues
as compared to other pre-treatment methods (Chu et al., 2009). Through ozonation,
biorecalcitrant polymeric HMW organic compounds can be broken down into easily

6
biodegradable low molecular weight (LMW) compounds (Santos et al., 2013). Moreover, it
disinfects pathogens; hence has gained great interest for AD pre-treatment (Ariunbaatar et al.,
2014). Whereas ozonation has been shown to improve wastewater biodegradability, its
effectiveness and mechanisms should be further explored especially for the production of
high quality biomass substrates (Kim et al., 2014). Processes including (i) sludge
solubilisation mechanisms (ii) reduction of organic compounds from HMW to LMW, and
(iii) biodegradability and toxicity analyses, during ozonation and their effect on the ensuing
AD should be explored, for an in-depth understanding of this pre-treatment process.

The main role of ozonation pre-treatment should be to partially oxidise the biorecalcitrant
part and release biodegradable intermediates (Oller et al., 2011). In order to achieve this, the
ozonation dose and time have to be limited (Chaiprapat and Laklam, 2011). Moreover, ozone
is highly selective leading to partial or non-oxidation of the biorecalcitrant organic
constituents of interest (Achisa et al., 2016). The time limitation and high selectivity can in
some instances allow the biorecalcitrant compounds not fully ozonised to escape into the
subsequent AD process and later into the AD effluent. In such instances, a further robust
post-treatment method would be needed for the AD effluent to ensure complete removal of
the remaining micropollutants. Apart from biodegradation, photodegradation presents another
route for destroying biorecalcitrant and toxic organic compounds in water (Oller et al., 2011).

2.2.3. Photodegradation
Photocatalytic degradation using ultraviolet light and the widely used titanium dioxide (TiO 2)
catalyst, is capable of removing the recalcitrant organic compounds (Otieno et al., 2016). For
effective photocatalysis however, there is a need for the development of photocatalysts with
high quantum efficiency and improved substrate adsorption capability. This can be achieved
through coupling of TiO2 with other semiconductors such as zinc oxide (ZnO), and
introduction of adsorbents materials such as activated carbon (AC) and zeolite, as support for
the catalyst (Otieno et al., 2017). Moreover, there are drawbacks in using photocatalysts in a
powdered form, such as aggregation of the powder especially at high concentrations and the
costly post-treatment separation of the nanopowder from wastewater after treatment (Asiltürk
& Şener 2012). Supporting TiO2 onto the low-cost zeolite support, for enhanced adsorption of
substrate and ease of separation after treatment, presents a feasible route for improving the
photocatalytic process (Durgakumari et al., 2002). Pre-concentration of organic compounds
on the catalyst surface by the zeolite adsorbent support can lead to reduction in energy

7
requirements since TiO2 quantum yields increase linearly with concentration (Haque et al.,
2005).

2.3. Integrated anaerobic digestion and advanced oxidation processes

For effective treatment of industrial and municipal wastewaters, more than one treatment
technique is needed. This calls for integration of the widely-used AD with pre- or post-
treatment techniques such as AOPs. The integration is aimed at enhancing the AD process
leading to maximum biogas recovery, and ensuring that an effluent that complies with the set
discharge standards is obtained. In integrating AD with AOPs, the overall aim should be to
reduce cost by minimising AOP treatment and maximising the AD stage. It is thus important
to put into consideration the characteristics of each individual treatment step and its effect on
the ensuing steps (Oller et al., 2011). The photodegradation process is less selective and
therefore not recommended for application as pre-treatment to AD. This is because of
possible competition between the biodegradable components and the recalcitrant compound
during photodegradation, resulting in a longer period of UV irradiation and high chemical
consumption. Moreover, the highly turbid raw wastewater will hinder light penetration thus
limiting photodegradation. Photodegrdation should therefore be applied as a post-treatment
method for micropollutants removal (Apollo and Aoyi, 2016). Ozonation has been reported to
improve wastewater biodegradability hence suitable for application as a pre-treatment. Also,
ozonation involves bubbling of ozone gas through the wastewater and hence is minimally
hindered by turbidity (Achisa et al., 2016).

8
3. Methodology
3.1. Equipment and materials
Equipment that will be used in this study include: a bioreactor, ozone generator, a
photoreactor, ozonation reactor, centrifugal pump and air compressor. All the reactors will be
designed and constructed, while the ozone generator will be bought. The photoreactor will
consist of a 25 UVC lamp of 254 nm wavelength. The wastewaters to be treated, distillery
wastewater and municipal wastewater, will be sourced from local distilleries and municipal
wastewater treatment works, respectively. Prepared phenolic wastewater of known
composition and characteristics will be first used to optimise the treatment processes and
determine the reaction intermediates and mechanisms involved in the ozonation and
photocatalytic processes. Potassium iodide (KI) and sodium thiosulphate to be used in the
determination of ozone concentration will be purchased. Commercial titanium dioxide (TiO 2)
to be used in photocatalytic degradation will be obtained. Natural zeolite will be sourced and
used as biomass and catalysts support during biodegradation and photodegradation,
respectively.

3.2. Experimental procedure

For individual processes, ozonation of the wastewater inside the ozone reactor will be applied
first to reduce colour and convert the biorecalcitrants to biodegradable compounds.
Thereafter, anaerobic digestion for biogas production and organic load reduction will be
carried out in the bioreactor. After anaerobic digestion, photodegradation of the anaerobic
effluent will be done for complete removal of the remaining colour and recalcitrant
pollutants. In the integrated AD-AOPs process, the reactors will be connected in series
starting with ozone reactor, followed by the bioreactor and finally the photoreactor.

3.2.1. Ozonation
Ozonation will be carried out by adopting a method reported by Achisa et al. (2016). Ozone
will be generated from the ozone generator and bubbled through the wastewater contained in
the ozone reactor. Ozone will be bubbled from the bottom of the reactor via a gas diffuser.
The ozone flow rate will be determined using gas rotameter. Unutilised ozone will be
captured in the off gas and directed through KI solution in a gas absorption container. The
concentration of the unutilised ozone will then be determined. During ozonation, samples will
be taken at predetermined time intervals and analysed to determine the extent of organic
solids solubilisation and increase in biodegradability. This will be determined through the

9
analysis of dissolved/undissolved chemical oxygen demand (COD), total suspended solids
(TSS), biochemical oxygen demand (BOD), COD/BOD ratio and methane potential. The
ozonation intermediate and final products will be determined as well as their toxicity effect.

3.2.2. Anaerobic digestion

Batch anaerobic digestion will be carried out in the anaerobic digester (fluidised bed).
Fluidization of the AD digester will be achieved by using a centrifugal pump to circulate the
substrate undergoing digestion. Appropriate seed inoculum, source of microorganisms, will
be prepared and fed together with the wastewater to the anaerobic digester. The annular space
of the digester will be packed with zeolite for biomass support. The AD setup and process
will follow a similar one reported by Apollo and Aoyi (2016). A heating tape wrapped around
the digester will be used to maintain the temperature at 37 0C (mesophilic) during digestion.
Samples will be drawn periodically to monitor the digestion process, determine the effect of
process parameters and organic load reduction. The biogas produced will be sampled and
analysed to determine its quality in terms of methane content. The toxicity effect of the AD
products will be determined.

3.2.3. Catalyst preparation and photodegradation

Natural zeolite will be crushed, then sieved to obtain a desired particle size before being
washed with deionized water to remove dissolved contaminants and fine particles, and finally
dried. The commercial TiO2 catalyst will hereafter be supported onto the dry zeolite by
adopting a solid-state dispersion (SSD) method to obtain TiO 2/Zeolite photocatalyst.
Photodegradation experiments of the effluent obtained from the anaerobic process will be
carried out in the UVC photoreactor (wavelength of 254 nm). The substrate will be first
mixed with the TiO2/Zeolite photocatalyst and stirred in the dark to obtain adsorption-
desorption equilibrium, before being transferred to the UVC photoreactor for irradiation. The
UVC photoreactor will be fluidised by air from an air compressor to ensure uniform
suspension of the catalyst during degradation. Samples will be taken at different time periods
during photodegradation and analysed to determine extent of micropollutant removal,
mineralisation and products and intermediates formation, and their toxicity effect.

3.3. Catalyst characterization and chemical analyses, and determination of reaction

mechanisms
The morphologies of the zeolite support and TiO 2/Zeolite photocatalyst will be studied using
scanning electron microscopy (SEM) with an integrated energy dispersive X-ray
10
spectroscopy (EDX). Nitrogen adsorption will be used to determine the specific surface areas
of the support and photocatalyst, based on the Brunauer-Emmett-Teller (BET) equation. The
crystalline structure and composition of the support and photocatalyst will be determined
using X-ray diffraction (XRD).

The extent of organic load reduction will be determined from BOD, COD and total organic
carbon (TOC) analyses, while biodegradability will be determined from COD: BOD ratio.
Total organic carbon reduction will be used in determining the extent of organic carbon
mineralization. For the COD analysis, a closed reflux method using dichromate solution as
oxidant, and Nanocolor colorimeter will be used for analysis. TSS and BOD will be
determined using standard procedures (Clesceri et al., 2005). Colour analyses will be done
using a UV-vis spectrophotometer.

Ion Chromatography will be used to monitor formation of inorganic products such as nitrates
and phosphates during AD and photodegradation. The intermediate and final products formed
during photodegration and ozonation will be analysed and determined using Gas
chromatography-mass spectrometry (GC-MS) and Liquid chromatography–mass
spectrometry (LC-MS). The intermediates and products formed during the AOPs will assist
in proposing possible degradation paths and reaction mechanisms followed.

3.4. Toxicity analyses

The toxicity effect of intermediate and final products formed at each stage of the integrated
process will be determined from the influence of products formed, on inhibition of bacteria
(Escherichia coli) respiration, a microorganism widely employed for toxicity studies (Karci,
2014). This test is reported to be suitable for toxicity screening of effluents, as it is easy to
use and capable of providing repeatable and reproducible results. The colony count method to
be adopted from Talebian et al. (2013), will be used for respiration inhibition test. According
to the method, bacteria (E. coli) cultures will be grown in a broth supplemented with
substrate samples. A culture free of the substrate will be used as a blank. The number of
colonies forming units (CFUs) will be counted after 24 hours of incubation at 37oC.

3.5. Experimental design, statistical, data and error analyses

One factor at a time (OFAT) and factorial experimental designs will be applied in this study.
The OFAT design will be used when carrying out preliminary experiments and to investigate
the effect of independent variables on individual processes such as anaerobic digestion,

11
ozonation and photodegradation. For the factorial experiments, central composite CCD using
response surface methodology (RSM) will be used to design and optimise major operational
parameters for the individual processes and for the integrated process. RSM will be applied to
determine the individual and interactive effect of the major operational parameters, and
explore the relationship between the explanatory variables and the response variables. All
data analysis will be done using Microsoft Excel while STATA (statistical software) will be
used for statistical analysis. Further, analysis of variance (ANOVA) will be used in error
analysis.

3.6. Work plan

The study is expected to take three years with thesis submission for examination in the first
quarter of the year 2020. Activities and corresponding timelines are indicated in Table 1.

Table 1: Timeline of activities

YEAR 2017 2018 2019 2020
Activity/Quarter 2 3 4 1 2 3 4 1 2 3 4 1
Literature review
Proposal writing and submission
Reagents and equipment acquisition
Data collection and analyses
Research and conference papers
Thesis writing
Thesis submission
Key; Each quarter contains three months

3.7. Budget
A total of R135 000.00 is expected to be spent during this study for the purchase of
equipment, materials and specialised analysis as shown in Table 2.

Table 2: Budget
MATERIAL/ACTIVITY COST (R)
Bioreactor, photoreactor, ozone reactor 60 000,00
Chemical reagents, materials, catalysts 20 000,00

Specialized analysis (GC-MS, HPLC-MS) 30 000,00

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 Subsistence, travelling, field work 25 000,00
TOTAL 135 000,00
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