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PERFORMANCE OF POWDERED AND GRANULAR SUGARCANE BAGASSE
ACTIVATED CARBON IN REMOVING POLLUTANTS OF CAR WASH
WASTEWATER
NADZIRAH BINTI ZAYADI
UNIVERSITI TUN HUSSEIN ONN MALAYSIA
PERFORMANCE OF POWDERED AND GRANULAR SUGARCANE BAGASSE
ACTIVATED CARBON IN REMOVING POLLUTANTS OF CAR WASH
WASTEWATER
NADZIRAH BINTI ZAYADI
A thesis submitted in
fulfillment of the requirement for the award of the
Degree of Master of Civil Engineering
Faculty of Civil and Environmental Engineering
University Tun Hussein Onn Malaysia
MARCH 2017
iii
DEDICATION
Every challenging work needs self efforts as well as guidance
of elders especially those who were very close to our heart.
My humble efforts I dedicate to my loving
PARENTS
Whose affection, love, encouragement and prays make me
able to get such success and honor,
Along with hardworking and respected supervisors
ASSOC. PROF. DR. Nor Haslina Binti Hashim
ASSOC. PROF. Prof Dr. Rafidah Binti Hamdan
ASSOC. PROF. Dr. Aeslina Binti Abd Kadir
iv
ACKNOWLEDGEMENT
In the name of Allah, The Most Gracious and Merciful, I would like to express my
sincere appreciation to my supervisor, Assoc. Prof. Dr. Nor Haslina Binti Hashim, my
co supervisor Assoc. Prof. Dr Rafidah Hamdan and Assoc. Prof. Dr. Aeslina Abd Kadir
for the support given through out the duration for this research. The cooperation given
by the Faculty of Civil and Environment Engineering at Universiti Tun Hussein Onn
Malaysia is also highly appreciated. Appreciation also goes to everyone involved
directly or indirectly towards the compilation of this thesis.
v
ABSTRACT
Water pollution is a challenge due to non source point of car wash wastewater, carries
toxicity with little water quality treatment. Among various technologies of membrane
application, oil separator and else, activated carbon is more promising. Research have
been focused towards converting the agricultural wastes of sugarcane bagasse or
Saccharum Officinarum into valuable product of activated carbon, due to adsorption
properties. The objectives of this study are to characterize the car wash wastewater,
optimized the activated carbon preparation and determine the optimum conditions for
powdered and granular sugarcane bagasse activated carbon of Langmuir and
Freundlich adsorption isotherms. In achieving the objectives, from wastewater
characterization, an average value of chemical oxygen demand (COD), oil and grease
(O&G), and surfactant as methylene blue absorbing substances (MBAS) were 461 ±
3 mg/L, 83 ± 5 mg/L, and 78 ± 47 mg/L respectively. Activated carbon prepared
through chemical activation using phosphoric acid with different process parameters
such as impregnation, carbonization temperature, and time. The optimum conditions
achieved (20 % impregnation, 500 °C temperature for 2 hours) with 52 % and 41 %
of COD and O&G removal, and constitutes microporous structure with iodine number
of 749 mg/g and ash content of 12 %. About 81 % of carbon, 17 % oxide, and 95 %
ethylene comprising of aromatics, hydroxyls and alcohol groups responsible to adsorb
pollutants. The optimized conditions on pH, adsorbent dosage, size and contact time
analysed between powdered and granular forms. The powdered size of 0.063 mm,
attained maximum removal of COD, O&G and MBAS with 95 %, 94 % and 100 % at
pH 8, dosage of 2 g/150 ml, for 3 hours contact. While, granular of 1.18 mm size have
similar optimized conditions with 93 %, 85 %, and 90 % for COD, O&G and MBAS
removal. The adsorption isotherm of Langmuir best fitted for powdered adsorbent,
with maximum qmax of 0.031 mg/g and 0.006 mg/g for COD and O&G. This study
highlighted the sugarcane bagasse activated carbon as an alternative adsorbent in
removing pollutants of COD, O&G and MBAS of car wash wastewater.
vi
ABSTRAK
Pencemaran air merupakan suatu cabaran untuk air dari sisa cucian kenderaan, kerana
merupakan sumber pencemaran bukan titik, yang membawa sisa toksik tanpa rawatan.
Selain daripada penggunaan membrane, separator minyak dan sebagainya, karbon
aktif adalah contoh teknologi yang sesuai. Kajian telah dilakukan terhadap penukaran
sisa agrikultur dari hampas tebu atau Saccharum Officinarum kepada karbon aktif,
berdasarkan ciri-ciri penjerapan. Objektif kajian adalah, mengelaskan air sisa cucian
kenderaan, pengoptimuman dalam penyediaan karbon aktif hampas tebu, dan
pengoptimuman kondisi antara serbuk dan bentuk granular bersama Langmuir dan
Freundlich isoterm. Untuk mencapai objektif tersebut, berdasarkan pengkelasan air,
keperluan oksigen kimia (COD), minyak dan gris (O&G), dan surfaktan sebagai bahan
penjerap methylene biru (MBAS) adalah 461 ± 3 mg/L, 83 ± 5 mg/L, and 78 ± 47
mg/L. Karbon aktif disediakan melalui proses aktivasi kimia menggunakan asid
fosforik berdasarkan parameter penjerapan, suhu dan masa pembakaran. Nilai
optimum penjerap adalah pada (20 % penyerapan, 500 °C dan 2 jam pembakaran)
dengan 52 % dan 41 % nilai penyingkiran COD dan O&G, struktur mikropora dan
nilai iodin sebanyak 749 mg/g dan kandungan debu 12 %. Sebanyak 81 % kandungan
karbon, 17 % oksida, dan 95 % ethylene mempunyai kumpulan aromatik, hidroksil,
dan alkohol. Kajian optimum terhadap sampel digunakan untuk mencari kadar dos
penjerap, saiz, dan masa antara serbuk dan bentuk granular. Karbon aktif serbuk pada
saiz 0.063 mm adalah maksimum 95 %, 94 % and 100 % pada COD, O&G dan MBAS
pada pH 8, dos 2 g/150 ml pada 3 jam. Sementara itu, granular dengan saiz 1.18 mm
mempunyai nilai optimum yang sama seperti bentuk serbuk dengan 93 %, 85 %, dan
90 % untuk COD, O&G dan MBAS. Penjerapan isoterm Langmuir adalah baik pada
bentuk serbuk karbon aktif, dengan nilai maksimum qmax of 0.031 mg/g dan 0.006
mg/g untuk COD dan O&G. Kajian ini membincangkan karbon aktif hampas tebu
sebagai salah satu alternatif untuk menyingkirkan COD, O&G and MBAS dari air
sisa cucian kenderaaan.
CONTENTS
STATUS CONFIRMATION FOR MASTER’S
THESIS
TITLE i
DECLARATION ii
DEDICATION iii
ACKNOWLEDGEMENT iv
ABSTRACT v
ABSTRAK vi
CONTENTS vii
LIST OF TABLES xiv
LIST OF FIGURES xvi
LIST OF EQUATIONS xx
LIST OF SYMBOLS AND ABBREVIATIONS xxi
LIST OF APPENDICES xxiii
CHAPTER 1 INTRODUCTION
1.1 Background of study 1
1.2 Problems statement 2
1.3 Objectives of study 4
1.4 Scope of study 4
1.5 Significance of the study 6
CHAPTER 2 LITERATURE REVIEW
2.1 Introduction 7
viii
2.2 Management of car wash industry in 8
Malaysia
2.3 Characteristic of car wash wastewater 9
2.4 Effect of car wash wastewater towards
environment
11
2.5 Water consuming in car washing 13
2.6 Legislation standards of car wash wastewater 14
2.7 Overview of car wash wastewater treatment 16
2.8 Production and Properties of Activated Carbon 19
2.8.1 Production of Activated Carbon 19
2.8.2 Physicochemical Properties of
Activated Carbon
23
2.8.2.1 Iodine number of activated
carbon
23
2.8.2.2 Ash content of activated
carbon
24
2.8.3 Factors affecting production of activated
carbon
25
2.8.3.1 Impregnating agent 25
2.8.3.2 Carbonization temperature 27
2.8.3.3 Carbonization time 28
2.8.4 Optimization parameter of activated
carbon
29
2.8.4.1 pH 29
2.8.4.2 Adsorbent sizes 30
2.8.4.3 Adsorbent dosage 31
2.8.4.4 Contact time 32
2.9 Adsorption of activated carbon from local
agricultural wastes
33
2.10 Criterias of sugarcane bagasse as an activated
carbon
37
2.11 Adsorption Equilibrium Study 43
2.11.1 Langmuir Isotherm 43
ix
2.11.2 Freundlich Isotherm 44
2.12 Recycling of Spent Activated Carbon 45
2.13 Concluding remarks 46
CHAPTER 3 METHODOLOGY
3.1 Sampling location 49
3.2 Sampling method 52
3.3 Materials and apparatus 54
3.3.1 Materials 54
3.3.2 Chemicals 54
3.3.3 Equipments 56
3.4 Characterization of car wash wastewater 57
3.5 Analytical Method 57
3.5.1 Determination of pH 58
3.5.2 Determination of chemical oxygen
demand
59
3.5.3 Determination of oil and grease 59
3.5.4 Determination of surfactant as
methylene blue absorbing substances
60
3.5.5 Determination of heavy metals 63
3.5.6 Determination of anion molecules 63
3.5.7 Determination of total carbon 64
3.5.8 Determination of alkalinity 64
3.6 Preparation of synthetic car wash wastewater 65
3.7 Characterization of sugarcane bagasse
activated carbon
68
3.7.1 Element composition analysis 68
3.7.2 Surface chemistry analysis 68
3.7.3 Microscopy analysis 69
3.7.4 Particle distribution size analysis 70
3.8 Adsorption test of sugarcane bagasse
activated carbon
70
x
3.8.1 Determination of iodine number 70
3.8.2 Determination of ash content 71
3.9 Preparation of sugarcane bagasse activated
carbon
72
3.10 Batch studies on effect of impregnating
percentage with phosphoric acid, temperature
and time of carbonization
74
3.10.1 Effect of impregnating percentage
with phosphoric acid in removal of
chemical oxygen demand and oil
and grease
76
3.10.2 Effect of carbonization temperature
in removal of chemical oxygen
demand and oil and grease
76
3.10.3 Effect of carbonization time in
removal of chemical oxygen demand
and oil and grease
76
3.11 Optimization studies of sugarcane bagasse
activated carbon
77
3.11.1 Determination of optimum pH 77
3.11.2 Determination of optimum adsorbent
dosage
78
3.11.3 Determination of optimum adsorbent
size
79
3.11.4 Determination of optimum contact
time
79
3.12 Adsorption experiments 80
3.13 Concluding remarks 82
CHAPTER 4 RESULTS AND DISCUSSIONS
4.1 Introduction 83
4.2 Characterization of car wash wastewater 83
xi
4.3 Characterization of sugarcane bagasse
activated carbon as adsorbent
86
4.3.1 X-Ray Fluorescence Analysis 86
4.3.2 Field Electroscopy Scanning
Electron Microscopy Energy
Dispersive X-ray Analysis
88
4.3.3 Fourier Transform-Infrared
Analysis
93
4.3.4 Particle size distribution of
sugarcane bagasse activated
carbon
95
4.4 Adsorption test of sugarcane bagasse
activated carbon
97
4.4.1 Iodine number of sugarcane
bagasse activated carbon
97
4.4.2 Ash content of sugarcane bagasse
activated carbon
100
4.5 Batch studies on preparation of sugarcane
bagasse activated carbon
102
4.5.1 Effect of time, temperature of
carbonization and impregnating
percentage with phosphoric acid
on chemical oxygen demand
removal
102
4.5.2 Effect of time, temperature of
carbonization and impregnating
percentage of phosphoric acid on
oil and grease removal
104
4.6 Optimization studies of powdered and
granular sugarcane bagasse activated carbon
109
4.6.1 Optimization of pH 109
4.6.2 Optimization of adsorbent dosage 113
4.6.3 Optimization of adsorbent sizes 116
xii
4.6.4 Optimization of contact time 120
4.7 Mechanism of adsorption isotherm 123
4.7.1 Adsorption isotherms of chemical
oxygen demand
123
4.7.1.1 Langmuir adsorption
isotherms of chemical
oxygen demand
123
4.7.1.2 Freundlich adsorption
isotherms of chemical
oxygen demand
125
4.7.2 Adsorption isotherms of oil and
grease
127
4.7.2.1 Langmuir adsorption
isotherms of oil and
grease
127
4.7.2.2 Freundlich adsorption
isotherms of oil and
grease
129
4.7.3 Adsorption isotherms of
surfactant as methylene blue
absorbing substances
130
4.7.4 Adsorption isotherm constants of
chemical oxygen demand, oil and
grease, and surfactant as
methylene blue absorbing
substances
131
4.8 Concluding remarks 134
CHAPTER 5 CONCLUSIONS AND RECOMMENDATIONS
5.1 Conclusions 135
5.2 Recommendations 136
xiii
REFERENCES 139
APPENDICES 149
xiv
LIST OF TABLES
2.1 Characteristic of car wash wastewater 9
2.2 Parameter limit of Industrial effluents for
Standard A and Standard B
14
2.3 Treatment of car wash wastewater 16
2.4 Different impregnating agent in chemical
activation of activated carbon preparation
26
2.5 Local agricultural wastes as an activated
carbon
33
2.6 Functional group of sugarcane bagasse and
sugarcane bagasse activated carbon
41
3.1 Summary of sampling and handling
requirements
53
3.2 List of chemicals 55
3.3 List of equipments 56
3.4 Composition of car wash wastewater 65
3.5 Summarization of chemical activation and
carbonization processes
75
3.6 (a) Working condition of isotherms study for
powdered and granular sugarcane bagasse
activated carbon
80
3.6 (b) Isotherm models used in present study 81
4.1 Car wash wastewater characteristics (n=8) 85
4.2 Chemical composition of untreated and
sugarcane bagasse activated carbon
87
xv
4.3 (a) Element compositions of untreated sugarcane
bagasse and treated sugarcane bagasse
activated carbon
91
4.3 (b) Comparison of element composition for other
sugarcane bagasse activated carbon
92
4.4 Particle size distribution of sugarcane bagasse
activated carbon
96
4.5 Iodine number of sugarcane bagasse and
commercial activated carbon
98
4.6 Ash content of sugarcane bagasse and
commercial activated carbon
100
4.7 (a) Langmuir isotherm of powdered and granular
sugarcane bagasse activated carbon
133
4.7 (b) Freundlich isotherm of powdered and
granular sugarcane bagasse activated carbon
133
4.7 (c) Comparison of isotherm models with other
sugarcane bagasse activated carbon
133
xvi
LIST OF FIGURES
2.1 SEM image (a) kapok fibre with 50μm and 500
magnification (Wahi et al., 2013) (b) sugarcane
bagasse activated carbon with 20μm and 1000
magnification (Devnarain et al., 2002) (c) coal
activated carbon and (d) coconut shell activated
carbon (Jabit, 2007)
22
2.2 The acumulation of molecules adsorbate; the oil
and grease (O&G) molecules from solution of
aqueous phase on the surface of adsorbent;
activated carbon (Wahi, et al., 2013)
36
2.3 (a) Untreated bagasse (Lara et al., 2010);
Sugarcane bagasse activated carbon (b) With
nitric acid (Worathanakul et al., 2010) (c) With
potassium hydroxide (Irfan et al., 2011) (d)
With phosphoric acid (Adinaveen et al., 2013)
39
3.1 Overview of study 48
3.2 (a) Drainage of car wash station 49
3.2 (b) Layout of car wash station 50
3.2 (c) Car washing activity 50
3.2 (d) Snow jet pressure car wash pumps 51
3.2 (e) Car wash wastewater effluents 51
3.3 Sugarcane bagasse activated carbon that have
been settled after stirred for one hour
58
xvii
3.4 (a) Pink colour of phenolphthalein slowly
disappeared
61
3.4 (b) Car wash wastewater and chlorofom part 61
3.4 (c) Chlorofom part turns bit bluish 61
3.4 (d) Chlorofom part was drained 61
3.5 (a) Surfactant extractions (colorless bit bluish
colours)
62
3.5 (b) Standard calibration curve for methylene blue
absorbing substances measurement
62
3.6 (a) Synthetic solution mixture 67
3.6 (b) Homogenization of synthetic solution 67
3.6 (c) Relative contributions of chemical oxygen
demand, surfactant as methylene blue absorbing
substances, and oil and grease of synthetic car
wash wastewater
67
3.7 (a) Bagasses after oven dried and cut in 1 cm size 72
3.7 (b) Sugarcane bagasse activated carbon 73
3.7 (c) Sugarcane bagasse activated carbon with flakes
form
74
3.7 (d) Schematic diagram for preparation of sugarcane
bagasse activated carbon
74
3.8 Shaking process of sugarcane bagasse activated
carbon
78
4.1 (a) Untreated sugarcane bagasse in 100 magnification 89
4.1 (b) Untreated sugarcane bagasse in 1000
magnification
89
4.1 (c) Sugarcane bagasse activated carbon in 100
magnification
89
4.1 (d) Sugarcane bagasse activated carbon in 1000
magnification
89
xviii
4.1 (e) Untreated sugarcane bagasse (Lara et al., 2010) 89
4.1 (f) Sugarcane bagasse activated carbon with
phosphoric acid (Adinaveen et al., 2013)
89
4.2 (a) EDX spectrum analysis of untreated sugarcane
bagasse
90
4.2 (b) EDX spectrum analysis of treated sugarcane
bagasse activated carbon
91
4.3 FT-IR analysis of untreated sugarcane bagasse
and treated sugarcane bagasse activated carbon
94
4.4 Percentage particle sizes of sugarcane bagasse
activated carbon
97
4.5 (a) Effect of time, temperature of carbonization and
impregnating percentage of phosphoric acid on
chemical oxygen demand removal
107
4.5 (b) Effect of time, temperature of carbonization and
impregnating percentage with phosphoric acid
on oil and grease removal
108
4.6 (a) Removal percentage pollutants on powdered
and granular sugarcane bagasse activated
carbon (%) via optimization of pH (adsorbent
dosage of 2 g/150 ml for 1 hours stirring time;
adsorbent size powdered: 0.063 mm; granular:
2.36 mm)
112
4.6 (b) Removal percentage pollutants on powdered
and granular sugarcane bagasse activated
carbon (%) via optimization of adsorbent
dosage (adsorbent size powdered: 0.063 mm;
granular: 2.36 mm; pH 8; 1 hours stirring time)
115
4.6 (c) Removal percentage pollutants on powdered
sugarcane bagasse activated carbon (%) via
optimization of particle sizes (adsorbent size
dosage: 2g/150 ml for 1 hours stirring time; pH
8)
118
xix
4.6 (d) Removal percentage pollutants on granular
sugarcane bagasse activated carbon (%) via
optimization of particle sizes (adsorbent size
dosage: 2g/150 ml for 1 hours stirring time; pH
8)
119
4.6 (e) Removal percentage pollutants on powdered
and granular sugarcane bagasse activated
carbon (%) via optimization of contact time
(adsorbent size dosage: 2g/150 ml; adsorbent
size powdered: 0.063 mm; granular: 1.18 mm;
pH 8)
122
4.7 (a) Langmuir isotherm of chemical oxygen demand
by powdered sugarcane bagasse activated
carbon
124
4.7 (b) Langmuir isotherm of chemical oxygen demand
by granular sugarcane bagasse activated carbon
124
4.7 (c) Freundlich isotherm of chemical oxygen
demand by powdered sugarcane bagasse
activated carbon
126
4.7 (d) Freundlich isotherm of chemical oxygen
demand by granular sugarcane bagasse
activated carbon
126
4.8 (a) Langmuir isotherm of oil and grease by
powdered sugarcane bagasse activated carbon
128
4.8 (b) Langmuir isotherm of oil and grease by granular
sugarcane bagasse activated carbon
128
4.8 (c) Freundich isotherm of oil and grease by
powdered sugarcane bagasse activated carbon
129
4.8 (d) Freundlich isotherm of oil and grease by
granular sugarcane bagasse activated carbon
130
xx
LIST OF EQUATIONS
2.1 Langmuir equation 43
2.2 Freundlich equation 44
3.1 Chemical oxygen demand concentration 59
3.2 Oil and grease concentration 60
3.3 Surfactant as methylene blue absorbing
substances
63
3.4 (a) Phenolphthalein alkalinity 65
3.4 (b) Total alkalinity 65
3.5 Iodine number 71
3.6 Ash content 72
xxi
LIST OF SYMBOLS AND ABBREVIATIONS
ICP-MS - Inductively Coupled Plasma-Mass Spectrometer
XRF - X-Ray Fluorescence
FE-SEM
EDX
- Fine Electron Scanning Electron Microscopy-Energy Dispersive
X-Ray
FT-IR - Fourier Transformed-Infrared Spectroscopy
UTHM - Universiti Tun Hussein Onn Malaysia
mg/ L - milligram per litre
mg/ g - milligram per gram
°C - Degree Celsius
% - Percent
g - gram
ml - millilitre
MBAS - surfactant as Methylene Blue Absorbing Substances
pH - Potential of hydrogen
SS - Suspended solids
SBAC - Sugarcane bagasse activated carbon
CAC - Commercial activated carbon
COD - Chemical oxygen demand
O&G - Oil and grease
PSC - Powdered sugarcane bagasse activated carbon
GSC - Granular sugarcane bagasse activated carbon
PCC - Powdered commercial activated carbon
GCC - Granular commercial activated carbon
qmax - Maximum amount of concentration per unit weight of adsorbent
xxii
R2 - Correlation coefficeint
b - Constant related to the affinity of binding sites with the
adsorbent
Kf - Freundlich constant
n - Heterogeneity factor
Ce - Equilibrium sorption capacity
xxiii
LIST OF APPENDICES
A Determination of surfactant in water 149
B Calculation of synthetic car wash wastewater 151
C Characteristic of car wash wastewater 152
D1 Iodine number 157
D2 Ash content 161
E Optimum condition for preparation of
sugarcane bagasse activated carbon
165
F Optimization of pH, dosage, adsorbent size
and contact time
166
G1 Chemical Oxygen Demand, COD (Langmuir
& Freundlich isotherm)
174
G2 Oil and grease, O&G (Langmuir isotherm &
Freundlich isotherm)
176
G3 Mehylene Blue Absorbing Substances,
MBAS (Langmuir isotherm & Freundlich
isotherm)
178
1
CHAPTER 1
INTRODUCTION
1.1 Background of Study
Wastewater characteristics, which depend on wastewater source, are increasingly and
becoming more toxic in recent times (Alade et al., 2011). A wastewater system can
not mixed with the stormwater system, where it can contribute to the permeation of
other pollutants towards the aquatic animals (Sanderson et al., 2006; Sablayrolles et
al., 2010).
Car wash is defined as a non-domestic installation for internal and external
cleaning of cars by using water, cleaning solutions applying with finish products. Car
washing wastewater consists of oils, elements from brake linings, rust, trace amounts
of possibly chromium and soap used to wash the cars introduces phenols, dyes, acids,
and ammonia (Zayadi et al., 2015). Car wash contains oily wastewater with toxic
substances such as phenols, polyaromatic hydrocarbons, which are inhibitory to plant
and animal growth, equally mutagenic and carcinogenic to human beings (Lan et al.,
2009). Moreover, the wastewater from car washes may contain nutrients such as
phosphorus, chemicals including nonyl phenols, linear alkylbenzene sulphonates
(LAS) which are the most important synthetic anionic surfactants, and the principal
constituents of surfactants subject pollutants from car wash wastewater which is slow
to biodegrade generally (Oknich, 2002). Many particles and chemicals have been
found in car wash wastewaters, hence the concentration and severity each element
should be assessed and considered in treating the pollutants.
The increases number of cars on roads have increased the number of car washes
nowadays. The Environmental Pollution Agency (EPA) have reported, car washes is
a non point source of pollution where the types and contaminants present during
2
washing cars will have a major effect upon the effluent characteristics (Brown, 2002).
Hence, several treatments on car wash wastewater treatment have been used,
such as ultrafiltration and nanofiltration membrane, oil separator and else (Zayadi et
al., 2015). In Malaysia, the effluent discharges of car wash wastewater used Standard
A and Standard B regulations based on Malaysia Sewage and Industrial Effluent
Discharge. Malaysia cities currently, have increased in car volumes on the road. It
have boost the car wash industry, leading to increase of car washes service, particularly
in high population of residential area along the roads. However, car wash stations in
Malaysia commonly have poor and improper sanitary drainage system of car wash
wastewater discharges. They may have directly flowing their untreated effluents to the
drains, then discharged it to streams, rivers and bays. Whereas, some effluents directly
discharged to the ground, leads to the ground contamination.
1.2 Problems Statement
The increase in car numbers on roads altogether, have furthered increased the car wash
stations in Malaysia where, each car washing have generated 150 L to 600 L of
wastewater. The oil and grease, O&G, chemical oxygen demand, COD and surfactants
as MBAS (Methylene Blue Absorbing Substances) have been reported as most
contaminants in car wash wastewater (Brown, 2002; Yasin et al., 2012; Baddor et al.,
2014; Shete & Shinkar, 2014). Though Malaysia have their own environmental quality
regulations of Standard A and Standard B for Discharge of Industrial Effluent or
Mixed Effluent 2009, but this particular regulation is seldom enforced leads to little
attention is given to the car wash industry (Lau et al., 2013).
Treatment of car wash wastewater includes membrane application (Lau et al.,
2013; Shete & Shinkar, 2014), oil separator (Al- Odwani et al., 2007; Fall et al., 2007)
and else. An example of on site conventional treatments includes the oil separator
usually focused on organic removal such as COD and O&G but, less investigation
were made on inorganic such as MBAS removal. Surfactant as MBAS carries alkaline
chemical compounds together with alcohol in solvents and other complex agents.
However, when using the oil separator, it was failed to keep values to permissible limit
of Standard B, 10 mg/L. The formation of O&G emulsions due to MBAS where the,
MBAS molecule surround O&G droplets with a layer of MBAS molecule give them
3
a water-soluble coating, have reducing the efficiency amount of O&G and MBAS
removal (Yasin et al., 2012).
Recent years, adsorption had been carried out as an alternative of conventional
treatment. Adsorption of car wash wastewater such as flocculation, coagulation
(Butler et al., 2013); alum and ferrous sulphate as coagulants have been applied by
using low cost adsorbents (Radin Mohamed et al., 2014). However, the selective
adsorbents should be chosen from promising adsorbents with least costs, economic
friendly and readily available materials.
Adsorption via activated carbon from local agricultural wastes such as chitosan
(Wahi et al., 2013); rice husk (Nekoo & Shohreh, 2013), and else have removed 70 %
to 99 % of O&G in car wash wastewater with limited researchs on COD and MBAS
removal. Previous studies on sugarcane bagasse or Saccharum officinarum towards
industrial wastewater have succeedly removed 46 % to 84 % of COD (Nekoo &
Shohreh, 2013; Azmi et al., 2014; Gaikwad & Mane, 2015), 80 % of O&G (Sarkheil
& Tavakoli, 2015) and 77 % to 95 % of MBAS (Co et al., 2012; Bilal et al., 2013). It
has 50 % cellulose, 27 % polyoses, and 23 % lignin with hydroxyl, carbonyl, aromatic
group and other composition of polymers responsible for an excellent adsorbent
capacity (Gusmao et al., 2012). In adsorption processes, to ensure the porosity of the
fibrous bagasse stems produced the best quality of an activated carbon, the activated
carbon preparation should be optimized in term of the temperature, time and
impregnation percentage (Adinaveen et al., 2013).
Moreover, it is important to study the different environmental parameters such
as pH, adsorbent dosage, sizes, contact time, and the morphological analysis to ensure
sugarcane bagasse activated carbon can be performed at optimum condition. The
adsorbent sizes of powder and granule yields different performances towards pollutant
removals. For example, a study on membrane process on granular activated carbon
have removed 95 % of MBAS, whereas the powdered activated carbon, the problems
reported including a long backwash time and cake formation over membrane surfaces
(Taylor & Zahoor, 2014).
Hence, there is a need for Malaysia to develop on site treatments using locally
available material of sugarcane bagasse. Thus, it is significant to study on
characterization and optimization of sugarcane bagasse activated carbon in both
powder and granule forms.
4
1.3 Objectives of Study
This study aims to investigate the capability of sugarcane bagasse activated carbon in
removing pollutants from car wash wastewater. Three correlative objectives were
outlined to achieve the aims.
1) To characterize the physical and chemical composition of car wash wastewater
discharges.
2) To optimize the impregnation of carbonized sugarcane bagasse activated
carbon via optimum value of phosphoric acid impregnating percentage,
temperature and carbonization time.
3) To optimize the value of pH, adsorbent dosage, size, and contact time of
powdered sugarcane bagasse activated carbon, and granular sugarcane
bagasse activated carbon and with the adsorption isotherms.
1.4 Scope of Study
The study consist of field activities and laboratory work. Field activities were
carried out at Johor Bahru, where samples were collected from car wash station. Field
activities were carried out at early stage for characterization of wastewater, during
preparation of activated carbon and last stage of batch study for powdered and granular
activated carbon. Laboratory work including preliminary study, preparation of
activated carbon, adsorption test, optimization study, adsorbent characteristic before
and after treatment of optimization study, removal efficiency of COD, surfactant as
MBAS and O&G via optimum study. The experiments were conducted in accordance
with standard operations of Standard Method for the Examination of Water and
Wastewater (2012) for collections and measurements promulgated for eight weeks.
i. Preliminary study involving the characterization of car wash wastewater and
working ranges of car wash wastewater.
5
ii. Preparation of sugarcane bagasse activated carbon as an adsorbent for
optimization consisting the percentage of impregnated bagasse via phosphoric
acid for 10 %, 20 %, 30 %, 40 % and 50 % for temperature carbonization of
500 °C, 600 °C, 700 °C at 1 hour, 2 hours and 3 hours for 2 g of adsorbent at
125 rpm on room conditions. The optimization then, was determined based on
the removal efficiency on car wash wastewater for COD and O&G parameters.
iii. Powdered sugarcane bagasse and granular sugarcane bagasse were prepared
from sugarcane bagasse activated carbon produced with the optimum
preparation conditions; 20 % of phosphoric acid impregnation, at 500 °C for 2
hours carbonization. The sugarcane bagasse activated carbon were classified
based on ASTM D2862 test method. The selected sizes were powdered with
(0.3 mm, 0.212 mm, 0.15 mm, 0.075 mm, 0.063 mm) and granular (2.36 mm,
2 mm, 1.4 mm, 1.18 mm, 0.6 mm).
iv. For optimization study, the values of pH were varied to pH 3, 7, 8, and 9;
adsorbent dosage of 0.6 g, 1 g, 2 g, 4 g and 6 g whereas, the contact time of
0.5 hours, 1 hour, 3 hours, 12 hours, and 24 hours for all selected sizes of
powdered and granular sugarcane bagasse activated carbon. The optimized
value then, analysed for the adsorption of Langmuir and Freundlich isotherm
for COD, O&G, and MBAS pollutants.
v. The morphological characteristics of the adsorbent were carried out by using
FE-SEM EDX, functional group with FTIR and element composition with
XRF.
1.5 Significance of Study
Car wash treatments including of membranes, oxidation, and else. However,
the car wash owners seldom applied the treatment for their stations due to the
affordability, where the low cost treatment is a need (Radin Mohamed et al., 2014).
Generally, the conventional treatment of oil separator may remove above 70 % of
COD and O&G, but seldom analysed to MBAS removal, even the pollutant have been
6
awared by Environmental Pollution Agency in 1980 (Bilal et al., 2013). Therefore, it
is important to study and propose treatment suitable to remove those pollutants using
other alternative treatment.
For industrial wastewater treatment, the other potential treatment usually
applied are commercial activated carbon. Literature survey indicates, rather than
commercial activated carbon, varieties of local agricultural wastes were
manufacturing as an activated carbon (Gottipati, 2012).
Sugarcane bagasse available abundantly, with 54 million dry tones bagasse are
produced annually around the world (Fasoto et al., 2014). The bagasse generates a lot
of waste that could serve as a reliable feedstock to obtain carbons with good adsorptive
properties. Reuse the sugarcane bagasse wastes, throw by the sugarcane juice stalls and
sugar industry for its sucrose content, will reduce the amount of wastes throw every
day. The conversion of sugarcane bagasse to activated carbon would have dual
advantages of producing a low cost adsorbent material for environmental protection,
while at the same time reduce the need for land filling, disposal and open burning.
This process is also an economic friendly treatment, as it is non polluting to our
environment.
In Malaysia, sugarcane bagasse were available obtained with cheap,
reasonable prices, high carbon and low inorganics content, favourable for the
production of activated carbon. Moreover, it has high potential to remove 90 % of
pollutants in wastewater, than other local agricultural wastes (Bilal et al., 2013).
Hence, adsorption of sugarcane bagasse activated carbon will be a technically feasible
and economically attractive approach replacing conventional treatments.
Therefore, this study offers, an economic low cost agricultral wastes as an
activated carbon from sugarcane bagasse wastes for car wash wastewater treatment.
7
CHAPTER 2
LITERATURE REVIEW
2.1 Introduction
With the increasing development of the economy and improvement of human life,
wastewater discharged by the municipal, industrial and commercial sectors have been
adversely affected and threatening our environment. In Malaysia, with total population
of 28 million peoples, the vehicles sales report revealed that the total vehicle sales
volume in 2012, between January was 301 units, June was 224 units and, forecasted
to reach a new record of 615,000 units at the end of 2012 compared to 605,156 units
and 600,123 units in 2010 and 2011, respectively (Radin Mohamed et al., 2014). Due
to the demand in vehicle own nowadays, large number of cars were seen on roads,
leading the mushrooming of car wash industry sectors (Bhatti et al., 2011). It offer
consumers an easy, time saving, and practical way to wash and remove the dirt, grime
and oil from their cars.
Car washes providing the external and internal cleaning of cars, consisting of
a roll over (in which the washing installation moves over the car), an automatic car
wash (in which the car is pulled through the washing installation) and a self-car wash
(Boussu et al., 2007). The processes removing of oil and dirt, and then treatment to
provide protection. Degreasing solvents and cleaning agents remove traffic grime and
particulate matter on cars, then the subsequent application of wax, polishes and
protects coatings (Genuino et al., 2012).
Car washing consume large capacities of fresh water on a daily basis. Our
modern daily life and restricted schedules nowadays forcing people often take their
cars for cleaning and rinsing purposes resulting high amount of wastewater generated,
rather than washing cars at home. A car wash study in Kuwait have stated that if the
car wash station operates 12 hours/ day, and an assumption of one car being washed
8
per hour, then there are 25,200 cars washed on a daily basis. An average of 100
galloons of fresh water used to wash a car makes the total fresh water consumption
above 2.5 million galloons/day. However, the large capacity of water contains
hazardous pollutants in the wastewater, including the sand and dust, phosphates, oil
and grease, organic matter, heavy metals and surfactants which may go into the
stormwater system and eventually ending up into rivers causing severe damage to
aquatic systems (Al-Odwani et al., 2007; Lau et al., 2013).
2.2 Management of car wash industry in Malaysia
Most countries including of Malaysia were still behind in developing conscious for the
wastewater produced by car wash industries (Bhatti et al., 2011). Cars that are washed
in the street with the improper management of wastewater discharges can pollute the
rivers. The surfactants, oil and grease and other pollutants that run off the car into the
drains, will eventually flow to the storm water system without any treatment. Even,
the measured pollutant concentrations in car wash discharge were more similar to the
levels found in wastewater, than in runoff stormwater (Azhari, 2010; Sablayrolles et
al., 2010). The accumulated sediments during washing cars consisting concentrations
of contaminants, where the sludge is considered a controlled or hazardous waste,
including of metals, elevated levels of oil and grease, and unacceptable levels of
acidity or alkalinity (Azhari, 2010).
The awareness of the environmental issues and restricting the environmental
regulations on effluent discharged from industries is increased. Malaysia have their
own environmental quality regulations, but this particular regulation is seldom
enforced to the car wash industry. It is generally perceived by the public that the
wastewater from car washing is not severely contaminated compared with other
industrial wastewaters (Lau et al., 2013). Hence, little attention is given to the car wash
industry (Abagale et al., 2013).
9
2.3 Characteristic of car wash wastewater
Car washing consumed greater amount of water during cleaning process involving the
use of chemicals and hence, producing wastewater with a high concentration of
surfactants, oils, greases and other organic matters where, the mixed effluents makes
the car wash wastewater toxic to aquatic life (Zaneti et al., 2011). The characteristics
of car wash wastewater were characterized as summarized in Table 2.1.
Table 2.1: Characteristic of car wash wastewater
Parameter Units Values Researchers
Minimum Maximum Mean
pH - - - 8 Tony & Bedri (2014)
- - 8 Yasin et al., (2012)
- - 8-9 Radin Mohamed et
al., (2014)
- - 9 Shete & Shinkar
(2014)
Chemical Oxygen
Demand (COD)
mg/L 78 738 408 Lau et al., (2013)
- - 288 Shete & Shinkar
(2014)
- - 572 Kuokkanen et al.,
(2013)
- - 1330 Yasin et al., (2012)
- - 241 Zaneti et al., (2011)
- - 488 Juarez et al., (2015)
Biochemical
oxygen demand
(BOD5)
mg/L - - 178 Kuokkanen et al.,
(2013)
- - 133 Zaneti et al., (2011)
11 12 - Lau et al., (2013)
- - 540 Yasin et al., (2012)
Surfactant as
methylene blue
absorbing
substances
(MBAS)
mg/L - - 96 Kuokkanen et al.,
(2013)
- - 35 Baddor et al., (2014)
10
Table 2.1 (continued)
24 32 28 Shahbazi et al.,
(2013)
- - 68 Juarez et al., (2015)
Oil and grease
(O&G)
mg/L 10 1750 880 Zaneti et al., (2011)
1 84 - Bhatti et al., (2011)
670 1530 - Yasin et al., (2012)
Suspended solids
(SS)
mg/L 147 202 - Radin Mohamed et
al., (2014)
110 644 - Bhatti et al., (2011)
- - 286 Good et al., (2011)
230 Hsu et al., (2011)
A number of studies reported the pH of car wash wastewater normally were 8
(Yasin et al., 2012; Tony & Bedri, 2014), 8 to 9 (Radin Mohamed et al., 2014), and 9
(Shete & Shinkar, 2014). The pH 8 was observed from the hand car wash stations
(Yasin et al., 2012; Tony & Bedri, 2014). Compared with the slightly high value of
alkaline surfactants ingredients applied during automatic car washes, resulting pH 9
(Radin Mohamed et al., 2014; Shete & Shinkar, 2014).
Chemical oxygen demand (COD) presented by Lau et al., (2013) in car wash
stations in the city of Johor Bahru shows the COD were within ranges of 78 mg/L till
738 mg/L. The foreign countries such as India recorded 288 mg/L of COD (Shete &
Shinkar, 2014); Italy with 572 mg/L (Kuokkanen et al., 2013); and Brazil with 241
mg/L (Zaneti et al., 2011). The higher COD observed in Pakistan with 1330 mg/L
where the sampling were taken at service oil station, contributing by diesel, gasoline,
waste engine oil, and oil emulsions from washing cars (Yasin et al., 2012).
BOD shows the biodegradable organic contaminants present in the wastewater.
BOD based on review by Kuokkanen et al., (2013) have nearly BOD values of 178
mg/L in Italy and 133 mg/L in Brazil (Zaneti et al., 2014). A study of BOD by Lau et
al., (2013) in Johor Bahru have lower value than the other reviews, 11 mg/L to 12
mg/L. In car wash wastewater, BOD was caused by the animal dung and bird
droppings that are washed away with water. Emulsified oil from engine washing and
detergents used to wash vehicles contributes to higher levels of BOD. Though there
was an oil water separator used as on site treatments to treat car wash wastewater, the
11
rarely used have caused all wash water goes into the sewer system directly, resulting
the high concentration of 540 mg/L (Yasin et al., 2012).
Panizza et al., (2005) have summarized the use of surfactants as the cleaning
agent for car washing purposes. Surfactant comprising of water-soluble (hydrophilic)
and a water-insoluble (hydrophobic) component. As a result of this structure, the
molecules of surfactants align themselves and surrounds the oil and grease (O&G)
droplets with a layer of surfactant molecule to enable the water soluble coating to
remove the dirts (Zaneti et al., 2011). Generally, synthetic detergents used for cars
washing are anionic surfactants as (MBAS). Kuokkanen et al., (2013) has 96 mg/L
MBAS, higher than Baddor et al., (2014) and Shahbazi et al., (2013), with 32 mg/L
and 24 mg/L respectively. The MBAS with high chemical contents of Linear
alkylbenzene sulfonates (LAS) might surround the O&G droplets with a layer of
MBAS molecules to give them a water soluble coating. Hence, failed to have less
values in effluent (Yasin et al., 2012).
On the other hand, Zaneti et al., (2014) and Yasin et al., (2012) reported with
1750 mg/L and 1530 mg/L of O&G respectively. According to the Zaneti et al., (2014),
oil separator devices have no efficiency in removing O&G, due to the formation of
stable emulsions in the wastewater caused by MBAS.
Sand, silts and soils present as suspended solids (SS) in car wash wastewater.
These colloidal materials make the wastewater turbid as well. The SS were within 110
mg/L to 286 mg/L based on reviews. The following SS were 230 mg/L SS (Hsu et al.,
2011); 147 mg/L to 202 mg/L SS (Radin Mohamed et al., 2014); and 286 mg/L of SS
from Good et al., (2011). A maximum concentration of 644 mg/L of SS denoted by
Bhatti et al., (2011). SS are predominantly inorganic matter, that can be mainly
explained by the particles and dust attached to the wheels and body parts of cars. Based
on the reviews in Table 2.1, the organic contaminants were higher than the inorganic
in car wash wastewater. Therefore, the organic contaminants including of the COD,
O&G and MBAS were selected as the important parameters in this study.
2.4 Effect of car wash wastewater towards environment
People nowadays are still behind to develop conscious for the wastewater
produced by car wash industries. In Malaysia, the car wash stations does not have
improper management on managing the car wash wastewater, where the wastewater
12
were discharged to the drains or grounds without further any treatment. The surfactants
as (MBAS), oil and grease (O&G) and other pollutants that run off the car into the
drains, go into the storm water system. Bhatti et al., (2011) have emphasized that any
pollutants in storm water end up in river was considered non point source pollution.
Moreover, stormwater that enters the river does not undergo treatment before it is
discharged into waterways. Therefore, wastewater carried were polluted to the rivers
and our stormwater system.
The most common sources of car wash wastewater are organic matters which
contributing the high concentration of chemical oxygen demand (COD). The sand,
silts, muds and dusts were released particles from the road surfaces and the tires of the
cars. COD in wastewater shows the presence of contaminants that are stable and not
easily biodegradable. Diesel, gasoline, waste engine oil, surfactants, all contributes
COD in car wash wastewater. The presence of those pollutants to stormwater leads to
aesthetic losses caused by foam, which can cause toxic effects on ecosystems and
changes in biodiversity (Nekoo et al., 2013).
When the surfactant as MBAS was being applied to wash cars, the other
alkaline chemical components such as alcohols in solvents and other complex agents
were released. An increase in MBAS to a surface water body leads to excessive plant
growth and decays. This creates low dissolved oxygen levels, changes in animal
populations, and an overall degradation of water quality and aquatic habitat (Zaneti et
al., 2014).
A study by Yasin et al., (2012) have stated that the oil and grease (O&G) were
present in the wastewater because of the vehicles have leaked engines and oil spills on
the washing floors, flowing to stormwater system. Though the oil separator used as on
site treatments, it was failed to keep values of O&G to 10 mg/L in effluent because of
the formation of O&G emulsions due to MBAS. Compounds in petroleum
hydrocarbons in O&G are highly toxic. In the surface water environment, from Wahi
et al., (2013), it can cause harm to wildlife through direct physical contact,
contamination by ingestion, and the destruction of food sources and habitats.
Moreover, the formation of O&G layer limits the oxygen penetration into water and
thus, caused toxic effects on microorganisms responsible for biological treatment of
wastewater. Overall, the car wash wastewater when released to stormwater system,
without being treated were harmful to environment and ecosystem system. Hence, to
13
control the amount of pollutants, an effective and low cost treatment should be awared
and developed in managing the car wash wastewater.
2.5 Water consuming in car washing
Car wash stations located in Kuwait based on Al-Odwani et al., (2007) are among
those activities that consume great capacity of water produced. An average of 50 to
100 gallons of fresh water is consumed to perform a complete professional wash on a
single car. It is estimated that 2.5 million gallons of freshwater is consumed daily in
car wash stations. Besides, about 25 % of freshwater have been used to perform final
rinses during cleaning cars. This large capacity of water carried away pollutants from
car wash wastewater, which may eventually end up in the sea, causing severe damage
to the marine life environment (Al-Odwani et al., 2007).
Bhatti et al., (2011) presents a study about water consuming during washing
cars. An average of 100 L water is consumed per car and at least 10m3 of water is
discharged from a car wash station per day, there is still a large amount of water
consumed in city. Besides, a study in Malaysia from Lau et al., (2013), an average of
150 L to 600 L of car wash wastewater were produced from every car washing, where
there is no restricted amount regulated for every car washing. However, for example
in Queensland, Australia and some countries in Europe, it is restricted to use less than
70 L of fresh water for a car wash (Lau et al., 2013).
Due to the amount of the water usage and the water quality, from a viewpoint
of environmental protection, an effective treatments should be applied to ensure an
effective utilization of water resources. Furthermore, a small space and high efficient
treatments with low cost maintenances are required for car wash station. Considering
the greater amount of wastewater discharged, the installation of a wastewater treatment
system is not just a process to cope with the environmental problem to meet the
environmental discharge requirements. Therefore, a ways to recover the rinsed water
for reuse purpose should be awared to create a sustainable solution in this industry
(Lau et al., 2013).
14
2.6 Legislation standards of car wash wastewater
Greywater standard on car wash wastewater have been established in other countries
United States (Queensland, Massachusetts and Washington), Australia (New South
Wales), and Europe (Swedish).
In United States, countries such as Queensland, Massachusetts and Washington
have included the standards for the car wash wastewater including in greywater
system. The chemical oxygen demand, COD and oil and grease, O&G was less
applicable in United States and Australia countries, where the pollutant focused are
surfactant as methylene blue absorbing substances, MBAS releasing phosphorus (P)
element, suspended solid (SS) and else.
Moreover, the permissible limit of phosphorus element, must be less than 27
mg in Queensland country, less than 37 mg in Massachusetts, and less than 26 mg in
Washington. Apart from that, the Swedish Environmental Protection Agency (EPA)
in Europe, has standardized the COD with 588 mg/L and phosphorus with 7.5 mg/L.
Malaysia has not established greywater standard for the quality of effluent
discharges to receiving waters. However, the effluent discharges of car wash
wastewater used Standard A and Standard B based on Malaysia Sewage and Industrial
Effluent Discharge.
Literature survey present the researchs of car wash wastewater in Malaysia
generally focused on COD, O&G and SS, however less focused on MBAS
concentration (Lau et al., 2013). Table 2.2 shows the parameter limits of effluents for
Standard A and Standard B. The COD permissible limit is 200 mg/L, O&G with 10
mg/L, and no standard limit applicable for MBAS.
Table 2.2: Parameter limit of Industrial effluents for Standard A and Standard B
Parameter Unit Standard
A B
Temperature °C 40 40
pH - 6-9 5.5-9
Biochemical Oxygen Demand
(BOD5 at 20 °C)
mg/L 2 40
Chemical Oxygen Demand
(COD)
mg/L 80 200
15
Table 2.2 (continued)
Suspended solids (SS) mg/L 50 100
Mercury (Hg) mg/L 0.005 0.05
Cadmium (Cd) mg/L 0.01 0.02
Chromium, Hexavalent (Cr6) mg/L 0.05 0.05
Chromium, Trivalent (Cr3) mg/L 0.2 0.1
Arsenic (As) mg/L 0.05 0.10
Cyanide (Cn) mg/L 0.05 0.10
Lead (Pb) mg/L 0.1 0.5
Manganese (Mn) mg/L 0.2 1
Nickel mg/L 0.2 1
Tin mg/L 0.2 1
Zinc (Zn) mg/L 2 2
Boron (B) mg/L 1 4
Iron (Fe) mg/L 1 5
Silver (Ag) mg/L 0.1 1
Aluminium (Al) mg/L 10 15
Selenium (Se) mg/L 0.02 0.5
Barium (Ba) mg/L 1 2
Fluoride (F) mg/L 2 5
Formaldehyde mg/L 1 2
Phenol mg/L 0.001 1
Free Chlorine (Cl) mg/L 1 2
Sulphide (S) mg/L 0.5 0.5
Oil and grease (O&G) mg/L 1 10
Ammoniacal Nitrogen (AN) mg/L 10 20
Colour ADMI 100 200
Source: Department of Environmental Quality Act (Industrial Effluents) Regulations
2012
Based on the standard from the other countries, the standard applied in
Malaysia should should awared by the surfactant released MBAS discharges, from car
wash wastewater adopted with effluents for Standard A and Standard B.
16
2.7 Overview of car wash wastewater treatment
A few number of technologies have been adopted as a treatment for car wash
wastewater. The details of the treatment is in Table 2.3 indicates that each treatments
has its own different removal efficiency in term concentration of organic and inorganic
pollutants via physical-chemical treatments as reviewed (Zayadi et al., 2015).
Table 2.3: Treatment of car wash wastewater
No Type of
treatments Results Parameter
Percentage
removal (%) Reference
1 Membranes
Ultrafiltration membrane
TOC
75
Panpanit, S.
(2001)
PS-100 75
C-100 75
C-30 75
Nanofiltration membrane 98
Ultrafiltration membrane
COD
56.1 - 82.4
Lau, W. J. et
al., (2012)
PVDF 100
PES 30 54.9 - 83.9
Nanofiltration membrane 70.9 - 91.5
NF 270
Ultrafiltration membrane
TDS 82.2 Shete &
Shinkar
(2014)
TSS 81.1
COD 67.5
O&G 75
Non-woven membrane
filtration with bio-
carriers
COD 70.2 Hsu et al.,
(2011) SS 95.7
2
Membrane
bioreactor process
(MBR) with
biological
activated carbon
(BAC) process
MBR+BAC with dose of
2g/L
COD 95 - 97.5
Tri (2002)
O&G 98.3 - 99
MBR without BAC
COD 91 - 96.3
O&G 95.2 - 97.5
3
Hydrophilic and
hydrophobic
membrane
Hydrophilic membrane MBAS 85 - 100 Boussu et al.,
(2007) NF270 COD 78 - 98
Hydrophobic membrane MBAS 53 - 100
17
Table 2.3 (continued)
4
NFPES 10 COD 33 78
Ultraviolet
oxidation
COD 30 - 61 Perkowski et
al., (2006) BOD5 64 - 84
TOC 25 - 68
5 Hay bales and
grass
Cu (II) 55
Good et al.,
(2011)
Pb (II) 85.5
Zn (II) 65.9
TSS 85.9
25.3
TSS 69.4 - 90.4
6 Electrochemical
Fe-Fe electrode
COD
65.4 - 79.2
Das (2010) Al-Fe electrode 39.2 - 48.1
Al-Al electrode 56.2 - 69.2
7 Oil separator Gravity oil separator
O&G 80 Fall et al.,
(2007) TSS 88
COD 74
8
Chemical
oxidation by
aeration, alum (80
mg/L), waste
hydrogen
peroxide
(2.5 ml/L)
O&G 96
Bhatti et al.,
(2011)
COD 93
TDS 74
pH 14
Turbidity 94
DO 78
9
Flocculation
column flotation,
sand filtration and
final chlorination
TSS 91
Zaneti et al.,
(2014)
Turbidity 91
TC 95
Notes:
*PS-100= ultrafiltration membrane-polysulfone with molecular weight cut off (MWCO) 100 kDalton,
C-100= ultrafiltration membrane-cellulose with MWCO 100 kDalton, C-30= ultrafiltration membrane-
cellulose with MWCO 30 kDalton, PVDF 100= Polyvinylidene with 100 kDalton, PES 30=
Polyethersulfone with 30 kDalton, NF 270= polyamide with 300 Dalton, NF 270= polyamide with with
170 Dalton (hydrophilic membrane), NFPES 30= polyethersulfone with 1200 Dalton (hydrophobic
membrane) *COD= Chemical oxygen demand, TOC= Total organic carbon, TDS=Total dissolved
solid, TSS=Total suspended solids,O&G= Oil and grease, BOD5= Biochemical oxygen demand at day
PO43−
18
5, Cu (II)= Copper, Pb(II)= Lead, Zn(II)= Zinc, PO43-= Phosphate, DO= Dissolved oxygen, TC= Total
carbon
Membrane technologies commonly used in wastewater treatment in removing
COD, O&G, MBAS, and other biodegradable contaminants (Panpanit, 2001; Boussu
et al., 2007; Hsu et al., 2011; Lau et al., 2013; Shete & Shinkar, 2014). The O&G
attained removal between 70 % to 80 %, compared with MBAS, COD and else, which
above 80 % removal as reviewed in Table 2.3. The O&G was not absorbed directly to
the membranes due to the negative charge repulsion between anionic emulsion and
membrane surface, hence resulting the inefficiency removal than other pollutants.
However, a study by Tri (2002) present the removal above 90 % of O&G with
membrane technologies added with biological activated carbon in their study. The aid
of the activated carbon in membrane technologies helps in the adsorption of O&G
molecules and improved the bioreactor adsorption processes (Tri, 2002). Hydrophilic
membrane presents 85 % to 100 % of surfactant, higher removal than hydrophobic
membrane 53 % removal onwards (Boussu et al., 2007).
The treatment on car wash wastewater in removing O&G also presented with
performances of gravity oil separator (Fall et al., 2007) and oil separator (Al-Odwani
et al., 2007). Even the removal of O&G removed by gravity and oil separator were
above 90 %, however the authors concluded the system does not allow producing an
effluent that complies with the discharge limits established in the sewage system (Al-
Odwani et al., 2007; Fall et al., 2007).
Bhatti et al., (2011) presented study of chemical oxidation in removing
pollutant of O&G, COD, TSS and else in car wash wastewater. The chemical oxidation
including process of aeration for oil water separation, alum treatment for pollutant
removal with aid of hydrogen peroxide. The aeration responsible to separate the oil
and water by trapping the O&G by the air bubbles carrying oxygen, resulting 96 %
removal percentage of O&G and 93 % of COD. This study concluded, the chemical
oxidation processes has potential in reducing the maintenance cost and requires less
space without any pH control, yielding an alternative treatment in car wash wastewater
treatment.
Zaneti et al., (2014) studied on flocculation, filtration and chlorination
processes in car wash wastewater. Flocculation allows the removal of organic matters
and colours of wastewater. However, the treatment should be furthered studied with
19
the other processes, depends on the proper selection of flocculant and proper designed
of system to improve the operations, and proceeed for the next step of treatment.
During the chlorination, the chlorine disinfection deactivated the microorganism lives
resulting death of different mechanisms. As the results, the coupled system of the
treatment effective with removal of TSS, turbidity, TOC were 99 %, 91 %, and 95 %.
Overall, the treatment processes as presented in Table 2.3, have highlighted
and focused on the organic contaminants removal. However, less alternative towards
treatments were made towards MBAS, as it presented as the main cleaning agent of
cleaning processes during washing cars. In spite of using conventional methods and
simple treatment strategies for car wash wastewater treatment system, a wide range of
any low cost potential wastewater treatment should have been investigated and studied.
A study in adsorption processes by using activated carbon may offer the
advantages in car wash wastewater treatment, as it can removed those organic
contaminants. If it is possible in developing other low cost and simple treatment differ
from the treatment that have been reviewed, then these treatments may offer many
advantages and commercially attracting consumers and developers of car wash
stations, and hence contribute to the way of minimizing pollutants of car wash
wastewater (Zayadi et al., 2015).
2.8 Production and Properties of Activated Carbon
Activated carbon used extensively for adsorbing contaminants in wastewater
treatment. In section 2.8, discussion described on nature of activated carbon surfaces,
production processes, various basic properties of activated carbon, low cost adsorbent
of agricultural wastes, adsorption test method to characterize the ability of activated
carbons to adsorb molecules of different sizes with adsorption equilibria of Langmuir
isotherm.
2.8.1 Production of Activated Carbon
Activated carbon has been used for controlling air pollution, water pollution, odors,
and environmental protection causing its demands to increase. The term of activated
carbon is come from the word “carbon” and “active”. Carbon defined as raw material
20
undergoes carbonization process. Whereas, active is a material in carbon condition
which undergoes an activation process to open a pore of surface area to increase
adsorption rate of activated carbon (Zayadi et al., 2014).
Activation has two phase processes. It requiring burn off decomposition
products and enlargement of pores in the carbonized material (Bhatnagar & Minocha,
2006). The source material will be dehydrated and carbonized slowly by heating with
temperature ranging of 400 °C and 900 °C in the absence of air, followed by controlled
oxidation to activate the carbon. The reactions which occur during activation are of the
type shows in Eq. (2.1). The reactions cause solid carbon, C to be converted to gaseous
state. Thereby, it creating number of pores in the the carbon, and activation enlarges
the pore openings (Cooney, 2000).
𝐶 (𝑠𝑜𝑙𝑖𝑑) + 𝐻2𝑂(𝑓𝑙𝑢𝑖𝑑) → 𝐻2(𝑔𝑎𝑠) + 𝐶𝑂(𝑔𝑎𝑠)
𝐶 (𝑠𝑜𝑙𝑖𝑑) + 𝐶𝑂2(𝑔𝑎𝑠) → 2𝐶𝑂(𝑔𝑎𝑠)
𝐶 (𝑠𝑜𝑙𝑖𝑑) + 1 2⁄ 𝐻2𝑂 (𝑓𝑙𝑢𝑖𝑑) → 𝐶𝑂(𝑔𝑎𝑠) (2.1)
Moreover, the adsorption plays significant roles in environment pollution
control. The process of adsorption involved the separation of substances from one
phase by accumulation and concentration at the surface of another. The processes can
take place in solid liquid phase, solid solid phase and solid gas phases. During
adsorption processes, the adsorbing phase generally known as the adsorbate. Whereas,
the material adsorbed at the surface of the adsorbing phase is the adsorbate. The
processes of adsorption was resulted from the universal van der waals reaction and the
electrostatic forces interacted between the adsorbate and the atom of the adsorbent
surfaces (Kandasamy et al., 2012).
Ali et al., (2012) have described about adsorption. Adsorption used as one of
the wastewater treatment due to its ease, and inexpensive operation. Adsorption best
removed the organic pollutants, which it can be up to 99 % removal. During
adsorption, in wastewater treatment, the process occurred between solid adsorbent and
wastewater. Adsorbate known as the pollutants being adsorbed whereas, adsorbent is
the adsorbing phases (Ali et al., 2012).
Zaneti et al., (2011) summarized about the liquid phase adsorption in
wastewater. In liquid phase adsorption, the process considering the phenomenon
21
among adsorbing molecules of the liquid molecules with the adsorbent, where the
interactions occured between the sorbent and the liquid depend on structural and the
solid of sorbent surface.
The growth of microorganism, involving the production of biofilm were
observed on the surface of activated carbon after being used. Biofilm defined as the
accumulation of microorganism onto a surface mainly controlled by the bulk and
surface transport phenomena. The substrate must be transported from the bulk liquid
to the biofilms outer surface where it has to diffuse into the biofilm for its metabolism.
The factors that influence the rate of substrate utilization within a biofilm are substrate
mass transport to the biofilm, diffusion of the substrate into the biofilm, utilization
kinetics within the biofilm, the growth yield of the substrate and the physical factors
affecting the biofilm detachment (Chowdhury et al., 2012).
In adsorption, the important factor governing the pollutant adsorption by
natural adsorbent is the surface morphological structure. The distribution of pores in
activated carbons vary significant depending upon the raw material with Scanning
Electron Microscopy (SEM).
Figure 2.1 shows, microtube structure of kapok fibre (a), hollow cylindrical
tube of bagasse (b), honey combed structure with distinctive wall (c) and closed pore
structure of coconut shell (d).
(b) (a)
22
Figure 2.1: SEM image (a) kapok fibre with 50 µm and 500 magnification (Wahi et
al., 2013) (b) sugarcane bagasse activated carbon with 20 µm and 1000
magnification (Devnarain et al., 2002) (c) coal activated carbon and (d) coconut shell
activated carbon (Jabit, 2007)
Qureshi et al., (2008) have summarized that activated carbon have vast
network of pores with different sizes to bind and detach small and large molecules of
pollutants during adsorption processes. Generally, the adsorbents consisting of
different porous structures including of micropores (smaller than 2nm), mesopores
(between 2 to 50 nm), and macropores (larger than 50 nm).
Beside that, the adsorption in micropores of activated carbon commonly is a
pore filling processes, where the molecules of atoms or any pollutants was filling the
active sites of the pores on the surface of activated carbon.
Moreover, the size of adsorbate are comparable with the micropores size.
Micropores are very important for aqueous applications such as wastewater treatment,
as they are closest in size to many of the target pollutants. Whereas, the mesopores and
macropores providing a diffusion pathways to the internal pores and serve as
adsorption sites for larger compounds pollutants. However, the more packed closely
micropores were much better to access by molecules compared with mesopores and
macropores. Hence, large amount of adsorbent pores consisting of micropores were
essential in producing the greater adsorption processes towards pollutants (Qureshi et
al., 2008).
(c) (d)
23
2.8.2 Physicochemical Properties of Activated Carbon
Activated carbon is an excellent adsorbent due to its practical ability in removing
pollutants in wastewater commonly. It has strong affinity in binding organic
substances in wastewater. However, the activated carbon need to have good properties
in term of physical and chemical properties in order to have great active sites during
adsrption processes. As reviewed by Qureshi et al., (2008), the physical and chemical
or physicochemical properties was described as surface chemistry of activated carbon
consisting of iodine number, ash content, yield test, particle density test and else.
However, the iodine number and ash content were considered in this study.
2.8.2.1 Iodine number of activated carbon
The adsorption test for iodine is a simple and quick test indicating the surface area of
activated carbons (Mutegoa et al., 2014). The iodine number determination measuring
the adsorption of iodine from an aqueous solution on the adsorbents. Beside that,
iodine number quantify the amount of micropores where it indicates the surface area
of activated carbon (Itodo et al., 2010 and Mutegoa et al., 2014).
For example, the iodine number was 585 mg/g (Nimje et al., 2013) and 986
mg/g for coconut shell (Das, 2014). Whereas, Martinez et al., (2012) have iodine
number within 700 to 1100 mg/g due to the intensified activation condition during
preparation, where it produce a wider pore structure of coconut shell activated carbon
with high iodine number. Moreover, the iodine number were depends also to their
chemical activation processes, requiring the burn off raw material in producing
activated carbon (Martinez et al., 2012).
Different activated carbon resulting different amount of iodine number where
iodine number for sugarcane bagasse were 500 to 1593 mg/g (Journal et al., 2005;
Chen et al., 2012; Soussa et al., 2012; Fasoto et al., 2014; Mutegoa et al., 2014;
Gaikwad & Mane, 2015), coconut shell within 585 to 1000 mg/g (Martinez et al.,
2012; Nimje et al., 2013; Das, 2014) and cassava peel of 543 mg/g (Nimje et al., 2013).
Sugarcane bagasse have iodine number of 647.94 to 889.37 mg/g when impregnating
with 20 % phosphoric acid (Chen et al., 2012).
24
Gaikwad & Mane (2015) have stated that iodine number of 500 mg/g adsorbed
into adsorbent resulting an effective of activated carbon towards adsorption processes.
High activated carbon generally, were due to the high degree of activation temperature
during preparation of activated carbon. It is because, when the temperature of
activation were higher which in ranges of 400 °C to 900 °C, the pores on the surface
of activated carbon have enlarged and resulting the forming of new micropores on the
surface of adsorbents. Hence, the high iodine number were performing well in
removing small sized of pollutants in wastewater, rather than lower iodine number.
Moreover, the higher iodine number adsorbed affecting great results in the
adsorption process. When many micropores were found on the surface of activated
carbon, during the adsorption process between adsorbent and wastewater, the surface
of activated carbon itself will not being easily saturated, as it has a large number of
available pores to be occupied (Fasoto et al., 2014).
2.8.2.2 Ash content of activated carbon
In producing activated carbon, ash content is an indicator of the quality of an activated
carbon. Generally, ash forms due to the high buring of activated carbon and longer
contact time during production. When the number of ash content is higher, the decrease
in adsorption process happened. The ash will blocked the pores, resulting saturated
diffusion towards active binding site of activated carbon, and then lowered the removal
efficiency of pollutants during wastewater treatment. Hence, a good activated carbon
should have lower in ash content value, and high carbon content to ensure its good
results in adsorption processes (Chowdury et al., 2012).
The best activated carbon should have lower ash content. The ash content were
as followed where, sugarcane bagasse with 18 % and 20 % (Hugo, 2010), 16 % and
27 % (Fasoto et al., 2014), and 15 % (Gaikwad & Mane, 2015). As described by Fasoto
et al., (2014), the higher ash content consists mostly higher metal oxides. The metal
oxides commonly contaminating the activated carbon itself, hence resulting
inefficiency when using in wastewater treatment. The best activated carbon should
have low ash contents (Hugo, 2010). This hence, results the ash content of coconut
shell with 2 % and 5 % (Nimje et al., 2013; Das, 2014), rice husk and oil cake with 4
% and 6 % respectively (Das, 2014).
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