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Introduction
Organic matters refer to degradable carbon based compounds. In water and wastewater treatment, organic
matter is one of the major pollutants. Organic compounds, such as PCBs, pesticides and herbicides, polycylic
aromatic hydrocarbons (PAHs), aliphatic and heterocyclic compounds are often prevalent in wastewater and
can compromise the safety of people as well as the environment.
The amount of organic compounds in wastewater is generally evaluated by the chemical oxygen
demand (COD) test and the biological oxygen demand (BOD) test. The basis for the COD test is that nearly
all organic compounds can be fully oxidized to carbon dioxide with a strong oxidizing agent under acidic
conditions. The COD value is always measured using acidic potassium permanganate and potassium
dichromate and could reflect the pollution degree of reducing matter in water including ammonia and reducing
sulfide. Thus, COD value often overestimate organic pollutants in wastewater with high quantity of organic
matter. BOD value is the amount of dissolved oxygen needed by aerobic biological organisms in a body of
water to break down organic material present in a given water sample at certain temperature over a specific
time period. The BOD value is most commonly expressed in milligrams of oxygen consumed per liter of
sample during 5 days of incubation at 20 C. This is not a precise quantitative test, although it is widely used
as an indication of the organic quality of water. Both COD and BOD test could quickly reflect the organic
pollution in the wastewater although they cannot reflect the types of organic matter and composition of the
water and therefore cannot reflect the total amount of the same total organic carbon pollution caused by
different consequences.
Due to the prevalence of organic matter in water and wastewater sources, many different technologies
have been developed throughout the years dedicated to the removal of organic pollutants. Some of these
technologies was invented as early as the beginning of 19th century. These technologies are listed under past
technologies in this review report. Although developed in the past, these technologies are still used in certain
parts of the world. Since then, newer technologies have been developed and are slowly replacing past
technologies. These technologies are listed as present technologies. There is also a section for future
technologies which reviews advanced removal techniques are still being researched and developed.

Review and Evaluation


Past Technologies
1.

Constructed Wetlands

Natural wetlands are land areas saturated with water and certain characteristic vegetation of aquatic plants and
various microorganisms. Constructed wetlands are specifically engineered systems that contains a built,
controlled and sustained wetland environment designed to treat wastewater by utilising the natural processes
carried out by the vegetation and microorganisms present in the wetland ecosystem (Vymazal, 2014).
Although the construction of wetlands requires large plots of land, energy consumption as well as operational
requirements are relatively lower than compared to other wastewater treatment technologies (Wu et al., 2014).

1.1 Types and Classifications


According to Wu et al (2014), constructed wetlands (CWs) can be largely classified into three categories
namely traditional CWs, hybrid CWs and enhanced CWs. The diagram below illustrates the types and
classifications of constructed wetlands. As a limiting scope, enhanced CWs will not be discussed in this report.

Figure 1.1: The Classification of CWs Used in Wastewater Treatment (Wu et al, 2014).

1.1.1 Traditional CWs


As seen in figure 1.1, traditional CWs can be grouped into free water surface CWs (FWS CWs) and subsurface
CWs which are further divided into horizontal flow CWs (HF CWs) and vertical flow CWs (VF CWs). Free
water surface constructed wetlands, as the name suggests, consists of a relatively shallow depth of water with
a free surface and its vegetation partially or totally submerged in the water. The vegetation are supported by a
layer of substrate containing soil situated at the bottom of the wetland (Wu et al, 2014). According to Vymazal
(2014), the existence of a free water surface allows for the diffusion of oxygen gas into the water forming a
decreasing oxygen concentration gradient down the water depth. This give rise to the major presence of
aerobic microorganisms near the free surface as well as a small population of anaerobic microorganisms near
the bottom of the wetland where little to no oxygen molecules are present.

Wastewater enters the wetland horizontally along and through the water channel. Sufficiently large
and heavy organic waste will settle and removed passively by deposition and filtration. Both attached and
suspended microbes in the wetlands will degrade and oxidise the organic waste aerobically and anaerobically
though aerobic oxidisation will be dominant to the large amount of oxygen dissolved in the water. Coverage
provided by the submerged vegetation prevents the penetration of sunlight into the wetlands and thus limiting
the growth of algae. Besides the removal of organic carbon compounds, nitrogenous compounds are also
removed through nitrification and denitrification processes. The availability of dissolved oxygen allows for
efficient nitrification by aerobic microbes followed by denitrification by anaerobic microbes resulting in an
effective removal of nitrogen. Phosphorus in FWF CW systems are removed through adsorption and
absorption by surrounding soil though less effective compared to the removal of nitrogen due to the minimal
contact between soil and water (Vymazal, 2014).

In subsurface (SSF) CWs, the vegetation planted on the substrate containing soil is located above the
water surface of the wetland. This eliminates the presence of a free water surface and wastewater enters the
wetland through the porous medium under the surface of the soil supporting the vegetation (Zhang et al, 2014).
Due to the configuration of SSF CWs which does not have a free water surface available for the diffusion of
oxygen, a smaller amount of aerobic microorganisms will be present compared to anoxic and anaerobic ones,
each separated into their own zones are present in the ecosystem. Aerobic microorganisms are usually present
near the roots and rhizomes of the vegetation where dissolved oxygen is plentiful while anoxic and anaerobic

microbial can be found near the bottom of the wetland. There are two types of SSF-CWs namely the horizontal
subsurface flow CW (HSSF-CW) and vertical subsurface flow CW (VSSF-CW) as shown in the diagram
below.

Figure 1.2: Structures of Constructed Wetlands. (a) SF-CW; (b) HSSF-CW; (c) VSSF-CW (Li et al.,
2014).

1.1.2 Hybrid CWs


In the previous section, it is evident that each CWs have their own strengths and weaknesses in terms of
efficiency in removing different types of waste. Thus, it is a common practice to link several two different
CW systems together in series or parallel to enhance the wastewater treatment performance. Common
combinations include VF-HF CWs, HF-VF CWs, HF-FWS CWs and FWS-HF CWs. There are also multistage
CW systems which combine more than two CWs in series or parallel as mentioned in figure 1.1 (Wu et al.,
2014).

1.2 Design and Operation Parameters


There are several criteria and factors that need to be considered in the design, construction and operation of a
CW. One of the more trivial factor to account for is the location or site of the wetland as this will in turn
determine the type of soil and vegetation available as well as any variations in seasons or weather which can
threaten the survival of the vegetation and microbial community. Other main parameters concerning the CW
itself include the type of vegetation (plants) and substrate, depth of water, hydraulic load and retention time
(HRT) and influent feeding mode i.e. batch, continuous or intermittent (Wu et al., 2014).

1.2.1 Plant Selection


Plant vegetated on substrates in wetlands play a major role in removing nitrogen and phosphorus compounds
as well as other toxic pollutants such as antibiotics and heavy metals. Thus, it is important to select species of
plants that have a large capacity in absorbing pollutants and a high tolerance towards wastewater of high
strength. Therefore, the choice of plants used is also affected by the type of wastewater to be treated as
wastewater from different sources will contain different kinds of pollutants. For example, agricultural waste
which contains high amount of ammonia requires plants with high tolerance towards ammonia such as Zornia
latifolia. Highly saline water are tolerated by species such as Arundo donax and Sarcocornia fruticosa which
are very effective in removing organics, nitrogen and phosphorus. (Wu et al., 2014).

1.2.2 Substrate Selection


Similar to the function of the plants as wetland vegetation, the substrate also plays a role in absorbing certain
pollutants while providing a medium for the growth of plants and facilitating the movement of wastewater. A
good substrate should be able to allow wastewater to freely percolate through it in VSSF CWs as well as a
high pollutant absorption capacity. Typical natural materials used as a substrate include sand, gravel, clay and
peat while artificial materials such as activated carbon and compost are also suitable (Wu et al., 2014).

1.2.3 Hydraulic Load and Retention Time


Hydraulic loading rate (HLR) is a quantitative indicator of the flow rate of wastewater entering into the CW
while hydraulic retention time (HRT) indicates the amount of time the wastewater is retained inside the
wetlands. There two parameters are consistently monitored throughout the operation of the CWs. A high HLR
will cause the value of the HRT to decrease as wastewater are rapidly forced out of the wetlands due to large
amount of influent wastewater. On the other hand, a larger HRT value is usually preferred as a longer period
of retention time will ensure a more complete removal of pollutants by the microorganisms, substrates and
plants in the wetlands (Zhang et. al, 2014). However, this implies that a larger land area and cost will be
needed enlarging the area of the wetland will directly increases the HRT value. Therefore, an optimisation
point between these two variables must be determined to enhance the performance of wetlands.

1.2.4 Influent Feeding Mode


Like many other wastewater treatment technologies, CWs can be operated in a number of different modes
namely batch, intermittent and continuous. The usage of different influent feeding modes will affect the
oxygen transfer and hence the oxidation-reduction conditions in wetlands. Overall, batch operations
performed better than continuous operations as they provide more oxidised conditions. Also, it has been
showed that a higher ammonium removal can be achieved in batch systems than in continuous systems (Zhang
et al., 2012). A similar result is observed in intermittent mode CWs where COD and nitrogenous compound
removal are both higher than continuous mode CWs (Saeed & Sun, 2012).

1.3 Removal of Organics


In terms of classification, wetlands can be considered as a biological secondary treatment of wastewater. Due
to its rich content of microorganisms and absorbing plants and substrates, wetlands are popularly used to
remove organics in terms of BOD as well as nutrients such as nitrogen and phosphorus compounds. The
following diagram shows the efficiency in the removal of BOD as well as other pollutants.

Figure 1.3: Average Removal of Pollutants in Various CW Systems (Zhang et al., 2014)
From the figure above, it can be seen that CWs are most effective in removing BOD and COD as all
types of systems plot a higher bar in average removal of BOD and COD compared to total suspended solids
(TSS), total phosphorus (TP) and nitrogen. Wetlands are also preferred in areas with large lands and high
amount of vegetation. Although the wetland treatment technology is less energy intensive and more
environmentally friendly, it is unsuitable in treating large continuous amount of wastewater and is limited to
treating relatively low strength wastewater.

Present Technologies
2.

Submerged Membrane Bioreactor (SMBR)

Membrane Bioreactor (MBR) can be evaluated as one of the most promising technology for water and
wastewater treatment especially the submerged (SMBR) which uses both physical and biological processes in
wastewater organic removal. SMBR has been acquiring attention on wastewater treatment for its preferable
effluent quality and lower production of sludge.

There are mainly three types of MBR models. The first is the biomass kinetic model. It is mainly based
on activated sludge models (ASMs) where they were modified to account for the formation and degradation
of soluble microbial product (SMPs) in the membrane. The second is membrane fouling. This MBR is based
on solid-liquid separation and the simulation filtration processes as ideal settler with unitary efficiency on
fouling phenomenon. The third category considers the formation and degradation of SMP and integrated with
the first and second models.

2.1

Membrane Module Characteristics and Comparison with an Activated Sludge System

The MBR membrane can be placed either inside or outside the bioreactor. Membranes placed inside the
bioreactor is known as SMBR while outside the bioreactor is known as external membrane bioreactor. In
municipal applications, hollow fibre SMBR configuration would be useful for medium to large size
wastewater treatment plants. For a smaller plant size, plate and frame technologies would have more
advantages where it could be designed with secondary or tertiary treatment followed by membrane filtration

and ultrafiltration. In SMBR configurations, membrane in aeration basin acts as filters and improve the
biological treatment of effluent. The permeate flux is removed by suction at around 0.5 pressure bar. While
for external configuration, the amount of permeate flux varies and the pressure bar in the range of 14 bar.
Thus, the submerged configuration appears to be more economical based on energy consumption.
The following are the advantages of SMBR over the traditional activated sludge system.
i) Energy consumption and capital cost for fabrication and maintenance are lower for submerged
system.
ii) The traditional secondary clarifier is replaced by a membrane module which is better in compact and
quality of rejected water is independent of the variations of sludge settling velocity.
iii) The process can be run at higher solid retention time, which favour the development of slow growing
micro-organism and ultimately lead to better removal of refractory organic matter and making the
system robust to load variation and toxic shock.

The figure and table below show the pilot plant layout as well as the main features of the membrane and the
general operating conditions respectively.

Figure 2.1: A Zenon Zeeweed (ZW 10) Pilot Plant in Palermo, Italy Fed with Municipal Wastewater
from the Acqua dei Corsari (Palermo) WWTP.

Table 2.1: General Operational Parameters of a Pilot MBR


Parameter
Unit
Average Minimum Maximum
HRT
h
11.9
11.4
12.4
3
1
VLR
kg COD m day
1.1
1
1.2
2 1
Permeate flux
Lm h
21.5
20.5
22
Suction period
min
9

Backwash period
min
1

1
O.D.
mg L
3.9
0.5
7.7
Temperature
C
22
15
30
pH

8
7.3
8.2

2.2

Operation Process

Pre-screen of wastewater through a 2 millimetres screen is used to remove small substances debris, hair, rags,
sand and others. It is then enter the aeration tank where organic matter, phosphorus and nitrogen were
removed. The permeate was draw from the membrane module and pass through in a tank and the concentrated
sludge was remain in the aeration tank.

The SMBR influent was stored in a tank (volume of 1500 L) where the influent was diluted in order
to maintain a constant influent COD concentration to operate with a constant volumetric loading rate (VLR)
of 1.1 Kg COD m3 day1 and an average hydraulic retention time (HRT) of 11.9 h. Table 2 shows the influent
characteristics.
The permeate was extracted by imposing an average flux of 21.5 L m2 h1 on the membrane surface
and a maximum negative pressure of 0.3 bar. In particular, the membrane was periodically backwashed (every
9 min) by pumping a fraction of permeate back through the membrane for a period of 1 min. The effluent
effective mean flux resulted of 19.3 L m2 h1. More specifically, the bioreactor was indicated by an operating
volume of approximately 190 L and it was equipped with a level controller and a pump to regulate the feeding
and to discharge the effluent, respectively.

Average
Minimum
Maximum

COD
(mg/L)
510
310
705

Table 2.2 Influent Characteristics


BOD
TSS
VSS
NNH4 NNO2
(mg/L) (mg/L) (mg/L) (mg/L) (mg/L)
255
274
262
35.8
0.07
150
122
180
18.5
<0.02
360
372
352
50.0
1.0

NNO3
(mg/L)
0.78
<0.01
3.4

NNTOT
(mg/L)
53.9
30.0
81.0

The bioreactor was aerated and stirred by two fine bubble air diffusers placed on the bottom of the
reactor. An air flow is around of 2.5 m3 h1. The other air blower is then directly connected on the bottom of
membrane module, produced a constant air flow (3 m3 h1) to generate strong turbulence to continuously clean
the surface of the membrane. Moreover, an analogical manometer was installed on the membrane bioreactor
and it was connected to the head of membrane module for monitoring the transmembrane pressure.
The whole process was divided in two phases: the first one where the SMBR pilot plant was startedup without inoculum of activated sludge in order to dispose a spontaneous selection of the biomass; the second
phase where the SMBR was started-up with inoculum of activated sludge in order to investigate the main
differences in fouling increase during the start-up. For this phase, SMBR worked in accordance with the same
operational conditions of the previous phase. The pilot plant was in total of 130 days of operation, 65 days for
each phase. Throughout the first phase (without inoculum), the system was continually in operation and no
chemical cleaning was necessary. In addition, no sludge withdrawal was processed. Meanwhile in the second
phase (with initial inoculum), the total suspended concentration (TSS) was maintained meanly constant,
between 14 and 17 g L1, with periodic sludge withdrawal. The sludge retention time, in this circumstance
was maintained at around 3235 days. The modelling examination described was carried out only on the
second phase.
The influent concentration, the mixed liquor and the permeate were sampled three times per week and
analysed of the total and volatile suspended solids (TSS and VSS), total and soluble COD, BOD, NNH4, N
NO2, NNO3 and NTOT.

2.3

Membrane Modules Fouling

Even with the expansion in physical and biological models improve the wastewater management, fouling
mechanisms is still a complication in wastewater treatment. Fouling in MBR can be internal as blocking in
pore of membrane or externally deposition of cake for both organic and inorganic substances.

Chemical nature of membrane and the membrane operational parameters such as bubbling and suction
are the influences of membrane fouling. Hollow-fibre microfiltration membrane induces transmembrane
pressure gradient that will have an impact on flux rates. The flux depends on the design of hollow-fiber and
also the properties of the cake. The structure of the membrane pores also play an important role on fouling,
the rougher the surface of the membrane, the faster the fouling by attachment of colloid and particulate matters
on the membrane surface.
The limiting factor for further process development is membrane fouling resulting are the:
i.
ii.

3.

Formation of a layer or cake on the membrane or the intrusion of the molecules, colloids and particles
in the porous structure
Preferential adsorption on the membrane surface. Fouling induces transmembrane flux reduction,
when the flux is increased by biological activity, and the progression in this field is relatively slow.

Adsorption Technology

Adsorption technology has gained importance as an effective purification and separation method in water and
wastewater treatment over the last few decades. It provides no sludge handling problem and discharges a high
quality effluent. Moreover, it has advantages over the other methods because of simple design and can involve
low investment in term of both initial cost and land required. Hence, the adsorption technology is extensively
used for treatment of industrial wastewater from organic and inorganic pollutants and meet the great attention
from the researchers. Latterly, the exploration for low-cost adsorbents that have pollutantbinding capacities
has escalated. Materials locally available likes natural materials, agricultural wastes and industrial wastes can
be utilized as low-cost adsorbents. Activated carbon manufactured from these materials can be used as
adsorbent for wastewater treatment (Crini, 2005).

3.1

Adsorption Phenomenon

Adsorption is a surface phenomenon with conventional mechanism for both organic and inorganic pollutants
removal in water and wastewater treatment. It take place when a solution containing absorbable solute comes
into contact with a solid having a highly porous surface structure. The liquid-solid intermolecular forces of
attraction cause some of the solute molecules from the solution to be concentrated and deposited at the solid
surface. The solute which retained on the solid surface in adsorption processes is called adsorbate, while, the
solid on which it is retained is called as an adsorbent. This surface accumulation of adsorbate on adsorbent is
called adsorption. At last, the creation of an adsorbed phase with a composition different from that of the bulk
fluid phase forms the cornerstone of separation by adsorption technology.
In a bulk material, all the bonding requirements such as ionic, covalent, or metallic of the constituent
atoms of the material are filled by other atoms in the material. However, atoms on the surface of the adsorbent
are not wholly surrounded by other adsorbent atoms and hence they can attract adsorbates. In fact, the exact
nature of the bonding depends on the details of the species involved. But, in general, the adsorption process
can be classified as physisorption (characteristic of weak Van Der Waals forces) and chemisorption
(characteristic of covalent bonding). Somehow, it may also occur due to electrostatic attraction. Besides,
adsorption is nearly always an exothermic process.

Physical adsorption takes place quickly and may be mono-molecular (unimolecular) layer or
monolayer, or 2, 3 or more layers thick (multi-molecular). As physical adsorption occurs, it begins as a
monolayer. It can then become multi-layer, and then, if the pores are close to the size of the molecules, more
adsorption occurs until the pores are filled with adsorbate. Duly, the maximum capacity of a porous adsorbent
can be more related to the pore volume than to the surface area.

On the other hand, chemisorption involves the formation of chemical bonds between the adsorbate and
adsorbent is a monolayer, often with a release of heat much larger than the heat of condensation.
Chemisorption from a gas generally takes place only at temperatures greater than 300C, and may be slow
and irreversible. Most commercial adsorbents rely on physical adsorption; while catalysis relies on
chemisorption.
As the adsorption progress, an equilibrium of adsorption of the solute between the solution and
adsorbent is attained (where the adsorption of solute is from the bulk onto the adsorbent is minimum). The
adsorption amount (qe, mmol g-1) of the molecules at the equilibrium step was determined according to the
following equation:
qe =

Where,
V is the solution volume (L);
M is the mass of monolithic adsorbents (g); and
C0 and Ce are the initial and equilibrium adsorbate concentrations, respectively.
In the other words, adsorption process is a mass transfer process by which a substance is transferred from the
liquid phase to the surface of a solid, and becomes bound by physical and/or chemical interactions. Large
surface area leads to high adsorption capacity and surface reactivity (Kurniawan and Lo, 2009).

3.2

Adsorption Isotherm and Models

An adsorption isotherm is the demonstration of the amount of solute adsorbed per unit weight of adsorbent as
a function of the equilibrium concentration in the bulk solution at constant temperature. Langmuir and
Freundlich adsorption isotherms are commonly used for the description of adsorption data.

The Langmuir equation is expressed as:


qe

Where,
Ce is the equilibrium concentration of solute (mmol L-1),
qe is the amount of solute adsorbed per unit weight of adsorbent (mmol g-1 of clay),
Xm is the adsorption capacity (mmol g-1), or monolayer capacity, and
b is a constant (L mmol-1 )

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On the other hand, the Freundlich isotherm illustrates heterogeneous surface adsorption. The energy
distribution for adsorptive sites (in Freundlich isotherm) follows an exponential type function which is close
to the real situation. The rate of adsorption/desorption changes with the strength of the energy at the adsorptive
sites. The Freundlich equation is expressed as:
log qe = log +

1
log

Where,
k (mmol g1) and
1/n are the constant characteristics of the system

3.3

Types of adsorbents

Adsorbents are grouped into natural adsorbents and synthetic adsorbents. Natural adsorbents include charcoal,
clays, clay minerals, zeolites, and ores. These natural materials, in many instances are relatively cheap,
abundant in supply and have significant potential for modification and ultimately enhancement of their
adsorption capabilities. Synthetic adsorbents are adsorbents prepared from agricultural products and wastes,
house hold wastes, industrial wastes, sewage sludge and polymeric adsorbents. Each adsorbent has its own
characteristics such as porosity, pore structure and nature of its adsorbing surfaces. Many waste materials used
include fruit wastes, coconut shell, scrap tyres, bark and other tannin-rich materials, sawdust, rice husk,
petroleum wastes, fertilizer wastes, fly ash, sugar industry wastes blast furnace slag, chitosan and seafood
processing wastes, seaweed and algae, peat moss, clays, red mud, zeolites, sediment and soil, ore minerals etc.

3.4

Activated Carbon

Activated carbon can be produced from carbonaceous material, including coal (bituminous, subbituminous,
and lignite), peat, wood, or nutshells (i.e. coconut). The manufacturing process consists of two phases,
carbonization and activation. The carbonization process includes drying and then heating to separate byproducts, including tars and other hydrocarbons, from the raw material, as well as to drive off any gases
generated. The carbonization process is finish made by heating the material at 400600C in an oxygendeficient atmosphere that cannot support combustion.
Activated carbons (AC) (both granular activated carbon (GAC) and powdered activated carbons
(PAC)) are common adsorbents used for the removal of undesirable odour, colour, taste, and other organic
and inorganic impurities from domestic and industrial waste water owing to their large surface area, micro
porous structure nonpolar character and due to its economic viability. Powdered activated carbon is made up
of crushed or ground carbon particles, 95100% of which will pass through a designated mesh sieve or sieves.
Granular activated carbon can be either in the granular form or extruded. In addition, active carbons contain
other hetero atoms such as hydrogen, nitrogen, sulfur, and oxygen.

3.5

Adsorption on Activated Carbon

Methyl tert-butyl ether (MTBE) is an organic pollutants used commonly as a fuel component in fuel in
gasoline engine and also as a solvent. The adsorption of methyl tert-butyl ether (MTBE) by granular activated
carbon (GAC) was studied, the maximum adsorption capacity of MTBE on granular activated carbon was
204.1 mg/g. Results demonstrate that granular activated carbon (GAC) is an effective adsorbent for methyl
tert-butyl ether and also provide specific guidance into adsorption of methyl tert-butyl ether on granular
activated carbon (GAC) in contaminated groundwater (Chen, Zhang and Chen, 2010).

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Five commercially available types of activated carbon (GAC 1240, GCN 1240, RB 1, pK 1-3, ROW
0.8 SUPRA ) are prepared and used to remove organic chlorinated compounds from wastewater of a chemical
plant. The various types of activated carbon were tested on the basis of Freundlich adsorption isotherms for
14 pure organic chlorinated compounds, of molecular weight ranging from that of dichloromethane (MW
84.93 g mol-1) to hexachlorobenzene (MW 284.78 g mol-1). The best adsorbent (GAC 1240 granulated
activated carbon) was selected and used in a laboratory fixed bed column to assess its removal efficiency with
respect to the tested organic chlorinated compounds. Removal efficiency was always higher than 90% (Pavoni
et al., 2006).

Table 3.1: Removal Efficiency (%) of Chlorinated Compounds from Wastewater by Five
Commercially Available Types of Activated Carbon (Pavoni et al., 2006).
Substance
Dichloromethane
Trichloromethane
1,1,1- Trichloromethane
Carbon tetrachloride
1,2-Dichloroethane
Trichloroethylene
1,1,2- Trichloroethane
Tetrachloroethylene
1,1,1,2- Tetrachloroethane
Trans 1,4-dichloro-2-butene
1,2,4-Trichlorobenzene
1,2,3-Trichlorobenzene
Hexachloro-1,3-butadiene
Hexachlorobenzene

Percentage of Adsorption Efficiency (%)


98.3
98.8
99.0
99.0
82.8
94.7
86.3
91.6
87.3
94.2
99.2
90.5
99.4
95.1

Bottom ash is a kind of waste material generated from thermal coal-fired power plants. It is commonly
used in road bases and building materials. Bottom ash was used to remove the organic pollutants in coking
wastewater and papermaking wastewater. Particular attention was paid on the effect of bottom ash particle
size and dosage on the removal of chemical oxygen demand (COD). The results indicate that the COD removal
efficiencies increase with decreasing particle sizes of bottom ash, and the COD removal efficiency for coking
wastewater is much higher than that for papermaking wastewater due to its high percentage of particle organic
carbon (POC). Different trends of COD removal efficiency with bottom ash dosage are also observed for
coking and papermaking wastewaters because of their different POC concentrations (Sun et al., 2008).

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4.

Chemical Oxidation Technologies

Advanced chemical oxidation processes make use of oxidants to remove both organic and oxidizable inorganic
components, which also lowers down COD and BOD levels (Lennech, n.d.). The processes can completely
oxidize organic materials to carbon dioxide and water. Nowadays, the conventional biological methods cannot
be used for complete treatment of the effluent due to the increasing presence of molecules, refractory to the
microorganisms in the wastewater streams. Newer technology such as chemical oxidation technology which
uses chemical oxidant (H2O2, O3, ClO2, K2MnO4, K2 FeO4 and so on as shown in Table 1) has been introduced
to oxidize pollutant to slightly toxic, harmless substances or transform it into manageable form (Zheng et al.,
2013).

Table 4.1: Relative oxidation activity of some oxidizing agents (Munter, 2001; US Peroxide, n.d.).
Oxidizing Agent
Positively charged hole on titanium dioxide, TiO2
Fluorine
Hydroxyl radical
Atomic oxygen
Ozone
Hydrogen peroxide
Perhydroxyl radical
Permanganate
Hypobromous acid
Chlorine dioxide
Hypochlorous acid
Hypiodus acid
Chlorine
Bromine
Iodine

Relative Oxidation Activity


2.35
2.23
2.05
1.78
1.52
1.31
1.21
1.24
1.17
1.15
1.10
1.07
1.00
0.80
0.54

Some AOPs are enhanced with ultrasound, ultraviolet and catalysts to improve the oxidation
performance. They are capable to remove organics and inorganics substances, biologically toxic or nondegradable materials such as aromatics, pesticides, petroleum constituents, and volatile organic compounds in
waste water (AST Clean Water Technologies, n.d.). In the chemical oxidation technologies, some oxidizing
agents such as ozone and hydrogen peroxide exhibit lower rates of degradation. Therefore, advanced oxidation
processes (AOPs) are introduced with the capability of exploiting the high reactivity of hydroxyl radicals in
driving the oxidation reaction that have today emerged a promising technology for the treatment of
wastewaters containing refractory organic compounds.
External energy sources such as electric power, ultraviolet radiation (UV) or solar light are required
for AOPs, leading these processes to cost more expensive than conventional biological wastewater treatment
(Mazille & Spuhler, n.d.). Besides overall COD reduction, AOPs are also able to provide sludge treatment,
specific pollutant destruction, increased bioavailability of recalcitrant organics and color and odor reduction.
This technology does not produce toxic or hazardous waste as the end products are stable inorganic compounds
such as water, carbon dioxide and salts (AST Clean Water Technologies, n.d.).

There are a few AOPs that are introduced today for the removal of organics in the wastewater treatment
plant. This includes ozone water processes, photolysis, UV/ozone, UV/H2O2 and UV/O3/H2O2 processes,
photocatalysis, Fentons processes, photoassisted Fenton processes, electro-Fenton processes, and wet

13

oxidation process such as wet peroxide process, wet air oxidation, catalytic wet air oxidation and supercritical
wet air oxidation (Heponiemi et al., 2012). The main difference of these AOPs is the source of radicals.

AOPs today can be applied in the food industry, agricultural field, oil milling production, paper milling
industries, textile wastewater, wastewater containing pharmaceutical, pesticides and herbicides and many
industrial waste streams.

Past technologies started with Fentons processes which were reported at the year 1894, currently the
AOPs have been advanced to more catalytic treatments such as photocatalysis, catalytic ozonation, wet air
catalytic oxidation (WACO) and wet hydrogen peroxide catalytic oxidation (WHPCO) (Centi et al,. 2012). In
the future, these AOPs can be integrated with other treatments such as in biological and in physical treatment.
Some proposed to combine with electrochemical process and this lead to an improvement on the AOPs to
EAOPs (Electrochemical Advanced Oxidation Processes), which is reported of its capability to remove a
wider range of organic substances in the wastewater (Oturan et al., 2007).

4.1

Hydrogen Peroxide

Hydrogen peroxide (H2O2) is an environment friendly oxidant which could oxidize organic pollutants
efficiently and economically. The standard reduction potentials (1.77V, 0.88V) of hydrogen peroxide imply
that it is a strong oxidant in both acidic and basic solutions to oxidize many kinds of organic contaminants in
wastewater directly (Zheng et al., 2013).
H2O2 +2H+ +2e 2H2O E = 1.77V
HO2 +H2O + 2e 3OH E = 0.88V
Hydrogen peroxide has been used for detoxification of cyanide, nitrite and hypochlorite, for the
destruction of phenol aromatics, formaldehyde, and removal of sulfite, thiosulfate and sulfide compounds.
However, the application of hydrogen peroxide alone present major problems such as very low rates for
applications involving complex materials, stability of H2O2 and mass transfer limitations. Hence, use of
hydrogen peroxide alone is not likely a recommendable option for industrial wastewater treatment. Today, it
can be enhanced by homogeneous and/or heterogeneous catalysts, the progress named wet hydrogen peroxide
catalytic oxidation (WHPCO). WHPCO operates at temperatures in the 20-80 range and atmospheric
pressure (Zheng et al., 2013). It is an enhanced technology from Wet Peroxide Oxidation (WPO), adapted
from Fentons Process. WPO has the same oxidation mechanism as Fentons process and the only difference
between WPO and Fenton is the operating reaction temperature. WPO operates at higher temperature
(>100oC) so that more efficient TOC removal can be obtained (Heponiemi & Lassi, 2012).

4.1.1 WHPCO
WHPCO process has been proposed for a variety of agro-food and industrial effluents: removal of dyestuffs
from textile, treat sewage sludge, purifies wastewater from pharmaceutical and chemical production, dumping
site, or from cellulose production and pre-treat water streams from food-processing industries (olive oil mills,
distilleries, sugar refineries, coffee production, tanneries, etc.) (Zheng et al., 2013). It can also be used in
cosmetic industries that present a high organic load on their wastewater (Bautista et al., 2010).

14

Introduction of hydrogen peroxide into the waste stream is critical due to lower stability of hydrogen
peroxide. H2O2 in the pollutant stream should be given a larger residence time, but due to the practical
constraints and poor mixing conditions, injection of H2O2 in line is not always possible and an additional
holding tank is required. The simplest, faster and cheapest method for injection of hydrogen peroxide is gravity
feed system. Pump feed systems can also be used, but it requires regular attention.

Figure 4.1: Typical Reactor Used for WHPCO Technology (Zheng et al., 2013).

In figure 4.1, the WHPCO is used for the treatment of olive oil milling waste water using Fe-ZSM-5
solid catalysts. In the flow diagram, there is a fixed bed reactor and a main vessel for WHPCO (Zheng et al,
2013). H2O2 is added progressively at the top of a fixed bed catalytic reactor before a static mixer to maximize
its local concentration. Iron solution is added on the top of the reactor to maintain catalyst activity constant.
The feed solution is recirculated to and from a tank in order to have good turbulence in the catalyst bed, but
also to guarantee the necessary total residence time to obtain the required level of removal of phytotoxic
chemicals.

The performance of WHPCO depends on the catalysts used. The main catalyst or the active phase used
for WHPCO is iron but there are also many researches include different catalyst in this chemical oxidation
process, including Fe/-Al2O3, Fe/AC, TiO2 -CeO2, Fe/TiO2 -CeO2, Cu-zeolite, Cu-pillared clay, CuO
impregnated with activated carbon (CuAC), Au/AC, Al-Fe and Zr-Fe pillared clays and other many other
catalysts that is under research. Today, several supports that reported can be used for the catalyst are alumina,
pillared clay, silica, zeolites and activated carbon (AC) (Bautista et al, 2010).

In the experiment reported by Bautista et al. in 2010, two samples of wastewater with significantly
different values of COD (4730 and 2300 mg/L) and total organic carbon (TOC) (1220 and 686 mg/L) were
used. In the authors, study, aerobic biodegradability of the wastewaters was assessed by the BOD5/COD ratio.
This ratio is a well widespread biodegradability index for industrial wastewaters. The BOD5/COD ratio was
0.085 and 0.220, respectively, showing low biodegradability. The calcination temperatures were at 350oC and
400oC for the Fe/-Al2O3 catalyst. At the calcination temperature of 300oC, two catalysts were prepared with
4% and 8% of Fe content respectively. The operating conditions were: pHo = 3, T = 5585 C, and P = 1 atm
for the experiments. The results are as follows:

15

Figure 4.2: Effect of the calcination temperature of the catalyst (Al4%Fe; CODo = 2070 mg/L;
TOCo = 617 mg/L; [H2O2]o = 4400 mg/L; T = 85 C) (Bautista et al., 2010).
Table 4.1: Effect of the Fe load of the alumina-supported catalysts (CODo = 2070 mg/L;
TOCo = 617 mg/L; [H2O2]o = 4400 mg/L; T = 85 C) (Bautista et al., 2010).
Catalyst
XCOD (%) XTOC (%)
Al4%FeT300
83.5
55.9
Al8%FeT300
75.5
52.0

XH2O2 (%)
69.5
76.1

Feleached (%)
0.26
0.28

Table 4.2: Effect of the temperature in the CWPO of cosmetic wastewaters with the Al4%FeT300
catalyst (CODo = 2070 mg/L; TOCo = 617 mg/L; [H2O2]o = 4400 mg/L) (Bautista et al., 2010).
Temperature (C)
55
70
85

XCOD (%)
23.6
44.1
83.5

XTOC (%)
16.6
15.2
55.9

XH2O2(%)
12.3
37.4
69.5

Feleached (%)
0.05
0.16
0.26

Figure 4.2 shows the use of Fe/alumina catalyst calcined at 300oC and 450oC. The graph shows that the
removal of COD and TOC increases over time but at higher calcination temperature, the COD removal and
TOC reduction on the wastewater sample is lower. Table 2 shows the use of catalysts calcined at 300oC with
4% and 8% Fe content. From the table, lower Fe content at 4% shows a higher COD and TOC reduction with
lower H2O2 dosage and lower leaching of Fe content from the catalyst. In Table 3, higher temperature displays
a higher removal of COD and TOC, but also with higher dosage of hydrogen peroxide and higher leaching of
Fe content from the catalyst. According to the authors, temperature about 70 to 85oC will be the optimum
temperature for COD to be reduced to an allowable COD limit for the industrial wastewater discharge. The
biodegradability of these wastewaters was also found to be improved from an initial BOD5/COD ratio of 0.22
to 0.53 after 4 h reaction time at 85 C.

16

4.1.2 Fenton
The Fenton's process has its origin in the discovery reported in 1894 by H. J. H. Fenton that ferrous ion strongly
promotes the hydrogen peroxide oxidation of tartaric acid (Lenntech, n.d.). It is sometimes known as Fentons
reaction and its oxidation mechanism can be summarized by the following step: a mixture of H2O2 and ferrous
iron in acidic solution in the presence of FeSO4 catalyst generates the hydroxyl radicals which will
subsequently attack the organic compounds present in the solution (Herney-Ramirez et al., 2010).
Fe2++H2O2Fe3++HO+HO
As iron (II) acts as a catalyst, it has to be regenerated by decomposing H2O2 again, which seems to occur
through the following scheme:
Fe3++H2O2Fe-OOH2++H+
Fe-OOH2+Fe2++HO2

The important mechanistic feature of the Fentons reaction is the electron transfer from Fe2+ to H2O2
and generates hydroxyl radicals and hydroxide anions. Hydroxyl radicals (as shown in Table 1) are extremely
powerful oxidizing species to abstract one electron from an electron rich organic substrate or any other species
present in the medium to form hydroxide anion. The oxidation potential of hydroxyl radicals has been
estimated as +2.8 and +2.0V at pH 0 and 14, respectively. The high reactivity of hydroxyl radical (HO) is
capable to react with a wide range of organic compounds. Fentons reaction gives rise to CO2 and the
heteroatoms also form the corresponding oxygenated species such as NOx, SOx and POx, indicating that the
carbons and heteroatoms of the organic substrate are converted to inorganic species (Zheng et al., 2013).

The performance of Fentons oxidation application to wastewater treatment was based on the following
parameters: operating pH, amount of ferrous ions, concentration of hydrogen peroxide, initial concentration
of the pollutant, type of buffer used for pH adjustment, operating temperature and chemical coagulation
(Zheng et al. 2013; US Peroxide, n.d.). Parameter pH is the major factor affecting the performance of Fentons
reaction. Optimum pH has been observed to be 3 in the majority of the cases, but it could also be in the range
of 3 to 6 (Lennech, n.d.). At higher pH, the iron precipitate Fe(OH)3 will form and decompose H2O2 into
oxygen and water molecules (US Peroxide, n.d.). The pollutant removal efficiency increases with an increase
in the dosage of ferrous ions and hydrogen peroxide but higher dosage will lead to environmental problem
and high treatment cost. In commercial application, most Fentons reaction operates at temperature between
20 to 40oC. Higher temperature will decrease the oxidation performance as H2O2 could decompose into O2
and water molecule (US Peroxide, n.d.).

The conventional Fentons reaction to produce hydroxyl radicals is a homogeneous catalytic reaction.
Major problems encountered for homogeneous catalyst include catalyst separation, regeneration, etc. Today,
there are heterogeneous catalysts Fentons reaction, i.e., solids containing transition metal cations (mostly iron
ions) being developed and tested (Navalon et al., 2010).

A batch Fentons reactor consists of a non-pressurized stirred reactor with metering pumps for the
addition of acid, base, a ferrous sulfate catalyst solution and industrial strength (35-50%) hydrogen peroxide.
The reactor vessel should be coated with an acid-resistant material, because the Fentons reagent is very

17

aggressive and corrosion can be a serious problem as it contains some residual H2SO4 (US Peroxide, n.d.).
The pH of the solution must be adjusted at 6, usually iron hydroxide is formed. For many organic pollutants,
the ideal pH for the Fenton reaction is between 3 and 4, and the optimum catalyst to peroxide ratio is usually
1:5 wt/wt (Zheng et al., 2013). Addition of reactants is done in the following sequence: dilute sulfuric acid
catalyst in acidic solutions, pH adjusting agent (adjustment of pH at 3-4) and lastly added hydrogen peroxide
slowly (Lennech, n.d.). Effluent of the Fentons reactor (oxidation tank) is fed into a neutralizing tank for
adjusting the pH (adjustment of pH at 9), then the stream followed by a flocculation tank and a solid-liquid
separation tank for removing the precipitate. A schematic representation of the Fentons oxidation treatment
has been shown in Figure 3 (Gogate & Pandit, 2004).

Figure 4.3: Typical Reactor used for Fentons Oxidation (Gogate & Pandit, 2004).
The main advantage of this process is its simplicity of design, implementation and its operation at near
ambient condition (Bautista et al, 2010). It also gains large attention for its ability to remove wide variety of
compounds. Fentons reagent has been used quite effectively for the treatment and pre-treatment of leachate
from composting of different wastes. Reported COD removal efficiencies range from 45% to 85%, and
reported final BOD5/COD ratio can be increased from less than 0.10 initially to values ranging from 0.14 to
more than 0.60, depending on leachate characteristic and dosages of Fenton reagents (Deng & Englehardt,
2006). The optimal conditions for Fentons reaction were found at a ratio [Fe2+]/[COD] equal to 0.1. Both
leachates were significantly oxidized under these conditions in terms of COD removal 77-75% and BOD5
removal 90-98% (Trujillo et al., 2006). Fentons oxidation was also used to degrade complexing agents such
as N-bis[2-(1,2-dicarboxyethoxy) ethyl)] glysine (BCA5), N-bis[2-(1,2-dicarboxyethoxy)ethyl]aspartic acid
(BCA6) and EDTA from bleaching wastewater (Pirkanniemi et al., 2007). It was reported that an almost
complete removal of EDTA was attained at its concentration of 76 mM. There are also other compounds such
as m- and p-xylenes concentration being reduced significantly. It was reported that there is a 81.8% reduction
in the organic contaminant mass using Fentons reaction, and it was also found to be effectively mineralizing
methyl tert-butyl ether (MTBE) in the wastewater (Bergendahl & OShaughnessy, n.d.).

Figure 4.4: Reduction in COD of an Industrial WW with Fentons Oxidation.

18

Figure 4.4 shows the result of a bench-scale experiment using Fentons reaction for the evaluation on
the potential in COD reduction using Fentons reagent. It was found that the process was able to reduce the
COD up to 96% from its initial concentration (Bergendahl & OShaughnessy, n.d.).
Fentons processes can be applied in many industries today, such as chemical, pharmaceutical, pulp
and paper, textile, food, cork processing, and landfill leachates (Bautista et al., 2008). Chemical industries are
major contributors to nowadays problems of industrial wastes, in terms of discharge volume and the hazardous
pollutants in the effluent. Phenolic resin manufacturing industry is one of the chemical industries that generate
high concentration of phenol and derivatives, which are extremely toxic and refractory. Kavitha and
Palanivelu evaluated the efficiency of different Fenton-related processes, such as Fenton and solar-Fenton, for
the degradation of phenol in industrial wastewaters. The effluent was taken from a resin-manufacturing
industry in India containing 2904 mg/L COD, 933 mg/L dissolved organic carbon (DOC) and 1215 mg/L
phenol. The reaction is run at pH of 3, H2O2/COD weight ratio of 2.2, Fe2+/H2O2 molar ratio of 0.026 for
Fenton and 0.013 for solar-Fenton. It was reported that phenol was completely removed in 5 min reaction
time. In Fentons reaction, COD removal and DOC mineralization is 82 and 41% respectively, whereas in
solar-Fentons reaction, almost complete COD reduction and 97% mineralization of DOC were achieved in 2
hours of reaction time.

Future Technologies
5.

Ultrasound (US) and Advanced Oxidation Processes (AOP)

As mentioned previously, AOP are the usage of chemicals to decompose and remove organic or inorganic
pollutants, using light to catalyse the process. These treatments have long been known, but are not widespread
in industry due to their high costs or difficulties in the process. However, recently, the finding that AOP may
utilize ultrasound as well instead of just UV light became popular among researches, and such process is
termed as sonolysis.

Figure 5.1: Schematic Representations of (a) Effective Reaction Zone in Cavitation Bubbles (b)
Catalytic Surface.

19

Sonolysis uses the compression and expansion cycles of ultrasonic waves to pull water molecules away
from each other, causing voids, which are known as acoustic cavitations. Figure 2 shows diagram of cavitation
bubbles. The cavitation bubbles entrap vapors from the medium, eventually reaching its critical size of several
hundred micrometers before implosion of bubble occurs. The implosion of cavitation generates high
temperature and pressure. The timescale of the collapse is less than 0.1 microseconds, and the collapse of
cavitation bubbles may generate high-speed microjets of 100 m/s, causing direct damage to other nearby micro
particles, which hinders their agglomeration, allowing higher active surface area for subsequent reaction. As
explained, since only vapors are entrapped in the cavitation bubble, this process is only suitable for destroying
high volatility compounds that are hydrophobic. Hydrophilic compounds or non-volatile compounds are
decomposed by another mechanism, which will be explained below, through the generation of OH radicals.

Aside from using sonolysis to directly decompose pollutants, sonolysis have good affinity with many
AOPs. One example is the the combination of sonolysis in Fentons Process, in the in-situ production of
Hydrogen Peroxide. In aqueous medium, the ultrasound waves provoke the formation and collapse of
cavitation bubbles. Cavitation produces local spots of high temperature and pressure for a short time, which
also causes the splitting of water molecules into OH- and H+ radicals during the collapse. Though, an estimated
80% of them recombines back into water before they decompose pollutants, and cannot be improved with
ultrasound. Regardless, investigations have found that the combination of utilizing ultrasound improved
mineralization in the presence of O3 from 30% with methyl orange to 80% with ultrasound, caused by the
increased yield of OH- radicals from O3 molecules under ultrasound. Aside from that, the activity of catalytic
processes also improved by the synergized effect induced by ultrasound waves, which is cause by increased
active surface area and increased concentration of OH- radicals.

A second example is the addition of ultrasound into TiO2/ZnO/UV photocatalyst systems. With
ultrasound, complete degradation was achieved in 4 hours while in the absence of ultrasound, only 79%
degradation was achieved. A third example is the use of ultrasound with copper oxide (CuO) catalyst. Guo et
al. found that the degradation rate of 2,4-dinitrophenol after 4 hours of ultrasonic irradiation increased from
14% to 96% in the presence of CuO/H2O2/air.

The economics study of sonolysis concluded that sonolysis alone is not sufficiently cost effective for
water treatments for both organic pollutants and inorganic pollutants. However, sonolysis can be used as an
auxiliary tool for AOPs such as increasing OH- radicals production in Fentons Process explained above to
allow more economical and more efficient AOPs.

6.

Electrochemical Treatment

Electrochemical has been found to be more effective than conventional treatments in removing organic
compounds as well as nitrates. Organic compounds are removed by electrochemical oxidation at the anode.
Oxidation can occur directly on the anode surface, as well as indirectly when electrochemical method is
incorporated with oxidizing agents.

One example is by oxidizing chlorine into hyprochlorous acid, which then oxidizes organic matter.
However oxidation of organic compounds by hyprochlorous acid produces organochlorine compounds, which
are carcinogenic in nature. Another effective method is the incorporation of electrochemical treatment with
Fentons method. In this method, the ferrous ions can be continuously regenerated, hence allowing economical
and efficient removal of organic compounds when compared to the conventional Fentons process.

20

For the performance of direct anodic oxidation process, it was found to have high COD and BOD
removal of 92.4% and 78% respectively from pond water. However, this method is extremely expensive due
to the use of Ti/RuO2-TiO2 anode. Several performance of direct and indirect anodic oxidation obtained from
experiments are listed below.

Table 6.1: Organic Compound Removal from Different Wastewater Types using Different Anode and
Cathode Materials.
Anode/Cathode Material
Ti / Ti
BDD / BDD

Type of Wastewater
Aquaculture Wastewater
Seawater containing chlorine ion

Results
97.3% Organic Compound removal
88% COD removal

Other than the above, electrochemical method may also be added to biological treatment systems, and
it is known as bio-electrochemical technology. These systems use microorganisms as catalyst for
electrochemical reactions. These systems are divided into two major groups. One which is microbial fuel cell
(MFC), which produces electrical energy from organic material in waste water, and the other one is microbial
electrolysis cell (MEC), which utilizes external electricity to convert organic materials into other products.
These systems are considered as clean technology as it produces much less sludge than conventional systems.
The following table shows the performance of bio-electrochemical oxidation of organic matter.

Table 6.2: Performance of Bio-electrochemical Oxidation of Organic Matter from Synthetic


Wastewater for Different Anode and Cathode Materials.
Anode / Cathode Material
Graphite / Graphite
Graphite / Graphite
Graphite / Bio-Cathode

Type of Wastewater
Synthetic Wastewater

Results
93.6% Organic Matters Removal
74.2% COD removal
98.8% COD removal

Conclusion
As a conclusion, the treatment technologies for organic wastewater of past, present and future were reviewed
and evaluated. This includes a variety of technologies such as biological treatment, chemical oxidation
technologies, adsorption technology and the others were introduced. There are many more other technologies
that cannot be covered within the scope of this report. Furthermore, each of these technology, old or new, are
still being researched and studied upon until this day. This shows that no single technology is perfect and there
is still ample room for improvement in the future.

21

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