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Biochemical Oxygen Demand (BOD) & Chemical Oxygen Demand (COD) Reduction in POME
Biochemical Oxygen Demand (BOD) & Chemical Oxygen Demand (COD) Reduction in POME
JUNE 2018
INVESTIGATION OF THE PERFORMANCE
OF ULTRASONIC BATH, FERRIC CHLORIDE
AND CHITOSAN COUPLED WITH
ACTIVATED CARBON FOR TREATMENT OF
PALM OIL MILL EFFLUENT
JUNE 2018
UNIVERSITY COLLEGE OF TECHNOLOGY SARAWAK
__________________________ __________________________
(WONG GING KING) (DR.LEE MAN DJUN)
i
DECLARATION
I hereby declare that this project report is the result of my original work except for
citations and quotations which have been duly acknowledge. I also declare that it has not
been previously and concurrently submitted for candidature of any other degree in
University College of Technology Sarawak or other institution.
Signature :
Name :
ID. No :
Date :
ii
Approved by,
Signature :
Supervisor :
Date :
iii
iv
The copyright of this report belongs to the author under the term of copyright Act 1987 as
qualified by Intellectual Property Policy of University College of Technology Sarawak.
Due acknowledgement shall always be made of the use of any material contained in, or
derived from, this report.
ACKNOWLEDGEMENTS
First and foremost, I would like to express my greatest gratitude towards my supervisor, Dr. Lee
Man Djun, for his patient guidance, advice, motivation and encouragement he has offered
throughout my final year project period. Under his supervision, I managed to finish my research
with satisfying result. I would like to thank my co-supervisor, Dr. Augustine Chioma Affam, for
knowledgeable advices and useful informations he has given during my experiment. Without
him, I cannot finish my experiment in time.
My appreciation extends to the lab technician, Miss Regina, who always helped me in the
laboratory in term of equipment and procedure when using the equipment. Her dedication in
working make my research went smooth all the way until it is completed.
Last but not least, nobody has been more important to me in the pursuit of this research
than my family members. Their fully support gave me a sense of recognition and determined to
continue my research until I achieve my objective.
vi
ABSTRACT
The present study investigate the pollutants removal in palm oil mill effluent (POME) by
using advanced oxidation process, coagulation treatment and adsorption treatment. Palm
oil mill effluent is classified as highly contaminating wastewater as it contains high level
of chemical oxygen demand (COD) and biochemical oxygen demand (BOD). In
Malaysia, more than 85% of palm oil mills adopt ponding system to reduce the
biochemical oxygen demand of POME due to its low equipment cost and easy to operate.
However, ponding system requires long hydraulic retention time, huge land, release
greenhouse gases (methane) and most importantly, many mills are unable to achieve the
discharge limit. Owing to this, attempt is made to find an efficient treatment method to
polish bio-treated pome before discharging. In this investigation, ultrasonic technology,
natural and synthetic coagulants (chitosan and ferric chloride) and activated carbon have
been used. At defined optimum experimental conditions (Ultrasound cavitation: pH:11,
time:60min; Chitosan: dosage:100ppm, pH:4.5; Ferric chloride: dosage:450ppm, pH:5;
Activated carbon: dosage:4000ppm), the hybrid treatment of ultrasound cavitation +
ferric chloride + activated carbon are able to remove BOD 5, COD, colour and total
suspended solid up to 89.74%, 88.05%, 99.9% and 99.5%, respectively. The final value
of these parameters are within the discharge limit set by Department of Environment.
Chitosan is recommended to be used in reducing the pollutant in wastewater which
mostly contributed by suspended solid and palm oil mill can produce activated carbon by
using their by-product which is kernel shell.
vii
TABLE OF CONTENTS
DECLARATION I
ACKNOWLEDGEMENTS IV
ABSTRACT V
TABLE OF CONTENTS VI
LIST OF TABLES XI
CHAPTER 1 1
INTRODUCTION 1
CHAPTER 2 7
LITERATURE REVIEW 7
CHAPTER 3 29
ix
METHODOLOGY 29
3.1 Introduction 29
CHAPTER 4 36
4.1 Introduction 36
CHAPTER 5 57
5.1 Conclusions 57
5.2 Implications 59
5.3 Recommendations 60
REFERENCES 61
APPENDICES 68
LIST OF TABLES
Table 1: Characteristic of Raw and Treated POME and DOE Discharge Limit.................3
Table 2: Parameter Limits for Watercourse Discharge.......................................................8
Table 3: Characteristic of Different Sources of Wastewater.............................................10
Table 4: Properties of Raw POME....................................................................................12
Table 5: The Application of AOPs for POME Polishing..................................................19
Table 6: The Application of Membrane Technologies for POME Polishing....................22
Table 7: Application of Adsorption for POME Polishing.................................................23
Table 8: Application of Coagulation-flocculation for POME Polishing...........................25
Table 9: List of Equipment................................................................................................33
Table 10: Design of Experiment........................................................................................35
Table 11: Ultrasound Cavitation + Chitosan.....................................................................50
Table 12: Ultrasound Cavitation + FeCl3 Treatment.........................................................50
Table 13: Ultrasound Cavitation + (FeCl3 + Chitosan Treatment)....................................51
Table 14: US + Chitosan + FeCl3 Treatment.....................................................................51
Table 15: US + FeCl3 + Chitosan Treatment.....................................................................52
Table 16: Comparison of Sample POME, DOE Discharge Limit and Treated POME.....55
xiii
LIST OF FIGURES
CHAPTER 1
INTRODUCTION
In Malaysia, palm oil mill industry is a major industry sector and play a significant role in
Malaysia’s economy. Malaysia is one of the largest palm oil producer in the entire world.
Other main palm oil production country are Thailand, Indonesia, Columbia and other
tropical country [1]. Malaysia contributes about 39% of the world palm oil production
and also 44% of palm oil world export [2]. Therefore, palm oil is a very important sector
in Malaysia and significantly affect the gross domestic product (GDP) of Malaysia.
Due to the importance of palm oil industry, large area of land have been
converted into oil palm plantation estate at the same time more and more palm oil mill
have been built to process the increasing amount of oil palm fresh fruit bunch (FFB) into
crude palm oil. In Malaysia, there are 400 hectares land is planted with oil palm in year
1920, subsequently with 54,000 hectares in year 1960, 2,692,286 hectares in year 1996
and 5,229,739 hectares in year 2013. At year 2011, a record of total 426 palm oil mills
are in operation in Malaysia with 250 mills in peninsular Malaysia and 176 mills in
Sabah and Sarawak[1]. The growth of the industry at the same time indicates the
2
increasing of waste water or palm oil mill effluent (POME) produced and being released
into the watercourse which will bring harm to the environment.
The process of extracting crude palm oil from the fresh fruit bunch consumes a lot
of water and therefore produce large volume of waste water. In Malaysia, a record of 0.67
cubic meters of POME will be generated in order to process one ton of FFB [1]. It is
approximate 5-7.5 tons of water is required to produce one ton of crude palm oil and
more than 50% of these water would become POME [2]. It is approximately 48-72
million tons and 49-74 million tons POME were generated in year 2013 and 2014
respectively. In year 2014, it was estimated 19.66 million tons of crude palm oil produced
with approximately 44 million cubic meter of POME generated [3].
The most popular method to treat the POME in Malaysia is ponding system as its
low equipment cost and easy to operate. In Malaysia, there are more than 85% of palm oil
mills adopt this method to reduce the BOD of POME into an acceptable limit which is
less than 100mg/L in West Malaysia and 50mg/L in East Malaysia. In ponding system,
3
the POME is undergo biological treatments which include anaerobic digestion process
followed by aerobic ponding with hydraulic retention time of 40 days or above.
However, ponding system also cause some drawbacks which are long hydraulic
retention time (HRT), huge land needed and the release of greenhouse gases (methane).
There are also many palm oil mills which are unable to achieve the discharge limit by
using ponding system.[3]. Table 1 shows the characteristic of raw and treated POME
obtained from the discharge point of local palm oil mill in Malaysia and also DOE
discharge limit. The BOD is higher than the discharge limit set by Department of
Environment (DOE) [2].
Table 1: Characteristic of Raw and Treated POME and DOE Discharge Limit [2]
According to DOE, if untreated POME is discharged into watercourse, these POME will
undergo biodegradation and used up dissolved oxygen in the water which will kill the
fish in the river. Excessive nitrogen discharge can pose several pollution and health
issues. Nitrogen in the form of ammonia will create oxygen demand on a receiving
stream. Ammonia itself is high in pH and also toxic to fish. The nitrogen discharged will
enhance the growth of algae (eutrophication). Furthermore, the presence of nitrates in
drinking water can cause methemoglobinemia or blue baby syndrome. The high
concentration of suspended solid will settle to the bottom of the river and undergoing
biodegradation which cause sludge oxygen demand (SOD) and deplete the dissolved
oxygen.
The untreated POME which is acidic will cause the watercourse turns acidic and
affect the aquatic life. The oil content in untreated POME will form a thick layer on the
water surface which prevent absorption of oxygen. The dark brown colour and smelly
POME will turn the stream into brownish and unsuitable for public consumption. The
smelly stream is objectionable to most people. Other than that, raw untreated POME will
has high temperature up to 85oC. High temperature will has lower oxygen concentration
which subsequently affect aquatic life.
In this aspect, the central concern for this study is to reduce the BOD and COD in the
palm oil mill effluent (POME) by using ultrasound cavitation, coagulants and absorbent.
The main objective of this study is to degrade the palm oil mill effluent (POME) through
the combination of ultrasound cavitation with natural and synthetic coagulants (chitosan
and ferric chloride) coupled with absorption by activated carbon. In particular, the
specific objective of such project is defined as:
This study is to decrease the pollutant in the POME to minimal amount before discharged
into the watercourse. This is done by applying the tertiary polishing to the conventional
treated POME. The tertiary polishing method in this study is the combination of
advanced oxidation process, coagulation process and adsorption process. An effective
POME polishing method will ensure the palm oil mill discharge their POME which meet
the discharge standard.
6
The particular scope of study toward investigating the optimum condition for
different coagulants, adsorbent and ultrasound cavitation in POME polishing to reduce
biochemical oxygen demand (BOD) and chemical oxygen demand (COD):
This study aim to decrease the pollutant in the POME to minimal amount before
discharged into the watercourse. The decrease of pollutants in the POME discharged into
the watercourse will bring less impact to the environment as well as the society. This is
because clean water is significant in daily operation of various activities in the society.
Additionally, natural coagulant used together with the synthetic coagulant in the
coagulation process will decrease the demand of synthetic coagulant. Natural coagulant is
biodegradable while synthetic coagulant is non-biodegradable.
Besides, this study could help the palm oil mill industry effectively decrease the
BOD and COD of POME discharged until the discharge parameter or even lower at lower
cost. This will help the palm oil mill operator comply with Department of Environment
discharge parameter and at the same time maximize the revenue of the palm oil mill.
In term of economy, palm oil industry is a big industry in producing edible oil to
the world consumer. However, there are many products aims to eliminate the usage of
palm oil in their products. This is due to the awareness of the impact of processing oil
palm which produce pollutant which bring harm to the environment. However, if these
pollutants can be effectively treated before discharged, these concerns can be overcame.
Malaysia as a major palm oil production country would definitely benefited from this.
7
CHAPTER 2
LITERATURE REVIEW
The POME generated generally a thick brownish liquid which consists of 95%-96% of
water, 0.6%-0.7% oil and 4-5% of total solids including 2-4% suspended solids. The raw
POME generated is normally hot with temperature about 85oC. Table 2 shows the
department of Environment (DOE) discharge limit [1]. Figure 1 shows the discharge limit
of BOD set by Department of Environment (DOE) since year 1978. The more strictly
discharge limit is set by authority due to the increasingly awareness of society toward the
quality of environment.
8
4000
3000
2000
1000
0
1978 1979 1980 1981 1982 1983 1984 -2017
Year
In a palm oil mill operation using conventional manufacturing process, there are three
major processing operations responsible for producing the POME are sterilization of
FFB, clarification of the extracted crude palm oil and hydro-cyclone separation of
cracked mixture of kernel and shell.
mesocarp to ease the oil extraction. This station contributes approximately 36% of total
POME [1].
Clarification process is to separate the oil produced from the press station which
is mixed with water and solid from the bunch fiber. The oil is normally separated from
the mixture in the clarifier tank by the use of gravity, de-sander and also decanter. This
station contribute the majority part of the POME which is 60% [4].
The nuts from the nut silo are cracked in a nut cracker called ripple mill. These
cracked kernel and shell mixture is separated in air columns and by a water bath in
hydrocyclone. This station produces around 4% of POME. The POME generated from
sterilizer condensate, clarification of oil and hydro-cyclone is in the ratio of 9:15:1 (36% :
60% : 4%). Table 3 shows the characteristics of different source of waste water in palm
oil mill that combined to produce POME [1].
In term of organic content, based on the biochemical oxygen demand (BOD), raw POME
has an average BOD of 25,000mg/L. Raw POME is highly acidic. Biodegradability of
effluent can be determined from BOD/COD ratio. COD stands for chemical oxygen
demand. BOD/COD ratio indicate the fraction of chemically oxidized organics which is
eligible for biological degradation. In East Malaysia, the POME is discharged when the
BOD is less than 50mg/L as required by Department of Environment (DOE).
The pollution load of POME generated in a palm oil mill in a day can be
calculated as following Equation (1) and (2):
m3
POME Flow Rate , x Concentration , mg/ L
kg d
Pollution Load , =
d 1000
(1)
m3 ton FFB
POME Flow Rate , =Process capacity x Process Efficiency , %
d h
h m3
x Operating Hours , x POME generated ,
d ton
(2)
The POME from different mills would different characteristics. The factors that make the
characteristic of POME different include oil extraction technique, FFB quality, climate,
12
condition of palm oil processing and mill requirement on POME discharge limit are
possible reasons for the dissimilarity [4].
POME is a mixture of water (up to 95%), oil and fine suspended solids [5]. The
suspended solid are vegetative matter such as cell walls, organelles, short fibers, water-
soluble carbohydrates (glucose, reducing sugar and pectin), nitrogenous compound
(protein and amino acid), free organic acid, lipids and also the combined small organic
and mineral constituents [6]. The POME is non-toxic as the palm oil mill does not use
any chemical in the entire milling process. [1]
The natural chemical properties of the POME make it easily treated by biological
approach. Currently there are three biological processes employed in the palm oil
industry which are anaerobic, facultative anaerobic, and aerobic treatments. The
anaerobic treatment is the major part which in removing pollutant (BOD). Anaerobic
treatment can remove BOD up to 95% [8]. In anaerobic treatment process, it involved
four main stages which are hydrolytic, acidogenic, acetogenesis and methanogenic.
Hydrolysis: The process begin with bacteria hydrolysis of insoluble organic polymers
(carbohydrate) and complex organic compound (protein and lipid) to make them
available for other bacteria. Hydrolytic microorganisms will secrete extracellular
enzymes for hydrolysis. This process will convert organics into simpler molecule such as
amino acids, glycerol, triglycerides, sugar and fatty acids.
Acidogenesis: In this process, the hydrolyzed or soluble products from the first stage are
further broken down by acidogen into simpler organic compound such as volatile fatty
acid (VFA), ammonia, carbon dioxide, hydrogen and hydrogen sulfide.
Acetogenesis: The simple molecule from the previous stage are further digested by
acetogens to produce carbon dioxide, hydrogen and acetic acid.
Methanogenesis: The acetic acid, hydrogen and volatile fatty acid (VFA) are converted to
methane, carbon dioxide and water by methanogens.
14
In constructing the ponds, the depth is the main consideration for different ponds.
The length and the width is differ based on the availability of the land. The optimum
depth for the anaerobic pond is 5-7m, facultative anaerobic pond is 1-1.5m and aerobic
pond is 0.5-1m. The effective hydraulic retention time (HRT) of anaerobic, facultative
anaerobic and aerobic ponds are 45, 20 and 14 days, respectively [8].
The problems arise from the ponding system is the formation of scum. Scum is
formed when the bubbles rise to the surface together with the fine suspended solids. This
is caused by the by the oil and grease presence in the POME. Another drawback of the
ponding system is the solid sludge accumulates at the bottom of the ponds. This will
affect the effectiveness of the pond as it decrease the volumetric capacity and hydraulics
retention time (HRT) [8]. Therefore, de-sludging is required when the sludge is more
than one third of the pond.
This treatment combines an open digester tank with a series of ponds. Digester tank can
be built with various volumetric capacities ranging from 600 until 3600m3. In this
treatment method, digester has same function as anaerobic pond. It carries out the
anaerobic digestion. The output of the POME from digester will then enter facultative
anaerobic ponds and then algae (aerobic) ponds.
15
Digester can decrease the BOD in a shorter time than pond. The hydraulics
retention time (HRT) for digester is only 20-25 days which is a lot shorter than anaerobic
ponding system. Although it is proven that the digester is more effective than anaerobic
ponds, it brings some drawback to the operator. The disadvantages of digester include
scum formation on the top, sludge accumulation at the bottom and the corrosion of the
steel structure of the digesters due to long exposure to hydrogen sulfide. There are
incidents which reported that the digester burst and collapsed [8].
In these few years, there are many researches were conducted to investigate alternative
POME treatment technologies especially tertiary treatment. The technologies that are
widely investigate are adsorption, coagulation or flocculation, membrane filtration and
advanced oxidation processes. Most of these investigations are in laboratory scale but
they show potential to overcome the drawback of conventional ponding system [2].
Figure 2 shows the overview of recent POME polishing technologies.
16
Advance Oxidation Processes (AOPs) are the processes which degrade the organic
pollutant by the powerful and reactive hydroxyl radical (OH∙). Hydroxyl radical (OH∙)
generated would have oxidation potential of 2.8eV [9]. OH∙ can be generated through
either one or a combined of chemical oxidation by using H2O2, ozone, ultrasound and
radiation assisted source (ultraviolet) [10]. During the treatment of waste water, OH∙ will
attack the organic pollutants and convert them to CO 2, H2O and inorganic salt [11]. AOPs
can effectively degrade the pollutants and have its advantages of non-selectively,
mineralization of pollutants and ease of operation compared to the conventional methods.
cavitation uses ultrasound to oxidize the pollutants. AOPs are more effective when
combined two or more AOPs together due to more OH∙ is generated, lower catalyst
consumption and shorter process time [15]. AOPs have been successfully adopted as
tertiary treatment of wastewater such as olive oil mill wastewater (OOWW),
agrochemicals, pulp and paper, textile wastewater and pharmaceutical [2].
2.6.1.1 Photo-catalysis
For photo-catalysis, it uses a semiconductor metal oxide and irradiation to degrade the
recalcitrant pollutants in waste water. Metal oxide in aqueous suspension is illuminated
with irradiation which have photon energy (hv) equal to or greater than its band gap
energy. This process will generate valence band holes and conduction band electrons
which can react with water and hydroxyl ion to generate OH∙.
Among all the potential catalysts for photo-catalysis, TiO 2 is most used, as it has
good chemical and thermal stability, strong mechanical properties, super-hydrophilicity
and low excitation energy (3.2eV). However, TiO2 is only limited to UV radiation
application as it has wide band gap. The effectiveness of photo-catalysis depends on
photo-catalyst and the radiation source intensity [16]. A research is conducted by using
UV-responsive TiO2, 10g/L TiO2 and 70mL/min O2 was able to remove 52% of COD
[16].
For Fenton oxidation, it is a process which uses the reaction between Fe 2+ and H2O2 to
produce OH∙ [12]. Fenton oxidation experiment conducted by Saeed [17] removed COD
up to 85% under optimum condition of pH 3.5 at the reaction time of 90 min. Another
18
Solar-Fenton oxidation is another new polishing technology which use direct solar
irradiation. Solar-Fenton oxidation showed COD and colour removal as competence as
conventional Fenton oxidation as it is slightly higher than conventional Fenton [2]. This
is important as it can increase the efficiency of the process by decreasing the H 2O2
demand at the same time decrease the treatment cost.
For ultrasound cavitation, cavitation is the formation, growth and subsequent collapse of
bubbles over a small time period which resulting in the generation of large magnitudes of
energy over specific location [3]. There are four types of cavitation which are acoustic
(ultrasound), hydrodynamic, optic and particle cavitation. Among these four types of
cavitation, acoustic cavitation and hydrodynamic cavitation is the most common and have
been investigated. US cavitation is occurring when a passage of very high frequency
sound wave of 16-100 kHz transmit through the waste water. Hydrodynamic cavitation is
occurring when a liquid is passing through a constriction. [2]. Figure 3 shows the
ultrasound cavitation bath.
19
Ultrasound cavitation which degrade the pollutants can occur either through
pyrolysis of pollutants or through the production of OH∙ [19]. Pollutants which are
volatile, non-polar and hydrophobic can easily enter into the cavitation bubbles and
exposed to the collapsing conditions of bubbles [3]. This make the pollutants degraded
through pyrolysis. Ultrasound cavitation is always combined with other AOPs or
physicochemical processes to enhance its water treatment efficiency [2].
Besides advance oxidation processes (AOPs), membrane technology is also one of the
popular polishing method of POME. The advantages of membrane technologies are high
removal rate, modularity, and ability to integrate with other water treatment method.
However, main drawback of membrane technologies is the membrane fouling which
causes reduction in permeate flus due to the surface and pore blocking of the membrane.
The high capital cost and high costly maintenance fee have limit the application of the
membrane. The most common membrane used in membrane technologies are
microfiltration (MF), ultrafiltration (UF), nano-filtration (NF) and reverse osmosis (RO)
[2].
There is an argument about membrane technologies can remove more COD from
POME compared to other technology. A study had shown that ultrafiltration membrane
was able to remove total suspended solid (TSS), COD and total dissolve solid (TDS) up
to 97.7%, 57% and 6.5% respectively at the high pressure of 0.8MPa. This pressure cause
the level of membrane fouling up to 85.8%. Higher pressure might have higher treatment
efficiency but at the same time have higher level of membrane fouling. The effectiveness
of membrane technologies in POME treatment is depends on the properties of the
membrane. Nano-filtration perform better than ultrafiltration but have higher level of
fouling compare to ultrafiltration. Membrane technologies can be combined with other
technology such as coagulation and flocculation to increase its treatment effectiveness
[2]. Table 6 shows the application of membrane technologies for POME polishing.
22
(adsorbate) is absorbed onto the surface of the adsorbent. Adsorption can be a reversible
process which offering possibility of adsorbent regeneration through desorption [35].
Adsorption mechanism mainly influenced by the physical forces (physisorption) or
chemical interactions (chemisorption) between the absorbent and adsorbate. The
adsorption will also be influenced by characteristics of the adsorbent such as specific
surface area, porosity and also surface charge. Chemical structure of the adsorbate and
environmental condition such as temperature, pH, solubility and ionic strength will
influence the adsorption performance [36].
FB/Resin: 3 - 72 64 - [42]
0.3mBH
BP/Zeolite: 10g/L 3 50 - - - [43]
For coagulation, it is commonly used as pretreatment to remove the organic matter and
suspended solid (SS) from the wastewater. In coagulation process, chemical is added into
the wastewater to enhance the flocculation and sedimentation. This can help in removing
dissolved solid and suspended solid from the wastewater. The chemical added for
coagulation normally aluminum and iron based compound.
The drawbacks of these chemical are high cost, non-biodegradable and possible
adverse effect of chemical. To overcome these drawbacks, natural and biodegradable
materials such as chitosan, cotton, moringa oleifera, natural seed gum and Jatropha
curcus seeds are employ in the investigation. The major drawback of coagulation
processes is a lot of sludge will be generated [2].
A research had shown that alum as coagulant can remove COD up to 59% in
optimum condition [44]. This low efficiency might cause by the short mixing time in the
study. Another research using poly-aluminum chloride (PAC) as coagulant was able to
remove COD of POME up to 93% [45]. The coagulation technologies can also combined
with other polishing technologies such as adsorption, membrane filtration and AOPs. A
research was conducted in a way of two steps process consisting of adsorption and
coagulation in the polishing of POME [39]. The POME was subjected to activated carbon
for adsorption before underwent coagulation using alum, FeCl 3 and PAC. Among these
three coagulants, FeCl3 was able to remove most COD and TSS in the POME. The
drawback of this treatment process is high treatment cost as activated carbon and
25
chemical coagulant are expensive. Low-cost carbon and natural coagulants such as
chitosan might be the alternative of the material used although the effectiveness of the
treatment might be lower. Table 8 shows the application of coagulation-flocculation for
POME polishing.
The conventional coagulants can be grouped into two categories which are aluminum
based and iron based (Renault et al, 2009). Coagulant such as Al(III) or Fe(III) can
remove higher molecular weight organic materials [49]. However, due to the concern of
26
high concentration of metal in the treated water could affect the health, application of
natural coagulant in water treatment is increasing nowadays [50].
The mechanisms involve in the coagulation can be divided into two main
categories which are charge neutralization or electrostatic interaction and sweep
coagulation/co-precipitation [55]. The chitosan coagulation process is charge
neutralization while ferric chloride (FeCl3) is sweep coagulation as shown in Figure 4
[56]. The flocs formed by charge neutralization are smaller than the flocs formed through
sweep coagulation [57]. The smaller sized flocs could bring fouling risk to the membrane
if membrane technologies is used.
27
A study was conducted by Ahmad in year 2005 by using chitosan to adsorb the oil
in the POME [54]. The result showed that the chitosan has excellent performance in
adsorbing the oil in lower dosage due to its high charge density. Chitosan can effectively
adsorb the oil in acidic condition (pH 4.5 and below).
remove same amount of residue oil. Chitosan required dosage which 10 times less
synthetic coagulants. Chitosan is very competence in treating POME as it require low
dosage and at the same time environmental friendly.
From the researches that had been conducted. The following gaps were found:
In this study, all these POME treatments (US, coagulation and adsorption) are combined
to achieve maximum efficiency of COD removal in POME.
29
CHAPTER 3
METHODOLOGY
3.1 Introduction
This chapter is presenting the body of research methodology which include materials,
methods adopted, experiment procedures, tests conducted, safety, safety measure, quality
control and quality assurance. All these elements are control to obtain the result with high
consistency and precision.
30
The POME samples (aerobic pond) were collected from one of the palm oil mill in
Sarawak, Malaysia. The POME were freshly collected when needed as shown in Figure
6. Samples collected might be different from day to day due to climate and condition of
the palm oil processing.
The sample POME was tested before and after every treatment. The tested parameter
include chemical oxygen demand (COD), five-day biochemical oxygen demand (BOD5),
total suspended solid (TSS) and colour. The equipment used to carry out the experiment
are listed as shown in Table 9.
COD was measured according to the Hach method (Method 8000) using Hach
reagent. Colorimetric determination of COD was carried out at 620nm using a Hach
spectrophotometer DR 6000 as shown in Appendix-3.
32
The BOD5 was determined according to the Standard Method 5210 B. Dissolved
oxygen (DO) was measured by an YSI 5000 dissolved oxygen meter as shown in
Appendix-4.
TSS was determined according to the Standard Methods Section 2540 D. Total
Suspended Solids were dried at 103-105oC as shown in Appendix-6.
Colour was measured according to the Hach method (Method 8025). Colorimetric
determination of colour was carried out at 620nm using a Hach spectrophotometer DR
6000 as shown in Appendix-5.
Samples collected is tested to analyst its characteristic before the treatment start. Chitosan
were supplied by a local manufacturer. This chitosan was soluble in 1% diluted acetic
acid. FeCl3 were obtained from a local manufacturer in granule form. FeCl3 is dissolved
in distilled water. Granule activated carbon is crushed and sieved to get the size which
less than 75micrometer.
The experiment will be started with ultrasound cavitation treatment to identify the
optimum pH and time, followed by coagulant chitosan to identify optimum dosage,
coagulant FeCl3 to identify optimum pH and dosage as well as adsorbent activated
carbon to find out the optimum dosage. After the optimum conditions were defined,
ultrasound cavitation, chitosan and ferric chloride were combined in different order to
investigate the best combination in removing the pollutants. After the best combination
was identified, activated carbon adsorption was added as the last stage of treatment as
shown in Table 10.
34
35
A B C
Ultrasound Cavitation Chitosan FeCl3
pH: 3, 5, 7, 9,11 Dosage (mg): 10, 20, 40, Dosage (mg): 30, 60, 90,
80, 160, 320 120, 150, 180
Time (min): 30, 60, 90,
120, 150, 180 pH: 4.5 pH: 3, 5, 6, 7, 8, 11
Volume: 200mL Volume: 200mL
Volume: 200mL Mixing Time (min): 15 Mixing Time (min): 15
Settling Time (min): 60 Settling Time (min): 60
D E F
Activated Carbon Hybrid US, Chitosan and Hybrid ‘E’ and AC
Adsorption FeCl3 Adsorption
Dosage (mg): 160, 320, Dosage (g/L): A, B, C Dosage (g/L): E, D
480, 640, 800, 1600, 2400,
3200, 4000 pH: A, B, C pH: E
CHAPTER 4
4.1 Introduction
This chapter is discussing the results obtained from the experiment of waste water
treatment. The treatments include ultrasound cavitation, chitosan coagulation, ferric
chloride coagulation and activated carbon adsorption. The parameters used to defined the
treatment efficiency include BOD, COD, pH, and TSS.
The POME was treated in ultrasound cavitation bath. The POME was treated with
different pH (3-11) and different cavitation time (30 - 180 min) to obtain the removal in
term of COD and colour at its optimum condition.
37
The POME was adjusted with sulphuric acid (H 2SO4) and sodium hydroxide (NaOH) to
achieve each pH .About 200mL of POME was prepared with pH of 3, 5, 7, 9 and 11. The
temperature was set at the room temperature of 23.5 oC and the cavitation reaction time
was 60 minutes.
20
COD Removal, %
15
10
0
2 3 4 5 6 7 8 9 10 11 12
-5
pH
From Figure 7, it shows that the pH (3, 5, 7, 9) does not show significant COD removal.
This small percentage of removal are due to the errors such as preparation of COD
reagent and nature surface of tubes.
38
The 200mL of POME is left for cavitation for different durations which are 30, 60, 90,
120, 150, 180 minutes. The temperature is set at the room temperature which is 23.5 oC
and the pH is set as 11. The COD of the each sample before and after experiment is
measured and recorded.
60
60; 52.74
50
Percentage, %
40
Colour Removal
30 60; 26.32
COD Removal
20
10
0
0 30 60 90 120 150 180
From Figure 8, it shows that the COD and colour removal is increasing when the
cavitation time increased until it reached its highest removal which is 26.32% and
52.74% at 60 minutes. The further increase in time does not significantly increase the
COD and colour removal. The COD and colour removal rates fluctuate when the
cavitation time is longer than 60 minutes.
39
From the results of experiments conducted, the best condition for ultrasound cavitation
treatment is 60 min of cavitation time and pH of 11. The COD removal is 26.32% and
color of removal is 52.74% for this treatment duration. The further increase of treatment
time does not significantly increase the COD and colour removal.
The sample was allowed to sediment for 90 min and the top portion of water is
collected to measure its COD, color intensity and TSS.
40
The 200mL of POME with pH of 4.5 is prepared for chitosan coagulation treatment.
Different dosages of chitosan (10mg, 20mg, 40mg, 80mg, 160mg, 320mg) were added to
the POME to coagulate the pollutant. The COD, colour and TSS of the each sample
before and after experiment is measured and recorded.
41
97
100 85.79
50
Percentage ,%
Colour Removal,%
15.39
TSS Removal,%
0
0 50 100 150 200 250 300 350 COD Removal,%
-50
-108.87
-100
-150
Chitosan Dosage, mg
Figure 10: COD, Colour and TSS Removal against Chitosan Dosage
From Figure 10, the colour removal and TSS removal are very effective as its
removal rate increased to 85.79% and 97% respectively at dosage of 20mg. The further
increase of chitosan dosage does not significant increase the color and TSS removal rate.
The colour and TSS removal rate fluctuates when any addition of chitosan after 20mg.
On top of that, the COD removal is not significant by using chitosan as coagulant.
The highest COD removal is 15.39% at 20mg. The further increase in dosage will cause
the negative result of COD removal.
42
From the result of the experiment, the optimum condition for coagulation treatment using
chitosan as coagulant is 20mg for 200mL of POME (100ppm) at pH 4.5. The COD
removal, colour removal and TSS removal is 15.39%, 85.79 and 97%. The further
increase in dosage does not significantly increase the colour and TSS removal. At the
same time, further increase in dosage will cause the COD to increase.
The negative result of COD removal was observed when further addition of
chitosan. It is believed that the chitosan is a kind of natural biopolymer coagulants in
which itself is the impurities which cause COD to increase when the dosage exceed the
saturation point. The COD removal is not high enough is caused by the natural properties
of POME. A study from Musonge stated that the chitosan is not effective in removing
dissolved solid [58]. Raw POME has the total solid of 40000 mg/L while 34000 mg/L of
them is dissolved solid [2]. On top of that, TSS removal is also very effective at low
dosage. This TSS removal result have the same trend with the research that had been
conducted by Ahmad [47]. Chitosan can effectively remove colour and TSS, but not
COD as it can only remove COD which is contributed by total suspended solid (TSS), but
not total dissolved solid (TDS).
The POME was added with sulphuric acid (H2SO4) and sodium hydroxide (NaOH) to
produce the sample with different pH .The 200mL of POME is prepared with pH of 3, 5,
6, 7, 8, and 11. 50mg of FeCl3 is added into the POME to coagulate the pollutants. The
COD, colour and TSS of the each sample before and after experiment is measured and
recorded.
60.00
50.00 Colour Removal, %
COD Removal, %
40.00
5; 35.56
30.00
20.00
10.00
0.00
3 5 6 7 8 11
pH
From Figure 11, both the COD removal as well as colour removal is effective
when pH is less than 5. The COD and colour removal is increasing when the pH was
increased from 3 until it reach its peak which is pH5. At pH 5, the COD and colour
removal are 35.56% and 88.51% respectively. The further increase in pH caused both
COD and colour removal to decrease gradually until 7.89 and 20.46%. Figure 12 shows
the POME treated at different pH. From left, pH 3, pH 5, pH 8, pH 11 and raw POME.
44
100 90;88.64
91.5
90;
80
Percentage, %
Color removal, %
60
COD Removal, %
90; 38.54 TSS Removal, %
40
20
0
0 30 60 90 120 150 180
Figure 13: COD, Color and TSS Removal against Ferric Chloride Dosage
Figure 13 shows that the COD and colour removal showed similar trend in which
the removals are increasing when the dosage of FeCl3 is increased until it reached 90mg.
The removal at 90mg are 38.54% and 88.64% respectively. The further increase of the
FeCl3 dosage does not significantly increase those removal. COD, and colour removal
rate drop slightly and fluctuate when the FeCl3 is added after 90mg.
For TSS removal, the removal is also increasing when the dosage of FeCl3
increases until it reach 90mg with removal of 91.5%. Any further increase in FeCl3
dosage after 90mg does not significantly increase then TSS removal.
46
From the result of the experiment, the optimum condition for coagulation treatment using
FeCl3 as coagulant is 90mg for 200mL of POME (450ppm) at pH 5. The COD removal,
colour removal and TSS removal is 38.54%, 88.64 and 91.5% respectively.
The experiment was conducted by using different amount of dosage. The dosage is
ranging from 160mg to 4000mg. Granule activated carbon is crushed and sieved to get
the AC size of less than 75micrometer. The smaller particle size of adsorbent provided
larger specific surface area for adsorption to occur [36].
Jar tester is used to stir the sample. The stirring speed is maintained at 200rpm
and the stirring time is 60 minutes. The experiment is conducted at room temperature of
23.5oC. The sample is filtered to separate the AC and POME. The filtered POME is
collected to measure its COD, color intensity.
added to the POME to adsorb the pollutant. The COD and colour of the each sample
before and after experiment is measured and recorded.
99.16
100.00
80.00
Percentage, %
64.25
60.00 Color removal, %
COD Removal, %
40.00
20.00
0.00
0 500 1000 1500 2000 2500 3000 3500 4000 4500
Figure 14: COD and Colour Removal against Activated Carbon Dosage
In Figure 14, the COD and colour removal have similar trend as they are
increasing as the dosage of activated carbon (AC) increases. Both COD and colour
removal increase until they reach the saturated point which is 800mg of AC. At 800mg,
COD and colour removal are 64.25% and 99.16% respectively. Further increase in AC
dosage does not significantly increase either COD or colour removal. The removal rates
fluctuate when further increase of dosage after 800mg of AC.
48
From the experiment conducted, the result shows that the best adsorption occurs at
800mg of AC for 200mL of POME (4000ppm). At 800 mg, the COD and colour removal
are 64.25% and 99.16%. 99.16% of colour removal is very high as the colour of the
treated POME is very clear. The colour of AC treated POME with dosage of 160mg,
320mg, 480mg, 640mg and 800mg are as shown in Figure 15.
The COD and colour removal are increasing when the dosage of AC increase can
be explained as the increase of the specific surface area of the AC available [36]. The
specific surface area could be increased by increasing the dosage of activated carbon. The
larger specific surface area, the higher the rate of absorption.
In this study, ultrasound cavitation, chitosan and FeCl3 are combined in different ways to
find out the best combination and order of treatment. Every treatment method is
conducted by following the result of optimum condition obtained from previous
experiment.
The sample before and after each set of experiment is collected to measure the COD and
colour. The readings obtained is used to calculate the COD and colour removal. The
results is observed and recorded.
POME is treated at ultrasound bath followed by coagulation by chitosan. The COD and
colour removal is recorded as shown in Table 11.
50
POME is treated at ultrasound bath followed by coagulation by FeCl 3. The COD and
colour removal is recorded as shown in Table 12.
POME is treated at ultrasound bath followed by coagulation by both FeCl 3 and chitosan
together. The COD and colour removal is recorded as shown in Table 13.
POME is treated at ultrasound bath followed by chitosan coagulation and then followed
by FeCl3 coagulation. The COD and colour removal is recorded as shown in Table 14.
POME is treated at ultrasound bath followed by FeCl 3 coagulation and then followed by
chitosan coagulation. The COD and colour removal is recorded as shown in Table 15.
The results obtained from the hybrid treatment is used to plot the graph as shown in
Figure 16.
53
COD Removal,%
Color removal, %
100.00
92.41 90.85 92.17
89.93
90.00 86.81
80.00
70.00
Percentage, %
60.00 56.26
50.00
38.39 40.12 38.61
40.00 35.10
30.00
20.00
10.00
0.00
US-Chitosan US-FeCl3 US-FeCl3+Chitosan US-Chitosan-FeCl3 US-FeCl3-Chitosan
Combination
Figure 16: COD and Colour Removal against Different Treatment Combination
From the graph, it is obvious that the COD removal for the combination of US
cavitation followed by FeCl3 coagulation treatment is the highest which is 56.26%. The
colour removal for this combination is also the highest among other combinations which
is 92.41%.
On top of that, among all these combinations where chitosan is present, the COD
removal is less satisfying. The removal is around 35.1% to 40.12%. This can be seen at
the combination of US – FeCl3 which have COD removal of 56.26%, however, when
chitosan is added after it, the COD removal drops to 38.61%. This is caused by chitosan
in as it is the natural coagulant which is biodegradable [52]. Chitosan was not very
effective in coagulating the organic pollutant (COD) which dissolved in the POME [58].
Therefore, chitosan will become the pollutant which contribute to COD and cause the
COD removal to decrease.
54
The US + FeCl3 treated POME is undergoing adsorption treatment by using AC. 200mL
of US + FeCl3 treated POME is added with 800mg of AC. The sample added with AC is
stirred at 200rpm for 60 minutes. The BOD5, COD, colour and TSS of the each sample
before and after experiment is measured and recorded.
Colour, COD, BOD5 and TSS Removal for Hybrid US + FeCl3+ AC Treatment
102.00
99.90 99.50
100.00
98.00
96.00
Percentage, %
94.00
92.00
89.74
90.00
88.05
88.00
86.00
84.00
82.00
Color removal, % COD Removal,% BOD Removal, % TSS Removal,%
Type of Removal
Figure 17: Colour, COD, BOD5 and TSS Removal for Hybrid US + FeCl3+ AC
Treatment
From the graph as shown in Figure 17, hybrid treatment of US, FeCl3 and AC
have achieve the COD, BOD, colour and TSS removal up to 88.05%, 89.74%, 99.9% and
55
99.5. AC adsorption is able to increase the efficiency of COD removal from 56.26% (US-
FeCl3) to 88.05% (US-FeCl3-AC).
The hybrid treatment of US-FeCl3-AC manage to decrease the COD, BOD, TSS, colour
and pH until it is below of the discharge limit which set by Department of Environment
(DOE). The COD removal efficiency (88.05%) decreased the COD from 962mg/L to
115mg/L. At the same time, BOD removal (89.74%) was able to reduce the BOD from
468mg/L to 48mg/L which is lower than the discharge limit (West Malaysia: 100mg/L,
East Malaysia: 50mg/L).
In addition, colour removal (99.9%) from 2055 PtCo reached to 2 PtCo while TSS
removal (99.5%) reduced from 200mg/L to 1mg/L. The data obtained are compared with
DOE discharge limit as shown in Table 16. The colour and TSS removal is very high as
the efficiency is nearly 100%. This shows that the colour and TSS in POME are easier to
be removed compared to BOD and COD.
Table 16: Comparison of Sample POME, DOE Discharge Limit and Treated POME
Figure 18 shows the colour of the POME at different stage of treatment. From
left, the first bottle is the raw POME, second bottle US treated POME, third bottle is US-
FeCl3 treated POME and the forth bottle is US-FeCl3-AC treated POME. The last bottle
of POME is crystal clear and its colour intensity was only 2 PtCo.
CHAPTER 5
5.1 Conclusions
Advance oxidation processes, coagulation treatment and adsorption treatment are widely
used in wastewater treatment as they can provide promising result in removing pollutants
in the wastewater. In this study, advance oxidation processes used is ultrasound
cavitation. For coagulation treatment, natural coagulant which is chitosan and synthetic
coagulant which is FeCl3 are used. Activated carbon is used in adsorption treatment. The
following are conclusion made from the present study.
Increasing in pH (>11) can increase the COD removal due to more hydroxyl
radical (OH∙) present in alkali.
The optimum time for ultrasound cavitation is 60 minutes.
The COD and colour removal at pH 11 with cavitation time of 60 minutes are
26.32% and 52.74% respectively.
Both chitosan and FeCl3 require acidic medium for coagulation. (pH4.5 and
pH5).
Acidic medium condition exaggerates POME to form unstable flocs [54].
200mL of POME treated with 20mg of chitosan at pH 4.5 is able to remove
15.39% of COD, 85.79% of colour and 97% of TSS.
200mL of POME treated with 90mg of FeCl3 at pH 5 are able to remove 38.54%
of COD, 88.64% of colour and 91.5% of TSS.
FeCl3 can remove COD better than chitosan.
Chitosan can only remove organic material which suspended in POME but not
dissolved solid.
Chitosan is a natural coagulant which is biodegradable and can cause COD to
increase when excess dosage is added.
Dosage of chitosan have to be selected carefully when it is used in COD
removing.
Both chitosan and FeCl3 can effectively remove colour and TSS from the POME.
Different type of POME treatments are combined in different ways and orders and
combination of US-FeCl3 provide best result. (COD removal: 56.26%, colour
removal: 92.41%).
Combination which contain chitosan would give lower COD removal.
59
5.2 Implications
The result of this study can be used as a reference for the palm oil mill industry if the
industry are trying to find other methods to decrease the pollutant in wastewater prior
discharged. This is due to the more stringent discharge limit set by DOE while many of
the mills which adopt conventional ponding system are not able to meet the required
limit.
If this study have been applied to the palm oil mill effluent treatment system, the dosage
of chemicals required will be lesser compared to the one used in this study. This is
because the sample of POME in this study is taken from aerobic pond which is not the
final discharge point. When the POME polishing plant is set up at the final discharge
point, the pollutant in POME are definitely lower and would require less dosage of
60
chemical. The ferric chloride coagulant and activated carbon adsorbent are able to be
recycled.
5.3 Recommendations
Based on the finding, it is recommended that chitosan to be used to treat the wastewater
in which its pollutant is mostly contributed by suspended solid. POME which have
dissolved solid a lot more than suspended solid is not suitable to be treated with chitosan.
In addition, chitosan which is biodegradable and can remove colour and suspended solid
effectively at very low dosage make it a promising material to be used in water treatment
industry which aim for colour and suspended solid removing.
Last but not least, although activated carbon requires high dosage in order to provide a
very high removal efficiency but it may not be a problem to palm oil mill if the mill is
interested to use it as one of the treatment processes. This is because the palm oil mills
are possible to produce activated carbon by themselves. During the palm oil milling
processes, furnace is used to heat the boiler to create steam in order to run turbine to
create electricity and 5% of the processed fruit will eventually become kernel shell which
is a type of by-product of the factory. Therefore, this is possible for the factory to take the
advantage of the existing resource to heat the kernel shell until it become carbon and
activated it by using the steam. Research and development worth to be done to achieve
this goal.
61
REFERENCES
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perspectives,” J. Environ. Manage., vol. 198, pp. 170–182, 2017.
[5] S. Manickam et al., “Role of H2O2in the fluctuating patterns of COD (chemical
oxygen demand) during the treatment of palm oil mill effluent (POME) using pilot
scale triple frequency ultrasound cavitation reactor,” Ultrason. Sonochem., vol. 21,
no. 4, pp. 1519–1526, 2014.
[6] J. O. Edewor, “A Comparison of Treatment Methods for Palm Oil Mill Effluent
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[26] B. R. Babu and K. S. Meera, “Removal of Fatty Acids from Palm Oil Effluent by
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[28] N. A. A. Amat et al., “Journal of Water Process Engineering Tackling colour issue
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[30] N. S. Azmi and K. F. Yunos, “Wastewater Treatment of Palm Oil Mill Effluent
(POME) by Ultrafiltration Membrane Separation Technique Coupled with
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( POME ) treatment and bioresources recovery using ultrafiltration membrane :
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November 2004, pp. 245–255, 2005.
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APPENDICES
Week
1 1 1 1 1
Task 1 2 3 4 5 6 7 8 9 0 1 2 3 4
Project Title and Proposal
Problem Statement
Literature Review
Research Methodology
Reference
Submission of Proposal
Proposal Presentation
69
Week
1 1 1 1
Task 1 2 3 4 5 6 7 8 9 0 1 2 3 14
Experiment to achieve
Objective
Result and Discussion
Conclusion and
Recommendation
Reference
Submission of Final
Report
Final Report presentation
70