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BIOCHARS FROM SAGO EFFIJUENT ANn THE APPLICATIONS
Dyg Nurul Qhalila Bt Baling 8ahrin
Master of Sdenf~ (Organk Chemjstry)
2014
Pusat Khidmut Maklumal Akademik UN1VEKSI1l MALAY IA ARAWAK
BIOCHARS FROM SAGO EFFLUENT AND THE APPLICATIONS
DYG NURUL QHALILA BT BALING BAHRIN r
A thesis submitted In fulfillment of the requirements for the degree of Master of Science
(Organic Chemistry)
Faculty of Resource Science and Technology UNIVERSITI MALAYSIA SARA W AK
2014
I
DECLARATION
I hereby declare that no portion of the work referred to this thesis has been submitted
in support of an application for another degree or qualification to this or any other
university or institution of higher learning
(DYG NURUL QHALILA BT BALING BAHRIN)
Date 2~ DkTbStR 2OILf
11
J
J
LIST OF ACHIEVEMENTS
1 Patent No PI 2014700495 Ngaini Z amp Bahrin D N Q (2014) Process of
Producing Biochar and Uses Thereof
2 Bahrin D N Q Ngaini Z Wahi R amp Zulkhamain A (2013) Preparation
and Utilization of Biochar from Sago Effluent International Festival ofScience
Technology Engineering and Mathematics (STEMFEST) Universiti Malaysia
Sarawak
3 Bahrin D N Q Ngainj Z Wahi R amp Zulkhamain A (2013) Applications
of Biochar from Sago Waste International Conference on Water and Wastewater
Management (ICWWM) PWTC Kuala Lumpur
4 Ngaini Z Bahrin D N Q amp Wahi R (2013) Production of Biochar from
Sago Effluent and the Applications International Conference on Water and
Wastewater Management (ICWWM) PWTC Kuala Lumpur
5 Bahrin D N Q Ngaini Z Wahi R amp Zulkhamain A (2013) Preparation of
Solid Catalyst from Sago Activated Carbon 26th Regional Symposium of
Malaysia Analytical Sciences (SKAM26) Kuching
6 Bahrin D N Q amp Ngaini Z (2014) Production of Eco-Catalyst from Sago
Biomass BioBorneo Conference and Exhibition 2014 Universiti Malaysia
Sarawak (Awarded First Prize for Best Poster Design)
7 Ngaini Z Bahrin D N Q amp Zulkhamain A (2014) Eco-Biochar from Sago
Effluent and Industrial Applications Unimas RampD Exposition 2014 Universiti
Malaysia Sarawak (Awarded Silver Medal)
1ll
ACKNOWLEDGEMENT
First and foremost I would like to offer my unreserved gratitude and praises to
Almighty Allah for His generous blessing and shedding on me a good health and keep
my brain working to the extent of completing this research which I hope will
contribute to the welfare of my nation
I would like at this juncture to express my deepest appreciation and gratitude
to my kind supervisor Assoc Prof Dr Zainab Ngaini for her limitless assistance
enthusiasm inspiration and beneficial advice to explain things clearly and simply
throughout the period of my study Her supervision and support truly help the
progression and smoothness of my thesis This thesis work was enabled and sustained
by her great vision and brilliant ideas Thanks and appreciations are also extended to
my co-supervisor and examiners Dr Azham Zulkhamain
I am grateful to the staff at Faculty of Resource Science and Technology
UNIMAS for their invaluable help in many ways especially to En lsmadi and Tuan
Haji Kami and all helpful postgraduate students In addition special thanks also go to
management team of Centre of Graduate Studies
I would like to acknowledge the support of research grant from Ministry of
Energy Green Technology and Water Malaysia under Research Fund Mentoring
Programs IIPTA 1 Menteri Special thank also goesto Kementerian Pengajian Tinggi
Malaysia for the financial assistance through MyBrain15
Finally to my family especially to beloved parent Bahrin Hj Mohamad and
Dyg Siti Meriam Awg Abd Jalil for their love patience encouragement and financial
support To all your kindness is invaluable May Allah Subhanahu wa Taala reward
all of you with happiness and success now and in the hereafter
IV
ABSTRACT
( ReSidues from sago processing mill in Sarawak are commonly discharged into rivers
along with sago effiuent which contributed to serious environmental problems In this
study activated sludge process was introduced onto sago effiuent to afford sago
biomass (SB~ The pH of sago effluent has changed from pH 4 to pH 7 and
chemical oxygen demand (COD) showed intense decrease from 300plusmn033 mgL to
1667plusmn017 mgL after the activated sludge process SBM was transformed into sago
biochar (SBC) via microwave pyrolysis followed by chemical activation using NaOH
and HCI to obtain sago activated carbon (SAC) A great range of functional groups of
-OH C=O COOH and S=O were present in SBM SBC and SAC as evidenced by
Fourier transform infrared (FTIR) spectra Utilisation of SBC showed faster
germination process of the chilli plants SAC was applied as a filter of the effiuent and
showed the COD of effiuent decreased from 123plusmn082 mgL to 30plusmn046 mgL SAC
was also investigated for its potential in removing heavy metals such as Pb Cr and Zn
from aqueous solution Pb Cr and Zn showed highest adsorption onto SAC at 10 g
adsorbent dosage with 8293 3828 and 1478 respectively The study showed
that the adsorption of metals by SAC is dependent on the dosage of adsorbent and the
initial metal concentration The SAC was also applied as solid acid and base catalysts
which prepared by chemical activation using H2S04 and NaOH respectively These
solid carbon supported catalysts have been successfully utilised as heterogeneous
catalyst for esterification reaction in organic synthesis The bioconversion of sago
residue into these value added products could reduce the pollution effect from sago
processing industries
v
BIOCHAR DARlPADA KUMBAHAN SAGU DAN
PENGAPLlKASIANNYA
ABSTRAK
Sisa dari kilang pemprosesan sagu di Sarawak biasanya dialirkan ke sungai bersama
kumbahan sagu yang boleh menyumbang kepada masalah alam sekitar yang serius
Dalam kajian ini proses enapcemar teraktif lelah diperkenalkan dalam proses
rawatan kumbahan sagu dan seterusnya menghasilkan sagu biomas (SBM) Selepas
proses enapcemar teraktif pH kumbahan sagu telah berubah dari pH 4 ke pH 7 dan
permintaan oksigen kimia (COD) menunjukkan penurunan yang ketara dari
300plusmnO33 mgL ke 16 67plusmn017 mgL SBM telah diubahsuai menjadi biochar sagu
(SBC) melalui proses pirolisis gelombang mikro diikuti dengan pengaktifan kimia
menggunakan NaOH dan HCl untuk menghasilkan sagu karbon teraktif (SAC)
Kumpulan berfungsi -OH C=O COOH dan S=O kebanyakannya hadir dalam SBM
SBC dan SAC seperti yang dibuktikan oleh spektrum Fourier transform infrared
(FTIR) Penggunaan SBC mempercepatkan proses percambahan cili SAC telah
diaplikasikan sebagai penapis kumbahan dan COD menurun dari 123plusmn082 mgL to
30plusmn046 mgL SAC juga dikaji dari segi potensi untuk menyingkirkan logam berat
seperti Pb Cr dan Zn daripada larutan akueus Pb Cr dan Zn menunjukkan nilai
jerapan yang tinggi pada setiap 10 g dos penjerap sebanyak 8293 3828 dan
1478 masing-masing Kajian menunjukkan bahawa penjerapan logam oleh SAC
bergantung kepada jumlah dos penjerap dan kepekatan awal larutan logam SAC
juga diaplikasikan sebagai pemangkin asid dan bes yang diperbuat dari pengaktifan
kimia menggunakan H2S04 dan NaOH masing-masing Pemangkin karbon pepejal ini
VI
telah berjaya digunakan sebagai pemangkin heterogen untuk tindak balas esterifikasi
dalam sintesis organik Penukaran-bio kumbahan sagu kepada produk berniai ini
boleh menurunkan kesan pencemaran dari industri pemprosesan sagu
I
vii
Pu at Khidmllt Maklumlt AkademH UN1VERSm MALAYSIA SAltAWAK
TABLE OF CONTENTS
DECLARATION
LIST OF ACHIEVEMENTS
ACKNOWLEDGEMENT
ABSTRACT
ABSTRAK
T ABLE OF CONTENTS
LIST OF TABLES
LIST OF FIGURES
LIST OF SCHEMES
LIST OF ABBREVIATIONS
LIST OF SYMBOLS
CHAPTERl
INTRODUCTION
1 1 Research background
12 Problem statement
14 Research objectives
CHAPTER 2
LITERATURE REVIEW
21 Sago industries
22 Activated sludge process
221 Microorganism in activated sludge process
222 Aerobic oxidation of carbonaceous and nitrogenous matter
viii
Page
II
III
IV
V
VI
viii
xiii
XIV
XVl
XVll
XIX
4
5
6
7
8
9
~ ~~____-I
23 Biomass as a substrate for biochar 11
231 Biomass from activated sludge process 11
232 Biomass composition 12
24 Pyrolysis process of biomass 13
25 Operational condition and techniques of pyrolysis 13
26 Biochar and the pyrolytic products 14
27 Properties of biochar 15
28 Activated carbon from biochar 17
29 Activated carbon and the applications 18
29 1 Water filtration 18
292 Heavy metal adsorption 19
2921 Heavy metals 20
210 Solid phase organic synthesis 21
2101 Solid supported reagent 22
2102 Solid supported catalyst 23
21 021 Solid acid catalyst 24
21022 Solid base catalyst 26
CHAPTER 3
MATERIALS AND METHODS
31 Materials and instrumental 30
32 General methods 31
33 Production of biomass (SBM) from sago effiuent 33
331 Assessment of water quality after activated sludge process 33
3311 Detennination of pH 33
IX
--
II
I
331 2 Detennination of chemical oxygen demand (COD)
331 3 Detennination of total suspended solids (TSS)
3314 Detennination of ammoniacal nitrogen (AN)
332 Characterisation of SBM
3321 Moisture ash and volatile content analysis
3322 FTIR and SEM analysis
34 Production of sago biochar (SBC) from SBM via microwave
pyrolysis
341 Characterisation of SBC
3411 Moisture content analysis
3412 Ultimate analysis
3413 FTIR and SEM analysis
342 Application of SBC as plant enhancer
35 Preparation of sago activated carbon (SAC)
351 Preparation ofSAC1 from SBC
352 Preparation of SAC2 from sago hampas
35 3 Characterisation of SAC 1
3531 Moisture content analysis
3532 FTIR and SEM analysis
354 Application ofSAC1
3541 Water filter system
3542 Heavy metal adsorption
36 Preparation ofbiochar impregnated silica (BIS) as
solid phase reagent
361 Preparation of BIS
34
34
35
35
35
37
38
38
38
38
39
39 39
39
40
40
40
40
41
41
41
42
42
x
I
I
362 Characterisation ofBIS 43
363 Attempted solid phase organic synthesis using BIS 43
37 Preparation of solid base catalyst from SAC 1 43
371 Preparation of solid base catalyst from SACl 44
372 Transesterification of palm oil mill sludge (POMS)
using solid base catalyst 44
38 Preparation of solid acid catalyst from SACl 44
381 Hydrolysis of acetylsalicylic acid (ASA) to salicylic acid 44
382 Synthesis of methyl salicylate 45
CHAPTER 4
RESULTS AND DISCUSSION
41 Production of SBM from activated sludge process 46
411 Assessment of water quality after activated sludge process 47
412 Characterisation of SBM 47
4121 Moisture ash and volatile content analysis 47
4122 FTIR and SEM analysis 48
42 Production of SBC via microwave pyrolysis 50
421 Characterisation of SBC 50
4211 Moisture content analysis 50
4212 Analysis of organic matters 50
4213 FTIR and SEM analysis 51
422 Application of SBC as plant enhancer 53
43 Preparation of SAC 1 from SBC 56
431 Characterisation of SBM 56
Xl
4311 Moisture content analysis 56
4312 FTIR and SEM analysis 57
43 3 Application ofSAC1 60
4331 Water filter system 60
4332 Heavy metal adsorption 61
44 Preparation ofbiochar impregnated silica (BIS)
as solid phase reagent 65
441 Characterisation of BIS 66
442 Attempted solid phase organic synthesis using BIS 67
45 Application of solid base catalyst from SAC 1
in transesterification of palm oil mill sludge (POMS) 70
46 Application of solid acid catalyst in methyl salicylate
preparation
CHAPTER 5
76
CONCLUSION AND RECOMMENDATION
51 Conclusion 80
52 Recommendation 82
REFERENCES 84
APPENDIX A 93
APPENDIXB 95
APPENDIXC 97
APPENDIXD 100
APPENDIXE 102
XII
J
~ LIST OF TABLES I
Page Table 21 Example of solid catalysts and their applications 23
t Table 22 Types of solid base catalyst 26 [ Table 41 Ultimate analysis of SBC 51
Table 42 Analysis of chilli seedlings after 14 days 55 ITable 43 NPK content of SBC 56
Table 44 COD of sago effluent before and after filtration 61
i
1
Xlll
I shy
I
LIST OF FIGURES
Page
Figure 21 Schematic flow diagram for sago processing 7
Figure 22 Bmnsted acidity arising from inductive effect of Lewis 24
acid center coordinated to a silica support
Figure 31 (a) Modified household microwave oven (b) quartz 24
reactor attached to the oven
Figure 32 Methyl salicylate 45
Figure 42 The IR spectrum of SBM 49
Figure 43 The SEM micrograph ofSBM (1000x magnification) 49
Figure 44 The IR spectrum of SBC 52
Figure 45 The SEM micrograph of (a) surface SBC (l2000x 53
magnification) (b) SBC with internal diameter
measurement (l2000x magnification)
Figure 46 Top view of chilli plant after 3 Days 54
Figure 47 (a) Top view (b) Side view of chilli plant after 14 Days 55
Figure 48 The IR spectra of (a) SACI (b) CAC 58
Figure 49 The SEM micrograph of (a) surface SACI 59
(12000x magnification) (b) SAC 1 with internal
diameter measurement (l2000x magnification)
(c) CAC (l2000x magnification)
Figure 4l0 Water filter system using SACI as a filter 60
Figure 411 The effect of adsorbent disages to adsorption of Zn Cr 63
and Pb by SAC 1 at a fixed metal concentration of
5 mgIL
xiv
I
Figure 412 The effect of initia~ concentration to adsorption of Zn 65
Cr and Pb by SAC1 at a fixed adsorbent dosage of
01 g
Figure 413 The SEM micrograph of BIS (5000x magnification) 66
Figure 414 The XRD pattern of amorphous silica from BIS 67
Figure 415 The IR spectra of (a) solid BIS before reaction (b) solid 69
BIS after reaction
Figure 416 The SEM micrograph of (a) solid BIS before reaction 69
(b) solid BIS after reaction
Figure 417 The IR spectra of product using (a) 5 solid base 73
catalyst of SAC 1 (b) 10 solid base catalyst of SAC 1
(c) 5 solid base catalyst of SAC 1 containing silica
(d) 10 solid base catalyst of SAC 1 containing silica
(e) Raw POMS
Figure 418 The IR spectra of product using (a) 5 solid base 75
catalyst of SAC2
(b) 10 solid base catalyst ofSAC2 (c) 5 solid base
catalyst of SAC2 containing silica
(d) 10 solid base catalyst of SAC2 containing silica
(e) Raw POMS
Figure 419 The IR spectra of (a) salicylic acid (b) methyl 78
salicylate
Figure 420 The IH-NMR spectrum of methyl salicylate 79
xv
~ -~----------
Scheme 21
Scheme 41
Scheme 42
Scheme 43
Scheme 44
Scheme 45
LIST OF SCHEMES
Multi-step synthesis using polymer-supported reagents
Synthesis of biphenyl-4-carbonyl chloride
Transesterification of POMS
Mechanism of transesterification of POMS using solid
base catalyst
Esterification of salicylic acid
Mechanism of esterification of salicylic acid using
solid acid catalyst
Page
22
68
70
71
76
77
xvi
l
LIST OF ABBREVIATIONS
AN
ASTM
B1S
BOD
CAC
cBOD
CHN
COD
DCM
FAAS
FTlR
MCM
M41S
nBOD
NMR
NPK
POMS
SAC
SBA
SBC
SBM
SEM
TLC
Ammoniacal nitrogen
American society for testing and materials
Biochar impregnated silica
Biochemical oxygen demand
Commercia~ activated carbon
Carbonaceous biochemical oxygen demand
Carbon hydrogen nitrogen
Chemical oxygen demand
Dichloromethane
Flame atomic absorption spectrometer
Fourier transfonn infrared
Mobil catalytic material
Mesoporous silicate 41
Nitrogeneous biochemical oxygen demand
Nuclear magnetic resonance
Nitrogen phosphorous potassium
Palm oil mill sludge
Sago activated carbon
Santa barbara amorphous
Sago biochar
Sago biomass
Scanning electron microscope
Thin layer chromathography
xvii
TSS Total suspended solid
XRD X-Ray diffractometer
xviii
LIST OF SYMBOLS
degc Degree celsius
U max Maximum vibration
8 Chemical shift
xix
CHAPTER
INTRODUCTION
11 Research background
Sarawak is currently one of the world largest exporters of sago products About 25 000 - 40
000 tonnes of sago products were exported to several countries annually such as Singapore
Taiwan and Japan (Singhal et ai 2008) Approximately 7 tonnes of sago pith waste has been
produced daily from a single sago starch processing mill (Bujang et ai 1996) Sago industries
consume about 30 000 L of water to process one tonne of sago and the liquid residue were
released as wastewater (Banu et ai 2006) The sago residues were released into nearby
streams together with wastewater as sago effluent which can lead to serious environmental
problems and affect aquatic life (Awg-Adeni et ai 2010)
Sago effluent contains high biochemical oxygen demand (BOD) and chemical oxygen demand
(COD) (Awg-Adeni et ai 2010) The effluent also contains high total suspended solid (TSS)
(Rashid et ai 2010) and acidic in nature with high organic matter unpleasant odour and
irritating colour (Ayyasamy et ai 2008) One of the treatments that has been applied onto the
sago effluent was using a hybrid reactor on-site waste treatment with very short retention
periods which combines both fixed-film and up-flow anaerobic sludge blanket systems (Banu
et ai 2006) The sago effluent was treated by the hybrid reactor for the reduction of COD
(Banu et ai 2006) The hybrid reactor system is a combination of suspended-film and fixedshy
film growth processes (Shannon et ai 2002) Sago effluent was also utilised as an additional
carbon in anaerobic digesters for the production of biogas (Abd-Aziz 2002) Other application
of biomass produced from the treated sago effluent was as a supplement for prawn feed in
aquaculture industries (Vickineswary et at 1997)
Activated sludge process is a wastewater treatment process which utilising bacteria and
microorganism to degrade suspended and dissolved organic matter via aerobic or anaerobic
oxidation (Gerardi 2006) It is a process in which a mixture of sewage and activated sludge
are agitated and aerated The sludge residue from activated sludge process can be easily
removed from the water through simple sedimentation Other treatment method such as
anaerobic digestion of sago effluent seems to be costly and difficult to maintain the system
(Ganczarczyk 1983) As an alternative aerobic digestion was introduced via activated sludge
proce s to treat sago effluent This treatment has more advantage as it utilises aerobic
microbes which grow faster than anaerobic microbes and consist of a simple process only
(Ganczarczyk 1983) In this study the sago biomass generated from the activated sludge was
chemically treated to produce sago biochar
Nowadays biochars are being prepared manually for various applications Biochars were
usually applied in environmental management such as soil improvement waste management
climate change mitigation and energy production (Lehmann and Joseph 2009) Biochar is a
carbon rich product obtained from biomass that undergo thermal decomposition with little or
absence of air at elevated temperature via pyrolysis (Lehmann and Joseph 2009) Pyrolysis is
a thermo-chemical process in which organic material is converted into a carbon rich solid
which is char and volatile matter by heating in the absence of oxygen (Demirbas and Arin
2002) A higher amount of volatile matter released during pyrolysis of biomass produces
2
biochars with lower densities and higher porosities (Vassilev et at 2009) The various
functional groups on the surface of biochar such as C=O S=O and -OH influence the sorption
of adsorbate by the nature of their surface charge and by the availability of 1t electron
(Lehmann and Joseph 2009) Pyrolysis process is regularly used for biochar production as the
technique is relatively simple and inexpensive and allows considerable flexibility in both the
type and quality of the biomass feedstock (Laird et at 2009) Microwave pyrolysis is the
latest technology used to pyrolyse biomass Microwave pyrolysis offers more advantages over
conventional heated pyrolysis due to unifonn and efficient heating (Miura et at 2004)
Biochar has also been used as a precursor for the production of activated carbon Activated
carbon is effective and used in various applications such as in water treatment for drinking
water metal extraction and heterogeneous catalysts (Azargohar and Dalai 2006) However
the usage of commercial activated carbon is limited due to its higher preparation cost (Rao et
at 2009) Several studies reported on the utilisation of agricultural wastes for the production
of low cost activated carbon such as palm oil miH shells (Nik et at 2006) groundnut shells
(Malik et at 2007) physic nut wastes (Pechyen et at 2007) hulls of rice and wheat (Qiu et
at 2008 Rao et at 2009) and palm oil empty fruit bunch (Wahi et at 2009) However there
are no studies reported on the production of activated carbon from sago processing waste
either from sago pith or sago effluent
3
12 Problem statements
Mass production of agricultural waste has become an issue to the government and
environmentalists due to illegal disposal into the jungles or the rivers which destroy the
ecosystem Sago industries generate significant amount of wastes annually either as sago pith
or sago effluent Practically direct waste disposal to the rivers brings harmful effect to the
aquatic life This study was conducted to produce some value added products from the sago
effluent Limited reserve land for agricultural waste disposal leads to the transformation of the
waste into value added products Therefore there is a need to overcome the environmental
problem caused by the disposal of sago waste In this study the sago effluent was treated via
activated sludge process to produce biomass which then transformed into biochars and applied
for various applications The production of value added products from sago waste will provide
economical solution for waste management in sago industries
4
Pusat Khidmut Maklumal Akademik UN1VEKSI1l MALAY IA ARAWAK
BIOCHARS FROM SAGO EFFLUENT AND THE APPLICATIONS
DYG NURUL QHALILA BT BALING BAHRIN r
A thesis submitted In fulfillment of the requirements for the degree of Master of Science
(Organic Chemistry)
Faculty of Resource Science and Technology UNIVERSITI MALAYSIA SARA W AK
2014
I
DECLARATION
I hereby declare that no portion of the work referred to this thesis has been submitted
in support of an application for another degree or qualification to this or any other
university or institution of higher learning
(DYG NURUL QHALILA BT BALING BAHRIN)
Date 2~ DkTbStR 2OILf
11
J
J
LIST OF ACHIEVEMENTS
1 Patent No PI 2014700495 Ngaini Z amp Bahrin D N Q (2014) Process of
Producing Biochar and Uses Thereof
2 Bahrin D N Q Ngaini Z Wahi R amp Zulkhamain A (2013) Preparation
and Utilization of Biochar from Sago Effluent International Festival ofScience
Technology Engineering and Mathematics (STEMFEST) Universiti Malaysia
Sarawak
3 Bahrin D N Q Ngainj Z Wahi R amp Zulkhamain A (2013) Applications
of Biochar from Sago Waste International Conference on Water and Wastewater
Management (ICWWM) PWTC Kuala Lumpur
4 Ngaini Z Bahrin D N Q amp Wahi R (2013) Production of Biochar from
Sago Effluent and the Applications International Conference on Water and
Wastewater Management (ICWWM) PWTC Kuala Lumpur
5 Bahrin D N Q Ngaini Z Wahi R amp Zulkhamain A (2013) Preparation of
Solid Catalyst from Sago Activated Carbon 26th Regional Symposium of
Malaysia Analytical Sciences (SKAM26) Kuching
6 Bahrin D N Q amp Ngaini Z (2014) Production of Eco-Catalyst from Sago
Biomass BioBorneo Conference and Exhibition 2014 Universiti Malaysia
Sarawak (Awarded First Prize for Best Poster Design)
7 Ngaini Z Bahrin D N Q amp Zulkhamain A (2014) Eco-Biochar from Sago
Effluent and Industrial Applications Unimas RampD Exposition 2014 Universiti
Malaysia Sarawak (Awarded Silver Medal)
1ll
ACKNOWLEDGEMENT
First and foremost I would like to offer my unreserved gratitude and praises to
Almighty Allah for His generous blessing and shedding on me a good health and keep
my brain working to the extent of completing this research which I hope will
contribute to the welfare of my nation
I would like at this juncture to express my deepest appreciation and gratitude
to my kind supervisor Assoc Prof Dr Zainab Ngaini for her limitless assistance
enthusiasm inspiration and beneficial advice to explain things clearly and simply
throughout the period of my study Her supervision and support truly help the
progression and smoothness of my thesis This thesis work was enabled and sustained
by her great vision and brilliant ideas Thanks and appreciations are also extended to
my co-supervisor and examiners Dr Azham Zulkhamain
I am grateful to the staff at Faculty of Resource Science and Technology
UNIMAS for their invaluable help in many ways especially to En lsmadi and Tuan
Haji Kami and all helpful postgraduate students In addition special thanks also go to
management team of Centre of Graduate Studies
I would like to acknowledge the support of research grant from Ministry of
Energy Green Technology and Water Malaysia under Research Fund Mentoring
Programs IIPTA 1 Menteri Special thank also goesto Kementerian Pengajian Tinggi
Malaysia for the financial assistance through MyBrain15
Finally to my family especially to beloved parent Bahrin Hj Mohamad and
Dyg Siti Meriam Awg Abd Jalil for their love patience encouragement and financial
support To all your kindness is invaluable May Allah Subhanahu wa Taala reward
all of you with happiness and success now and in the hereafter
IV
ABSTRACT
( ReSidues from sago processing mill in Sarawak are commonly discharged into rivers
along with sago effiuent which contributed to serious environmental problems In this
study activated sludge process was introduced onto sago effiuent to afford sago
biomass (SB~ The pH of sago effluent has changed from pH 4 to pH 7 and
chemical oxygen demand (COD) showed intense decrease from 300plusmn033 mgL to
1667plusmn017 mgL after the activated sludge process SBM was transformed into sago
biochar (SBC) via microwave pyrolysis followed by chemical activation using NaOH
and HCI to obtain sago activated carbon (SAC) A great range of functional groups of
-OH C=O COOH and S=O were present in SBM SBC and SAC as evidenced by
Fourier transform infrared (FTIR) spectra Utilisation of SBC showed faster
germination process of the chilli plants SAC was applied as a filter of the effiuent and
showed the COD of effiuent decreased from 123plusmn082 mgL to 30plusmn046 mgL SAC
was also investigated for its potential in removing heavy metals such as Pb Cr and Zn
from aqueous solution Pb Cr and Zn showed highest adsorption onto SAC at 10 g
adsorbent dosage with 8293 3828 and 1478 respectively The study showed
that the adsorption of metals by SAC is dependent on the dosage of adsorbent and the
initial metal concentration The SAC was also applied as solid acid and base catalysts
which prepared by chemical activation using H2S04 and NaOH respectively These
solid carbon supported catalysts have been successfully utilised as heterogeneous
catalyst for esterification reaction in organic synthesis The bioconversion of sago
residue into these value added products could reduce the pollution effect from sago
processing industries
v
BIOCHAR DARlPADA KUMBAHAN SAGU DAN
PENGAPLlKASIANNYA
ABSTRAK
Sisa dari kilang pemprosesan sagu di Sarawak biasanya dialirkan ke sungai bersama
kumbahan sagu yang boleh menyumbang kepada masalah alam sekitar yang serius
Dalam kajian ini proses enapcemar teraktif lelah diperkenalkan dalam proses
rawatan kumbahan sagu dan seterusnya menghasilkan sagu biomas (SBM) Selepas
proses enapcemar teraktif pH kumbahan sagu telah berubah dari pH 4 ke pH 7 dan
permintaan oksigen kimia (COD) menunjukkan penurunan yang ketara dari
300plusmnO33 mgL ke 16 67plusmn017 mgL SBM telah diubahsuai menjadi biochar sagu
(SBC) melalui proses pirolisis gelombang mikro diikuti dengan pengaktifan kimia
menggunakan NaOH dan HCl untuk menghasilkan sagu karbon teraktif (SAC)
Kumpulan berfungsi -OH C=O COOH dan S=O kebanyakannya hadir dalam SBM
SBC dan SAC seperti yang dibuktikan oleh spektrum Fourier transform infrared
(FTIR) Penggunaan SBC mempercepatkan proses percambahan cili SAC telah
diaplikasikan sebagai penapis kumbahan dan COD menurun dari 123plusmn082 mgL to
30plusmn046 mgL SAC juga dikaji dari segi potensi untuk menyingkirkan logam berat
seperti Pb Cr dan Zn daripada larutan akueus Pb Cr dan Zn menunjukkan nilai
jerapan yang tinggi pada setiap 10 g dos penjerap sebanyak 8293 3828 dan
1478 masing-masing Kajian menunjukkan bahawa penjerapan logam oleh SAC
bergantung kepada jumlah dos penjerap dan kepekatan awal larutan logam SAC
juga diaplikasikan sebagai pemangkin asid dan bes yang diperbuat dari pengaktifan
kimia menggunakan H2S04 dan NaOH masing-masing Pemangkin karbon pepejal ini
VI
telah berjaya digunakan sebagai pemangkin heterogen untuk tindak balas esterifikasi
dalam sintesis organik Penukaran-bio kumbahan sagu kepada produk berniai ini
boleh menurunkan kesan pencemaran dari industri pemprosesan sagu
I
vii
Pu at Khidmllt Maklumlt AkademH UN1VERSm MALAYSIA SAltAWAK
TABLE OF CONTENTS
DECLARATION
LIST OF ACHIEVEMENTS
ACKNOWLEDGEMENT
ABSTRACT
ABSTRAK
T ABLE OF CONTENTS
LIST OF TABLES
LIST OF FIGURES
LIST OF SCHEMES
LIST OF ABBREVIATIONS
LIST OF SYMBOLS
CHAPTERl
INTRODUCTION
1 1 Research background
12 Problem statement
14 Research objectives
CHAPTER 2
LITERATURE REVIEW
21 Sago industries
22 Activated sludge process
221 Microorganism in activated sludge process
222 Aerobic oxidation of carbonaceous and nitrogenous matter
viii
Page
II
III
IV
V
VI
viii
xiii
XIV
XVl
XVll
XIX
4
5
6
7
8
9
~ ~~____-I
23 Biomass as a substrate for biochar 11
231 Biomass from activated sludge process 11
232 Biomass composition 12
24 Pyrolysis process of biomass 13
25 Operational condition and techniques of pyrolysis 13
26 Biochar and the pyrolytic products 14
27 Properties of biochar 15
28 Activated carbon from biochar 17
29 Activated carbon and the applications 18
29 1 Water filtration 18
292 Heavy metal adsorption 19
2921 Heavy metals 20
210 Solid phase organic synthesis 21
2101 Solid supported reagent 22
2102 Solid supported catalyst 23
21 021 Solid acid catalyst 24
21022 Solid base catalyst 26
CHAPTER 3
MATERIALS AND METHODS
31 Materials and instrumental 30
32 General methods 31
33 Production of biomass (SBM) from sago effiuent 33
331 Assessment of water quality after activated sludge process 33
3311 Detennination of pH 33
IX
--
II
I
331 2 Detennination of chemical oxygen demand (COD)
331 3 Detennination of total suspended solids (TSS)
3314 Detennination of ammoniacal nitrogen (AN)
332 Characterisation of SBM
3321 Moisture ash and volatile content analysis
3322 FTIR and SEM analysis
34 Production of sago biochar (SBC) from SBM via microwave
pyrolysis
341 Characterisation of SBC
3411 Moisture content analysis
3412 Ultimate analysis
3413 FTIR and SEM analysis
342 Application of SBC as plant enhancer
35 Preparation of sago activated carbon (SAC)
351 Preparation ofSAC1 from SBC
352 Preparation of SAC2 from sago hampas
35 3 Characterisation of SAC 1
3531 Moisture content analysis
3532 FTIR and SEM analysis
354 Application ofSAC1
3541 Water filter system
3542 Heavy metal adsorption
36 Preparation ofbiochar impregnated silica (BIS) as
solid phase reagent
361 Preparation of BIS
34
34
35
35
35
37
38
38
38
38
39
39 39
39
40
40
40
40
41
41
41
42
42
x
I
I
362 Characterisation ofBIS 43
363 Attempted solid phase organic synthesis using BIS 43
37 Preparation of solid base catalyst from SAC 1 43
371 Preparation of solid base catalyst from SACl 44
372 Transesterification of palm oil mill sludge (POMS)
using solid base catalyst 44
38 Preparation of solid acid catalyst from SACl 44
381 Hydrolysis of acetylsalicylic acid (ASA) to salicylic acid 44
382 Synthesis of methyl salicylate 45
CHAPTER 4
RESULTS AND DISCUSSION
41 Production of SBM from activated sludge process 46
411 Assessment of water quality after activated sludge process 47
412 Characterisation of SBM 47
4121 Moisture ash and volatile content analysis 47
4122 FTIR and SEM analysis 48
42 Production of SBC via microwave pyrolysis 50
421 Characterisation of SBC 50
4211 Moisture content analysis 50
4212 Analysis of organic matters 50
4213 FTIR and SEM analysis 51
422 Application of SBC as plant enhancer 53
43 Preparation of SAC 1 from SBC 56
431 Characterisation of SBM 56
Xl
4311 Moisture content analysis 56
4312 FTIR and SEM analysis 57
43 3 Application ofSAC1 60
4331 Water filter system 60
4332 Heavy metal adsorption 61
44 Preparation ofbiochar impregnated silica (BIS)
as solid phase reagent 65
441 Characterisation of BIS 66
442 Attempted solid phase organic synthesis using BIS 67
45 Application of solid base catalyst from SAC 1
in transesterification of palm oil mill sludge (POMS) 70
46 Application of solid acid catalyst in methyl salicylate
preparation
CHAPTER 5
76
CONCLUSION AND RECOMMENDATION
51 Conclusion 80
52 Recommendation 82
REFERENCES 84
APPENDIX A 93
APPENDIXB 95
APPENDIXC 97
APPENDIXD 100
APPENDIXE 102
XII
J
~ LIST OF TABLES I
Page Table 21 Example of solid catalysts and their applications 23
t Table 22 Types of solid base catalyst 26 [ Table 41 Ultimate analysis of SBC 51
Table 42 Analysis of chilli seedlings after 14 days 55 ITable 43 NPK content of SBC 56
Table 44 COD of sago effluent before and after filtration 61
i
1
Xlll
I shy
I
LIST OF FIGURES
Page
Figure 21 Schematic flow diagram for sago processing 7
Figure 22 Bmnsted acidity arising from inductive effect of Lewis 24
acid center coordinated to a silica support
Figure 31 (a) Modified household microwave oven (b) quartz 24
reactor attached to the oven
Figure 32 Methyl salicylate 45
Figure 42 The IR spectrum of SBM 49
Figure 43 The SEM micrograph ofSBM (1000x magnification) 49
Figure 44 The IR spectrum of SBC 52
Figure 45 The SEM micrograph of (a) surface SBC (l2000x 53
magnification) (b) SBC with internal diameter
measurement (l2000x magnification)
Figure 46 Top view of chilli plant after 3 Days 54
Figure 47 (a) Top view (b) Side view of chilli plant after 14 Days 55
Figure 48 The IR spectra of (a) SACI (b) CAC 58
Figure 49 The SEM micrograph of (a) surface SACI 59
(12000x magnification) (b) SAC 1 with internal
diameter measurement (l2000x magnification)
(c) CAC (l2000x magnification)
Figure 4l0 Water filter system using SACI as a filter 60
Figure 411 The effect of adsorbent disages to adsorption of Zn Cr 63
and Pb by SAC 1 at a fixed metal concentration of
5 mgIL
xiv
I
Figure 412 The effect of initia~ concentration to adsorption of Zn 65
Cr and Pb by SAC1 at a fixed adsorbent dosage of
01 g
Figure 413 The SEM micrograph of BIS (5000x magnification) 66
Figure 414 The XRD pattern of amorphous silica from BIS 67
Figure 415 The IR spectra of (a) solid BIS before reaction (b) solid 69
BIS after reaction
Figure 416 The SEM micrograph of (a) solid BIS before reaction 69
(b) solid BIS after reaction
Figure 417 The IR spectra of product using (a) 5 solid base 73
catalyst of SAC 1 (b) 10 solid base catalyst of SAC 1
(c) 5 solid base catalyst of SAC 1 containing silica
(d) 10 solid base catalyst of SAC 1 containing silica
(e) Raw POMS
Figure 418 The IR spectra of product using (a) 5 solid base 75
catalyst of SAC2
(b) 10 solid base catalyst ofSAC2 (c) 5 solid base
catalyst of SAC2 containing silica
(d) 10 solid base catalyst of SAC2 containing silica
(e) Raw POMS
Figure 419 The IR spectra of (a) salicylic acid (b) methyl 78
salicylate
Figure 420 The IH-NMR spectrum of methyl salicylate 79
xv
~ -~----------
Scheme 21
Scheme 41
Scheme 42
Scheme 43
Scheme 44
Scheme 45
LIST OF SCHEMES
Multi-step synthesis using polymer-supported reagents
Synthesis of biphenyl-4-carbonyl chloride
Transesterification of POMS
Mechanism of transesterification of POMS using solid
base catalyst
Esterification of salicylic acid
Mechanism of esterification of salicylic acid using
solid acid catalyst
Page
22
68
70
71
76
77
xvi
l
LIST OF ABBREVIATIONS
AN
ASTM
B1S
BOD
CAC
cBOD
CHN
COD
DCM
FAAS
FTlR
MCM
M41S
nBOD
NMR
NPK
POMS
SAC
SBA
SBC
SBM
SEM
TLC
Ammoniacal nitrogen
American society for testing and materials
Biochar impregnated silica
Biochemical oxygen demand
Commercia~ activated carbon
Carbonaceous biochemical oxygen demand
Carbon hydrogen nitrogen
Chemical oxygen demand
Dichloromethane
Flame atomic absorption spectrometer
Fourier transfonn infrared
Mobil catalytic material
Mesoporous silicate 41
Nitrogeneous biochemical oxygen demand
Nuclear magnetic resonance
Nitrogen phosphorous potassium
Palm oil mill sludge
Sago activated carbon
Santa barbara amorphous
Sago biochar
Sago biomass
Scanning electron microscope
Thin layer chromathography
xvii
TSS Total suspended solid
XRD X-Ray diffractometer
xviii
LIST OF SYMBOLS
degc Degree celsius
U max Maximum vibration
8 Chemical shift
xix
CHAPTER
INTRODUCTION
11 Research background
Sarawak is currently one of the world largest exporters of sago products About 25 000 - 40
000 tonnes of sago products were exported to several countries annually such as Singapore
Taiwan and Japan (Singhal et ai 2008) Approximately 7 tonnes of sago pith waste has been
produced daily from a single sago starch processing mill (Bujang et ai 1996) Sago industries
consume about 30 000 L of water to process one tonne of sago and the liquid residue were
released as wastewater (Banu et ai 2006) The sago residues were released into nearby
streams together with wastewater as sago effluent which can lead to serious environmental
problems and affect aquatic life (Awg-Adeni et ai 2010)
Sago effluent contains high biochemical oxygen demand (BOD) and chemical oxygen demand
(COD) (Awg-Adeni et ai 2010) The effluent also contains high total suspended solid (TSS)
(Rashid et ai 2010) and acidic in nature with high organic matter unpleasant odour and
irritating colour (Ayyasamy et ai 2008) One of the treatments that has been applied onto the
sago effluent was using a hybrid reactor on-site waste treatment with very short retention
periods which combines both fixed-film and up-flow anaerobic sludge blanket systems (Banu
et ai 2006) The sago effluent was treated by the hybrid reactor for the reduction of COD
(Banu et ai 2006) The hybrid reactor system is a combination of suspended-film and fixedshy
film growth processes (Shannon et ai 2002) Sago effluent was also utilised as an additional
carbon in anaerobic digesters for the production of biogas (Abd-Aziz 2002) Other application
of biomass produced from the treated sago effluent was as a supplement for prawn feed in
aquaculture industries (Vickineswary et at 1997)
Activated sludge process is a wastewater treatment process which utilising bacteria and
microorganism to degrade suspended and dissolved organic matter via aerobic or anaerobic
oxidation (Gerardi 2006) It is a process in which a mixture of sewage and activated sludge
are agitated and aerated The sludge residue from activated sludge process can be easily
removed from the water through simple sedimentation Other treatment method such as
anaerobic digestion of sago effluent seems to be costly and difficult to maintain the system
(Ganczarczyk 1983) As an alternative aerobic digestion was introduced via activated sludge
proce s to treat sago effluent This treatment has more advantage as it utilises aerobic
microbes which grow faster than anaerobic microbes and consist of a simple process only
(Ganczarczyk 1983) In this study the sago biomass generated from the activated sludge was
chemically treated to produce sago biochar
Nowadays biochars are being prepared manually for various applications Biochars were
usually applied in environmental management such as soil improvement waste management
climate change mitigation and energy production (Lehmann and Joseph 2009) Biochar is a
carbon rich product obtained from biomass that undergo thermal decomposition with little or
absence of air at elevated temperature via pyrolysis (Lehmann and Joseph 2009) Pyrolysis is
a thermo-chemical process in which organic material is converted into a carbon rich solid
which is char and volatile matter by heating in the absence of oxygen (Demirbas and Arin
2002) A higher amount of volatile matter released during pyrolysis of biomass produces
2
biochars with lower densities and higher porosities (Vassilev et at 2009) The various
functional groups on the surface of biochar such as C=O S=O and -OH influence the sorption
of adsorbate by the nature of their surface charge and by the availability of 1t electron
(Lehmann and Joseph 2009) Pyrolysis process is regularly used for biochar production as the
technique is relatively simple and inexpensive and allows considerable flexibility in both the
type and quality of the biomass feedstock (Laird et at 2009) Microwave pyrolysis is the
latest technology used to pyrolyse biomass Microwave pyrolysis offers more advantages over
conventional heated pyrolysis due to unifonn and efficient heating (Miura et at 2004)
Biochar has also been used as a precursor for the production of activated carbon Activated
carbon is effective and used in various applications such as in water treatment for drinking
water metal extraction and heterogeneous catalysts (Azargohar and Dalai 2006) However
the usage of commercial activated carbon is limited due to its higher preparation cost (Rao et
at 2009) Several studies reported on the utilisation of agricultural wastes for the production
of low cost activated carbon such as palm oil miH shells (Nik et at 2006) groundnut shells
(Malik et at 2007) physic nut wastes (Pechyen et at 2007) hulls of rice and wheat (Qiu et
at 2008 Rao et at 2009) and palm oil empty fruit bunch (Wahi et at 2009) However there
are no studies reported on the production of activated carbon from sago processing waste
either from sago pith or sago effluent
3
12 Problem statements
Mass production of agricultural waste has become an issue to the government and
environmentalists due to illegal disposal into the jungles or the rivers which destroy the
ecosystem Sago industries generate significant amount of wastes annually either as sago pith
or sago effluent Practically direct waste disposal to the rivers brings harmful effect to the
aquatic life This study was conducted to produce some value added products from the sago
effluent Limited reserve land for agricultural waste disposal leads to the transformation of the
waste into value added products Therefore there is a need to overcome the environmental
problem caused by the disposal of sago waste In this study the sago effluent was treated via
activated sludge process to produce biomass which then transformed into biochars and applied
for various applications The production of value added products from sago waste will provide
economical solution for waste management in sago industries
4
I
DECLARATION
I hereby declare that no portion of the work referred to this thesis has been submitted
in support of an application for another degree or qualification to this or any other
university or institution of higher learning
(DYG NURUL QHALILA BT BALING BAHRIN)
Date 2~ DkTbStR 2OILf
11
J
J
LIST OF ACHIEVEMENTS
1 Patent No PI 2014700495 Ngaini Z amp Bahrin D N Q (2014) Process of
Producing Biochar and Uses Thereof
2 Bahrin D N Q Ngaini Z Wahi R amp Zulkhamain A (2013) Preparation
and Utilization of Biochar from Sago Effluent International Festival ofScience
Technology Engineering and Mathematics (STEMFEST) Universiti Malaysia
Sarawak
3 Bahrin D N Q Ngainj Z Wahi R amp Zulkhamain A (2013) Applications
of Biochar from Sago Waste International Conference on Water and Wastewater
Management (ICWWM) PWTC Kuala Lumpur
4 Ngaini Z Bahrin D N Q amp Wahi R (2013) Production of Biochar from
Sago Effluent and the Applications International Conference on Water and
Wastewater Management (ICWWM) PWTC Kuala Lumpur
5 Bahrin D N Q Ngaini Z Wahi R amp Zulkhamain A (2013) Preparation of
Solid Catalyst from Sago Activated Carbon 26th Regional Symposium of
Malaysia Analytical Sciences (SKAM26) Kuching
6 Bahrin D N Q amp Ngaini Z (2014) Production of Eco-Catalyst from Sago
Biomass BioBorneo Conference and Exhibition 2014 Universiti Malaysia
Sarawak (Awarded First Prize for Best Poster Design)
7 Ngaini Z Bahrin D N Q amp Zulkhamain A (2014) Eco-Biochar from Sago
Effluent and Industrial Applications Unimas RampD Exposition 2014 Universiti
Malaysia Sarawak (Awarded Silver Medal)
1ll
ACKNOWLEDGEMENT
First and foremost I would like to offer my unreserved gratitude and praises to
Almighty Allah for His generous blessing and shedding on me a good health and keep
my brain working to the extent of completing this research which I hope will
contribute to the welfare of my nation
I would like at this juncture to express my deepest appreciation and gratitude
to my kind supervisor Assoc Prof Dr Zainab Ngaini for her limitless assistance
enthusiasm inspiration and beneficial advice to explain things clearly and simply
throughout the period of my study Her supervision and support truly help the
progression and smoothness of my thesis This thesis work was enabled and sustained
by her great vision and brilliant ideas Thanks and appreciations are also extended to
my co-supervisor and examiners Dr Azham Zulkhamain
I am grateful to the staff at Faculty of Resource Science and Technology
UNIMAS for their invaluable help in many ways especially to En lsmadi and Tuan
Haji Kami and all helpful postgraduate students In addition special thanks also go to
management team of Centre of Graduate Studies
I would like to acknowledge the support of research grant from Ministry of
Energy Green Technology and Water Malaysia under Research Fund Mentoring
Programs IIPTA 1 Menteri Special thank also goesto Kementerian Pengajian Tinggi
Malaysia for the financial assistance through MyBrain15
Finally to my family especially to beloved parent Bahrin Hj Mohamad and
Dyg Siti Meriam Awg Abd Jalil for their love patience encouragement and financial
support To all your kindness is invaluable May Allah Subhanahu wa Taala reward
all of you with happiness and success now and in the hereafter
IV
ABSTRACT
( ReSidues from sago processing mill in Sarawak are commonly discharged into rivers
along with sago effiuent which contributed to serious environmental problems In this
study activated sludge process was introduced onto sago effiuent to afford sago
biomass (SB~ The pH of sago effluent has changed from pH 4 to pH 7 and
chemical oxygen demand (COD) showed intense decrease from 300plusmn033 mgL to
1667plusmn017 mgL after the activated sludge process SBM was transformed into sago
biochar (SBC) via microwave pyrolysis followed by chemical activation using NaOH
and HCI to obtain sago activated carbon (SAC) A great range of functional groups of
-OH C=O COOH and S=O were present in SBM SBC and SAC as evidenced by
Fourier transform infrared (FTIR) spectra Utilisation of SBC showed faster
germination process of the chilli plants SAC was applied as a filter of the effiuent and
showed the COD of effiuent decreased from 123plusmn082 mgL to 30plusmn046 mgL SAC
was also investigated for its potential in removing heavy metals such as Pb Cr and Zn
from aqueous solution Pb Cr and Zn showed highest adsorption onto SAC at 10 g
adsorbent dosage with 8293 3828 and 1478 respectively The study showed
that the adsorption of metals by SAC is dependent on the dosage of adsorbent and the
initial metal concentration The SAC was also applied as solid acid and base catalysts
which prepared by chemical activation using H2S04 and NaOH respectively These
solid carbon supported catalysts have been successfully utilised as heterogeneous
catalyst for esterification reaction in organic synthesis The bioconversion of sago
residue into these value added products could reduce the pollution effect from sago
processing industries
v
BIOCHAR DARlPADA KUMBAHAN SAGU DAN
PENGAPLlKASIANNYA
ABSTRAK
Sisa dari kilang pemprosesan sagu di Sarawak biasanya dialirkan ke sungai bersama
kumbahan sagu yang boleh menyumbang kepada masalah alam sekitar yang serius
Dalam kajian ini proses enapcemar teraktif lelah diperkenalkan dalam proses
rawatan kumbahan sagu dan seterusnya menghasilkan sagu biomas (SBM) Selepas
proses enapcemar teraktif pH kumbahan sagu telah berubah dari pH 4 ke pH 7 dan
permintaan oksigen kimia (COD) menunjukkan penurunan yang ketara dari
300plusmnO33 mgL ke 16 67plusmn017 mgL SBM telah diubahsuai menjadi biochar sagu
(SBC) melalui proses pirolisis gelombang mikro diikuti dengan pengaktifan kimia
menggunakan NaOH dan HCl untuk menghasilkan sagu karbon teraktif (SAC)
Kumpulan berfungsi -OH C=O COOH dan S=O kebanyakannya hadir dalam SBM
SBC dan SAC seperti yang dibuktikan oleh spektrum Fourier transform infrared
(FTIR) Penggunaan SBC mempercepatkan proses percambahan cili SAC telah
diaplikasikan sebagai penapis kumbahan dan COD menurun dari 123plusmn082 mgL to
30plusmn046 mgL SAC juga dikaji dari segi potensi untuk menyingkirkan logam berat
seperti Pb Cr dan Zn daripada larutan akueus Pb Cr dan Zn menunjukkan nilai
jerapan yang tinggi pada setiap 10 g dos penjerap sebanyak 8293 3828 dan
1478 masing-masing Kajian menunjukkan bahawa penjerapan logam oleh SAC
bergantung kepada jumlah dos penjerap dan kepekatan awal larutan logam SAC
juga diaplikasikan sebagai pemangkin asid dan bes yang diperbuat dari pengaktifan
kimia menggunakan H2S04 dan NaOH masing-masing Pemangkin karbon pepejal ini
VI
telah berjaya digunakan sebagai pemangkin heterogen untuk tindak balas esterifikasi
dalam sintesis organik Penukaran-bio kumbahan sagu kepada produk berniai ini
boleh menurunkan kesan pencemaran dari industri pemprosesan sagu
I
vii
Pu at Khidmllt Maklumlt AkademH UN1VERSm MALAYSIA SAltAWAK
TABLE OF CONTENTS
DECLARATION
LIST OF ACHIEVEMENTS
ACKNOWLEDGEMENT
ABSTRACT
ABSTRAK
T ABLE OF CONTENTS
LIST OF TABLES
LIST OF FIGURES
LIST OF SCHEMES
LIST OF ABBREVIATIONS
LIST OF SYMBOLS
CHAPTERl
INTRODUCTION
1 1 Research background
12 Problem statement
14 Research objectives
CHAPTER 2
LITERATURE REVIEW
21 Sago industries
22 Activated sludge process
221 Microorganism in activated sludge process
222 Aerobic oxidation of carbonaceous and nitrogenous matter
viii
Page
II
III
IV
V
VI
viii
xiii
XIV
XVl
XVll
XIX
4
5
6
7
8
9
~ ~~____-I
23 Biomass as a substrate for biochar 11
231 Biomass from activated sludge process 11
232 Biomass composition 12
24 Pyrolysis process of biomass 13
25 Operational condition and techniques of pyrolysis 13
26 Biochar and the pyrolytic products 14
27 Properties of biochar 15
28 Activated carbon from biochar 17
29 Activated carbon and the applications 18
29 1 Water filtration 18
292 Heavy metal adsorption 19
2921 Heavy metals 20
210 Solid phase organic synthesis 21
2101 Solid supported reagent 22
2102 Solid supported catalyst 23
21 021 Solid acid catalyst 24
21022 Solid base catalyst 26
CHAPTER 3
MATERIALS AND METHODS
31 Materials and instrumental 30
32 General methods 31
33 Production of biomass (SBM) from sago effiuent 33
331 Assessment of water quality after activated sludge process 33
3311 Detennination of pH 33
IX
--
II
I
331 2 Detennination of chemical oxygen demand (COD)
331 3 Detennination of total suspended solids (TSS)
3314 Detennination of ammoniacal nitrogen (AN)
332 Characterisation of SBM
3321 Moisture ash and volatile content analysis
3322 FTIR and SEM analysis
34 Production of sago biochar (SBC) from SBM via microwave
pyrolysis
341 Characterisation of SBC
3411 Moisture content analysis
3412 Ultimate analysis
3413 FTIR and SEM analysis
342 Application of SBC as plant enhancer
35 Preparation of sago activated carbon (SAC)
351 Preparation ofSAC1 from SBC
352 Preparation of SAC2 from sago hampas
35 3 Characterisation of SAC 1
3531 Moisture content analysis
3532 FTIR and SEM analysis
354 Application ofSAC1
3541 Water filter system
3542 Heavy metal adsorption
36 Preparation ofbiochar impregnated silica (BIS) as
solid phase reagent
361 Preparation of BIS
34
34
35
35
35
37
38
38
38
38
39
39 39
39
40
40
40
40
41
41
41
42
42
x
I
I
362 Characterisation ofBIS 43
363 Attempted solid phase organic synthesis using BIS 43
37 Preparation of solid base catalyst from SAC 1 43
371 Preparation of solid base catalyst from SACl 44
372 Transesterification of palm oil mill sludge (POMS)
using solid base catalyst 44
38 Preparation of solid acid catalyst from SACl 44
381 Hydrolysis of acetylsalicylic acid (ASA) to salicylic acid 44
382 Synthesis of methyl salicylate 45
CHAPTER 4
RESULTS AND DISCUSSION
41 Production of SBM from activated sludge process 46
411 Assessment of water quality after activated sludge process 47
412 Characterisation of SBM 47
4121 Moisture ash and volatile content analysis 47
4122 FTIR and SEM analysis 48
42 Production of SBC via microwave pyrolysis 50
421 Characterisation of SBC 50
4211 Moisture content analysis 50
4212 Analysis of organic matters 50
4213 FTIR and SEM analysis 51
422 Application of SBC as plant enhancer 53
43 Preparation of SAC 1 from SBC 56
431 Characterisation of SBM 56
Xl
4311 Moisture content analysis 56
4312 FTIR and SEM analysis 57
43 3 Application ofSAC1 60
4331 Water filter system 60
4332 Heavy metal adsorption 61
44 Preparation ofbiochar impregnated silica (BIS)
as solid phase reagent 65
441 Characterisation of BIS 66
442 Attempted solid phase organic synthesis using BIS 67
45 Application of solid base catalyst from SAC 1
in transesterification of palm oil mill sludge (POMS) 70
46 Application of solid acid catalyst in methyl salicylate
preparation
CHAPTER 5
76
CONCLUSION AND RECOMMENDATION
51 Conclusion 80
52 Recommendation 82
REFERENCES 84
APPENDIX A 93
APPENDIXB 95
APPENDIXC 97
APPENDIXD 100
APPENDIXE 102
XII
J
~ LIST OF TABLES I
Page Table 21 Example of solid catalysts and their applications 23
t Table 22 Types of solid base catalyst 26 [ Table 41 Ultimate analysis of SBC 51
Table 42 Analysis of chilli seedlings after 14 days 55 ITable 43 NPK content of SBC 56
Table 44 COD of sago effluent before and after filtration 61
i
1
Xlll
I shy
I
LIST OF FIGURES
Page
Figure 21 Schematic flow diagram for sago processing 7
Figure 22 Bmnsted acidity arising from inductive effect of Lewis 24
acid center coordinated to a silica support
Figure 31 (a) Modified household microwave oven (b) quartz 24
reactor attached to the oven
Figure 32 Methyl salicylate 45
Figure 42 The IR spectrum of SBM 49
Figure 43 The SEM micrograph ofSBM (1000x magnification) 49
Figure 44 The IR spectrum of SBC 52
Figure 45 The SEM micrograph of (a) surface SBC (l2000x 53
magnification) (b) SBC with internal diameter
measurement (l2000x magnification)
Figure 46 Top view of chilli plant after 3 Days 54
Figure 47 (a) Top view (b) Side view of chilli plant after 14 Days 55
Figure 48 The IR spectra of (a) SACI (b) CAC 58
Figure 49 The SEM micrograph of (a) surface SACI 59
(12000x magnification) (b) SAC 1 with internal
diameter measurement (l2000x magnification)
(c) CAC (l2000x magnification)
Figure 4l0 Water filter system using SACI as a filter 60
Figure 411 The effect of adsorbent disages to adsorption of Zn Cr 63
and Pb by SAC 1 at a fixed metal concentration of
5 mgIL
xiv
I
Figure 412 The effect of initia~ concentration to adsorption of Zn 65
Cr and Pb by SAC1 at a fixed adsorbent dosage of
01 g
Figure 413 The SEM micrograph of BIS (5000x magnification) 66
Figure 414 The XRD pattern of amorphous silica from BIS 67
Figure 415 The IR spectra of (a) solid BIS before reaction (b) solid 69
BIS after reaction
Figure 416 The SEM micrograph of (a) solid BIS before reaction 69
(b) solid BIS after reaction
Figure 417 The IR spectra of product using (a) 5 solid base 73
catalyst of SAC 1 (b) 10 solid base catalyst of SAC 1
(c) 5 solid base catalyst of SAC 1 containing silica
(d) 10 solid base catalyst of SAC 1 containing silica
(e) Raw POMS
Figure 418 The IR spectra of product using (a) 5 solid base 75
catalyst of SAC2
(b) 10 solid base catalyst ofSAC2 (c) 5 solid base
catalyst of SAC2 containing silica
(d) 10 solid base catalyst of SAC2 containing silica
(e) Raw POMS
Figure 419 The IR spectra of (a) salicylic acid (b) methyl 78
salicylate
Figure 420 The IH-NMR spectrum of methyl salicylate 79
xv
~ -~----------
Scheme 21
Scheme 41
Scheme 42
Scheme 43
Scheme 44
Scheme 45
LIST OF SCHEMES
Multi-step synthesis using polymer-supported reagents
Synthesis of biphenyl-4-carbonyl chloride
Transesterification of POMS
Mechanism of transesterification of POMS using solid
base catalyst
Esterification of salicylic acid
Mechanism of esterification of salicylic acid using
solid acid catalyst
Page
22
68
70
71
76
77
xvi
l
LIST OF ABBREVIATIONS
AN
ASTM
B1S
BOD
CAC
cBOD
CHN
COD
DCM
FAAS
FTlR
MCM
M41S
nBOD
NMR
NPK
POMS
SAC
SBA
SBC
SBM
SEM
TLC
Ammoniacal nitrogen
American society for testing and materials
Biochar impregnated silica
Biochemical oxygen demand
Commercia~ activated carbon
Carbonaceous biochemical oxygen demand
Carbon hydrogen nitrogen
Chemical oxygen demand
Dichloromethane
Flame atomic absorption spectrometer
Fourier transfonn infrared
Mobil catalytic material
Mesoporous silicate 41
Nitrogeneous biochemical oxygen demand
Nuclear magnetic resonance
Nitrogen phosphorous potassium
Palm oil mill sludge
Sago activated carbon
Santa barbara amorphous
Sago biochar
Sago biomass
Scanning electron microscope
Thin layer chromathography
xvii
TSS Total suspended solid
XRD X-Ray diffractometer
xviii
LIST OF SYMBOLS
degc Degree celsius
U max Maximum vibration
8 Chemical shift
xix
CHAPTER
INTRODUCTION
11 Research background
Sarawak is currently one of the world largest exporters of sago products About 25 000 - 40
000 tonnes of sago products were exported to several countries annually such as Singapore
Taiwan and Japan (Singhal et ai 2008) Approximately 7 tonnes of sago pith waste has been
produced daily from a single sago starch processing mill (Bujang et ai 1996) Sago industries
consume about 30 000 L of water to process one tonne of sago and the liquid residue were
released as wastewater (Banu et ai 2006) The sago residues were released into nearby
streams together with wastewater as sago effluent which can lead to serious environmental
problems and affect aquatic life (Awg-Adeni et ai 2010)
Sago effluent contains high biochemical oxygen demand (BOD) and chemical oxygen demand
(COD) (Awg-Adeni et ai 2010) The effluent also contains high total suspended solid (TSS)
(Rashid et ai 2010) and acidic in nature with high organic matter unpleasant odour and
irritating colour (Ayyasamy et ai 2008) One of the treatments that has been applied onto the
sago effluent was using a hybrid reactor on-site waste treatment with very short retention
periods which combines both fixed-film and up-flow anaerobic sludge blanket systems (Banu
et ai 2006) The sago effluent was treated by the hybrid reactor for the reduction of COD
(Banu et ai 2006) The hybrid reactor system is a combination of suspended-film and fixedshy
film growth processes (Shannon et ai 2002) Sago effluent was also utilised as an additional
carbon in anaerobic digesters for the production of biogas (Abd-Aziz 2002) Other application
of biomass produced from the treated sago effluent was as a supplement for prawn feed in
aquaculture industries (Vickineswary et at 1997)
Activated sludge process is a wastewater treatment process which utilising bacteria and
microorganism to degrade suspended and dissolved organic matter via aerobic or anaerobic
oxidation (Gerardi 2006) It is a process in which a mixture of sewage and activated sludge
are agitated and aerated The sludge residue from activated sludge process can be easily
removed from the water through simple sedimentation Other treatment method such as
anaerobic digestion of sago effluent seems to be costly and difficult to maintain the system
(Ganczarczyk 1983) As an alternative aerobic digestion was introduced via activated sludge
proce s to treat sago effluent This treatment has more advantage as it utilises aerobic
microbes which grow faster than anaerobic microbes and consist of a simple process only
(Ganczarczyk 1983) In this study the sago biomass generated from the activated sludge was
chemically treated to produce sago biochar
Nowadays biochars are being prepared manually for various applications Biochars were
usually applied in environmental management such as soil improvement waste management
climate change mitigation and energy production (Lehmann and Joseph 2009) Biochar is a
carbon rich product obtained from biomass that undergo thermal decomposition with little or
absence of air at elevated temperature via pyrolysis (Lehmann and Joseph 2009) Pyrolysis is
a thermo-chemical process in which organic material is converted into a carbon rich solid
which is char and volatile matter by heating in the absence of oxygen (Demirbas and Arin
2002) A higher amount of volatile matter released during pyrolysis of biomass produces
2
biochars with lower densities and higher porosities (Vassilev et at 2009) The various
functional groups on the surface of biochar such as C=O S=O and -OH influence the sorption
of adsorbate by the nature of their surface charge and by the availability of 1t electron
(Lehmann and Joseph 2009) Pyrolysis process is regularly used for biochar production as the
technique is relatively simple and inexpensive and allows considerable flexibility in both the
type and quality of the biomass feedstock (Laird et at 2009) Microwave pyrolysis is the
latest technology used to pyrolyse biomass Microwave pyrolysis offers more advantages over
conventional heated pyrolysis due to unifonn and efficient heating (Miura et at 2004)
Biochar has also been used as a precursor for the production of activated carbon Activated
carbon is effective and used in various applications such as in water treatment for drinking
water metal extraction and heterogeneous catalysts (Azargohar and Dalai 2006) However
the usage of commercial activated carbon is limited due to its higher preparation cost (Rao et
at 2009) Several studies reported on the utilisation of agricultural wastes for the production
of low cost activated carbon such as palm oil miH shells (Nik et at 2006) groundnut shells
(Malik et at 2007) physic nut wastes (Pechyen et at 2007) hulls of rice and wheat (Qiu et
at 2008 Rao et at 2009) and palm oil empty fruit bunch (Wahi et at 2009) However there
are no studies reported on the production of activated carbon from sago processing waste
either from sago pith or sago effluent
3
12 Problem statements
Mass production of agricultural waste has become an issue to the government and
environmentalists due to illegal disposal into the jungles or the rivers which destroy the
ecosystem Sago industries generate significant amount of wastes annually either as sago pith
or sago effluent Practically direct waste disposal to the rivers brings harmful effect to the
aquatic life This study was conducted to produce some value added products from the sago
effluent Limited reserve land for agricultural waste disposal leads to the transformation of the
waste into value added products Therefore there is a need to overcome the environmental
problem caused by the disposal of sago waste In this study the sago effluent was treated via
activated sludge process to produce biomass which then transformed into biochars and applied
for various applications The production of value added products from sago waste will provide
economical solution for waste management in sago industries
4
LIST OF ACHIEVEMENTS
1 Patent No PI 2014700495 Ngaini Z amp Bahrin D N Q (2014) Process of
Producing Biochar and Uses Thereof
2 Bahrin D N Q Ngaini Z Wahi R amp Zulkhamain A (2013) Preparation
and Utilization of Biochar from Sago Effluent International Festival ofScience
Technology Engineering and Mathematics (STEMFEST) Universiti Malaysia
Sarawak
3 Bahrin D N Q Ngainj Z Wahi R amp Zulkhamain A (2013) Applications
of Biochar from Sago Waste International Conference on Water and Wastewater
Management (ICWWM) PWTC Kuala Lumpur
4 Ngaini Z Bahrin D N Q amp Wahi R (2013) Production of Biochar from
Sago Effluent and the Applications International Conference on Water and
Wastewater Management (ICWWM) PWTC Kuala Lumpur
5 Bahrin D N Q Ngaini Z Wahi R amp Zulkhamain A (2013) Preparation of
Solid Catalyst from Sago Activated Carbon 26th Regional Symposium of
Malaysia Analytical Sciences (SKAM26) Kuching
6 Bahrin D N Q amp Ngaini Z (2014) Production of Eco-Catalyst from Sago
Biomass BioBorneo Conference and Exhibition 2014 Universiti Malaysia
Sarawak (Awarded First Prize for Best Poster Design)
7 Ngaini Z Bahrin D N Q amp Zulkhamain A (2014) Eco-Biochar from Sago
Effluent and Industrial Applications Unimas RampD Exposition 2014 Universiti
Malaysia Sarawak (Awarded Silver Medal)
1ll
ACKNOWLEDGEMENT
First and foremost I would like to offer my unreserved gratitude and praises to
Almighty Allah for His generous blessing and shedding on me a good health and keep
my brain working to the extent of completing this research which I hope will
contribute to the welfare of my nation
I would like at this juncture to express my deepest appreciation and gratitude
to my kind supervisor Assoc Prof Dr Zainab Ngaini for her limitless assistance
enthusiasm inspiration and beneficial advice to explain things clearly and simply
throughout the period of my study Her supervision and support truly help the
progression and smoothness of my thesis This thesis work was enabled and sustained
by her great vision and brilliant ideas Thanks and appreciations are also extended to
my co-supervisor and examiners Dr Azham Zulkhamain
I am grateful to the staff at Faculty of Resource Science and Technology
UNIMAS for their invaluable help in many ways especially to En lsmadi and Tuan
Haji Kami and all helpful postgraduate students In addition special thanks also go to
management team of Centre of Graduate Studies
I would like to acknowledge the support of research grant from Ministry of
Energy Green Technology and Water Malaysia under Research Fund Mentoring
Programs IIPTA 1 Menteri Special thank also goesto Kementerian Pengajian Tinggi
Malaysia for the financial assistance through MyBrain15
Finally to my family especially to beloved parent Bahrin Hj Mohamad and
Dyg Siti Meriam Awg Abd Jalil for their love patience encouragement and financial
support To all your kindness is invaluable May Allah Subhanahu wa Taala reward
all of you with happiness and success now and in the hereafter
IV
ABSTRACT
( ReSidues from sago processing mill in Sarawak are commonly discharged into rivers
along with sago effiuent which contributed to serious environmental problems In this
study activated sludge process was introduced onto sago effiuent to afford sago
biomass (SB~ The pH of sago effluent has changed from pH 4 to pH 7 and
chemical oxygen demand (COD) showed intense decrease from 300plusmn033 mgL to
1667plusmn017 mgL after the activated sludge process SBM was transformed into sago
biochar (SBC) via microwave pyrolysis followed by chemical activation using NaOH
and HCI to obtain sago activated carbon (SAC) A great range of functional groups of
-OH C=O COOH and S=O were present in SBM SBC and SAC as evidenced by
Fourier transform infrared (FTIR) spectra Utilisation of SBC showed faster
germination process of the chilli plants SAC was applied as a filter of the effiuent and
showed the COD of effiuent decreased from 123plusmn082 mgL to 30plusmn046 mgL SAC
was also investigated for its potential in removing heavy metals such as Pb Cr and Zn
from aqueous solution Pb Cr and Zn showed highest adsorption onto SAC at 10 g
adsorbent dosage with 8293 3828 and 1478 respectively The study showed
that the adsorption of metals by SAC is dependent on the dosage of adsorbent and the
initial metal concentration The SAC was also applied as solid acid and base catalysts
which prepared by chemical activation using H2S04 and NaOH respectively These
solid carbon supported catalysts have been successfully utilised as heterogeneous
catalyst for esterification reaction in organic synthesis The bioconversion of sago
residue into these value added products could reduce the pollution effect from sago
processing industries
v
BIOCHAR DARlPADA KUMBAHAN SAGU DAN
PENGAPLlKASIANNYA
ABSTRAK
Sisa dari kilang pemprosesan sagu di Sarawak biasanya dialirkan ke sungai bersama
kumbahan sagu yang boleh menyumbang kepada masalah alam sekitar yang serius
Dalam kajian ini proses enapcemar teraktif lelah diperkenalkan dalam proses
rawatan kumbahan sagu dan seterusnya menghasilkan sagu biomas (SBM) Selepas
proses enapcemar teraktif pH kumbahan sagu telah berubah dari pH 4 ke pH 7 dan
permintaan oksigen kimia (COD) menunjukkan penurunan yang ketara dari
300plusmnO33 mgL ke 16 67plusmn017 mgL SBM telah diubahsuai menjadi biochar sagu
(SBC) melalui proses pirolisis gelombang mikro diikuti dengan pengaktifan kimia
menggunakan NaOH dan HCl untuk menghasilkan sagu karbon teraktif (SAC)
Kumpulan berfungsi -OH C=O COOH dan S=O kebanyakannya hadir dalam SBM
SBC dan SAC seperti yang dibuktikan oleh spektrum Fourier transform infrared
(FTIR) Penggunaan SBC mempercepatkan proses percambahan cili SAC telah
diaplikasikan sebagai penapis kumbahan dan COD menurun dari 123plusmn082 mgL to
30plusmn046 mgL SAC juga dikaji dari segi potensi untuk menyingkirkan logam berat
seperti Pb Cr dan Zn daripada larutan akueus Pb Cr dan Zn menunjukkan nilai
jerapan yang tinggi pada setiap 10 g dos penjerap sebanyak 8293 3828 dan
1478 masing-masing Kajian menunjukkan bahawa penjerapan logam oleh SAC
bergantung kepada jumlah dos penjerap dan kepekatan awal larutan logam SAC
juga diaplikasikan sebagai pemangkin asid dan bes yang diperbuat dari pengaktifan
kimia menggunakan H2S04 dan NaOH masing-masing Pemangkin karbon pepejal ini
VI
telah berjaya digunakan sebagai pemangkin heterogen untuk tindak balas esterifikasi
dalam sintesis organik Penukaran-bio kumbahan sagu kepada produk berniai ini
boleh menurunkan kesan pencemaran dari industri pemprosesan sagu
I
vii
Pu at Khidmllt Maklumlt AkademH UN1VERSm MALAYSIA SAltAWAK
TABLE OF CONTENTS
DECLARATION
LIST OF ACHIEVEMENTS
ACKNOWLEDGEMENT
ABSTRACT
ABSTRAK
T ABLE OF CONTENTS
LIST OF TABLES
LIST OF FIGURES
LIST OF SCHEMES
LIST OF ABBREVIATIONS
LIST OF SYMBOLS
CHAPTERl
INTRODUCTION
1 1 Research background
12 Problem statement
14 Research objectives
CHAPTER 2
LITERATURE REVIEW
21 Sago industries
22 Activated sludge process
221 Microorganism in activated sludge process
222 Aerobic oxidation of carbonaceous and nitrogenous matter
viii
Page
II
III
IV
V
VI
viii
xiii
XIV
XVl
XVll
XIX
4
5
6
7
8
9
~ ~~____-I
23 Biomass as a substrate for biochar 11
231 Biomass from activated sludge process 11
232 Biomass composition 12
24 Pyrolysis process of biomass 13
25 Operational condition and techniques of pyrolysis 13
26 Biochar and the pyrolytic products 14
27 Properties of biochar 15
28 Activated carbon from biochar 17
29 Activated carbon and the applications 18
29 1 Water filtration 18
292 Heavy metal adsorption 19
2921 Heavy metals 20
210 Solid phase organic synthesis 21
2101 Solid supported reagent 22
2102 Solid supported catalyst 23
21 021 Solid acid catalyst 24
21022 Solid base catalyst 26
CHAPTER 3
MATERIALS AND METHODS
31 Materials and instrumental 30
32 General methods 31
33 Production of biomass (SBM) from sago effiuent 33
331 Assessment of water quality after activated sludge process 33
3311 Detennination of pH 33
IX
--
II
I
331 2 Detennination of chemical oxygen demand (COD)
331 3 Detennination of total suspended solids (TSS)
3314 Detennination of ammoniacal nitrogen (AN)
332 Characterisation of SBM
3321 Moisture ash and volatile content analysis
3322 FTIR and SEM analysis
34 Production of sago biochar (SBC) from SBM via microwave
pyrolysis
341 Characterisation of SBC
3411 Moisture content analysis
3412 Ultimate analysis
3413 FTIR and SEM analysis
342 Application of SBC as plant enhancer
35 Preparation of sago activated carbon (SAC)
351 Preparation ofSAC1 from SBC
352 Preparation of SAC2 from sago hampas
35 3 Characterisation of SAC 1
3531 Moisture content analysis
3532 FTIR and SEM analysis
354 Application ofSAC1
3541 Water filter system
3542 Heavy metal adsorption
36 Preparation ofbiochar impregnated silica (BIS) as
solid phase reagent
361 Preparation of BIS
34
34
35
35
35
37
38
38
38
38
39
39 39
39
40
40
40
40
41
41
41
42
42
x
I
I
362 Characterisation ofBIS 43
363 Attempted solid phase organic synthesis using BIS 43
37 Preparation of solid base catalyst from SAC 1 43
371 Preparation of solid base catalyst from SACl 44
372 Transesterification of palm oil mill sludge (POMS)
using solid base catalyst 44
38 Preparation of solid acid catalyst from SACl 44
381 Hydrolysis of acetylsalicylic acid (ASA) to salicylic acid 44
382 Synthesis of methyl salicylate 45
CHAPTER 4
RESULTS AND DISCUSSION
41 Production of SBM from activated sludge process 46
411 Assessment of water quality after activated sludge process 47
412 Characterisation of SBM 47
4121 Moisture ash and volatile content analysis 47
4122 FTIR and SEM analysis 48
42 Production of SBC via microwave pyrolysis 50
421 Characterisation of SBC 50
4211 Moisture content analysis 50
4212 Analysis of organic matters 50
4213 FTIR and SEM analysis 51
422 Application of SBC as plant enhancer 53
43 Preparation of SAC 1 from SBC 56
431 Characterisation of SBM 56
Xl
4311 Moisture content analysis 56
4312 FTIR and SEM analysis 57
43 3 Application ofSAC1 60
4331 Water filter system 60
4332 Heavy metal adsorption 61
44 Preparation ofbiochar impregnated silica (BIS)
as solid phase reagent 65
441 Characterisation of BIS 66
442 Attempted solid phase organic synthesis using BIS 67
45 Application of solid base catalyst from SAC 1
in transesterification of palm oil mill sludge (POMS) 70
46 Application of solid acid catalyst in methyl salicylate
preparation
CHAPTER 5
76
CONCLUSION AND RECOMMENDATION
51 Conclusion 80
52 Recommendation 82
REFERENCES 84
APPENDIX A 93
APPENDIXB 95
APPENDIXC 97
APPENDIXD 100
APPENDIXE 102
XII
J
~ LIST OF TABLES I
Page Table 21 Example of solid catalysts and their applications 23
t Table 22 Types of solid base catalyst 26 [ Table 41 Ultimate analysis of SBC 51
Table 42 Analysis of chilli seedlings after 14 days 55 ITable 43 NPK content of SBC 56
Table 44 COD of sago effluent before and after filtration 61
i
1
Xlll
I shy
I
LIST OF FIGURES
Page
Figure 21 Schematic flow diagram for sago processing 7
Figure 22 Bmnsted acidity arising from inductive effect of Lewis 24
acid center coordinated to a silica support
Figure 31 (a) Modified household microwave oven (b) quartz 24
reactor attached to the oven
Figure 32 Methyl salicylate 45
Figure 42 The IR spectrum of SBM 49
Figure 43 The SEM micrograph ofSBM (1000x magnification) 49
Figure 44 The IR spectrum of SBC 52
Figure 45 The SEM micrograph of (a) surface SBC (l2000x 53
magnification) (b) SBC with internal diameter
measurement (l2000x magnification)
Figure 46 Top view of chilli plant after 3 Days 54
Figure 47 (a) Top view (b) Side view of chilli plant after 14 Days 55
Figure 48 The IR spectra of (a) SACI (b) CAC 58
Figure 49 The SEM micrograph of (a) surface SACI 59
(12000x magnification) (b) SAC 1 with internal
diameter measurement (l2000x magnification)
(c) CAC (l2000x magnification)
Figure 4l0 Water filter system using SACI as a filter 60
Figure 411 The effect of adsorbent disages to adsorption of Zn Cr 63
and Pb by SAC 1 at a fixed metal concentration of
5 mgIL
xiv
I
Figure 412 The effect of initia~ concentration to adsorption of Zn 65
Cr and Pb by SAC1 at a fixed adsorbent dosage of
01 g
Figure 413 The SEM micrograph of BIS (5000x magnification) 66
Figure 414 The XRD pattern of amorphous silica from BIS 67
Figure 415 The IR spectra of (a) solid BIS before reaction (b) solid 69
BIS after reaction
Figure 416 The SEM micrograph of (a) solid BIS before reaction 69
(b) solid BIS after reaction
Figure 417 The IR spectra of product using (a) 5 solid base 73
catalyst of SAC 1 (b) 10 solid base catalyst of SAC 1
(c) 5 solid base catalyst of SAC 1 containing silica
(d) 10 solid base catalyst of SAC 1 containing silica
(e) Raw POMS
Figure 418 The IR spectra of product using (a) 5 solid base 75
catalyst of SAC2
(b) 10 solid base catalyst ofSAC2 (c) 5 solid base
catalyst of SAC2 containing silica
(d) 10 solid base catalyst of SAC2 containing silica
(e) Raw POMS
Figure 419 The IR spectra of (a) salicylic acid (b) methyl 78
salicylate
Figure 420 The IH-NMR spectrum of methyl salicylate 79
xv
~ -~----------
Scheme 21
Scheme 41
Scheme 42
Scheme 43
Scheme 44
Scheme 45
LIST OF SCHEMES
Multi-step synthesis using polymer-supported reagents
Synthesis of biphenyl-4-carbonyl chloride
Transesterification of POMS
Mechanism of transesterification of POMS using solid
base catalyst
Esterification of salicylic acid
Mechanism of esterification of salicylic acid using
solid acid catalyst
Page
22
68
70
71
76
77
xvi
l
LIST OF ABBREVIATIONS
AN
ASTM
B1S
BOD
CAC
cBOD
CHN
COD
DCM
FAAS
FTlR
MCM
M41S
nBOD
NMR
NPK
POMS
SAC
SBA
SBC
SBM
SEM
TLC
Ammoniacal nitrogen
American society for testing and materials
Biochar impregnated silica
Biochemical oxygen demand
Commercia~ activated carbon
Carbonaceous biochemical oxygen demand
Carbon hydrogen nitrogen
Chemical oxygen demand
Dichloromethane
Flame atomic absorption spectrometer
Fourier transfonn infrared
Mobil catalytic material
Mesoporous silicate 41
Nitrogeneous biochemical oxygen demand
Nuclear magnetic resonance
Nitrogen phosphorous potassium
Palm oil mill sludge
Sago activated carbon
Santa barbara amorphous
Sago biochar
Sago biomass
Scanning electron microscope
Thin layer chromathography
xvii
TSS Total suspended solid
XRD X-Ray diffractometer
xviii
LIST OF SYMBOLS
degc Degree celsius
U max Maximum vibration
8 Chemical shift
xix
CHAPTER
INTRODUCTION
11 Research background
Sarawak is currently one of the world largest exporters of sago products About 25 000 - 40
000 tonnes of sago products were exported to several countries annually such as Singapore
Taiwan and Japan (Singhal et ai 2008) Approximately 7 tonnes of sago pith waste has been
produced daily from a single sago starch processing mill (Bujang et ai 1996) Sago industries
consume about 30 000 L of water to process one tonne of sago and the liquid residue were
released as wastewater (Banu et ai 2006) The sago residues were released into nearby
streams together with wastewater as sago effluent which can lead to serious environmental
problems and affect aquatic life (Awg-Adeni et ai 2010)
Sago effluent contains high biochemical oxygen demand (BOD) and chemical oxygen demand
(COD) (Awg-Adeni et ai 2010) The effluent also contains high total suspended solid (TSS)
(Rashid et ai 2010) and acidic in nature with high organic matter unpleasant odour and
irritating colour (Ayyasamy et ai 2008) One of the treatments that has been applied onto the
sago effluent was using a hybrid reactor on-site waste treatment with very short retention
periods which combines both fixed-film and up-flow anaerobic sludge blanket systems (Banu
et ai 2006) The sago effluent was treated by the hybrid reactor for the reduction of COD
(Banu et ai 2006) The hybrid reactor system is a combination of suspended-film and fixedshy
film growth processes (Shannon et ai 2002) Sago effluent was also utilised as an additional
carbon in anaerobic digesters for the production of biogas (Abd-Aziz 2002) Other application
of biomass produced from the treated sago effluent was as a supplement for prawn feed in
aquaculture industries (Vickineswary et at 1997)
Activated sludge process is a wastewater treatment process which utilising bacteria and
microorganism to degrade suspended and dissolved organic matter via aerobic or anaerobic
oxidation (Gerardi 2006) It is a process in which a mixture of sewage and activated sludge
are agitated and aerated The sludge residue from activated sludge process can be easily
removed from the water through simple sedimentation Other treatment method such as
anaerobic digestion of sago effluent seems to be costly and difficult to maintain the system
(Ganczarczyk 1983) As an alternative aerobic digestion was introduced via activated sludge
proce s to treat sago effluent This treatment has more advantage as it utilises aerobic
microbes which grow faster than anaerobic microbes and consist of a simple process only
(Ganczarczyk 1983) In this study the sago biomass generated from the activated sludge was
chemically treated to produce sago biochar
Nowadays biochars are being prepared manually for various applications Biochars were
usually applied in environmental management such as soil improvement waste management
climate change mitigation and energy production (Lehmann and Joseph 2009) Biochar is a
carbon rich product obtained from biomass that undergo thermal decomposition with little or
absence of air at elevated temperature via pyrolysis (Lehmann and Joseph 2009) Pyrolysis is
a thermo-chemical process in which organic material is converted into a carbon rich solid
which is char and volatile matter by heating in the absence of oxygen (Demirbas and Arin
2002) A higher amount of volatile matter released during pyrolysis of biomass produces
2
biochars with lower densities and higher porosities (Vassilev et at 2009) The various
functional groups on the surface of biochar such as C=O S=O and -OH influence the sorption
of adsorbate by the nature of their surface charge and by the availability of 1t electron
(Lehmann and Joseph 2009) Pyrolysis process is regularly used for biochar production as the
technique is relatively simple and inexpensive and allows considerable flexibility in both the
type and quality of the biomass feedstock (Laird et at 2009) Microwave pyrolysis is the
latest technology used to pyrolyse biomass Microwave pyrolysis offers more advantages over
conventional heated pyrolysis due to unifonn and efficient heating (Miura et at 2004)
Biochar has also been used as a precursor for the production of activated carbon Activated
carbon is effective and used in various applications such as in water treatment for drinking
water metal extraction and heterogeneous catalysts (Azargohar and Dalai 2006) However
the usage of commercial activated carbon is limited due to its higher preparation cost (Rao et
at 2009) Several studies reported on the utilisation of agricultural wastes for the production
of low cost activated carbon such as palm oil miH shells (Nik et at 2006) groundnut shells
(Malik et at 2007) physic nut wastes (Pechyen et at 2007) hulls of rice and wheat (Qiu et
at 2008 Rao et at 2009) and palm oil empty fruit bunch (Wahi et at 2009) However there
are no studies reported on the production of activated carbon from sago processing waste
either from sago pith or sago effluent
3
12 Problem statements
Mass production of agricultural waste has become an issue to the government and
environmentalists due to illegal disposal into the jungles or the rivers which destroy the
ecosystem Sago industries generate significant amount of wastes annually either as sago pith
or sago effluent Practically direct waste disposal to the rivers brings harmful effect to the
aquatic life This study was conducted to produce some value added products from the sago
effluent Limited reserve land for agricultural waste disposal leads to the transformation of the
waste into value added products Therefore there is a need to overcome the environmental
problem caused by the disposal of sago waste In this study the sago effluent was treated via
activated sludge process to produce biomass which then transformed into biochars and applied
for various applications The production of value added products from sago waste will provide
economical solution for waste management in sago industries
4
ACKNOWLEDGEMENT
First and foremost I would like to offer my unreserved gratitude and praises to
Almighty Allah for His generous blessing and shedding on me a good health and keep
my brain working to the extent of completing this research which I hope will
contribute to the welfare of my nation
I would like at this juncture to express my deepest appreciation and gratitude
to my kind supervisor Assoc Prof Dr Zainab Ngaini for her limitless assistance
enthusiasm inspiration and beneficial advice to explain things clearly and simply
throughout the period of my study Her supervision and support truly help the
progression and smoothness of my thesis This thesis work was enabled and sustained
by her great vision and brilliant ideas Thanks and appreciations are also extended to
my co-supervisor and examiners Dr Azham Zulkhamain
I am grateful to the staff at Faculty of Resource Science and Technology
UNIMAS for their invaluable help in many ways especially to En lsmadi and Tuan
Haji Kami and all helpful postgraduate students In addition special thanks also go to
management team of Centre of Graduate Studies
I would like to acknowledge the support of research grant from Ministry of
Energy Green Technology and Water Malaysia under Research Fund Mentoring
Programs IIPTA 1 Menteri Special thank also goesto Kementerian Pengajian Tinggi
Malaysia for the financial assistance through MyBrain15
Finally to my family especially to beloved parent Bahrin Hj Mohamad and
Dyg Siti Meriam Awg Abd Jalil for their love patience encouragement and financial
support To all your kindness is invaluable May Allah Subhanahu wa Taala reward
all of you with happiness and success now and in the hereafter
IV
ABSTRACT
( ReSidues from sago processing mill in Sarawak are commonly discharged into rivers
along with sago effiuent which contributed to serious environmental problems In this
study activated sludge process was introduced onto sago effiuent to afford sago
biomass (SB~ The pH of sago effluent has changed from pH 4 to pH 7 and
chemical oxygen demand (COD) showed intense decrease from 300plusmn033 mgL to
1667plusmn017 mgL after the activated sludge process SBM was transformed into sago
biochar (SBC) via microwave pyrolysis followed by chemical activation using NaOH
and HCI to obtain sago activated carbon (SAC) A great range of functional groups of
-OH C=O COOH and S=O were present in SBM SBC and SAC as evidenced by
Fourier transform infrared (FTIR) spectra Utilisation of SBC showed faster
germination process of the chilli plants SAC was applied as a filter of the effiuent and
showed the COD of effiuent decreased from 123plusmn082 mgL to 30plusmn046 mgL SAC
was also investigated for its potential in removing heavy metals such as Pb Cr and Zn
from aqueous solution Pb Cr and Zn showed highest adsorption onto SAC at 10 g
adsorbent dosage with 8293 3828 and 1478 respectively The study showed
that the adsorption of metals by SAC is dependent on the dosage of adsorbent and the
initial metal concentration The SAC was also applied as solid acid and base catalysts
which prepared by chemical activation using H2S04 and NaOH respectively These
solid carbon supported catalysts have been successfully utilised as heterogeneous
catalyst for esterification reaction in organic synthesis The bioconversion of sago
residue into these value added products could reduce the pollution effect from sago
processing industries
v
BIOCHAR DARlPADA KUMBAHAN SAGU DAN
PENGAPLlKASIANNYA
ABSTRAK
Sisa dari kilang pemprosesan sagu di Sarawak biasanya dialirkan ke sungai bersama
kumbahan sagu yang boleh menyumbang kepada masalah alam sekitar yang serius
Dalam kajian ini proses enapcemar teraktif lelah diperkenalkan dalam proses
rawatan kumbahan sagu dan seterusnya menghasilkan sagu biomas (SBM) Selepas
proses enapcemar teraktif pH kumbahan sagu telah berubah dari pH 4 ke pH 7 dan
permintaan oksigen kimia (COD) menunjukkan penurunan yang ketara dari
300plusmnO33 mgL ke 16 67plusmn017 mgL SBM telah diubahsuai menjadi biochar sagu
(SBC) melalui proses pirolisis gelombang mikro diikuti dengan pengaktifan kimia
menggunakan NaOH dan HCl untuk menghasilkan sagu karbon teraktif (SAC)
Kumpulan berfungsi -OH C=O COOH dan S=O kebanyakannya hadir dalam SBM
SBC dan SAC seperti yang dibuktikan oleh spektrum Fourier transform infrared
(FTIR) Penggunaan SBC mempercepatkan proses percambahan cili SAC telah
diaplikasikan sebagai penapis kumbahan dan COD menurun dari 123plusmn082 mgL to
30plusmn046 mgL SAC juga dikaji dari segi potensi untuk menyingkirkan logam berat
seperti Pb Cr dan Zn daripada larutan akueus Pb Cr dan Zn menunjukkan nilai
jerapan yang tinggi pada setiap 10 g dos penjerap sebanyak 8293 3828 dan
1478 masing-masing Kajian menunjukkan bahawa penjerapan logam oleh SAC
bergantung kepada jumlah dos penjerap dan kepekatan awal larutan logam SAC
juga diaplikasikan sebagai pemangkin asid dan bes yang diperbuat dari pengaktifan
kimia menggunakan H2S04 dan NaOH masing-masing Pemangkin karbon pepejal ini
VI
telah berjaya digunakan sebagai pemangkin heterogen untuk tindak balas esterifikasi
dalam sintesis organik Penukaran-bio kumbahan sagu kepada produk berniai ini
boleh menurunkan kesan pencemaran dari industri pemprosesan sagu
I
vii
Pu at Khidmllt Maklumlt AkademH UN1VERSm MALAYSIA SAltAWAK
TABLE OF CONTENTS
DECLARATION
LIST OF ACHIEVEMENTS
ACKNOWLEDGEMENT
ABSTRACT
ABSTRAK
T ABLE OF CONTENTS
LIST OF TABLES
LIST OF FIGURES
LIST OF SCHEMES
LIST OF ABBREVIATIONS
LIST OF SYMBOLS
CHAPTERl
INTRODUCTION
1 1 Research background
12 Problem statement
14 Research objectives
CHAPTER 2
LITERATURE REVIEW
21 Sago industries
22 Activated sludge process
221 Microorganism in activated sludge process
222 Aerobic oxidation of carbonaceous and nitrogenous matter
viii
Page
II
III
IV
V
VI
viii
xiii
XIV
XVl
XVll
XIX
4
5
6
7
8
9
~ ~~____-I
23 Biomass as a substrate for biochar 11
231 Biomass from activated sludge process 11
232 Biomass composition 12
24 Pyrolysis process of biomass 13
25 Operational condition and techniques of pyrolysis 13
26 Biochar and the pyrolytic products 14
27 Properties of biochar 15
28 Activated carbon from biochar 17
29 Activated carbon and the applications 18
29 1 Water filtration 18
292 Heavy metal adsorption 19
2921 Heavy metals 20
210 Solid phase organic synthesis 21
2101 Solid supported reagent 22
2102 Solid supported catalyst 23
21 021 Solid acid catalyst 24
21022 Solid base catalyst 26
CHAPTER 3
MATERIALS AND METHODS
31 Materials and instrumental 30
32 General methods 31
33 Production of biomass (SBM) from sago effiuent 33
331 Assessment of water quality after activated sludge process 33
3311 Detennination of pH 33
IX
--
II
I
331 2 Detennination of chemical oxygen demand (COD)
331 3 Detennination of total suspended solids (TSS)
3314 Detennination of ammoniacal nitrogen (AN)
332 Characterisation of SBM
3321 Moisture ash and volatile content analysis
3322 FTIR and SEM analysis
34 Production of sago biochar (SBC) from SBM via microwave
pyrolysis
341 Characterisation of SBC
3411 Moisture content analysis
3412 Ultimate analysis
3413 FTIR and SEM analysis
342 Application of SBC as plant enhancer
35 Preparation of sago activated carbon (SAC)
351 Preparation ofSAC1 from SBC
352 Preparation of SAC2 from sago hampas
35 3 Characterisation of SAC 1
3531 Moisture content analysis
3532 FTIR and SEM analysis
354 Application ofSAC1
3541 Water filter system
3542 Heavy metal adsorption
36 Preparation ofbiochar impregnated silica (BIS) as
solid phase reagent
361 Preparation of BIS
34
34
35
35
35
37
38
38
38
38
39
39 39
39
40
40
40
40
41
41
41
42
42
x
I
I
362 Characterisation ofBIS 43
363 Attempted solid phase organic synthesis using BIS 43
37 Preparation of solid base catalyst from SAC 1 43
371 Preparation of solid base catalyst from SACl 44
372 Transesterification of palm oil mill sludge (POMS)
using solid base catalyst 44
38 Preparation of solid acid catalyst from SACl 44
381 Hydrolysis of acetylsalicylic acid (ASA) to salicylic acid 44
382 Synthesis of methyl salicylate 45
CHAPTER 4
RESULTS AND DISCUSSION
41 Production of SBM from activated sludge process 46
411 Assessment of water quality after activated sludge process 47
412 Characterisation of SBM 47
4121 Moisture ash and volatile content analysis 47
4122 FTIR and SEM analysis 48
42 Production of SBC via microwave pyrolysis 50
421 Characterisation of SBC 50
4211 Moisture content analysis 50
4212 Analysis of organic matters 50
4213 FTIR and SEM analysis 51
422 Application of SBC as plant enhancer 53
43 Preparation of SAC 1 from SBC 56
431 Characterisation of SBM 56
Xl
4311 Moisture content analysis 56
4312 FTIR and SEM analysis 57
43 3 Application ofSAC1 60
4331 Water filter system 60
4332 Heavy metal adsorption 61
44 Preparation ofbiochar impregnated silica (BIS)
as solid phase reagent 65
441 Characterisation of BIS 66
442 Attempted solid phase organic synthesis using BIS 67
45 Application of solid base catalyst from SAC 1
in transesterification of palm oil mill sludge (POMS) 70
46 Application of solid acid catalyst in methyl salicylate
preparation
CHAPTER 5
76
CONCLUSION AND RECOMMENDATION
51 Conclusion 80
52 Recommendation 82
REFERENCES 84
APPENDIX A 93
APPENDIXB 95
APPENDIXC 97
APPENDIXD 100
APPENDIXE 102
XII
J
~ LIST OF TABLES I
Page Table 21 Example of solid catalysts and their applications 23
t Table 22 Types of solid base catalyst 26 [ Table 41 Ultimate analysis of SBC 51
Table 42 Analysis of chilli seedlings after 14 days 55 ITable 43 NPK content of SBC 56
Table 44 COD of sago effluent before and after filtration 61
i
1
Xlll
I shy
I
LIST OF FIGURES
Page
Figure 21 Schematic flow diagram for sago processing 7
Figure 22 Bmnsted acidity arising from inductive effect of Lewis 24
acid center coordinated to a silica support
Figure 31 (a) Modified household microwave oven (b) quartz 24
reactor attached to the oven
Figure 32 Methyl salicylate 45
Figure 42 The IR spectrum of SBM 49
Figure 43 The SEM micrograph ofSBM (1000x magnification) 49
Figure 44 The IR spectrum of SBC 52
Figure 45 The SEM micrograph of (a) surface SBC (l2000x 53
magnification) (b) SBC with internal diameter
measurement (l2000x magnification)
Figure 46 Top view of chilli plant after 3 Days 54
Figure 47 (a) Top view (b) Side view of chilli plant after 14 Days 55
Figure 48 The IR spectra of (a) SACI (b) CAC 58
Figure 49 The SEM micrograph of (a) surface SACI 59
(12000x magnification) (b) SAC 1 with internal
diameter measurement (l2000x magnification)
(c) CAC (l2000x magnification)
Figure 4l0 Water filter system using SACI as a filter 60
Figure 411 The effect of adsorbent disages to adsorption of Zn Cr 63
and Pb by SAC 1 at a fixed metal concentration of
5 mgIL
xiv
I
Figure 412 The effect of initia~ concentration to adsorption of Zn 65
Cr and Pb by SAC1 at a fixed adsorbent dosage of
01 g
Figure 413 The SEM micrograph of BIS (5000x magnification) 66
Figure 414 The XRD pattern of amorphous silica from BIS 67
Figure 415 The IR spectra of (a) solid BIS before reaction (b) solid 69
BIS after reaction
Figure 416 The SEM micrograph of (a) solid BIS before reaction 69
(b) solid BIS after reaction
Figure 417 The IR spectra of product using (a) 5 solid base 73
catalyst of SAC 1 (b) 10 solid base catalyst of SAC 1
(c) 5 solid base catalyst of SAC 1 containing silica
(d) 10 solid base catalyst of SAC 1 containing silica
(e) Raw POMS
Figure 418 The IR spectra of product using (a) 5 solid base 75
catalyst of SAC2
(b) 10 solid base catalyst ofSAC2 (c) 5 solid base
catalyst of SAC2 containing silica
(d) 10 solid base catalyst of SAC2 containing silica
(e) Raw POMS
Figure 419 The IR spectra of (a) salicylic acid (b) methyl 78
salicylate
Figure 420 The IH-NMR spectrum of methyl salicylate 79
xv
~ -~----------
Scheme 21
Scheme 41
Scheme 42
Scheme 43
Scheme 44
Scheme 45
LIST OF SCHEMES
Multi-step synthesis using polymer-supported reagents
Synthesis of biphenyl-4-carbonyl chloride
Transesterification of POMS
Mechanism of transesterification of POMS using solid
base catalyst
Esterification of salicylic acid
Mechanism of esterification of salicylic acid using
solid acid catalyst
Page
22
68
70
71
76
77
xvi
l
LIST OF ABBREVIATIONS
AN
ASTM
B1S
BOD
CAC
cBOD
CHN
COD
DCM
FAAS
FTlR
MCM
M41S
nBOD
NMR
NPK
POMS
SAC
SBA
SBC
SBM
SEM
TLC
Ammoniacal nitrogen
American society for testing and materials
Biochar impregnated silica
Biochemical oxygen demand
Commercia~ activated carbon
Carbonaceous biochemical oxygen demand
Carbon hydrogen nitrogen
Chemical oxygen demand
Dichloromethane
Flame atomic absorption spectrometer
Fourier transfonn infrared
Mobil catalytic material
Mesoporous silicate 41
Nitrogeneous biochemical oxygen demand
Nuclear magnetic resonance
Nitrogen phosphorous potassium
Palm oil mill sludge
Sago activated carbon
Santa barbara amorphous
Sago biochar
Sago biomass
Scanning electron microscope
Thin layer chromathography
xvii
TSS Total suspended solid
XRD X-Ray diffractometer
xviii
LIST OF SYMBOLS
degc Degree celsius
U max Maximum vibration
8 Chemical shift
xix
CHAPTER
INTRODUCTION
11 Research background
Sarawak is currently one of the world largest exporters of sago products About 25 000 - 40
000 tonnes of sago products were exported to several countries annually such as Singapore
Taiwan and Japan (Singhal et ai 2008) Approximately 7 tonnes of sago pith waste has been
produced daily from a single sago starch processing mill (Bujang et ai 1996) Sago industries
consume about 30 000 L of water to process one tonne of sago and the liquid residue were
released as wastewater (Banu et ai 2006) The sago residues were released into nearby
streams together with wastewater as sago effluent which can lead to serious environmental
problems and affect aquatic life (Awg-Adeni et ai 2010)
Sago effluent contains high biochemical oxygen demand (BOD) and chemical oxygen demand
(COD) (Awg-Adeni et ai 2010) The effluent also contains high total suspended solid (TSS)
(Rashid et ai 2010) and acidic in nature with high organic matter unpleasant odour and
irritating colour (Ayyasamy et ai 2008) One of the treatments that has been applied onto the
sago effluent was using a hybrid reactor on-site waste treatment with very short retention
periods which combines both fixed-film and up-flow anaerobic sludge blanket systems (Banu
et ai 2006) The sago effluent was treated by the hybrid reactor for the reduction of COD
(Banu et ai 2006) The hybrid reactor system is a combination of suspended-film and fixedshy
film growth processes (Shannon et ai 2002) Sago effluent was also utilised as an additional
carbon in anaerobic digesters for the production of biogas (Abd-Aziz 2002) Other application
of biomass produced from the treated sago effluent was as a supplement for prawn feed in
aquaculture industries (Vickineswary et at 1997)
Activated sludge process is a wastewater treatment process which utilising bacteria and
microorganism to degrade suspended and dissolved organic matter via aerobic or anaerobic
oxidation (Gerardi 2006) It is a process in which a mixture of sewage and activated sludge
are agitated and aerated The sludge residue from activated sludge process can be easily
removed from the water through simple sedimentation Other treatment method such as
anaerobic digestion of sago effluent seems to be costly and difficult to maintain the system
(Ganczarczyk 1983) As an alternative aerobic digestion was introduced via activated sludge
proce s to treat sago effluent This treatment has more advantage as it utilises aerobic
microbes which grow faster than anaerobic microbes and consist of a simple process only
(Ganczarczyk 1983) In this study the sago biomass generated from the activated sludge was
chemically treated to produce sago biochar
Nowadays biochars are being prepared manually for various applications Biochars were
usually applied in environmental management such as soil improvement waste management
climate change mitigation and energy production (Lehmann and Joseph 2009) Biochar is a
carbon rich product obtained from biomass that undergo thermal decomposition with little or
absence of air at elevated temperature via pyrolysis (Lehmann and Joseph 2009) Pyrolysis is
a thermo-chemical process in which organic material is converted into a carbon rich solid
which is char and volatile matter by heating in the absence of oxygen (Demirbas and Arin
2002) A higher amount of volatile matter released during pyrolysis of biomass produces
2
biochars with lower densities and higher porosities (Vassilev et at 2009) The various
functional groups on the surface of biochar such as C=O S=O and -OH influence the sorption
of adsorbate by the nature of their surface charge and by the availability of 1t electron
(Lehmann and Joseph 2009) Pyrolysis process is regularly used for biochar production as the
technique is relatively simple and inexpensive and allows considerable flexibility in both the
type and quality of the biomass feedstock (Laird et at 2009) Microwave pyrolysis is the
latest technology used to pyrolyse biomass Microwave pyrolysis offers more advantages over
conventional heated pyrolysis due to unifonn and efficient heating (Miura et at 2004)
Biochar has also been used as a precursor for the production of activated carbon Activated
carbon is effective and used in various applications such as in water treatment for drinking
water metal extraction and heterogeneous catalysts (Azargohar and Dalai 2006) However
the usage of commercial activated carbon is limited due to its higher preparation cost (Rao et
at 2009) Several studies reported on the utilisation of agricultural wastes for the production
of low cost activated carbon such as palm oil miH shells (Nik et at 2006) groundnut shells
(Malik et at 2007) physic nut wastes (Pechyen et at 2007) hulls of rice and wheat (Qiu et
at 2008 Rao et at 2009) and palm oil empty fruit bunch (Wahi et at 2009) However there
are no studies reported on the production of activated carbon from sago processing waste
either from sago pith or sago effluent
3
12 Problem statements
Mass production of agricultural waste has become an issue to the government and
environmentalists due to illegal disposal into the jungles or the rivers which destroy the
ecosystem Sago industries generate significant amount of wastes annually either as sago pith
or sago effluent Practically direct waste disposal to the rivers brings harmful effect to the
aquatic life This study was conducted to produce some value added products from the sago
effluent Limited reserve land for agricultural waste disposal leads to the transformation of the
waste into value added products Therefore there is a need to overcome the environmental
problem caused by the disposal of sago waste In this study the sago effluent was treated via
activated sludge process to produce biomass which then transformed into biochars and applied
for various applications The production of value added products from sago waste will provide
economical solution for waste management in sago industries
4
ABSTRACT
( ReSidues from sago processing mill in Sarawak are commonly discharged into rivers
along with sago effiuent which contributed to serious environmental problems In this
study activated sludge process was introduced onto sago effiuent to afford sago
biomass (SB~ The pH of sago effluent has changed from pH 4 to pH 7 and
chemical oxygen demand (COD) showed intense decrease from 300plusmn033 mgL to
1667plusmn017 mgL after the activated sludge process SBM was transformed into sago
biochar (SBC) via microwave pyrolysis followed by chemical activation using NaOH
and HCI to obtain sago activated carbon (SAC) A great range of functional groups of
-OH C=O COOH and S=O were present in SBM SBC and SAC as evidenced by
Fourier transform infrared (FTIR) spectra Utilisation of SBC showed faster
germination process of the chilli plants SAC was applied as a filter of the effiuent and
showed the COD of effiuent decreased from 123plusmn082 mgL to 30plusmn046 mgL SAC
was also investigated for its potential in removing heavy metals such as Pb Cr and Zn
from aqueous solution Pb Cr and Zn showed highest adsorption onto SAC at 10 g
adsorbent dosage with 8293 3828 and 1478 respectively The study showed
that the adsorption of metals by SAC is dependent on the dosage of adsorbent and the
initial metal concentration The SAC was also applied as solid acid and base catalysts
which prepared by chemical activation using H2S04 and NaOH respectively These
solid carbon supported catalysts have been successfully utilised as heterogeneous
catalyst for esterification reaction in organic synthesis The bioconversion of sago
residue into these value added products could reduce the pollution effect from sago
processing industries
v
BIOCHAR DARlPADA KUMBAHAN SAGU DAN
PENGAPLlKASIANNYA
ABSTRAK
Sisa dari kilang pemprosesan sagu di Sarawak biasanya dialirkan ke sungai bersama
kumbahan sagu yang boleh menyumbang kepada masalah alam sekitar yang serius
Dalam kajian ini proses enapcemar teraktif lelah diperkenalkan dalam proses
rawatan kumbahan sagu dan seterusnya menghasilkan sagu biomas (SBM) Selepas
proses enapcemar teraktif pH kumbahan sagu telah berubah dari pH 4 ke pH 7 dan
permintaan oksigen kimia (COD) menunjukkan penurunan yang ketara dari
300plusmnO33 mgL ke 16 67plusmn017 mgL SBM telah diubahsuai menjadi biochar sagu
(SBC) melalui proses pirolisis gelombang mikro diikuti dengan pengaktifan kimia
menggunakan NaOH dan HCl untuk menghasilkan sagu karbon teraktif (SAC)
Kumpulan berfungsi -OH C=O COOH dan S=O kebanyakannya hadir dalam SBM
SBC dan SAC seperti yang dibuktikan oleh spektrum Fourier transform infrared
(FTIR) Penggunaan SBC mempercepatkan proses percambahan cili SAC telah
diaplikasikan sebagai penapis kumbahan dan COD menurun dari 123plusmn082 mgL to
30plusmn046 mgL SAC juga dikaji dari segi potensi untuk menyingkirkan logam berat
seperti Pb Cr dan Zn daripada larutan akueus Pb Cr dan Zn menunjukkan nilai
jerapan yang tinggi pada setiap 10 g dos penjerap sebanyak 8293 3828 dan
1478 masing-masing Kajian menunjukkan bahawa penjerapan logam oleh SAC
bergantung kepada jumlah dos penjerap dan kepekatan awal larutan logam SAC
juga diaplikasikan sebagai pemangkin asid dan bes yang diperbuat dari pengaktifan
kimia menggunakan H2S04 dan NaOH masing-masing Pemangkin karbon pepejal ini
VI
telah berjaya digunakan sebagai pemangkin heterogen untuk tindak balas esterifikasi
dalam sintesis organik Penukaran-bio kumbahan sagu kepada produk berniai ini
boleh menurunkan kesan pencemaran dari industri pemprosesan sagu
I
vii
Pu at Khidmllt Maklumlt AkademH UN1VERSm MALAYSIA SAltAWAK
TABLE OF CONTENTS
DECLARATION
LIST OF ACHIEVEMENTS
ACKNOWLEDGEMENT
ABSTRACT
ABSTRAK
T ABLE OF CONTENTS
LIST OF TABLES
LIST OF FIGURES
LIST OF SCHEMES
LIST OF ABBREVIATIONS
LIST OF SYMBOLS
CHAPTERl
INTRODUCTION
1 1 Research background
12 Problem statement
14 Research objectives
CHAPTER 2
LITERATURE REVIEW
21 Sago industries
22 Activated sludge process
221 Microorganism in activated sludge process
222 Aerobic oxidation of carbonaceous and nitrogenous matter
viii
Page
II
III
IV
V
VI
viii
xiii
XIV
XVl
XVll
XIX
4
5
6
7
8
9
~ ~~____-I
23 Biomass as a substrate for biochar 11
231 Biomass from activated sludge process 11
232 Biomass composition 12
24 Pyrolysis process of biomass 13
25 Operational condition and techniques of pyrolysis 13
26 Biochar and the pyrolytic products 14
27 Properties of biochar 15
28 Activated carbon from biochar 17
29 Activated carbon and the applications 18
29 1 Water filtration 18
292 Heavy metal adsorption 19
2921 Heavy metals 20
210 Solid phase organic synthesis 21
2101 Solid supported reagent 22
2102 Solid supported catalyst 23
21 021 Solid acid catalyst 24
21022 Solid base catalyst 26
CHAPTER 3
MATERIALS AND METHODS
31 Materials and instrumental 30
32 General methods 31
33 Production of biomass (SBM) from sago effiuent 33
331 Assessment of water quality after activated sludge process 33
3311 Detennination of pH 33
IX
--
II
I
331 2 Detennination of chemical oxygen demand (COD)
331 3 Detennination of total suspended solids (TSS)
3314 Detennination of ammoniacal nitrogen (AN)
332 Characterisation of SBM
3321 Moisture ash and volatile content analysis
3322 FTIR and SEM analysis
34 Production of sago biochar (SBC) from SBM via microwave
pyrolysis
341 Characterisation of SBC
3411 Moisture content analysis
3412 Ultimate analysis
3413 FTIR and SEM analysis
342 Application of SBC as plant enhancer
35 Preparation of sago activated carbon (SAC)
351 Preparation ofSAC1 from SBC
352 Preparation of SAC2 from sago hampas
35 3 Characterisation of SAC 1
3531 Moisture content analysis
3532 FTIR and SEM analysis
354 Application ofSAC1
3541 Water filter system
3542 Heavy metal adsorption
36 Preparation ofbiochar impregnated silica (BIS) as
solid phase reagent
361 Preparation of BIS
34
34
35
35
35
37
38
38
38
38
39
39 39
39
40
40
40
40
41
41
41
42
42
x
I
I
362 Characterisation ofBIS 43
363 Attempted solid phase organic synthesis using BIS 43
37 Preparation of solid base catalyst from SAC 1 43
371 Preparation of solid base catalyst from SACl 44
372 Transesterification of palm oil mill sludge (POMS)
using solid base catalyst 44
38 Preparation of solid acid catalyst from SACl 44
381 Hydrolysis of acetylsalicylic acid (ASA) to salicylic acid 44
382 Synthesis of methyl salicylate 45
CHAPTER 4
RESULTS AND DISCUSSION
41 Production of SBM from activated sludge process 46
411 Assessment of water quality after activated sludge process 47
412 Characterisation of SBM 47
4121 Moisture ash and volatile content analysis 47
4122 FTIR and SEM analysis 48
42 Production of SBC via microwave pyrolysis 50
421 Characterisation of SBC 50
4211 Moisture content analysis 50
4212 Analysis of organic matters 50
4213 FTIR and SEM analysis 51
422 Application of SBC as plant enhancer 53
43 Preparation of SAC 1 from SBC 56
431 Characterisation of SBM 56
Xl
4311 Moisture content analysis 56
4312 FTIR and SEM analysis 57
43 3 Application ofSAC1 60
4331 Water filter system 60
4332 Heavy metal adsorption 61
44 Preparation ofbiochar impregnated silica (BIS)
as solid phase reagent 65
441 Characterisation of BIS 66
442 Attempted solid phase organic synthesis using BIS 67
45 Application of solid base catalyst from SAC 1
in transesterification of palm oil mill sludge (POMS) 70
46 Application of solid acid catalyst in methyl salicylate
preparation
CHAPTER 5
76
CONCLUSION AND RECOMMENDATION
51 Conclusion 80
52 Recommendation 82
REFERENCES 84
APPENDIX A 93
APPENDIXB 95
APPENDIXC 97
APPENDIXD 100
APPENDIXE 102
XII
J
~ LIST OF TABLES I
Page Table 21 Example of solid catalysts and their applications 23
t Table 22 Types of solid base catalyst 26 [ Table 41 Ultimate analysis of SBC 51
Table 42 Analysis of chilli seedlings after 14 days 55 ITable 43 NPK content of SBC 56
Table 44 COD of sago effluent before and after filtration 61
i
1
Xlll
I shy
I
LIST OF FIGURES
Page
Figure 21 Schematic flow diagram for sago processing 7
Figure 22 Bmnsted acidity arising from inductive effect of Lewis 24
acid center coordinated to a silica support
Figure 31 (a) Modified household microwave oven (b) quartz 24
reactor attached to the oven
Figure 32 Methyl salicylate 45
Figure 42 The IR spectrum of SBM 49
Figure 43 The SEM micrograph ofSBM (1000x magnification) 49
Figure 44 The IR spectrum of SBC 52
Figure 45 The SEM micrograph of (a) surface SBC (l2000x 53
magnification) (b) SBC with internal diameter
measurement (l2000x magnification)
Figure 46 Top view of chilli plant after 3 Days 54
Figure 47 (a) Top view (b) Side view of chilli plant after 14 Days 55
Figure 48 The IR spectra of (a) SACI (b) CAC 58
Figure 49 The SEM micrograph of (a) surface SACI 59
(12000x magnification) (b) SAC 1 with internal
diameter measurement (l2000x magnification)
(c) CAC (l2000x magnification)
Figure 4l0 Water filter system using SACI as a filter 60
Figure 411 The effect of adsorbent disages to adsorption of Zn Cr 63
and Pb by SAC 1 at a fixed metal concentration of
5 mgIL
xiv
I
Figure 412 The effect of initia~ concentration to adsorption of Zn 65
Cr and Pb by SAC1 at a fixed adsorbent dosage of
01 g
Figure 413 The SEM micrograph of BIS (5000x magnification) 66
Figure 414 The XRD pattern of amorphous silica from BIS 67
Figure 415 The IR spectra of (a) solid BIS before reaction (b) solid 69
BIS after reaction
Figure 416 The SEM micrograph of (a) solid BIS before reaction 69
(b) solid BIS after reaction
Figure 417 The IR spectra of product using (a) 5 solid base 73
catalyst of SAC 1 (b) 10 solid base catalyst of SAC 1
(c) 5 solid base catalyst of SAC 1 containing silica
(d) 10 solid base catalyst of SAC 1 containing silica
(e) Raw POMS
Figure 418 The IR spectra of product using (a) 5 solid base 75
catalyst of SAC2
(b) 10 solid base catalyst ofSAC2 (c) 5 solid base
catalyst of SAC2 containing silica
(d) 10 solid base catalyst of SAC2 containing silica
(e) Raw POMS
Figure 419 The IR spectra of (a) salicylic acid (b) methyl 78
salicylate
Figure 420 The IH-NMR spectrum of methyl salicylate 79
xv
~ -~----------
Scheme 21
Scheme 41
Scheme 42
Scheme 43
Scheme 44
Scheme 45
LIST OF SCHEMES
Multi-step synthesis using polymer-supported reagents
Synthesis of biphenyl-4-carbonyl chloride
Transesterification of POMS
Mechanism of transesterification of POMS using solid
base catalyst
Esterification of salicylic acid
Mechanism of esterification of salicylic acid using
solid acid catalyst
Page
22
68
70
71
76
77
xvi
l
LIST OF ABBREVIATIONS
AN
ASTM
B1S
BOD
CAC
cBOD
CHN
COD
DCM
FAAS
FTlR
MCM
M41S
nBOD
NMR
NPK
POMS
SAC
SBA
SBC
SBM
SEM
TLC
Ammoniacal nitrogen
American society for testing and materials
Biochar impregnated silica
Biochemical oxygen demand
Commercia~ activated carbon
Carbonaceous biochemical oxygen demand
Carbon hydrogen nitrogen
Chemical oxygen demand
Dichloromethane
Flame atomic absorption spectrometer
Fourier transfonn infrared
Mobil catalytic material
Mesoporous silicate 41
Nitrogeneous biochemical oxygen demand
Nuclear magnetic resonance
Nitrogen phosphorous potassium
Palm oil mill sludge
Sago activated carbon
Santa barbara amorphous
Sago biochar
Sago biomass
Scanning electron microscope
Thin layer chromathography
xvii
TSS Total suspended solid
XRD X-Ray diffractometer
xviii
LIST OF SYMBOLS
degc Degree celsius
U max Maximum vibration
8 Chemical shift
xix
CHAPTER
INTRODUCTION
11 Research background
Sarawak is currently one of the world largest exporters of sago products About 25 000 - 40
000 tonnes of sago products were exported to several countries annually such as Singapore
Taiwan and Japan (Singhal et ai 2008) Approximately 7 tonnes of sago pith waste has been
produced daily from a single sago starch processing mill (Bujang et ai 1996) Sago industries
consume about 30 000 L of water to process one tonne of sago and the liquid residue were
released as wastewater (Banu et ai 2006) The sago residues were released into nearby
streams together with wastewater as sago effluent which can lead to serious environmental
problems and affect aquatic life (Awg-Adeni et ai 2010)
Sago effluent contains high biochemical oxygen demand (BOD) and chemical oxygen demand
(COD) (Awg-Adeni et ai 2010) The effluent also contains high total suspended solid (TSS)
(Rashid et ai 2010) and acidic in nature with high organic matter unpleasant odour and
irritating colour (Ayyasamy et ai 2008) One of the treatments that has been applied onto the
sago effluent was using a hybrid reactor on-site waste treatment with very short retention
periods which combines both fixed-film and up-flow anaerobic sludge blanket systems (Banu
et ai 2006) The sago effluent was treated by the hybrid reactor for the reduction of COD
(Banu et ai 2006) The hybrid reactor system is a combination of suspended-film and fixedshy
film growth processes (Shannon et ai 2002) Sago effluent was also utilised as an additional
carbon in anaerobic digesters for the production of biogas (Abd-Aziz 2002) Other application
of biomass produced from the treated sago effluent was as a supplement for prawn feed in
aquaculture industries (Vickineswary et at 1997)
Activated sludge process is a wastewater treatment process which utilising bacteria and
microorganism to degrade suspended and dissolved organic matter via aerobic or anaerobic
oxidation (Gerardi 2006) It is a process in which a mixture of sewage and activated sludge
are agitated and aerated The sludge residue from activated sludge process can be easily
removed from the water through simple sedimentation Other treatment method such as
anaerobic digestion of sago effluent seems to be costly and difficult to maintain the system
(Ganczarczyk 1983) As an alternative aerobic digestion was introduced via activated sludge
proce s to treat sago effluent This treatment has more advantage as it utilises aerobic
microbes which grow faster than anaerobic microbes and consist of a simple process only
(Ganczarczyk 1983) In this study the sago biomass generated from the activated sludge was
chemically treated to produce sago biochar
Nowadays biochars are being prepared manually for various applications Biochars were
usually applied in environmental management such as soil improvement waste management
climate change mitigation and energy production (Lehmann and Joseph 2009) Biochar is a
carbon rich product obtained from biomass that undergo thermal decomposition with little or
absence of air at elevated temperature via pyrolysis (Lehmann and Joseph 2009) Pyrolysis is
a thermo-chemical process in which organic material is converted into a carbon rich solid
which is char and volatile matter by heating in the absence of oxygen (Demirbas and Arin
2002) A higher amount of volatile matter released during pyrolysis of biomass produces
2
biochars with lower densities and higher porosities (Vassilev et at 2009) The various
functional groups on the surface of biochar such as C=O S=O and -OH influence the sorption
of adsorbate by the nature of their surface charge and by the availability of 1t electron
(Lehmann and Joseph 2009) Pyrolysis process is regularly used for biochar production as the
technique is relatively simple and inexpensive and allows considerable flexibility in both the
type and quality of the biomass feedstock (Laird et at 2009) Microwave pyrolysis is the
latest technology used to pyrolyse biomass Microwave pyrolysis offers more advantages over
conventional heated pyrolysis due to unifonn and efficient heating (Miura et at 2004)
Biochar has also been used as a precursor for the production of activated carbon Activated
carbon is effective and used in various applications such as in water treatment for drinking
water metal extraction and heterogeneous catalysts (Azargohar and Dalai 2006) However
the usage of commercial activated carbon is limited due to its higher preparation cost (Rao et
at 2009) Several studies reported on the utilisation of agricultural wastes for the production
of low cost activated carbon such as palm oil miH shells (Nik et at 2006) groundnut shells
(Malik et at 2007) physic nut wastes (Pechyen et at 2007) hulls of rice and wheat (Qiu et
at 2008 Rao et at 2009) and palm oil empty fruit bunch (Wahi et at 2009) However there
are no studies reported on the production of activated carbon from sago processing waste
either from sago pith or sago effluent
3
12 Problem statements
Mass production of agricultural waste has become an issue to the government and
environmentalists due to illegal disposal into the jungles or the rivers which destroy the
ecosystem Sago industries generate significant amount of wastes annually either as sago pith
or sago effluent Practically direct waste disposal to the rivers brings harmful effect to the
aquatic life This study was conducted to produce some value added products from the sago
effluent Limited reserve land for agricultural waste disposal leads to the transformation of the
waste into value added products Therefore there is a need to overcome the environmental
problem caused by the disposal of sago waste In this study the sago effluent was treated via
activated sludge process to produce biomass which then transformed into biochars and applied
for various applications The production of value added products from sago waste will provide
economical solution for waste management in sago industries
4
BIOCHAR DARlPADA KUMBAHAN SAGU DAN
PENGAPLlKASIANNYA
ABSTRAK
Sisa dari kilang pemprosesan sagu di Sarawak biasanya dialirkan ke sungai bersama
kumbahan sagu yang boleh menyumbang kepada masalah alam sekitar yang serius
Dalam kajian ini proses enapcemar teraktif lelah diperkenalkan dalam proses
rawatan kumbahan sagu dan seterusnya menghasilkan sagu biomas (SBM) Selepas
proses enapcemar teraktif pH kumbahan sagu telah berubah dari pH 4 ke pH 7 dan
permintaan oksigen kimia (COD) menunjukkan penurunan yang ketara dari
300plusmnO33 mgL ke 16 67plusmn017 mgL SBM telah diubahsuai menjadi biochar sagu
(SBC) melalui proses pirolisis gelombang mikro diikuti dengan pengaktifan kimia
menggunakan NaOH dan HCl untuk menghasilkan sagu karbon teraktif (SAC)
Kumpulan berfungsi -OH C=O COOH dan S=O kebanyakannya hadir dalam SBM
SBC dan SAC seperti yang dibuktikan oleh spektrum Fourier transform infrared
(FTIR) Penggunaan SBC mempercepatkan proses percambahan cili SAC telah
diaplikasikan sebagai penapis kumbahan dan COD menurun dari 123plusmn082 mgL to
30plusmn046 mgL SAC juga dikaji dari segi potensi untuk menyingkirkan logam berat
seperti Pb Cr dan Zn daripada larutan akueus Pb Cr dan Zn menunjukkan nilai
jerapan yang tinggi pada setiap 10 g dos penjerap sebanyak 8293 3828 dan
1478 masing-masing Kajian menunjukkan bahawa penjerapan logam oleh SAC
bergantung kepada jumlah dos penjerap dan kepekatan awal larutan logam SAC
juga diaplikasikan sebagai pemangkin asid dan bes yang diperbuat dari pengaktifan
kimia menggunakan H2S04 dan NaOH masing-masing Pemangkin karbon pepejal ini
VI
telah berjaya digunakan sebagai pemangkin heterogen untuk tindak balas esterifikasi
dalam sintesis organik Penukaran-bio kumbahan sagu kepada produk berniai ini
boleh menurunkan kesan pencemaran dari industri pemprosesan sagu
I
vii
Pu at Khidmllt Maklumlt AkademH UN1VERSm MALAYSIA SAltAWAK
TABLE OF CONTENTS
DECLARATION
LIST OF ACHIEVEMENTS
ACKNOWLEDGEMENT
ABSTRACT
ABSTRAK
T ABLE OF CONTENTS
LIST OF TABLES
LIST OF FIGURES
LIST OF SCHEMES
LIST OF ABBREVIATIONS
LIST OF SYMBOLS
CHAPTERl
INTRODUCTION
1 1 Research background
12 Problem statement
14 Research objectives
CHAPTER 2
LITERATURE REVIEW
21 Sago industries
22 Activated sludge process
221 Microorganism in activated sludge process
222 Aerobic oxidation of carbonaceous and nitrogenous matter
viii
Page
II
III
IV
V
VI
viii
xiii
XIV
XVl
XVll
XIX
4
5
6
7
8
9
~ ~~____-I
23 Biomass as a substrate for biochar 11
231 Biomass from activated sludge process 11
232 Biomass composition 12
24 Pyrolysis process of biomass 13
25 Operational condition and techniques of pyrolysis 13
26 Biochar and the pyrolytic products 14
27 Properties of biochar 15
28 Activated carbon from biochar 17
29 Activated carbon and the applications 18
29 1 Water filtration 18
292 Heavy metal adsorption 19
2921 Heavy metals 20
210 Solid phase organic synthesis 21
2101 Solid supported reagent 22
2102 Solid supported catalyst 23
21 021 Solid acid catalyst 24
21022 Solid base catalyst 26
CHAPTER 3
MATERIALS AND METHODS
31 Materials and instrumental 30
32 General methods 31
33 Production of biomass (SBM) from sago effiuent 33
331 Assessment of water quality after activated sludge process 33
3311 Detennination of pH 33
IX
--
II
I
331 2 Detennination of chemical oxygen demand (COD)
331 3 Detennination of total suspended solids (TSS)
3314 Detennination of ammoniacal nitrogen (AN)
332 Characterisation of SBM
3321 Moisture ash and volatile content analysis
3322 FTIR and SEM analysis
34 Production of sago biochar (SBC) from SBM via microwave
pyrolysis
341 Characterisation of SBC
3411 Moisture content analysis
3412 Ultimate analysis
3413 FTIR and SEM analysis
342 Application of SBC as plant enhancer
35 Preparation of sago activated carbon (SAC)
351 Preparation ofSAC1 from SBC
352 Preparation of SAC2 from sago hampas
35 3 Characterisation of SAC 1
3531 Moisture content analysis
3532 FTIR and SEM analysis
354 Application ofSAC1
3541 Water filter system
3542 Heavy metal adsorption
36 Preparation ofbiochar impregnated silica (BIS) as
solid phase reagent
361 Preparation of BIS
34
34
35
35
35
37
38
38
38
38
39
39 39
39
40
40
40
40
41
41
41
42
42
x
I
I
362 Characterisation ofBIS 43
363 Attempted solid phase organic synthesis using BIS 43
37 Preparation of solid base catalyst from SAC 1 43
371 Preparation of solid base catalyst from SACl 44
372 Transesterification of palm oil mill sludge (POMS)
using solid base catalyst 44
38 Preparation of solid acid catalyst from SACl 44
381 Hydrolysis of acetylsalicylic acid (ASA) to salicylic acid 44
382 Synthesis of methyl salicylate 45
CHAPTER 4
RESULTS AND DISCUSSION
41 Production of SBM from activated sludge process 46
411 Assessment of water quality after activated sludge process 47
412 Characterisation of SBM 47
4121 Moisture ash and volatile content analysis 47
4122 FTIR and SEM analysis 48
42 Production of SBC via microwave pyrolysis 50
421 Characterisation of SBC 50
4211 Moisture content analysis 50
4212 Analysis of organic matters 50
4213 FTIR and SEM analysis 51
422 Application of SBC as plant enhancer 53
43 Preparation of SAC 1 from SBC 56
431 Characterisation of SBM 56
Xl
4311 Moisture content analysis 56
4312 FTIR and SEM analysis 57
43 3 Application ofSAC1 60
4331 Water filter system 60
4332 Heavy metal adsorption 61
44 Preparation ofbiochar impregnated silica (BIS)
as solid phase reagent 65
441 Characterisation of BIS 66
442 Attempted solid phase organic synthesis using BIS 67
45 Application of solid base catalyst from SAC 1
in transesterification of palm oil mill sludge (POMS) 70
46 Application of solid acid catalyst in methyl salicylate
preparation
CHAPTER 5
76
CONCLUSION AND RECOMMENDATION
51 Conclusion 80
52 Recommendation 82
REFERENCES 84
APPENDIX A 93
APPENDIXB 95
APPENDIXC 97
APPENDIXD 100
APPENDIXE 102
XII
J
~ LIST OF TABLES I
Page Table 21 Example of solid catalysts and their applications 23
t Table 22 Types of solid base catalyst 26 [ Table 41 Ultimate analysis of SBC 51
Table 42 Analysis of chilli seedlings after 14 days 55 ITable 43 NPK content of SBC 56
Table 44 COD of sago effluent before and after filtration 61
i
1
Xlll
I shy
I
LIST OF FIGURES
Page
Figure 21 Schematic flow diagram for sago processing 7
Figure 22 Bmnsted acidity arising from inductive effect of Lewis 24
acid center coordinated to a silica support
Figure 31 (a) Modified household microwave oven (b) quartz 24
reactor attached to the oven
Figure 32 Methyl salicylate 45
Figure 42 The IR spectrum of SBM 49
Figure 43 The SEM micrograph ofSBM (1000x magnification) 49
Figure 44 The IR spectrum of SBC 52
Figure 45 The SEM micrograph of (a) surface SBC (l2000x 53
magnification) (b) SBC with internal diameter
measurement (l2000x magnification)
Figure 46 Top view of chilli plant after 3 Days 54
Figure 47 (a) Top view (b) Side view of chilli plant after 14 Days 55
Figure 48 The IR spectra of (a) SACI (b) CAC 58
Figure 49 The SEM micrograph of (a) surface SACI 59
(12000x magnification) (b) SAC 1 with internal
diameter measurement (l2000x magnification)
(c) CAC (l2000x magnification)
Figure 4l0 Water filter system using SACI as a filter 60
Figure 411 The effect of adsorbent disages to adsorption of Zn Cr 63
and Pb by SAC 1 at a fixed metal concentration of
5 mgIL
xiv
I
Figure 412 The effect of initia~ concentration to adsorption of Zn 65
Cr and Pb by SAC1 at a fixed adsorbent dosage of
01 g
Figure 413 The SEM micrograph of BIS (5000x magnification) 66
Figure 414 The XRD pattern of amorphous silica from BIS 67
Figure 415 The IR spectra of (a) solid BIS before reaction (b) solid 69
BIS after reaction
Figure 416 The SEM micrograph of (a) solid BIS before reaction 69
(b) solid BIS after reaction
Figure 417 The IR spectra of product using (a) 5 solid base 73
catalyst of SAC 1 (b) 10 solid base catalyst of SAC 1
(c) 5 solid base catalyst of SAC 1 containing silica
(d) 10 solid base catalyst of SAC 1 containing silica
(e) Raw POMS
Figure 418 The IR spectra of product using (a) 5 solid base 75
catalyst of SAC2
(b) 10 solid base catalyst ofSAC2 (c) 5 solid base
catalyst of SAC2 containing silica
(d) 10 solid base catalyst of SAC2 containing silica
(e) Raw POMS
Figure 419 The IR spectra of (a) salicylic acid (b) methyl 78
salicylate
Figure 420 The IH-NMR spectrum of methyl salicylate 79
xv
~ -~----------
Scheme 21
Scheme 41
Scheme 42
Scheme 43
Scheme 44
Scheme 45
LIST OF SCHEMES
Multi-step synthesis using polymer-supported reagents
Synthesis of biphenyl-4-carbonyl chloride
Transesterification of POMS
Mechanism of transesterification of POMS using solid
base catalyst
Esterification of salicylic acid
Mechanism of esterification of salicylic acid using
solid acid catalyst
Page
22
68
70
71
76
77
xvi
l
LIST OF ABBREVIATIONS
AN
ASTM
B1S
BOD
CAC
cBOD
CHN
COD
DCM
FAAS
FTlR
MCM
M41S
nBOD
NMR
NPK
POMS
SAC
SBA
SBC
SBM
SEM
TLC
Ammoniacal nitrogen
American society for testing and materials
Biochar impregnated silica
Biochemical oxygen demand
Commercia~ activated carbon
Carbonaceous biochemical oxygen demand
Carbon hydrogen nitrogen
Chemical oxygen demand
Dichloromethane
Flame atomic absorption spectrometer
Fourier transfonn infrared
Mobil catalytic material
Mesoporous silicate 41
Nitrogeneous biochemical oxygen demand
Nuclear magnetic resonance
Nitrogen phosphorous potassium
Palm oil mill sludge
Sago activated carbon
Santa barbara amorphous
Sago biochar
Sago biomass
Scanning electron microscope
Thin layer chromathography
xvii
TSS Total suspended solid
XRD X-Ray diffractometer
xviii
LIST OF SYMBOLS
degc Degree celsius
U max Maximum vibration
8 Chemical shift
xix
CHAPTER
INTRODUCTION
11 Research background
Sarawak is currently one of the world largest exporters of sago products About 25 000 - 40
000 tonnes of sago products were exported to several countries annually such as Singapore
Taiwan and Japan (Singhal et ai 2008) Approximately 7 tonnes of sago pith waste has been
produced daily from a single sago starch processing mill (Bujang et ai 1996) Sago industries
consume about 30 000 L of water to process one tonne of sago and the liquid residue were
released as wastewater (Banu et ai 2006) The sago residues were released into nearby
streams together with wastewater as sago effluent which can lead to serious environmental
problems and affect aquatic life (Awg-Adeni et ai 2010)
Sago effluent contains high biochemical oxygen demand (BOD) and chemical oxygen demand
(COD) (Awg-Adeni et ai 2010) The effluent also contains high total suspended solid (TSS)
(Rashid et ai 2010) and acidic in nature with high organic matter unpleasant odour and
irritating colour (Ayyasamy et ai 2008) One of the treatments that has been applied onto the
sago effluent was using a hybrid reactor on-site waste treatment with very short retention
periods which combines both fixed-film and up-flow anaerobic sludge blanket systems (Banu
et ai 2006) The sago effluent was treated by the hybrid reactor for the reduction of COD
(Banu et ai 2006) The hybrid reactor system is a combination of suspended-film and fixedshy
film growth processes (Shannon et ai 2002) Sago effluent was also utilised as an additional
carbon in anaerobic digesters for the production of biogas (Abd-Aziz 2002) Other application
of biomass produced from the treated sago effluent was as a supplement for prawn feed in
aquaculture industries (Vickineswary et at 1997)
Activated sludge process is a wastewater treatment process which utilising bacteria and
microorganism to degrade suspended and dissolved organic matter via aerobic or anaerobic
oxidation (Gerardi 2006) It is a process in which a mixture of sewage and activated sludge
are agitated and aerated The sludge residue from activated sludge process can be easily
removed from the water through simple sedimentation Other treatment method such as
anaerobic digestion of sago effluent seems to be costly and difficult to maintain the system
(Ganczarczyk 1983) As an alternative aerobic digestion was introduced via activated sludge
proce s to treat sago effluent This treatment has more advantage as it utilises aerobic
microbes which grow faster than anaerobic microbes and consist of a simple process only
(Ganczarczyk 1983) In this study the sago biomass generated from the activated sludge was
chemically treated to produce sago biochar
Nowadays biochars are being prepared manually for various applications Biochars were
usually applied in environmental management such as soil improvement waste management
climate change mitigation and energy production (Lehmann and Joseph 2009) Biochar is a
carbon rich product obtained from biomass that undergo thermal decomposition with little or
absence of air at elevated temperature via pyrolysis (Lehmann and Joseph 2009) Pyrolysis is
a thermo-chemical process in which organic material is converted into a carbon rich solid
which is char and volatile matter by heating in the absence of oxygen (Demirbas and Arin
2002) A higher amount of volatile matter released during pyrolysis of biomass produces
2
biochars with lower densities and higher porosities (Vassilev et at 2009) The various
functional groups on the surface of biochar such as C=O S=O and -OH influence the sorption
of adsorbate by the nature of their surface charge and by the availability of 1t electron
(Lehmann and Joseph 2009) Pyrolysis process is regularly used for biochar production as the
technique is relatively simple and inexpensive and allows considerable flexibility in both the
type and quality of the biomass feedstock (Laird et at 2009) Microwave pyrolysis is the
latest technology used to pyrolyse biomass Microwave pyrolysis offers more advantages over
conventional heated pyrolysis due to unifonn and efficient heating (Miura et at 2004)
Biochar has also been used as a precursor for the production of activated carbon Activated
carbon is effective and used in various applications such as in water treatment for drinking
water metal extraction and heterogeneous catalysts (Azargohar and Dalai 2006) However
the usage of commercial activated carbon is limited due to its higher preparation cost (Rao et
at 2009) Several studies reported on the utilisation of agricultural wastes for the production
of low cost activated carbon such as palm oil miH shells (Nik et at 2006) groundnut shells
(Malik et at 2007) physic nut wastes (Pechyen et at 2007) hulls of rice and wheat (Qiu et
at 2008 Rao et at 2009) and palm oil empty fruit bunch (Wahi et at 2009) However there
are no studies reported on the production of activated carbon from sago processing waste
either from sago pith or sago effluent
3
12 Problem statements
Mass production of agricultural waste has become an issue to the government and
environmentalists due to illegal disposal into the jungles or the rivers which destroy the
ecosystem Sago industries generate significant amount of wastes annually either as sago pith
or sago effluent Practically direct waste disposal to the rivers brings harmful effect to the
aquatic life This study was conducted to produce some value added products from the sago
effluent Limited reserve land for agricultural waste disposal leads to the transformation of the
waste into value added products Therefore there is a need to overcome the environmental
problem caused by the disposal of sago waste In this study the sago effluent was treated via
activated sludge process to produce biomass which then transformed into biochars and applied
for various applications The production of value added products from sago waste will provide
economical solution for waste management in sago industries
4
telah berjaya digunakan sebagai pemangkin heterogen untuk tindak balas esterifikasi
dalam sintesis organik Penukaran-bio kumbahan sagu kepada produk berniai ini
boleh menurunkan kesan pencemaran dari industri pemprosesan sagu
I
vii
Pu at Khidmllt Maklumlt AkademH UN1VERSm MALAYSIA SAltAWAK
TABLE OF CONTENTS
DECLARATION
LIST OF ACHIEVEMENTS
ACKNOWLEDGEMENT
ABSTRACT
ABSTRAK
T ABLE OF CONTENTS
LIST OF TABLES
LIST OF FIGURES
LIST OF SCHEMES
LIST OF ABBREVIATIONS
LIST OF SYMBOLS
CHAPTERl
INTRODUCTION
1 1 Research background
12 Problem statement
14 Research objectives
CHAPTER 2
LITERATURE REVIEW
21 Sago industries
22 Activated sludge process
221 Microorganism in activated sludge process
222 Aerobic oxidation of carbonaceous and nitrogenous matter
viii
Page
II
III
IV
V
VI
viii
xiii
XIV
XVl
XVll
XIX
4
5
6
7
8
9
~ ~~____-I
23 Biomass as a substrate for biochar 11
231 Biomass from activated sludge process 11
232 Biomass composition 12
24 Pyrolysis process of biomass 13
25 Operational condition and techniques of pyrolysis 13
26 Biochar and the pyrolytic products 14
27 Properties of biochar 15
28 Activated carbon from biochar 17
29 Activated carbon and the applications 18
29 1 Water filtration 18
292 Heavy metal adsorption 19
2921 Heavy metals 20
210 Solid phase organic synthesis 21
2101 Solid supported reagent 22
2102 Solid supported catalyst 23
21 021 Solid acid catalyst 24
21022 Solid base catalyst 26
CHAPTER 3
MATERIALS AND METHODS
31 Materials and instrumental 30
32 General methods 31
33 Production of biomass (SBM) from sago effiuent 33
331 Assessment of water quality after activated sludge process 33
3311 Detennination of pH 33
IX
--
II
I
331 2 Detennination of chemical oxygen demand (COD)
331 3 Detennination of total suspended solids (TSS)
3314 Detennination of ammoniacal nitrogen (AN)
332 Characterisation of SBM
3321 Moisture ash and volatile content analysis
3322 FTIR and SEM analysis
34 Production of sago biochar (SBC) from SBM via microwave
pyrolysis
341 Characterisation of SBC
3411 Moisture content analysis
3412 Ultimate analysis
3413 FTIR and SEM analysis
342 Application of SBC as plant enhancer
35 Preparation of sago activated carbon (SAC)
351 Preparation ofSAC1 from SBC
352 Preparation of SAC2 from sago hampas
35 3 Characterisation of SAC 1
3531 Moisture content analysis
3532 FTIR and SEM analysis
354 Application ofSAC1
3541 Water filter system
3542 Heavy metal adsorption
36 Preparation ofbiochar impregnated silica (BIS) as
solid phase reagent
361 Preparation of BIS
34
34
35
35
35
37
38
38
38
38
39
39 39
39
40
40
40
40
41
41
41
42
42
x
I
I
362 Characterisation ofBIS 43
363 Attempted solid phase organic synthesis using BIS 43
37 Preparation of solid base catalyst from SAC 1 43
371 Preparation of solid base catalyst from SACl 44
372 Transesterification of palm oil mill sludge (POMS)
using solid base catalyst 44
38 Preparation of solid acid catalyst from SACl 44
381 Hydrolysis of acetylsalicylic acid (ASA) to salicylic acid 44
382 Synthesis of methyl salicylate 45
CHAPTER 4
RESULTS AND DISCUSSION
41 Production of SBM from activated sludge process 46
411 Assessment of water quality after activated sludge process 47
412 Characterisation of SBM 47
4121 Moisture ash and volatile content analysis 47
4122 FTIR and SEM analysis 48
42 Production of SBC via microwave pyrolysis 50
421 Characterisation of SBC 50
4211 Moisture content analysis 50
4212 Analysis of organic matters 50
4213 FTIR and SEM analysis 51
422 Application of SBC as plant enhancer 53
43 Preparation of SAC 1 from SBC 56
431 Characterisation of SBM 56
Xl
4311 Moisture content analysis 56
4312 FTIR and SEM analysis 57
43 3 Application ofSAC1 60
4331 Water filter system 60
4332 Heavy metal adsorption 61
44 Preparation ofbiochar impregnated silica (BIS)
as solid phase reagent 65
441 Characterisation of BIS 66
442 Attempted solid phase organic synthesis using BIS 67
45 Application of solid base catalyst from SAC 1
in transesterification of palm oil mill sludge (POMS) 70
46 Application of solid acid catalyst in methyl salicylate
preparation
CHAPTER 5
76
CONCLUSION AND RECOMMENDATION
51 Conclusion 80
52 Recommendation 82
REFERENCES 84
APPENDIX A 93
APPENDIXB 95
APPENDIXC 97
APPENDIXD 100
APPENDIXE 102
XII
J
~ LIST OF TABLES I
Page Table 21 Example of solid catalysts and their applications 23
t Table 22 Types of solid base catalyst 26 [ Table 41 Ultimate analysis of SBC 51
Table 42 Analysis of chilli seedlings after 14 days 55 ITable 43 NPK content of SBC 56
Table 44 COD of sago effluent before and after filtration 61
i
1
Xlll
I shy
I
LIST OF FIGURES
Page
Figure 21 Schematic flow diagram for sago processing 7
Figure 22 Bmnsted acidity arising from inductive effect of Lewis 24
acid center coordinated to a silica support
Figure 31 (a) Modified household microwave oven (b) quartz 24
reactor attached to the oven
Figure 32 Methyl salicylate 45
Figure 42 The IR spectrum of SBM 49
Figure 43 The SEM micrograph ofSBM (1000x magnification) 49
Figure 44 The IR spectrum of SBC 52
Figure 45 The SEM micrograph of (a) surface SBC (l2000x 53
magnification) (b) SBC with internal diameter
measurement (l2000x magnification)
Figure 46 Top view of chilli plant after 3 Days 54
Figure 47 (a) Top view (b) Side view of chilli plant after 14 Days 55
Figure 48 The IR spectra of (a) SACI (b) CAC 58
Figure 49 The SEM micrograph of (a) surface SACI 59
(12000x magnification) (b) SAC 1 with internal
diameter measurement (l2000x magnification)
(c) CAC (l2000x magnification)
Figure 4l0 Water filter system using SACI as a filter 60
Figure 411 The effect of adsorbent disages to adsorption of Zn Cr 63
and Pb by SAC 1 at a fixed metal concentration of
5 mgIL
xiv
I
Figure 412 The effect of initia~ concentration to adsorption of Zn 65
Cr and Pb by SAC1 at a fixed adsorbent dosage of
01 g
Figure 413 The SEM micrograph of BIS (5000x magnification) 66
Figure 414 The XRD pattern of amorphous silica from BIS 67
Figure 415 The IR spectra of (a) solid BIS before reaction (b) solid 69
BIS after reaction
Figure 416 The SEM micrograph of (a) solid BIS before reaction 69
(b) solid BIS after reaction
Figure 417 The IR spectra of product using (a) 5 solid base 73
catalyst of SAC 1 (b) 10 solid base catalyst of SAC 1
(c) 5 solid base catalyst of SAC 1 containing silica
(d) 10 solid base catalyst of SAC 1 containing silica
(e) Raw POMS
Figure 418 The IR spectra of product using (a) 5 solid base 75
catalyst of SAC2
(b) 10 solid base catalyst ofSAC2 (c) 5 solid base
catalyst of SAC2 containing silica
(d) 10 solid base catalyst of SAC2 containing silica
(e) Raw POMS
Figure 419 The IR spectra of (a) salicylic acid (b) methyl 78
salicylate
Figure 420 The IH-NMR spectrum of methyl salicylate 79
xv
~ -~----------
Scheme 21
Scheme 41
Scheme 42
Scheme 43
Scheme 44
Scheme 45
LIST OF SCHEMES
Multi-step synthesis using polymer-supported reagents
Synthesis of biphenyl-4-carbonyl chloride
Transesterification of POMS
Mechanism of transesterification of POMS using solid
base catalyst
Esterification of salicylic acid
Mechanism of esterification of salicylic acid using
solid acid catalyst
Page
22
68
70
71
76
77
xvi
l
LIST OF ABBREVIATIONS
AN
ASTM
B1S
BOD
CAC
cBOD
CHN
COD
DCM
FAAS
FTlR
MCM
M41S
nBOD
NMR
NPK
POMS
SAC
SBA
SBC
SBM
SEM
TLC
Ammoniacal nitrogen
American society for testing and materials
Biochar impregnated silica
Biochemical oxygen demand
Commercia~ activated carbon
Carbonaceous biochemical oxygen demand
Carbon hydrogen nitrogen
Chemical oxygen demand
Dichloromethane
Flame atomic absorption spectrometer
Fourier transfonn infrared
Mobil catalytic material
Mesoporous silicate 41
Nitrogeneous biochemical oxygen demand
Nuclear magnetic resonance
Nitrogen phosphorous potassium
Palm oil mill sludge
Sago activated carbon
Santa barbara amorphous
Sago biochar
Sago biomass
Scanning electron microscope
Thin layer chromathography
xvii
TSS Total suspended solid
XRD X-Ray diffractometer
xviii
LIST OF SYMBOLS
degc Degree celsius
U max Maximum vibration
8 Chemical shift
xix
CHAPTER
INTRODUCTION
11 Research background
Sarawak is currently one of the world largest exporters of sago products About 25 000 - 40
000 tonnes of sago products were exported to several countries annually such as Singapore
Taiwan and Japan (Singhal et ai 2008) Approximately 7 tonnes of sago pith waste has been
produced daily from a single sago starch processing mill (Bujang et ai 1996) Sago industries
consume about 30 000 L of water to process one tonne of sago and the liquid residue were
released as wastewater (Banu et ai 2006) The sago residues were released into nearby
streams together with wastewater as sago effluent which can lead to serious environmental
problems and affect aquatic life (Awg-Adeni et ai 2010)
Sago effluent contains high biochemical oxygen demand (BOD) and chemical oxygen demand
(COD) (Awg-Adeni et ai 2010) The effluent also contains high total suspended solid (TSS)
(Rashid et ai 2010) and acidic in nature with high organic matter unpleasant odour and
irritating colour (Ayyasamy et ai 2008) One of the treatments that has been applied onto the
sago effluent was using a hybrid reactor on-site waste treatment with very short retention
periods which combines both fixed-film and up-flow anaerobic sludge blanket systems (Banu
et ai 2006) The sago effluent was treated by the hybrid reactor for the reduction of COD
(Banu et ai 2006) The hybrid reactor system is a combination of suspended-film and fixedshy
film growth processes (Shannon et ai 2002) Sago effluent was also utilised as an additional
carbon in anaerobic digesters for the production of biogas (Abd-Aziz 2002) Other application
of biomass produced from the treated sago effluent was as a supplement for prawn feed in
aquaculture industries (Vickineswary et at 1997)
Activated sludge process is a wastewater treatment process which utilising bacteria and
microorganism to degrade suspended and dissolved organic matter via aerobic or anaerobic
oxidation (Gerardi 2006) It is a process in which a mixture of sewage and activated sludge
are agitated and aerated The sludge residue from activated sludge process can be easily
removed from the water through simple sedimentation Other treatment method such as
anaerobic digestion of sago effluent seems to be costly and difficult to maintain the system
(Ganczarczyk 1983) As an alternative aerobic digestion was introduced via activated sludge
proce s to treat sago effluent This treatment has more advantage as it utilises aerobic
microbes which grow faster than anaerobic microbes and consist of a simple process only
(Ganczarczyk 1983) In this study the sago biomass generated from the activated sludge was
chemically treated to produce sago biochar
Nowadays biochars are being prepared manually for various applications Biochars were
usually applied in environmental management such as soil improvement waste management
climate change mitigation and energy production (Lehmann and Joseph 2009) Biochar is a
carbon rich product obtained from biomass that undergo thermal decomposition with little or
absence of air at elevated temperature via pyrolysis (Lehmann and Joseph 2009) Pyrolysis is
a thermo-chemical process in which organic material is converted into a carbon rich solid
which is char and volatile matter by heating in the absence of oxygen (Demirbas and Arin
2002) A higher amount of volatile matter released during pyrolysis of biomass produces
2
biochars with lower densities and higher porosities (Vassilev et at 2009) The various
functional groups on the surface of biochar such as C=O S=O and -OH influence the sorption
of adsorbate by the nature of their surface charge and by the availability of 1t electron
(Lehmann and Joseph 2009) Pyrolysis process is regularly used for biochar production as the
technique is relatively simple and inexpensive and allows considerable flexibility in both the
type and quality of the biomass feedstock (Laird et at 2009) Microwave pyrolysis is the
latest technology used to pyrolyse biomass Microwave pyrolysis offers more advantages over
conventional heated pyrolysis due to unifonn and efficient heating (Miura et at 2004)
Biochar has also been used as a precursor for the production of activated carbon Activated
carbon is effective and used in various applications such as in water treatment for drinking
water metal extraction and heterogeneous catalysts (Azargohar and Dalai 2006) However
the usage of commercial activated carbon is limited due to its higher preparation cost (Rao et
at 2009) Several studies reported on the utilisation of agricultural wastes for the production
of low cost activated carbon such as palm oil miH shells (Nik et at 2006) groundnut shells
(Malik et at 2007) physic nut wastes (Pechyen et at 2007) hulls of rice and wheat (Qiu et
at 2008 Rao et at 2009) and palm oil empty fruit bunch (Wahi et at 2009) However there
are no studies reported on the production of activated carbon from sago processing waste
either from sago pith or sago effluent
3
12 Problem statements
Mass production of agricultural waste has become an issue to the government and
environmentalists due to illegal disposal into the jungles or the rivers which destroy the
ecosystem Sago industries generate significant amount of wastes annually either as sago pith
or sago effluent Practically direct waste disposal to the rivers brings harmful effect to the
aquatic life This study was conducted to produce some value added products from the sago
effluent Limited reserve land for agricultural waste disposal leads to the transformation of the
waste into value added products Therefore there is a need to overcome the environmental
problem caused by the disposal of sago waste In this study the sago effluent was treated via
activated sludge process to produce biomass which then transformed into biochars and applied
for various applications The production of value added products from sago waste will provide
economical solution for waste management in sago industries
4
Pu at Khidmllt Maklumlt AkademH UN1VERSm MALAYSIA SAltAWAK
TABLE OF CONTENTS
DECLARATION
LIST OF ACHIEVEMENTS
ACKNOWLEDGEMENT
ABSTRACT
ABSTRAK
T ABLE OF CONTENTS
LIST OF TABLES
LIST OF FIGURES
LIST OF SCHEMES
LIST OF ABBREVIATIONS
LIST OF SYMBOLS
CHAPTERl
INTRODUCTION
1 1 Research background
12 Problem statement
14 Research objectives
CHAPTER 2
LITERATURE REVIEW
21 Sago industries
22 Activated sludge process
221 Microorganism in activated sludge process
222 Aerobic oxidation of carbonaceous and nitrogenous matter
viii
Page
II
III
IV
V
VI
viii
xiii
XIV
XVl
XVll
XIX
4
5
6
7
8
9
~ ~~____-I
23 Biomass as a substrate for biochar 11
231 Biomass from activated sludge process 11
232 Biomass composition 12
24 Pyrolysis process of biomass 13
25 Operational condition and techniques of pyrolysis 13
26 Biochar and the pyrolytic products 14
27 Properties of biochar 15
28 Activated carbon from biochar 17
29 Activated carbon and the applications 18
29 1 Water filtration 18
292 Heavy metal adsorption 19
2921 Heavy metals 20
210 Solid phase organic synthesis 21
2101 Solid supported reagent 22
2102 Solid supported catalyst 23
21 021 Solid acid catalyst 24
21022 Solid base catalyst 26
CHAPTER 3
MATERIALS AND METHODS
31 Materials and instrumental 30
32 General methods 31
33 Production of biomass (SBM) from sago effiuent 33
331 Assessment of water quality after activated sludge process 33
3311 Detennination of pH 33
IX
--
II
I
331 2 Detennination of chemical oxygen demand (COD)
331 3 Detennination of total suspended solids (TSS)
3314 Detennination of ammoniacal nitrogen (AN)
332 Characterisation of SBM
3321 Moisture ash and volatile content analysis
3322 FTIR and SEM analysis
34 Production of sago biochar (SBC) from SBM via microwave
pyrolysis
341 Characterisation of SBC
3411 Moisture content analysis
3412 Ultimate analysis
3413 FTIR and SEM analysis
342 Application of SBC as plant enhancer
35 Preparation of sago activated carbon (SAC)
351 Preparation ofSAC1 from SBC
352 Preparation of SAC2 from sago hampas
35 3 Characterisation of SAC 1
3531 Moisture content analysis
3532 FTIR and SEM analysis
354 Application ofSAC1
3541 Water filter system
3542 Heavy metal adsorption
36 Preparation ofbiochar impregnated silica (BIS) as
solid phase reagent
361 Preparation of BIS
34
34
35
35
35
37
38
38
38
38
39
39 39
39
40
40
40
40
41
41
41
42
42
x
I
I
362 Characterisation ofBIS 43
363 Attempted solid phase organic synthesis using BIS 43
37 Preparation of solid base catalyst from SAC 1 43
371 Preparation of solid base catalyst from SACl 44
372 Transesterification of palm oil mill sludge (POMS)
using solid base catalyst 44
38 Preparation of solid acid catalyst from SACl 44
381 Hydrolysis of acetylsalicylic acid (ASA) to salicylic acid 44
382 Synthesis of methyl salicylate 45
CHAPTER 4
RESULTS AND DISCUSSION
41 Production of SBM from activated sludge process 46
411 Assessment of water quality after activated sludge process 47
412 Characterisation of SBM 47
4121 Moisture ash and volatile content analysis 47
4122 FTIR and SEM analysis 48
42 Production of SBC via microwave pyrolysis 50
421 Characterisation of SBC 50
4211 Moisture content analysis 50
4212 Analysis of organic matters 50
4213 FTIR and SEM analysis 51
422 Application of SBC as plant enhancer 53
43 Preparation of SAC 1 from SBC 56
431 Characterisation of SBM 56
Xl
4311 Moisture content analysis 56
4312 FTIR and SEM analysis 57
43 3 Application ofSAC1 60
4331 Water filter system 60
4332 Heavy metal adsorption 61
44 Preparation ofbiochar impregnated silica (BIS)
as solid phase reagent 65
441 Characterisation of BIS 66
442 Attempted solid phase organic synthesis using BIS 67
45 Application of solid base catalyst from SAC 1
in transesterification of palm oil mill sludge (POMS) 70
46 Application of solid acid catalyst in methyl salicylate
preparation
CHAPTER 5
76
CONCLUSION AND RECOMMENDATION
51 Conclusion 80
52 Recommendation 82
REFERENCES 84
APPENDIX A 93
APPENDIXB 95
APPENDIXC 97
APPENDIXD 100
APPENDIXE 102
XII
J
~ LIST OF TABLES I
Page Table 21 Example of solid catalysts and their applications 23
t Table 22 Types of solid base catalyst 26 [ Table 41 Ultimate analysis of SBC 51
Table 42 Analysis of chilli seedlings after 14 days 55 ITable 43 NPK content of SBC 56
Table 44 COD of sago effluent before and after filtration 61
i
1
Xlll
I shy
I
LIST OF FIGURES
Page
Figure 21 Schematic flow diagram for sago processing 7
Figure 22 Bmnsted acidity arising from inductive effect of Lewis 24
acid center coordinated to a silica support
Figure 31 (a) Modified household microwave oven (b) quartz 24
reactor attached to the oven
Figure 32 Methyl salicylate 45
Figure 42 The IR spectrum of SBM 49
Figure 43 The SEM micrograph ofSBM (1000x magnification) 49
Figure 44 The IR spectrum of SBC 52
Figure 45 The SEM micrograph of (a) surface SBC (l2000x 53
magnification) (b) SBC with internal diameter
measurement (l2000x magnification)
Figure 46 Top view of chilli plant after 3 Days 54
Figure 47 (a) Top view (b) Side view of chilli plant after 14 Days 55
Figure 48 The IR spectra of (a) SACI (b) CAC 58
Figure 49 The SEM micrograph of (a) surface SACI 59
(12000x magnification) (b) SAC 1 with internal
diameter measurement (l2000x magnification)
(c) CAC (l2000x magnification)
Figure 4l0 Water filter system using SACI as a filter 60
Figure 411 The effect of adsorbent disages to adsorption of Zn Cr 63
and Pb by SAC 1 at a fixed metal concentration of
5 mgIL
xiv
I
Figure 412 The effect of initia~ concentration to adsorption of Zn 65
Cr and Pb by SAC1 at a fixed adsorbent dosage of
01 g
Figure 413 The SEM micrograph of BIS (5000x magnification) 66
Figure 414 The XRD pattern of amorphous silica from BIS 67
Figure 415 The IR spectra of (a) solid BIS before reaction (b) solid 69
BIS after reaction
Figure 416 The SEM micrograph of (a) solid BIS before reaction 69
(b) solid BIS after reaction
Figure 417 The IR spectra of product using (a) 5 solid base 73
catalyst of SAC 1 (b) 10 solid base catalyst of SAC 1
(c) 5 solid base catalyst of SAC 1 containing silica
(d) 10 solid base catalyst of SAC 1 containing silica
(e) Raw POMS
Figure 418 The IR spectra of product using (a) 5 solid base 75
catalyst of SAC2
(b) 10 solid base catalyst ofSAC2 (c) 5 solid base
catalyst of SAC2 containing silica
(d) 10 solid base catalyst of SAC2 containing silica
(e) Raw POMS
Figure 419 The IR spectra of (a) salicylic acid (b) methyl 78
salicylate
Figure 420 The IH-NMR spectrum of methyl salicylate 79
xv
~ -~----------
Scheme 21
Scheme 41
Scheme 42
Scheme 43
Scheme 44
Scheme 45
LIST OF SCHEMES
Multi-step synthesis using polymer-supported reagents
Synthesis of biphenyl-4-carbonyl chloride
Transesterification of POMS
Mechanism of transesterification of POMS using solid
base catalyst
Esterification of salicylic acid
Mechanism of esterification of salicylic acid using
solid acid catalyst
Page
22
68
70
71
76
77
xvi
l
LIST OF ABBREVIATIONS
AN
ASTM
B1S
BOD
CAC
cBOD
CHN
COD
DCM
FAAS
FTlR
MCM
M41S
nBOD
NMR
NPK
POMS
SAC
SBA
SBC
SBM
SEM
TLC
Ammoniacal nitrogen
American society for testing and materials
Biochar impregnated silica
Biochemical oxygen demand
Commercia~ activated carbon
Carbonaceous biochemical oxygen demand
Carbon hydrogen nitrogen
Chemical oxygen demand
Dichloromethane
Flame atomic absorption spectrometer
Fourier transfonn infrared
Mobil catalytic material
Mesoporous silicate 41
Nitrogeneous biochemical oxygen demand
Nuclear magnetic resonance
Nitrogen phosphorous potassium
Palm oil mill sludge
Sago activated carbon
Santa barbara amorphous
Sago biochar
Sago biomass
Scanning electron microscope
Thin layer chromathography
xvii
TSS Total suspended solid
XRD X-Ray diffractometer
xviii
LIST OF SYMBOLS
degc Degree celsius
U max Maximum vibration
8 Chemical shift
xix
CHAPTER
INTRODUCTION
11 Research background
Sarawak is currently one of the world largest exporters of sago products About 25 000 - 40
000 tonnes of sago products were exported to several countries annually such as Singapore
Taiwan and Japan (Singhal et ai 2008) Approximately 7 tonnes of sago pith waste has been
produced daily from a single sago starch processing mill (Bujang et ai 1996) Sago industries
consume about 30 000 L of water to process one tonne of sago and the liquid residue were
released as wastewater (Banu et ai 2006) The sago residues were released into nearby
streams together with wastewater as sago effluent which can lead to serious environmental
problems and affect aquatic life (Awg-Adeni et ai 2010)
Sago effluent contains high biochemical oxygen demand (BOD) and chemical oxygen demand
(COD) (Awg-Adeni et ai 2010) The effluent also contains high total suspended solid (TSS)
(Rashid et ai 2010) and acidic in nature with high organic matter unpleasant odour and
irritating colour (Ayyasamy et ai 2008) One of the treatments that has been applied onto the
sago effluent was using a hybrid reactor on-site waste treatment with very short retention
periods which combines both fixed-film and up-flow anaerobic sludge blanket systems (Banu
et ai 2006) The sago effluent was treated by the hybrid reactor for the reduction of COD
(Banu et ai 2006) The hybrid reactor system is a combination of suspended-film and fixedshy
film growth processes (Shannon et ai 2002) Sago effluent was also utilised as an additional
carbon in anaerobic digesters for the production of biogas (Abd-Aziz 2002) Other application
of biomass produced from the treated sago effluent was as a supplement for prawn feed in
aquaculture industries (Vickineswary et at 1997)
Activated sludge process is a wastewater treatment process which utilising bacteria and
microorganism to degrade suspended and dissolved organic matter via aerobic or anaerobic
oxidation (Gerardi 2006) It is a process in which a mixture of sewage and activated sludge
are agitated and aerated The sludge residue from activated sludge process can be easily
removed from the water through simple sedimentation Other treatment method such as
anaerobic digestion of sago effluent seems to be costly and difficult to maintain the system
(Ganczarczyk 1983) As an alternative aerobic digestion was introduced via activated sludge
proce s to treat sago effluent This treatment has more advantage as it utilises aerobic
microbes which grow faster than anaerobic microbes and consist of a simple process only
(Ganczarczyk 1983) In this study the sago biomass generated from the activated sludge was
chemically treated to produce sago biochar
Nowadays biochars are being prepared manually for various applications Biochars were
usually applied in environmental management such as soil improvement waste management
climate change mitigation and energy production (Lehmann and Joseph 2009) Biochar is a
carbon rich product obtained from biomass that undergo thermal decomposition with little or
absence of air at elevated temperature via pyrolysis (Lehmann and Joseph 2009) Pyrolysis is
a thermo-chemical process in which organic material is converted into a carbon rich solid
which is char and volatile matter by heating in the absence of oxygen (Demirbas and Arin
2002) A higher amount of volatile matter released during pyrolysis of biomass produces
2
biochars with lower densities and higher porosities (Vassilev et at 2009) The various
functional groups on the surface of biochar such as C=O S=O and -OH influence the sorption
of adsorbate by the nature of their surface charge and by the availability of 1t electron
(Lehmann and Joseph 2009) Pyrolysis process is regularly used for biochar production as the
technique is relatively simple and inexpensive and allows considerable flexibility in both the
type and quality of the biomass feedstock (Laird et at 2009) Microwave pyrolysis is the
latest technology used to pyrolyse biomass Microwave pyrolysis offers more advantages over
conventional heated pyrolysis due to unifonn and efficient heating (Miura et at 2004)
Biochar has also been used as a precursor for the production of activated carbon Activated
carbon is effective and used in various applications such as in water treatment for drinking
water metal extraction and heterogeneous catalysts (Azargohar and Dalai 2006) However
the usage of commercial activated carbon is limited due to its higher preparation cost (Rao et
at 2009) Several studies reported on the utilisation of agricultural wastes for the production
of low cost activated carbon such as palm oil miH shells (Nik et at 2006) groundnut shells
(Malik et at 2007) physic nut wastes (Pechyen et at 2007) hulls of rice and wheat (Qiu et
at 2008 Rao et at 2009) and palm oil empty fruit bunch (Wahi et at 2009) However there
are no studies reported on the production of activated carbon from sago processing waste
either from sago pith or sago effluent
3
12 Problem statements
Mass production of agricultural waste has become an issue to the government and
environmentalists due to illegal disposal into the jungles or the rivers which destroy the
ecosystem Sago industries generate significant amount of wastes annually either as sago pith
or sago effluent Practically direct waste disposal to the rivers brings harmful effect to the
aquatic life This study was conducted to produce some value added products from the sago
effluent Limited reserve land for agricultural waste disposal leads to the transformation of the
waste into value added products Therefore there is a need to overcome the environmental
problem caused by the disposal of sago waste In this study the sago effluent was treated via
activated sludge process to produce biomass which then transformed into biochars and applied
for various applications The production of value added products from sago waste will provide
economical solution for waste management in sago industries
4
23 Biomass as a substrate for biochar 11
231 Biomass from activated sludge process 11
232 Biomass composition 12
24 Pyrolysis process of biomass 13
25 Operational condition and techniques of pyrolysis 13
26 Biochar and the pyrolytic products 14
27 Properties of biochar 15
28 Activated carbon from biochar 17
29 Activated carbon and the applications 18
29 1 Water filtration 18
292 Heavy metal adsorption 19
2921 Heavy metals 20
210 Solid phase organic synthesis 21
2101 Solid supported reagent 22
2102 Solid supported catalyst 23
21 021 Solid acid catalyst 24
21022 Solid base catalyst 26
CHAPTER 3
MATERIALS AND METHODS
31 Materials and instrumental 30
32 General methods 31
33 Production of biomass (SBM) from sago effiuent 33
331 Assessment of water quality after activated sludge process 33
3311 Detennination of pH 33
IX
--
II
I
331 2 Detennination of chemical oxygen demand (COD)
331 3 Detennination of total suspended solids (TSS)
3314 Detennination of ammoniacal nitrogen (AN)
332 Characterisation of SBM
3321 Moisture ash and volatile content analysis
3322 FTIR and SEM analysis
34 Production of sago biochar (SBC) from SBM via microwave
pyrolysis
341 Characterisation of SBC
3411 Moisture content analysis
3412 Ultimate analysis
3413 FTIR and SEM analysis
342 Application of SBC as plant enhancer
35 Preparation of sago activated carbon (SAC)
351 Preparation ofSAC1 from SBC
352 Preparation of SAC2 from sago hampas
35 3 Characterisation of SAC 1
3531 Moisture content analysis
3532 FTIR and SEM analysis
354 Application ofSAC1
3541 Water filter system
3542 Heavy metal adsorption
36 Preparation ofbiochar impregnated silica (BIS) as
solid phase reagent
361 Preparation of BIS
34
34
35
35
35
37
38
38
38
38
39
39 39
39
40
40
40
40
41
41
41
42
42
x
I
I
362 Characterisation ofBIS 43
363 Attempted solid phase organic synthesis using BIS 43
37 Preparation of solid base catalyst from SAC 1 43
371 Preparation of solid base catalyst from SACl 44
372 Transesterification of palm oil mill sludge (POMS)
using solid base catalyst 44
38 Preparation of solid acid catalyst from SACl 44
381 Hydrolysis of acetylsalicylic acid (ASA) to salicylic acid 44
382 Synthesis of methyl salicylate 45
CHAPTER 4
RESULTS AND DISCUSSION
41 Production of SBM from activated sludge process 46
411 Assessment of water quality after activated sludge process 47
412 Characterisation of SBM 47
4121 Moisture ash and volatile content analysis 47
4122 FTIR and SEM analysis 48
42 Production of SBC via microwave pyrolysis 50
421 Characterisation of SBC 50
4211 Moisture content analysis 50
4212 Analysis of organic matters 50
4213 FTIR and SEM analysis 51
422 Application of SBC as plant enhancer 53
43 Preparation of SAC 1 from SBC 56
431 Characterisation of SBM 56
Xl
4311 Moisture content analysis 56
4312 FTIR and SEM analysis 57
43 3 Application ofSAC1 60
4331 Water filter system 60
4332 Heavy metal adsorption 61
44 Preparation ofbiochar impregnated silica (BIS)
as solid phase reagent 65
441 Characterisation of BIS 66
442 Attempted solid phase organic synthesis using BIS 67
45 Application of solid base catalyst from SAC 1
in transesterification of palm oil mill sludge (POMS) 70
46 Application of solid acid catalyst in methyl salicylate
preparation
CHAPTER 5
76
CONCLUSION AND RECOMMENDATION
51 Conclusion 80
52 Recommendation 82
REFERENCES 84
APPENDIX A 93
APPENDIXB 95
APPENDIXC 97
APPENDIXD 100
APPENDIXE 102
XII
J
~ LIST OF TABLES I
Page Table 21 Example of solid catalysts and their applications 23
t Table 22 Types of solid base catalyst 26 [ Table 41 Ultimate analysis of SBC 51
Table 42 Analysis of chilli seedlings after 14 days 55 ITable 43 NPK content of SBC 56
Table 44 COD of sago effluent before and after filtration 61
i
1
Xlll
I shy
I
LIST OF FIGURES
Page
Figure 21 Schematic flow diagram for sago processing 7
Figure 22 Bmnsted acidity arising from inductive effect of Lewis 24
acid center coordinated to a silica support
Figure 31 (a) Modified household microwave oven (b) quartz 24
reactor attached to the oven
Figure 32 Methyl salicylate 45
Figure 42 The IR spectrum of SBM 49
Figure 43 The SEM micrograph ofSBM (1000x magnification) 49
Figure 44 The IR spectrum of SBC 52
Figure 45 The SEM micrograph of (a) surface SBC (l2000x 53
magnification) (b) SBC with internal diameter
measurement (l2000x magnification)
Figure 46 Top view of chilli plant after 3 Days 54
Figure 47 (a) Top view (b) Side view of chilli plant after 14 Days 55
Figure 48 The IR spectra of (a) SACI (b) CAC 58
Figure 49 The SEM micrograph of (a) surface SACI 59
(12000x magnification) (b) SAC 1 with internal
diameter measurement (l2000x magnification)
(c) CAC (l2000x magnification)
Figure 4l0 Water filter system using SACI as a filter 60
Figure 411 The effect of adsorbent disages to adsorption of Zn Cr 63
and Pb by SAC 1 at a fixed metal concentration of
5 mgIL
xiv
I
Figure 412 The effect of initia~ concentration to adsorption of Zn 65
Cr and Pb by SAC1 at a fixed adsorbent dosage of
01 g
Figure 413 The SEM micrograph of BIS (5000x magnification) 66
Figure 414 The XRD pattern of amorphous silica from BIS 67
Figure 415 The IR spectra of (a) solid BIS before reaction (b) solid 69
BIS after reaction
Figure 416 The SEM micrograph of (a) solid BIS before reaction 69
(b) solid BIS after reaction
Figure 417 The IR spectra of product using (a) 5 solid base 73
catalyst of SAC 1 (b) 10 solid base catalyst of SAC 1
(c) 5 solid base catalyst of SAC 1 containing silica
(d) 10 solid base catalyst of SAC 1 containing silica
(e) Raw POMS
Figure 418 The IR spectra of product using (a) 5 solid base 75
catalyst of SAC2
(b) 10 solid base catalyst ofSAC2 (c) 5 solid base
catalyst of SAC2 containing silica
(d) 10 solid base catalyst of SAC2 containing silica
(e) Raw POMS
Figure 419 The IR spectra of (a) salicylic acid (b) methyl 78
salicylate
Figure 420 The IH-NMR spectrum of methyl salicylate 79
xv
~ -~----------
Scheme 21
Scheme 41
Scheme 42
Scheme 43
Scheme 44
Scheme 45
LIST OF SCHEMES
Multi-step synthesis using polymer-supported reagents
Synthesis of biphenyl-4-carbonyl chloride
Transesterification of POMS
Mechanism of transesterification of POMS using solid
base catalyst
Esterification of salicylic acid
Mechanism of esterification of salicylic acid using
solid acid catalyst
Page
22
68
70
71
76
77
xvi
l
LIST OF ABBREVIATIONS
AN
ASTM
B1S
BOD
CAC
cBOD
CHN
COD
DCM
FAAS
FTlR
MCM
M41S
nBOD
NMR
NPK
POMS
SAC
SBA
SBC
SBM
SEM
TLC
Ammoniacal nitrogen
American society for testing and materials
Biochar impregnated silica
Biochemical oxygen demand
Commercia~ activated carbon
Carbonaceous biochemical oxygen demand
Carbon hydrogen nitrogen
Chemical oxygen demand
Dichloromethane
Flame atomic absorption spectrometer
Fourier transfonn infrared
Mobil catalytic material
Mesoporous silicate 41
Nitrogeneous biochemical oxygen demand
Nuclear magnetic resonance
Nitrogen phosphorous potassium
Palm oil mill sludge
Sago activated carbon
Santa barbara amorphous
Sago biochar
Sago biomass
Scanning electron microscope
Thin layer chromathography
xvii
TSS Total suspended solid
XRD X-Ray diffractometer
xviii
LIST OF SYMBOLS
degc Degree celsius
U max Maximum vibration
8 Chemical shift
xix
CHAPTER
INTRODUCTION
11 Research background
Sarawak is currently one of the world largest exporters of sago products About 25 000 - 40
000 tonnes of sago products were exported to several countries annually such as Singapore
Taiwan and Japan (Singhal et ai 2008) Approximately 7 tonnes of sago pith waste has been
produced daily from a single sago starch processing mill (Bujang et ai 1996) Sago industries
consume about 30 000 L of water to process one tonne of sago and the liquid residue were
released as wastewater (Banu et ai 2006) The sago residues were released into nearby
streams together with wastewater as sago effluent which can lead to serious environmental
problems and affect aquatic life (Awg-Adeni et ai 2010)
Sago effluent contains high biochemical oxygen demand (BOD) and chemical oxygen demand
(COD) (Awg-Adeni et ai 2010) The effluent also contains high total suspended solid (TSS)
(Rashid et ai 2010) and acidic in nature with high organic matter unpleasant odour and
irritating colour (Ayyasamy et ai 2008) One of the treatments that has been applied onto the
sago effluent was using a hybrid reactor on-site waste treatment with very short retention
periods which combines both fixed-film and up-flow anaerobic sludge blanket systems (Banu
et ai 2006) The sago effluent was treated by the hybrid reactor for the reduction of COD
(Banu et ai 2006) The hybrid reactor system is a combination of suspended-film and fixedshy
film growth processes (Shannon et ai 2002) Sago effluent was also utilised as an additional
carbon in anaerobic digesters for the production of biogas (Abd-Aziz 2002) Other application
of biomass produced from the treated sago effluent was as a supplement for prawn feed in
aquaculture industries (Vickineswary et at 1997)
Activated sludge process is a wastewater treatment process which utilising bacteria and
microorganism to degrade suspended and dissolved organic matter via aerobic or anaerobic
oxidation (Gerardi 2006) It is a process in which a mixture of sewage and activated sludge
are agitated and aerated The sludge residue from activated sludge process can be easily
removed from the water through simple sedimentation Other treatment method such as
anaerobic digestion of sago effluent seems to be costly and difficult to maintain the system
(Ganczarczyk 1983) As an alternative aerobic digestion was introduced via activated sludge
proce s to treat sago effluent This treatment has more advantage as it utilises aerobic
microbes which grow faster than anaerobic microbes and consist of a simple process only
(Ganczarczyk 1983) In this study the sago biomass generated from the activated sludge was
chemically treated to produce sago biochar
Nowadays biochars are being prepared manually for various applications Biochars were
usually applied in environmental management such as soil improvement waste management
climate change mitigation and energy production (Lehmann and Joseph 2009) Biochar is a
carbon rich product obtained from biomass that undergo thermal decomposition with little or
absence of air at elevated temperature via pyrolysis (Lehmann and Joseph 2009) Pyrolysis is
a thermo-chemical process in which organic material is converted into a carbon rich solid
which is char and volatile matter by heating in the absence of oxygen (Demirbas and Arin
2002) A higher amount of volatile matter released during pyrolysis of biomass produces
2
biochars with lower densities and higher porosities (Vassilev et at 2009) The various
functional groups on the surface of biochar such as C=O S=O and -OH influence the sorption
of adsorbate by the nature of their surface charge and by the availability of 1t electron
(Lehmann and Joseph 2009) Pyrolysis process is regularly used for biochar production as the
technique is relatively simple and inexpensive and allows considerable flexibility in both the
type and quality of the biomass feedstock (Laird et at 2009) Microwave pyrolysis is the
latest technology used to pyrolyse biomass Microwave pyrolysis offers more advantages over
conventional heated pyrolysis due to unifonn and efficient heating (Miura et at 2004)
Biochar has also been used as a precursor for the production of activated carbon Activated
carbon is effective and used in various applications such as in water treatment for drinking
water metal extraction and heterogeneous catalysts (Azargohar and Dalai 2006) However
the usage of commercial activated carbon is limited due to its higher preparation cost (Rao et
at 2009) Several studies reported on the utilisation of agricultural wastes for the production
of low cost activated carbon such as palm oil miH shells (Nik et at 2006) groundnut shells
(Malik et at 2007) physic nut wastes (Pechyen et at 2007) hulls of rice and wheat (Qiu et
at 2008 Rao et at 2009) and palm oil empty fruit bunch (Wahi et at 2009) However there
are no studies reported on the production of activated carbon from sago processing waste
either from sago pith or sago effluent
3
12 Problem statements
Mass production of agricultural waste has become an issue to the government and
environmentalists due to illegal disposal into the jungles or the rivers which destroy the
ecosystem Sago industries generate significant amount of wastes annually either as sago pith
or sago effluent Practically direct waste disposal to the rivers brings harmful effect to the
aquatic life This study was conducted to produce some value added products from the sago
effluent Limited reserve land for agricultural waste disposal leads to the transformation of the
waste into value added products Therefore there is a need to overcome the environmental
problem caused by the disposal of sago waste In this study the sago effluent was treated via
activated sludge process to produce biomass which then transformed into biochars and applied
for various applications The production of value added products from sago waste will provide
economical solution for waste management in sago industries
4
--
II
I
331 2 Detennination of chemical oxygen demand (COD)
331 3 Detennination of total suspended solids (TSS)
3314 Detennination of ammoniacal nitrogen (AN)
332 Characterisation of SBM
3321 Moisture ash and volatile content analysis
3322 FTIR and SEM analysis
34 Production of sago biochar (SBC) from SBM via microwave
pyrolysis
341 Characterisation of SBC
3411 Moisture content analysis
3412 Ultimate analysis
3413 FTIR and SEM analysis
342 Application of SBC as plant enhancer
35 Preparation of sago activated carbon (SAC)
351 Preparation ofSAC1 from SBC
352 Preparation of SAC2 from sago hampas
35 3 Characterisation of SAC 1
3531 Moisture content analysis
3532 FTIR and SEM analysis
354 Application ofSAC1
3541 Water filter system
3542 Heavy metal adsorption
36 Preparation ofbiochar impregnated silica (BIS) as
solid phase reagent
361 Preparation of BIS
34
34
35
35
35
37
38
38
38
38
39
39 39
39
40
40
40
40
41
41
41
42
42
x
I
I
362 Characterisation ofBIS 43
363 Attempted solid phase organic synthesis using BIS 43
37 Preparation of solid base catalyst from SAC 1 43
371 Preparation of solid base catalyst from SACl 44
372 Transesterification of palm oil mill sludge (POMS)
using solid base catalyst 44
38 Preparation of solid acid catalyst from SACl 44
381 Hydrolysis of acetylsalicylic acid (ASA) to salicylic acid 44
382 Synthesis of methyl salicylate 45
CHAPTER 4
RESULTS AND DISCUSSION
41 Production of SBM from activated sludge process 46
411 Assessment of water quality after activated sludge process 47
412 Characterisation of SBM 47
4121 Moisture ash and volatile content analysis 47
4122 FTIR and SEM analysis 48
42 Production of SBC via microwave pyrolysis 50
421 Characterisation of SBC 50
4211 Moisture content analysis 50
4212 Analysis of organic matters 50
4213 FTIR and SEM analysis 51
422 Application of SBC as plant enhancer 53
43 Preparation of SAC 1 from SBC 56
431 Characterisation of SBM 56
Xl
4311 Moisture content analysis 56
4312 FTIR and SEM analysis 57
43 3 Application ofSAC1 60
4331 Water filter system 60
4332 Heavy metal adsorption 61
44 Preparation ofbiochar impregnated silica (BIS)
as solid phase reagent 65
441 Characterisation of BIS 66
442 Attempted solid phase organic synthesis using BIS 67
45 Application of solid base catalyst from SAC 1
in transesterification of palm oil mill sludge (POMS) 70
46 Application of solid acid catalyst in methyl salicylate
preparation
CHAPTER 5
76
CONCLUSION AND RECOMMENDATION
51 Conclusion 80
52 Recommendation 82
REFERENCES 84
APPENDIX A 93
APPENDIXB 95
APPENDIXC 97
APPENDIXD 100
APPENDIXE 102
XII
J
~ LIST OF TABLES I
Page Table 21 Example of solid catalysts and their applications 23
t Table 22 Types of solid base catalyst 26 [ Table 41 Ultimate analysis of SBC 51
Table 42 Analysis of chilli seedlings after 14 days 55 ITable 43 NPK content of SBC 56
Table 44 COD of sago effluent before and after filtration 61
i
1
Xlll
I shy
I
LIST OF FIGURES
Page
Figure 21 Schematic flow diagram for sago processing 7
Figure 22 Bmnsted acidity arising from inductive effect of Lewis 24
acid center coordinated to a silica support
Figure 31 (a) Modified household microwave oven (b) quartz 24
reactor attached to the oven
Figure 32 Methyl salicylate 45
Figure 42 The IR spectrum of SBM 49
Figure 43 The SEM micrograph ofSBM (1000x magnification) 49
Figure 44 The IR spectrum of SBC 52
Figure 45 The SEM micrograph of (a) surface SBC (l2000x 53
magnification) (b) SBC with internal diameter
measurement (l2000x magnification)
Figure 46 Top view of chilli plant after 3 Days 54
Figure 47 (a) Top view (b) Side view of chilli plant after 14 Days 55
Figure 48 The IR spectra of (a) SACI (b) CAC 58
Figure 49 The SEM micrograph of (a) surface SACI 59
(12000x magnification) (b) SAC 1 with internal
diameter measurement (l2000x magnification)
(c) CAC (l2000x magnification)
Figure 4l0 Water filter system using SACI as a filter 60
Figure 411 The effect of adsorbent disages to adsorption of Zn Cr 63
and Pb by SAC 1 at a fixed metal concentration of
5 mgIL
xiv
I
Figure 412 The effect of initia~ concentration to adsorption of Zn 65
Cr and Pb by SAC1 at a fixed adsorbent dosage of
01 g
Figure 413 The SEM micrograph of BIS (5000x magnification) 66
Figure 414 The XRD pattern of amorphous silica from BIS 67
Figure 415 The IR spectra of (a) solid BIS before reaction (b) solid 69
BIS after reaction
Figure 416 The SEM micrograph of (a) solid BIS before reaction 69
(b) solid BIS after reaction
Figure 417 The IR spectra of product using (a) 5 solid base 73
catalyst of SAC 1 (b) 10 solid base catalyst of SAC 1
(c) 5 solid base catalyst of SAC 1 containing silica
(d) 10 solid base catalyst of SAC 1 containing silica
(e) Raw POMS
Figure 418 The IR spectra of product using (a) 5 solid base 75
catalyst of SAC2
(b) 10 solid base catalyst ofSAC2 (c) 5 solid base
catalyst of SAC2 containing silica
(d) 10 solid base catalyst of SAC2 containing silica
(e) Raw POMS
Figure 419 The IR spectra of (a) salicylic acid (b) methyl 78
salicylate
Figure 420 The IH-NMR spectrum of methyl salicylate 79
xv
~ -~----------
Scheme 21
Scheme 41
Scheme 42
Scheme 43
Scheme 44
Scheme 45
LIST OF SCHEMES
Multi-step synthesis using polymer-supported reagents
Synthesis of biphenyl-4-carbonyl chloride
Transesterification of POMS
Mechanism of transesterification of POMS using solid
base catalyst
Esterification of salicylic acid
Mechanism of esterification of salicylic acid using
solid acid catalyst
Page
22
68
70
71
76
77
xvi
l
LIST OF ABBREVIATIONS
AN
ASTM
B1S
BOD
CAC
cBOD
CHN
COD
DCM
FAAS
FTlR
MCM
M41S
nBOD
NMR
NPK
POMS
SAC
SBA
SBC
SBM
SEM
TLC
Ammoniacal nitrogen
American society for testing and materials
Biochar impregnated silica
Biochemical oxygen demand
Commercia~ activated carbon
Carbonaceous biochemical oxygen demand
Carbon hydrogen nitrogen
Chemical oxygen demand
Dichloromethane
Flame atomic absorption spectrometer
Fourier transfonn infrared
Mobil catalytic material
Mesoporous silicate 41
Nitrogeneous biochemical oxygen demand
Nuclear magnetic resonance
Nitrogen phosphorous potassium
Palm oil mill sludge
Sago activated carbon
Santa barbara amorphous
Sago biochar
Sago biomass
Scanning electron microscope
Thin layer chromathography
xvii
TSS Total suspended solid
XRD X-Ray diffractometer
xviii
LIST OF SYMBOLS
degc Degree celsius
U max Maximum vibration
8 Chemical shift
xix
CHAPTER
INTRODUCTION
11 Research background
Sarawak is currently one of the world largest exporters of sago products About 25 000 - 40
000 tonnes of sago products were exported to several countries annually such as Singapore
Taiwan and Japan (Singhal et ai 2008) Approximately 7 tonnes of sago pith waste has been
produced daily from a single sago starch processing mill (Bujang et ai 1996) Sago industries
consume about 30 000 L of water to process one tonne of sago and the liquid residue were
released as wastewater (Banu et ai 2006) The sago residues were released into nearby
streams together with wastewater as sago effluent which can lead to serious environmental
problems and affect aquatic life (Awg-Adeni et ai 2010)
Sago effluent contains high biochemical oxygen demand (BOD) and chemical oxygen demand
(COD) (Awg-Adeni et ai 2010) The effluent also contains high total suspended solid (TSS)
(Rashid et ai 2010) and acidic in nature with high organic matter unpleasant odour and
irritating colour (Ayyasamy et ai 2008) One of the treatments that has been applied onto the
sago effluent was using a hybrid reactor on-site waste treatment with very short retention
periods which combines both fixed-film and up-flow anaerobic sludge blanket systems (Banu
et ai 2006) The sago effluent was treated by the hybrid reactor for the reduction of COD
(Banu et ai 2006) The hybrid reactor system is a combination of suspended-film and fixedshy
film growth processes (Shannon et ai 2002) Sago effluent was also utilised as an additional
carbon in anaerobic digesters for the production of biogas (Abd-Aziz 2002) Other application
of biomass produced from the treated sago effluent was as a supplement for prawn feed in
aquaculture industries (Vickineswary et at 1997)
Activated sludge process is a wastewater treatment process which utilising bacteria and
microorganism to degrade suspended and dissolved organic matter via aerobic or anaerobic
oxidation (Gerardi 2006) It is a process in which a mixture of sewage and activated sludge
are agitated and aerated The sludge residue from activated sludge process can be easily
removed from the water through simple sedimentation Other treatment method such as
anaerobic digestion of sago effluent seems to be costly and difficult to maintain the system
(Ganczarczyk 1983) As an alternative aerobic digestion was introduced via activated sludge
proce s to treat sago effluent This treatment has more advantage as it utilises aerobic
microbes which grow faster than anaerobic microbes and consist of a simple process only
(Ganczarczyk 1983) In this study the sago biomass generated from the activated sludge was
chemically treated to produce sago biochar
Nowadays biochars are being prepared manually for various applications Biochars were
usually applied in environmental management such as soil improvement waste management
climate change mitigation and energy production (Lehmann and Joseph 2009) Biochar is a
carbon rich product obtained from biomass that undergo thermal decomposition with little or
absence of air at elevated temperature via pyrolysis (Lehmann and Joseph 2009) Pyrolysis is
a thermo-chemical process in which organic material is converted into a carbon rich solid
which is char and volatile matter by heating in the absence of oxygen (Demirbas and Arin
2002) A higher amount of volatile matter released during pyrolysis of biomass produces
2
biochars with lower densities and higher porosities (Vassilev et at 2009) The various
functional groups on the surface of biochar such as C=O S=O and -OH influence the sorption
of adsorbate by the nature of their surface charge and by the availability of 1t electron
(Lehmann and Joseph 2009) Pyrolysis process is regularly used for biochar production as the
technique is relatively simple and inexpensive and allows considerable flexibility in both the
type and quality of the biomass feedstock (Laird et at 2009) Microwave pyrolysis is the
latest technology used to pyrolyse biomass Microwave pyrolysis offers more advantages over
conventional heated pyrolysis due to unifonn and efficient heating (Miura et at 2004)
Biochar has also been used as a precursor for the production of activated carbon Activated
carbon is effective and used in various applications such as in water treatment for drinking
water metal extraction and heterogeneous catalysts (Azargohar and Dalai 2006) However
the usage of commercial activated carbon is limited due to its higher preparation cost (Rao et
at 2009) Several studies reported on the utilisation of agricultural wastes for the production
of low cost activated carbon such as palm oil miH shells (Nik et at 2006) groundnut shells
(Malik et at 2007) physic nut wastes (Pechyen et at 2007) hulls of rice and wheat (Qiu et
at 2008 Rao et at 2009) and palm oil empty fruit bunch (Wahi et at 2009) However there
are no studies reported on the production of activated carbon from sago processing waste
either from sago pith or sago effluent
3
12 Problem statements
Mass production of agricultural waste has become an issue to the government and
environmentalists due to illegal disposal into the jungles or the rivers which destroy the
ecosystem Sago industries generate significant amount of wastes annually either as sago pith
or sago effluent Practically direct waste disposal to the rivers brings harmful effect to the
aquatic life This study was conducted to produce some value added products from the sago
effluent Limited reserve land for agricultural waste disposal leads to the transformation of the
waste into value added products Therefore there is a need to overcome the environmental
problem caused by the disposal of sago waste In this study the sago effluent was treated via
activated sludge process to produce biomass which then transformed into biochars and applied
for various applications The production of value added products from sago waste will provide
economical solution for waste management in sago industries
4
I
362 Characterisation ofBIS 43
363 Attempted solid phase organic synthesis using BIS 43
37 Preparation of solid base catalyst from SAC 1 43
371 Preparation of solid base catalyst from SACl 44
372 Transesterification of palm oil mill sludge (POMS)
using solid base catalyst 44
38 Preparation of solid acid catalyst from SACl 44
381 Hydrolysis of acetylsalicylic acid (ASA) to salicylic acid 44
382 Synthesis of methyl salicylate 45
CHAPTER 4
RESULTS AND DISCUSSION
41 Production of SBM from activated sludge process 46
411 Assessment of water quality after activated sludge process 47
412 Characterisation of SBM 47
4121 Moisture ash and volatile content analysis 47
4122 FTIR and SEM analysis 48
42 Production of SBC via microwave pyrolysis 50
421 Characterisation of SBC 50
4211 Moisture content analysis 50
4212 Analysis of organic matters 50
4213 FTIR and SEM analysis 51
422 Application of SBC as plant enhancer 53
43 Preparation of SAC 1 from SBC 56
431 Characterisation of SBM 56
Xl
4311 Moisture content analysis 56
4312 FTIR and SEM analysis 57
43 3 Application ofSAC1 60
4331 Water filter system 60
4332 Heavy metal adsorption 61
44 Preparation ofbiochar impregnated silica (BIS)
as solid phase reagent 65
441 Characterisation of BIS 66
442 Attempted solid phase organic synthesis using BIS 67
45 Application of solid base catalyst from SAC 1
in transesterification of palm oil mill sludge (POMS) 70
46 Application of solid acid catalyst in methyl salicylate
preparation
CHAPTER 5
76
CONCLUSION AND RECOMMENDATION
51 Conclusion 80
52 Recommendation 82
REFERENCES 84
APPENDIX A 93
APPENDIXB 95
APPENDIXC 97
APPENDIXD 100
APPENDIXE 102
XII
J
~ LIST OF TABLES I
Page Table 21 Example of solid catalysts and their applications 23
t Table 22 Types of solid base catalyst 26 [ Table 41 Ultimate analysis of SBC 51
Table 42 Analysis of chilli seedlings after 14 days 55 ITable 43 NPK content of SBC 56
Table 44 COD of sago effluent before and after filtration 61
i
1
Xlll
I shy
I
LIST OF FIGURES
Page
Figure 21 Schematic flow diagram for sago processing 7
Figure 22 Bmnsted acidity arising from inductive effect of Lewis 24
acid center coordinated to a silica support
Figure 31 (a) Modified household microwave oven (b) quartz 24
reactor attached to the oven
Figure 32 Methyl salicylate 45
Figure 42 The IR spectrum of SBM 49
Figure 43 The SEM micrograph ofSBM (1000x magnification) 49
Figure 44 The IR spectrum of SBC 52
Figure 45 The SEM micrograph of (a) surface SBC (l2000x 53
magnification) (b) SBC with internal diameter
measurement (l2000x magnification)
Figure 46 Top view of chilli plant after 3 Days 54
Figure 47 (a) Top view (b) Side view of chilli plant after 14 Days 55
Figure 48 The IR spectra of (a) SACI (b) CAC 58
Figure 49 The SEM micrograph of (a) surface SACI 59
(12000x magnification) (b) SAC 1 with internal
diameter measurement (l2000x magnification)
(c) CAC (l2000x magnification)
Figure 4l0 Water filter system using SACI as a filter 60
Figure 411 The effect of adsorbent disages to adsorption of Zn Cr 63
and Pb by SAC 1 at a fixed metal concentration of
5 mgIL
xiv
I
Figure 412 The effect of initia~ concentration to adsorption of Zn 65
Cr and Pb by SAC1 at a fixed adsorbent dosage of
01 g
Figure 413 The SEM micrograph of BIS (5000x magnification) 66
Figure 414 The XRD pattern of amorphous silica from BIS 67
Figure 415 The IR spectra of (a) solid BIS before reaction (b) solid 69
BIS after reaction
Figure 416 The SEM micrograph of (a) solid BIS before reaction 69
(b) solid BIS after reaction
Figure 417 The IR spectra of product using (a) 5 solid base 73
catalyst of SAC 1 (b) 10 solid base catalyst of SAC 1
(c) 5 solid base catalyst of SAC 1 containing silica
(d) 10 solid base catalyst of SAC 1 containing silica
(e) Raw POMS
Figure 418 The IR spectra of product using (a) 5 solid base 75
catalyst of SAC2
(b) 10 solid base catalyst ofSAC2 (c) 5 solid base
catalyst of SAC2 containing silica
(d) 10 solid base catalyst of SAC2 containing silica
(e) Raw POMS
Figure 419 The IR spectra of (a) salicylic acid (b) methyl 78
salicylate
Figure 420 The IH-NMR spectrum of methyl salicylate 79
xv
~ -~----------
Scheme 21
Scheme 41
Scheme 42
Scheme 43
Scheme 44
Scheme 45
LIST OF SCHEMES
Multi-step synthesis using polymer-supported reagents
Synthesis of biphenyl-4-carbonyl chloride
Transesterification of POMS
Mechanism of transesterification of POMS using solid
base catalyst
Esterification of salicylic acid
Mechanism of esterification of salicylic acid using
solid acid catalyst
Page
22
68
70
71
76
77
xvi
l
LIST OF ABBREVIATIONS
AN
ASTM
B1S
BOD
CAC
cBOD
CHN
COD
DCM
FAAS
FTlR
MCM
M41S
nBOD
NMR
NPK
POMS
SAC
SBA
SBC
SBM
SEM
TLC
Ammoniacal nitrogen
American society for testing and materials
Biochar impregnated silica
Biochemical oxygen demand
Commercia~ activated carbon
Carbonaceous biochemical oxygen demand
Carbon hydrogen nitrogen
Chemical oxygen demand
Dichloromethane
Flame atomic absorption spectrometer
Fourier transfonn infrared
Mobil catalytic material
Mesoporous silicate 41
Nitrogeneous biochemical oxygen demand
Nuclear magnetic resonance
Nitrogen phosphorous potassium
Palm oil mill sludge
Sago activated carbon
Santa barbara amorphous
Sago biochar
Sago biomass
Scanning electron microscope
Thin layer chromathography
xvii
TSS Total suspended solid
XRD X-Ray diffractometer
xviii
LIST OF SYMBOLS
degc Degree celsius
U max Maximum vibration
8 Chemical shift
xix
CHAPTER
INTRODUCTION
11 Research background
Sarawak is currently one of the world largest exporters of sago products About 25 000 - 40
000 tonnes of sago products were exported to several countries annually such as Singapore
Taiwan and Japan (Singhal et ai 2008) Approximately 7 tonnes of sago pith waste has been
produced daily from a single sago starch processing mill (Bujang et ai 1996) Sago industries
consume about 30 000 L of water to process one tonne of sago and the liquid residue were
released as wastewater (Banu et ai 2006) The sago residues were released into nearby
streams together with wastewater as sago effluent which can lead to serious environmental
problems and affect aquatic life (Awg-Adeni et ai 2010)
Sago effluent contains high biochemical oxygen demand (BOD) and chemical oxygen demand
(COD) (Awg-Adeni et ai 2010) The effluent also contains high total suspended solid (TSS)
(Rashid et ai 2010) and acidic in nature with high organic matter unpleasant odour and
irritating colour (Ayyasamy et ai 2008) One of the treatments that has been applied onto the
sago effluent was using a hybrid reactor on-site waste treatment with very short retention
periods which combines both fixed-film and up-flow anaerobic sludge blanket systems (Banu
et ai 2006) The sago effluent was treated by the hybrid reactor for the reduction of COD
(Banu et ai 2006) The hybrid reactor system is a combination of suspended-film and fixedshy
film growth processes (Shannon et ai 2002) Sago effluent was also utilised as an additional
carbon in anaerobic digesters for the production of biogas (Abd-Aziz 2002) Other application
of biomass produced from the treated sago effluent was as a supplement for prawn feed in
aquaculture industries (Vickineswary et at 1997)
Activated sludge process is a wastewater treatment process which utilising bacteria and
microorganism to degrade suspended and dissolved organic matter via aerobic or anaerobic
oxidation (Gerardi 2006) It is a process in which a mixture of sewage and activated sludge
are agitated and aerated The sludge residue from activated sludge process can be easily
removed from the water through simple sedimentation Other treatment method such as
anaerobic digestion of sago effluent seems to be costly and difficult to maintain the system
(Ganczarczyk 1983) As an alternative aerobic digestion was introduced via activated sludge
proce s to treat sago effluent This treatment has more advantage as it utilises aerobic
microbes which grow faster than anaerobic microbes and consist of a simple process only
(Ganczarczyk 1983) In this study the sago biomass generated from the activated sludge was
chemically treated to produce sago biochar
Nowadays biochars are being prepared manually for various applications Biochars were
usually applied in environmental management such as soil improvement waste management
climate change mitigation and energy production (Lehmann and Joseph 2009) Biochar is a
carbon rich product obtained from biomass that undergo thermal decomposition with little or
absence of air at elevated temperature via pyrolysis (Lehmann and Joseph 2009) Pyrolysis is
a thermo-chemical process in which organic material is converted into a carbon rich solid
which is char and volatile matter by heating in the absence of oxygen (Demirbas and Arin
2002) A higher amount of volatile matter released during pyrolysis of biomass produces
2
biochars with lower densities and higher porosities (Vassilev et at 2009) The various
functional groups on the surface of biochar such as C=O S=O and -OH influence the sorption
of adsorbate by the nature of their surface charge and by the availability of 1t electron
(Lehmann and Joseph 2009) Pyrolysis process is regularly used for biochar production as the
technique is relatively simple and inexpensive and allows considerable flexibility in both the
type and quality of the biomass feedstock (Laird et at 2009) Microwave pyrolysis is the
latest technology used to pyrolyse biomass Microwave pyrolysis offers more advantages over
conventional heated pyrolysis due to unifonn and efficient heating (Miura et at 2004)
Biochar has also been used as a precursor for the production of activated carbon Activated
carbon is effective and used in various applications such as in water treatment for drinking
water metal extraction and heterogeneous catalysts (Azargohar and Dalai 2006) However
the usage of commercial activated carbon is limited due to its higher preparation cost (Rao et
at 2009) Several studies reported on the utilisation of agricultural wastes for the production
of low cost activated carbon such as palm oil miH shells (Nik et at 2006) groundnut shells
(Malik et at 2007) physic nut wastes (Pechyen et at 2007) hulls of rice and wheat (Qiu et
at 2008 Rao et at 2009) and palm oil empty fruit bunch (Wahi et at 2009) However there
are no studies reported on the production of activated carbon from sago processing waste
either from sago pith or sago effluent
3
12 Problem statements
Mass production of agricultural waste has become an issue to the government and
environmentalists due to illegal disposal into the jungles or the rivers which destroy the
ecosystem Sago industries generate significant amount of wastes annually either as sago pith
or sago effluent Practically direct waste disposal to the rivers brings harmful effect to the
aquatic life This study was conducted to produce some value added products from the sago
effluent Limited reserve land for agricultural waste disposal leads to the transformation of the
waste into value added products Therefore there is a need to overcome the environmental
problem caused by the disposal of sago waste In this study the sago effluent was treated via
activated sludge process to produce biomass which then transformed into biochars and applied
for various applications The production of value added products from sago waste will provide
economical solution for waste management in sago industries
4
4311 Moisture content analysis 56
4312 FTIR and SEM analysis 57
43 3 Application ofSAC1 60
4331 Water filter system 60
4332 Heavy metal adsorption 61
44 Preparation ofbiochar impregnated silica (BIS)
as solid phase reagent 65
441 Characterisation of BIS 66
442 Attempted solid phase organic synthesis using BIS 67
45 Application of solid base catalyst from SAC 1
in transesterification of palm oil mill sludge (POMS) 70
46 Application of solid acid catalyst in methyl salicylate
preparation
CHAPTER 5
76
CONCLUSION AND RECOMMENDATION
51 Conclusion 80
52 Recommendation 82
REFERENCES 84
APPENDIX A 93
APPENDIXB 95
APPENDIXC 97
APPENDIXD 100
APPENDIXE 102
XII
J
~ LIST OF TABLES I
Page Table 21 Example of solid catalysts and their applications 23
t Table 22 Types of solid base catalyst 26 [ Table 41 Ultimate analysis of SBC 51
Table 42 Analysis of chilli seedlings after 14 days 55 ITable 43 NPK content of SBC 56
Table 44 COD of sago effluent before and after filtration 61
i
1
Xlll
I shy
I
LIST OF FIGURES
Page
Figure 21 Schematic flow diagram for sago processing 7
Figure 22 Bmnsted acidity arising from inductive effect of Lewis 24
acid center coordinated to a silica support
Figure 31 (a) Modified household microwave oven (b) quartz 24
reactor attached to the oven
Figure 32 Methyl salicylate 45
Figure 42 The IR spectrum of SBM 49
Figure 43 The SEM micrograph ofSBM (1000x magnification) 49
Figure 44 The IR spectrum of SBC 52
Figure 45 The SEM micrograph of (a) surface SBC (l2000x 53
magnification) (b) SBC with internal diameter
measurement (l2000x magnification)
Figure 46 Top view of chilli plant after 3 Days 54
Figure 47 (a) Top view (b) Side view of chilli plant after 14 Days 55
Figure 48 The IR spectra of (a) SACI (b) CAC 58
Figure 49 The SEM micrograph of (a) surface SACI 59
(12000x magnification) (b) SAC 1 with internal
diameter measurement (l2000x magnification)
(c) CAC (l2000x magnification)
Figure 4l0 Water filter system using SACI as a filter 60
Figure 411 The effect of adsorbent disages to adsorption of Zn Cr 63
and Pb by SAC 1 at a fixed metal concentration of
5 mgIL
xiv
I
Figure 412 The effect of initia~ concentration to adsorption of Zn 65
Cr and Pb by SAC1 at a fixed adsorbent dosage of
01 g
Figure 413 The SEM micrograph of BIS (5000x magnification) 66
Figure 414 The XRD pattern of amorphous silica from BIS 67
Figure 415 The IR spectra of (a) solid BIS before reaction (b) solid 69
BIS after reaction
Figure 416 The SEM micrograph of (a) solid BIS before reaction 69
(b) solid BIS after reaction
Figure 417 The IR spectra of product using (a) 5 solid base 73
catalyst of SAC 1 (b) 10 solid base catalyst of SAC 1
(c) 5 solid base catalyst of SAC 1 containing silica
(d) 10 solid base catalyst of SAC 1 containing silica
(e) Raw POMS
Figure 418 The IR spectra of product using (a) 5 solid base 75
catalyst of SAC2
(b) 10 solid base catalyst ofSAC2 (c) 5 solid base
catalyst of SAC2 containing silica
(d) 10 solid base catalyst of SAC2 containing silica
(e) Raw POMS
Figure 419 The IR spectra of (a) salicylic acid (b) methyl 78
salicylate
Figure 420 The IH-NMR spectrum of methyl salicylate 79
xv
~ -~----------
Scheme 21
Scheme 41
Scheme 42
Scheme 43
Scheme 44
Scheme 45
LIST OF SCHEMES
Multi-step synthesis using polymer-supported reagents
Synthesis of biphenyl-4-carbonyl chloride
Transesterification of POMS
Mechanism of transesterification of POMS using solid
base catalyst
Esterification of salicylic acid
Mechanism of esterification of salicylic acid using
solid acid catalyst
Page
22
68
70
71
76
77
xvi
l
LIST OF ABBREVIATIONS
AN
ASTM
B1S
BOD
CAC
cBOD
CHN
COD
DCM
FAAS
FTlR
MCM
M41S
nBOD
NMR
NPK
POMS
SAC
SBA
SBC
SBM
SEM
TLC
Ammoniacal nitrogen
American society for testing and materials
Biochar impregnated silica
Biochemical oxygen demand
Commercia~ activated carbon
Carbonaceous biochemical oxygen demand
Carbon hydrogen nitrogen
Chemical oxygen demand
Dichloromethane
Flame atomic absorption spectrometer
Fourier transfonn infrared
Mobil catalytic material
Mesoporous silicate 41
Nitrogeneous biochemical oxygen demand
Nuclear magnetic resonance
Nitrogen phosphorous potassium
Palm oil mill sludge
Sago activated carbon
Santa barbara amorphous
Sago biochar
Sago biomass
Scanning electron microscope
Thin layer chromathography
xvii
TSS Total suspended solid
XRD X-Ray diffractometer
xviii
LIST OF SYMBOLS
degc Degree celsius
U max Maximum vibration
8 Chemical shift
xix
CHAPTER
INTRODUCTION
11 Research background
Sarawak is currently one of the world largest exporters of sago products About 25 000 - 40
000 tonnes of sago products were exported to several countries annually such as Singapore
Taiwan and Japan (Singhal et ai 2008) Approximately 7 tonnes of sago pith waste has been
produced daily from a single sago starch processing mill (Bujang et ai 1996) Sago industries
consume about 30 000 L of water to process one tonne of sago and the liquid residue were
released as wastewater (Banu et ai 2006) The sago residues were released into nearby
streams together with wastewater as sago effluent which can lead to serious environmental
problems and affect aquatic life (Awg-Adeni et ai 2010)
Sago effluent contains high biochemical oxygen demand (BOD) and chemical oxygen demand
(COD) (Awg-Adeni et ai 2010) The effluent also contains high total suspended solid (TSS)
(Rashid et ai 2010) and acidic in nature with high organic matter unpleasant odour and
irritating colour (Ayyasamy et ai 2008) One of the treatments that has been applied onto the
sago effluent was using a hybrid reactor on-site waste treatment with very short retention
periods which combines both fixed-film and up-flow anaerobic sludge blanket systems (Banu
et ai 2006) The sago effluent was treated by the hybrid reactor for the reduction of COD
(Banu et ai 2006) The hybrid reactor system is a combination of suspended-film and fixedshy
film growth processes (Shannon et ai 2002) Sago effluent was also utilised as an additional
carbon in anaerobic digesters for the production of biogas (Abd-Aziz 2002) Other application
of biomass produced from the treated sago effluent was as a supplement for prawn feed in
aquaculture industries (Vickineswary et at 1997)
Activated sludge process is a wastewater treatment process which utilising bacteria and
microorganism to degrade suspended and dissolved organic matter via aerobic or anaerobic
oxidation (Gerardi 2006) It is a process in which a mixture of sewage and activated sludge
are agitated and aerated The sludge residue from activated sludge process can be easily
removed from the water through simple sedimentation Other treatment method such as
anaerobic digestion of sago effluent seems to be costly and difficult to maintain the system
(Ganczarczyk 1983) As an alternative aerobic digestion was introduced via activated sludge
proce s to treat sago effluent This treatment has more advantage as it utilises aerobic
microbes which grow faster than anaerobic microbes and consist of a simple process only
(Ganczarczyk 1983) In this study the sago biomass generated from the activated sludge was
chemically treated to produce sago biochar
Nowadays biochars are being prepared manually for various applications Biochars were
usually applied in environmental management such as soil improvement waste management
climate change mitigation and energy production (Lehmann and Joseph 2009) Biochar is a
carbon rich product obtained from biomass that undergo thermal decomposition with little or
absence of air at elevated temperature via pyrolysis (Lehmann and Joseph 2009) Pyrolysis is
a thermo-chemical process in which organic material is converted into a carbon rich solid
which is char and volatile matter by heating in the absence of oxygen (Demirbas and Arin
2002) A higher amount of volatile matter released during pyrolysis of biomass produces
2
biochars with lower densities and higher porosities (Vassilev et at 2009) The various
functional groups on the surface of biochar such as C=O S=O and -OH influence the sorption
of adsorbate by the nature of their surface charge and by the availability of 1t electron
(Lehmann and Joseph 2009) Pyrolysis process is regularly used for biochar production as the
technique is relatively simple and inexpensive and allows considerable flexibility in both the
type and quality of the biomass feedstock (Laird et at 2009) Microwave pyrolysis is the
latest technology used to pyrolyse biomass Microwave pyrolysis offers more advantages over
conventional heated pyrolysis due to unifonn and efficient heating (Miura et at 2004)
Biochar has also been used as a precursor for the production of activated carbon Activated
carbon is effective and used in various applications such as in water treatment for drinking
water metal extraction and heterogeneous catalysts (Azargohar and Dalai 2006) However
the usage of commercial activated carbon is limited due to its higher preparation cost (Rao et
at 2009) Several studies reported on the utilisation of agricultural wastes for the production
of low cost activated carbon such as palm oil miH shells (Nik et at 2006) groundnut shells
(Malik et at 2007) physic nut wastes (Pechyen et at 2007) hulls of rice and wheat (Qiu et
at 2008 Rao et at 2009) and palm oil empty fruit bunch (Wahi et at 2009) However there
are no studies reported on the production of activated carbon from sago processing waste
either from sago pith or sago effluent
3
12 Problem statements
Mass production of agricultural waste has become an issue to the government and
environmentalists due to illegal disposal into the jungles or the rivers which destroy the
ecosystem Sago industries generate significant amount of wastes annually either as sago pith
or sago effluent Practically direct waste disposal to the rivers brings harmful effect to the
aquatic life This study was conducted to produce some value added products from the sago
effluent Limited reserve land for agricultural waste disposal leads to the transformation of the
waste into value added products Therefore there is a need to overcome the environmental
problem caused by the disposal of sago waste In this study the sago effluent was treated via
activated sludge process to produce biomass which then transformed into biochars and applied
for various applications The production of value added products from sago waste will provide
economical solution for waste management in sago industries
4
J
~ LIST OF TABLES I
Page Table 21 Example of solid catalysts and their applications 23
t Table 22 Types of solid base catalyst 26 [ Table 41 Ultimate analysis of SBC 51
Table 42 Analysis of chilli seedlings after 14 days 55 ITable 43 NPK content of SBC 56
Table 44 COD of sago effluent before and after filtration 61
i
1
Xlll
I shy
I
LIST OF FIGURES
Page
Figure 21 Schematic flow diagram for sago processing 7
Figure 22 Bmnsted acidity arising from inductive effect of Lewis 24
acid center coordinated to a silica support
Figure 31 (a) Modified household microwave oven (b) quartz 24
reactor attached to the oven
Figure 32 Methyl salicylate 45
Figure 42 The IR spectrum of SBM 49
Figure 43 The SEM micrograph ofSBM (1000x magnification) 49
Figure 44 The IR spectrum of SBC 52
Figure 45 The SEM micrograph of (a) surface SBC (l2000x 53
magnification) (b) SBC with internal diameter
measurement (l2000x magnification)
Figure 46 Top view of chilli plant after 3 Days 54
Figure 47 (a) Top view (b) Side view of chilli plant after 14 Days 55
Figure 48 The IR spectra of (a) SACI (b) CAC 58
Figure 49 The SEM micrograph of (a) surface SACI 59
(12000x magnification) (b) SAC 1 with internal
diameter measurement (l2000x magnification)
(c) CAC (l2000x magnification)
Figure 4l0 Water filter system using SACI as a filter 60
Figure 411 The effect of adsorbent disages to adsorption of Zn Cr 63
and Pb by SAC 1 at a fixed metal concentration of
5 mgIL
xiv
I
Figure 412 The effect of initia~ concentration to adsorption of Zn 65
Cr and Pb by SAC1 at a fixed adsorbent dosage of
01 g
Figure 413 The SEM micrograph of BIS (5000x magnification) 66
Figure 414 The XRD pattern of amorphous silica from BIS 67
Figure 415 The IR spectra of (a) solid BIS before reaction (b) solid 69
BIS after reaction
Figure 416 The SEM micrograph of (a) solid BIS before reaction 69
(b) solid BIS after reaction
Figure 417 The IR spectra of product using (a) 5 solid base 73
catalyst of SAC 1 (b) 10 solid base catalyst of SAC 1
(c) 5 solid base catalyst of SAC 1 containing silica
(d) 10 solid base catalyst of SAC 1 containing silica
(e) Raw POMS
Figure 418 The IR spectra of product using (a) 5 solid base 75
catalyst of SAC2
(b) 10 solid base catalyst ofSAC2 (c) 5 solid base
catalyst of SAC2 containing silica
(d) 10 solid base catalyst of SAC2 containing silica
(e) Raw POMS
Figure 419 The IR spectra of (a) salicylic acid (b) methyl 78
salicylate
Figure 420 The IH-NMR spectrum of methyl salicylate 79
xv
~ -~----------
Scheme 21
Scheme 41
Scheme 42
Scheme 43
Scheme 44
Scheme 45
LIST OF SCHEMES
Multi-step synthesis using polymer-supported reagents
Synthesis of biphenyl-4-carbonyl chloride
Transesterification of POMS
Mechanism of transesterification of POMS using solid
base catalyst
Esterification of salicylic acid
Mechanism of esterification of salicylic acid using
solid acid catalyst
Page
22
68
70
71
76
77
xvi
l
LIST OF ABBREVIATIONS
AN
ASTM
B1S
BOD
CAC
cBOD
CHN
COD
DCM
FAAS
FTlR
MCM
M41S
nBOD
NMR
NPK
POMS
SAC
SBA
SBC
SBM
SEM
TLC
Ammoniacal nitrogen
American society for testing and materials
Biochar impregnated silica
Biochemical oxygen demand
Commercia~ activated carbon
Carbonaceous biochemical oxygen demand
Carbon hydrogen nitrogen
Chemical oxygen demand
Dichloromethane
Flame atomic absorption spectrometer
Fourier transfonn infrared
Mobil catalytic material
Mesoporous silicate 41
Nitrogeneous biochemical oxygen demand
Nuclear magnetic resonance
Nitrogen phosphorous potassium
Palm oil mill sludge
Sago activated carbon
Santa barbara amorphous
Sago biochar
Sago biomass
Scanning electron microscope
Thin layer chromathography
xvii
TSS Total suspended solid
XRD X-Ray diffractometer
xviii
LIST OF SYMBOLS
degc Degree celsius
U max Maximum vibration
8 Chemical shift
xix
CHAPTER
INTRODUCTION
11 Research background
Sarawak is currently one of the world largest exporters of sago products About 25 000 - 40
000 tonnes of sago products were exported to several countries annually such as Singapore
Taiwan and Japan (Singhal et ai 2008) Approximately 7 tonnes of sago pith waste has been
produced daily from a single sago starch processing mill (Bujang et ai 1996) Sago industries
consume about 30 000 L of water to process one tonne of sago and the liquid residue were
released as wastewater (Banu et ai 2006) The sago residues were released into nearby
streams together with wastewater as sago effluent which can lead to serious environmental
problems and affect aquatic life (Awg-Adeni et ai 2010)
Sago effluent contains high biochemical oxygen demand (BOD) and chemical oxygen demand
(COD) (Awg-Adeni et ai 2010) The effluent also contains high total suspended solid (TSS)
(Rashid et ai 2010) and acidic in nature with high organic matter unpleasant odour and
irritating colour (Ayyasamy et ai 2008) One of the treatments that has been applied onto the
sago effluent was using a hybrid reactor on-site waste treatment with very short retention
periods which combines both fixed-film and up-flow anaerobic sludge blanket systems (Banu
et ai 2006) The sago effluent was treated by the hybrid reactor for the reduction of COD
(Banu et ai 2006) The hybrid reactor system is a combination of suspended-film and fixedshy
film growth processes (Shannon et ai 2002) Sago effluent was also utilised as an additional
carbon in anaerobic digesters for the production of biogas (Abd-Aziz 2002) Other application
of biomass produced from the treated sago effluent was as a supplement for prawn feed in
aquaculture industries (Vickineswary et at 1997)
Activated sludge process is a wastewater treatment process which utilising bacteria and
microorganism to degrade suspended and dissolved organic matter via aerobic or anaerobic
oxidation (Gerardi 2006) It is a process in which a mixture of sewage and activated sludge
are agitated and aerated The sludge residue from activated sludge process can be easily
removed from the water through simple sedimentation Other treatment method such as
anaerobic digestion of sago effluent seems to be costly and difficult to maintain the system
(Ganczarczyk 1983) As an alternative aerobic digestion was introduced via activated sludge
proce s to treat sago effluent This treatment has more advantage as it utilises aerobic
microbes which grow faster than anaerobic microbes and consist of a simple process only
(Ganczarczyk 1983) In this study the sago biomass generated from the activated sludge was
chemically treated to produce sago biochar
Nowadays biochars are being prepared manually for various applications Biochars were
usually applied in environmental management such as soil improvement waste management
climate change mitigation and energy production (Lehmann and Joseph 2009) Biochar is a
carbon rich product obtained from biomass that undergo thermal decomposition with little or
absence of air at elevated temperature via pyrolysis (Lehmann and Joseph 2009) Pyrolysis is
a thermo-chemical process in which organic material is converted into a carbon rich solid
which is char and volatile matter by heating in the absence of oxygen (Demirbas and Arin
2002) A higher amount of volatile matter released during pyrolysis of biomass produces
2
biochars with lower densities and higher porosities (Vassilev et at 2009) The various
functional groups on the surface of biochar such as C=O S=O and -OH influence the sorption
of adsorbate by the nature of their surface charge and by the availability of 1t electron
(Lehmann and Joseph 2009) Pyrolysis process is regularly used for biochar production as the
technique is relatively simple and inexpensive and allows considerable flexibility in both the
type and quality of the biomass feedstock (Laird et at 2009) Microwave pyrolysis is the
latest technology used to pyrolyse biomass Microwave pyrolysis offers more advantages over
conventional heated pyrolysis due to unifonn and efficient heating (Miura et at 2004)
Biochar has also been used as a precursor for the production of activated carbon Activated
carbon is effective and used in various applications such as in water treatment for drinking
water metal extraction and heterogeneous catalysts (Azargohar and Dalai 2006) However
the usage of commercial activated carbon is limited due to its higher preparation cost (Rao et
at 2009) Several studies reported on the utilisation of agricultural wastes for the production
of low cost activated carbon such as palm oil miH shells (Nik et at 2006) groundnut shells
(Malik et at 2007) physic nut wastes (Pechyen et at 2007) hulls of rice and wheat (Qiu et
at 2008 Rao et at 2009) and palm oil empty fruit bunch (Wahi et at 2009) However there
are no studies reported on the production of activated carbon from sago processing waste
either from sago pith or sago effluent
3
12 Problem statements
Mass production of agricultural waste has become an issue to the government and
environmentalists due to illegal disposal into the jungles or the rivers which destroy the
ecosystem Sago industries generate significant amount of wastes annually either as sago pith
or sago effluent Practically direct waste disposal to the rivers brings harmful effect to the
aquatic life This study was conducted to produce some value added products from the sago
effluent Limited reserve land for agricultural waste disposal leads to the transformation of the
waste into value added products Therefore there is a need to overcome the environmental
problem caused by the disposal of sago waste In this study the sago effluent was treated via
activated sludge process to produce biomass which then transformed into biochars and applied
for various applications The production of value added products from sago waste will provide
economical solution for waste management in sago industries
4
I
LIST OF FIGURES
Page
Figure 21 Schematic flow diagram for sago processing 7
Figure 22 Bmnsted acidity arising from inductive effect of Lewis 24
acid center coordinated to a silica support
Figure 31 (a) Modified household microwave oven (b) quartz 24
reactor attached to the oven
Figure 32 Methyl salicylate 45
Figure 42 The IR spectrum of SBM 49
Figure 43 The SEM micrograph ofSBM (1000x magnification) 49
Figure 44 The IR spectrum of SBC 52
Figure 45 The SEM micrograph of (a) surface SBC (l2000x 53
magnification) (b) SBC with internal diameter
measurement (l2000x magnification)
Figure 46 Top view of chilli plant after 3 Days 54
Figure 47 (a) Top view (b) Side view of chilli plant after 14 Days 55
Figure 48 The IR spectra of (a) SACI (b) CAC 58
Figure 49 The SEM micrograph of (a) surface SACI 59
(12000x magnification) (b) SAC 1 with internal
diameter measurement (l2000x magnification)
(c) CAC (l2000x magnification)
Figure 4l0 Water filter system using SACI as a filter 60
Figure 411 The effect of adsorbent disages to adsorption of Zn Cr 63
and Pb by SAC 1 at a fixed metal concentration of
5 mgIL
xiv
I
Figure 412 The effect of initia~ concentration to adsorption of Zn 65
Cr and Pb by SAC1 at a fixed adsorbent dosage of
01 g
Figure 413 The SEM micrograph of BIS (5000x magnification) 66
Figure 414 The XRD pattern of amorphous silica from BIS 67
Figure 415 The IR spectra of (a) solid BIS before reaction (b) solid 69
BIS after reaction
Figure 416 The SEM micrograph of (a) solid BIS before reaction 69
(b) solid BIS after reaction
Figure 417 The IR spectra of product using (a) 5 solid base 73
catalyst of SAC 1 (b) 10 solid base catalyst of SAC 1
(c) 5 solid base catalyst of SAC 1 containing silica
(d) 10 solid base catalyst of SAC 1 containing silica
(e) Raw POMS
Figure 418 The IR spectra of product using (a) 5 solid base 75
catalyst of SAC2
(b) 10 solid base catalyst ofSAC2 (c) 5 solid base
catalyst of SAC2 containing silica
(d) 10 solid base catalyst of SAC2 containing silica
(e) Raw POMS
Figure 419 The IR spectra of (a) salicylic acid (b) methyl 78
salicylate
Figure 420 The IH-NMR spectrum of methyl salicylate 79
xv
~ -~----------
Scheme 21
Scheme 41
Scheme 42
Scheme 43
Scheme 44
Scheme 45
LIST OF SCHEMES
Multi-step synthesis using polymer-supported reagents
Synthesis of biphenyl-4-carbonyl chloride
Transesterification of POMS
Mechanism of transesterification of POMS using solid
base catalyst
Esterification of salicylic acid
Mechanism of esterification of salicylic acid using
solid acid catalyst
Page
22
68
70
71
76
77
xvi
l
LIST OF ABBREVIATIONS
AN
ASTM
B1S
BOD
CAC
cBOD
CHN
COD
DCM
FAAS
FTlR
MCM
M41S
nBOD
NMR
NPK
POMS
SAC
SBA
SBC
SBM
SEM
TLC
Ammoniacal nitrogen
American society for testing and materials
Biochar impregnated silica
Biochemical oxygen demand
Commercia~ activated carbon
Carbonaceous biochemical oxygen demand
Carbon hydrogen nitrogen
Chemical oxygen demand
Dichloromethane
Flame atomic absorption spectrometer
Fourier transfonn infrared
Mobil catalytic material
Mesoporous silicate 41
Nitrogeneous biochemical oxygen demand
Nuclear magnetic resonance
Nitrogen phosphorous potassium
Palm oil mill sludge
Sago activated carbon
Santa barbara amorphous
Sago biochar
Sago biomass
Scanning electron microscope
Thin layer chromathography
xvii
TSS Total suspended solid
XRD X-Ray diffractometer
xviii
LIST OF SYMBOLS
degc Degree celsius
U max Maximum vibration
8 Chemical shift
xix
CHAPTER
INTRODUCTION
11 Research background
Sarawak is currently one of the world largest exporters of sago products About 25 000 - 40
000 tonnes of sago products were exported to several countries annually such as Singapore
Taiwan and Japan (Singhal et ai 2008) Approximately 7 tonnes of sago pith waste has been
produced daily from a single sago starch processing mill (Bujang et ai 1996) Sago industries
consume about 30 000 L of water to process one tonne of sago and the liquid residue were
released as wastewater (Banu et ai 2006) The sago residues were released into nearby
streams together with wastewater as sago effluent which can lead to serious environmental
problems and affect aquatic life (Awg-Adeni et ai 2010)
Sago effluent contains high biochemical oxygen demand (BOD) and chemical oxygen demand
(COD) (Awg-Adeni et ai 2010) The effluent also contains high total suspended solid (TSS)
(Rashid et ai 2010) and acidic in nature with high organic matter unpleasant odour and
irritating colour (Ayyasamy et ai 2008) One of the treatments that has been applied onto the
sago effluent was using a hybrid reactor on-site waste treatment with very short retention
periods which combines both fixed-film and up-flow anaerobic sludge blanket systems (Banu
et ai 2006) The sago effluent was treated by the hybrid reactor for the reduction of COD
(Banu et ai 2006) The hybrid reactor system is a combination of suspended-film and fixedshy
film growth processes (Shannon et ai 2002) Sago effluent was also utilised as an additional
carbon in anaerobic digesters for the production of biogas (Abd-Aziz 2002) Other application
of biomass produced from the treated sago effluent was as a supplement for prawn feed in
aquaculture industries (Vickineswary et at 1997)
Activated sludge process is a wastewater treatment process which utilising bacteria and
microorganism to degrade suspended and dissolved organic matter via aerobic or anaerobic
oxidation (Gerardi 2006) It is a process in which a mixture of sewage and activated sludge
are agitated and aerated The sludge residue from activated sludge process can be easily
removed from the water through simple sedimentation Other treatment method such as
anaerobic digestion of sago effluent seems to be costly and difficult to maintain the system
(Ganczarczyk 1983) As an alternative aerobic digestion was introduced via activated sludge
proce s to treat sago effluent This treatment has more advantage as it utilises aerobic
microbes which grow faster than anaerobic microbes and consist of a simple process only
(Ganczarczyk 1983) In this study the sago biomass generated from the activated sludge was
chemically treated to produce sago biochar
Nowadays biochars are being prepared manually for various applications Biochars were
usually applied in environmental management such as soil improvement waste management
climate change mitigation and energy production (Lehmann and Joseph 2009) Biochar is a
carbon rich product obtained from biomass that undergo thermal decomposition with little or
absence of air at elevated temperature via pyrolysis (Lehmann and Joseph 2009) Pyrolysis is
a thermo-chemical process in which organic material is converted into a carbon rich solid
which is char and volatile matter by heating in the absence of oxygen (Demirbas and Arin
2002) A higher amount of volatile matter released during pyrolysis of biomass produces
2
biochars with lower densities and higher porosities (Vassilev et at 2009) The various
functional groups on the surface of biochar such as C=O S=O and -OH influence the sorption
of adsorbate by the nature of their surface charge and by the availability of 1t electron
(Lehmann and Joseph 2009) Pyrolysis process is regularly used for biochar production as the
technique is relatively simple and inexpensive and allows considerable flexibility in both the
type and quality of the biomass feedstock (Laird et at 2009) Microwave pyrolysis is the
latest technology used to pyrolyse biomass Microwave pyrolysis offers more advantages over
conventional heated pyrolysis due to unifonn and efficient heating (Miura et at 2004)
Biochar has also been used as a precursor for the production of activated carbon Activated
carbon is effective and used in various applications such as in water treatment for drinking
water metal extraction and heterogeneous catalysts (Azargohar and Dalai 2006) However
the usage of commercial activated carbon is limited due to its higher preparation cost (Rao et
at 2009) Several studies reported on the utilisation of agricultural wastes for the production
of low cost activated carbon such as palm oil miH shells (Nik et at 2006) groundnut shells
(Malik et at 2007) physic nut wastes (Pechyen et at 2007) hulls of rice and wheat (Qiu et
at 2008 Rao et at 2009) and palm oil empty fruit bunch (Wahi et at 2009) However there
are no studies reported on the production of activated carbon from sago processing waste
either from sago pith or sago effluent
3
12 Problem statements
Mass production of agricultural waste has become an issue to the government and
environmentalists due to illegal disposal into the jungles or the rivers which destroy the
ecosystem Sago industries generate significant amount of wastes annually either as sago pith
or sago effluent Practically direct waste disposal to the rivers brings harmful effect to the
aquatic life This study was conducted to produce some value added products from the sago
effluent Limited reserve land for agricultural waste disposal leads to the transformation of the
waste into value added products Therefore there is a need to overcome the environmental
problem caused by the disposal of sago waste In this study the sago effluent was treated via
activated sludge process to produce biomass which then transformed into biochars and applied
for various applications The production of value added products from sago waste will provide
economical solution for waste management in sago industries
4
I
Figure 412 The effect of initia~ concentration to adsorption of Zn 65
Cr and Pb by SAC1 at a fixed adsorbent dosage of
01 g
Figure 413 The SEM micrograph of BIS (5000x magnification) 66
Figure 414 The XRD pattern of amorphous silica from BIS 67
Figure 415 The IR spectra of (a) solid BIS before reaction (b) solid 69
BIS after reaction
Figure 416 The SEM micrograph of (a) solid BIS before reaction 69
(b) solid BIS after reaction
Figure 417 The IR spectra of product using (a) 5 solid base 73
catalyst of SAC 1 (b) 10 solid base catalyst of SAC 1
(c) 5 solid base catalyst of SAC 1 containing silica
(d) 10 solid base catalyst of SAC 1 containing silica
(e) Raw POMS
Figure 418 The IR spectra of product using (a) 5 solid base 75
catalyst of SAC2
(b) 10 solid base catalyst ofSAC2 (c) 5 solid base
catalyst of SAC2 containing silica
(d) 10 solid base catalyst of SAC2 containing silica
(e) Raw POMS
Figure 419 The IR spectra of (a) salicylic acid (b) methyl 78
salicylate
Figure 420 The IH-NMR spectrum of methyl salicylate 79
xv
~ -~----------
Scheme 21
Scheme 41
Scheme 42
Scheme 43
Scheme 44
Scheme 45
LIST OF SCHEMES
Multi-step synthesis using polymer-supported reagents
Synthesis of biphenyl-4-carbonyl chloride
Transesterification of POMS
Mechanism of transesterification of POMS using solid
base catalyst
Esterification of salicylic acid
Mechanism of esterification of salicylic acid using
solid acid catalyst
Page
22
68
70
71
76
77
xvi
l
LIST OF ABBREVIATIONS
AN
ASTM
B1S
BOD
CAC
cBOD
CHN
COD
DCM
FAAS
FTlR
MCM
M41S
nBOD
NMR
NPK
POMS
SAC
SBA
SBC
SBM
SEM
TLC
Ammoniacal nitrogen
American society for testing and materials
Biochar impregnated silica
Biochemical oxygen demand
Commercia~ activated carbon
Carbonaceous biochemical oxygen demand
Carbon hydrogen nitrogen
Chemical oxygen demand
Dichloromethane
Flame atomic absorption spectrometer
Fourier transfonn infrared
Mobil catalytic material
Mesoporous silicate 41
Nitrogeneous biochemical oxygen demand
Nuclear magnetic resonance
Nitrogen phosphorous potassium
Palm oil mill sludge
Sago activated carbon
Santa barbara amorphous
Sago biochar
Sago biomass
Scanning electron microscope
Thin layer chromathography
xvii
TSS Total suspended solid
XRD X-Ray diffractometer
xviii
LIST OF SYMBOLS
degc Degree celsius
U max Maximum vibration
8 Chemical shift
xix
CHAPTER
INTRODUCTION
11 Research background
Sarawak is currently one of the world largest exporters of sago products About 25 000 - 40
000 tonnes of sago products were exported to several countries annually such as Singapore
Taiwan and Japan (Singhal et ai 2008) Approximately 7 tonnes of sago pith waste has been
produced daily from a single sago starch processing mill (Bujang et ai 1996) Sago industries
consume about 30 000 L of water to process one tonne of sago and the liquid residue were
released as wastewater (Banu et ai 2006) The sago residues were released into nearby
streams together with wastewater as sago effluent which can lead to serious environmental
problems and affect aquatic life (Awg-Adeni et ai 2010)
Sago effluent contains high biochemical oxygen demand (BOD) and chemical oxygen demand
(COD) (Awg-Adeni et ai 2010) The effluent also contains high total suspended solid (TSS)
(Rashid et ai 2010) and acidic in nature with high organic matter unpleasant odour and
irritating colour (Ayyasamy et ai 2008) One of the treatments that has been applied onto the
sago effluent was using a hybrid reactor on-site waste treatment with very short retention
periods which combines both fixed-film and up-flow anaerobic sludge blanket systems (Banu
et ai 2006) The sago effluent was treated by the hybrid reactor for the reduction of COD
(Banu et ai 2006) The hybrid reactor system is a combination of suspended-film and fixedshy
film growth processes (Shannon et ai 2002) Sago effluent was also utilised as an additional
carbon in anaerobic digesters for the production of biogas (Abd-Aziz 2002) Other application
of biomass produced from the treated sago effluent was as a supplement for prawn feed in
aquaculture industries (Vickineswary et at 1997)
Activated sludge process is a wastewater treatment process which utilising bacteria and
microorganism to degrade suspended and dissolved organic matter via aerobic or anaerobic
oxidation (Gerardi 2006) It is a process in which a mixture of sewage and activated sludge
are agitated and aerated The sludge residue from activated sludge process can be easily
removed from the water through simple sedimentation Other treatment method such as
anaerobic digestion of sago effluent seems to be costly and difficult to maintain the system
(Ganczarczyk 1983) As an alternative aerobic digestion was introduced via activated sludge
proce s to treat sago effluent This treatment has more advantage as it utilises aerobic
microbes which grow faster than anaerobic microbes and consist of a simple process only
(Ganczarczyk 1983) In this study the sago biomass generated from the activated sludge was
chemically treated to produce sago biochar
Nowadays biochars are being prepared manually for various applications Biochars were
usually applied in environmental management such as soil improvement waste management
climate change mitigation and energy production (Lehmann and Joseph 2009) Biochar is a
carbon rich product obtained from biomass that undergo thermal decomposition with little or
absence of air at elevated temperature via pyrolysis (Lehmann and Joseph 2009) Pyrolysis is
a thermo-chemical process in which organic material is converted into a carbon rich solid
which is char and volatile matter by heating in the absence of oxygen (Demirbas and Arin
2002) A higher amount of volatile matter released during pyrolysis of biomass produces
2
biochars with lower densities and higher porosities (Vassilev et at 2009) The various
functional groups on the surface of biochar such as C=O S=O and -OH influence the sorption
of adsorbate by the nature of their surface charge and by the availability of 1t electron
(Lehmann and Joseph 2009) Pyrolysis process is regularly used for biochar production as the
technique is relatively simple and inexpensive and allows considerable flexibility in both the
type and quality of the biomass feedstock (Laird et at 2009) Microwave pyrolysis is the
latest technology used to pyrolyse biomass Microwave pyrolysis offers more advantages over
conventional heated pyrolysis due to unifonn and efficient heating (Miura et at 2004)
Biochar has also been used as a precursor for the production of activated carbon Activated
carbon is effective and used in various applications such as in water treatment for drinking
water metal extraction and heterogeneous catalysts (Azargohar and Dalai 2006) However
the usage of commercial activated carbon is limited due to its higher preparation cost (Rao et
at 2009) Several studies reported on the utilisation of agricultural wastes for the production
of low cost activated carbon such as palm oil miH shells (Nik et at 2006) groundnut shells
(Malik et at 2007) physic nut wastes (Pechyen et at 2007) hulls of rice and wheat (Qiu et
at 2008 Rao et at 2009) and palm oil empty fruit bunch (Wahi et at 2009) However there
are no studies reported on the production of activated carbon from sago processing waste
either from sago pith or sago effluent
3
12 Problem statements
Mass production of agricultural waste has become an issue to the government and
environmentalists due to illegal disposal into the jungles or the rivers which destroy the
ecosystem Sago industries generate significant amount of wastes annually either as sago pith
or sago effluent Practically direct waste disposal to the rivers brings harmful effect to the
aquatic life This study was conducted to produce some value added products from the sago
effluent Limited reserve land for agricultural waste disposal leads to the transformation of the
waste into value added products Therefore there is a need to overcome the environmental
problem caused by the disposal of sago waste In this study the sago effluent was treated via
activated sludge process to produce biomass which then transformed into biochars and applied
for various applications The production of value added products from sago waste will provide
economical solution for waste management in sago industries
4
~ -~----------
Scheme 21
Scheme 41
Scheme 42
Scheme 43
Scheme 44
Scheme 45
LIST OF SCHEMES
Multi-step synthesis using polymer-supported reagents
Synthesis of biphenyl-4-carbonyl chloride
Transesterification of POMS
Mechanism of transesterification of POMS using solid
base catalyst
Esterification of salicylic acid
Mechanism of esterification of salicylic acid using
solid acid catalyst
Page
22
68
70
71
76
77
xvi
l
LIST OF ABBREVIATIONS
AN
ASTM
B1S
BOD
CAC
cBOD
CHN
COD
DCM
FAAS
FTlR
MCM
M41S
nBOD
NMR
NPK
POMS
SAC
SBA
SBC
SBM
SEM
TLC
Ammoniacal nitrogen
American society for testing and materials
Biochar impregnated silica
Biochemical oxygen demand
Commercia~ activated carbon
Carbonaceous biochemical oxygen demand
Carbon hydrogen nitrogen
Chemical oxygen demand
Dichloromethane
Flame atomic absorption spectrometer
Fourier transfonn infrared
Mobil catalytic material
Mesoporous silicate 41
Nitrogeneous biochemical oxygen demand
Nuclear magnetic resonance
Nitrogen phosphorous potassium
Palm oil mill sludge
Sago activated carbon
Santa barbara amorphous
Sago biochar
Sago biomass
Scanning electron microscope
Thin layer chromathography
xvii
TSS Total suspended solid
XRD X-Ray diffractometer
xviii
LIST OF SYMBOLS
degc Degree celsius
U max Maximum vibration
8 Chemical shift
xix
CHAPTER
INTRODUCTION
11 Research background
Sarawak is currently one of the world largest exporters of sago products About 25 000 - 40
000 tonnes of sago products were exported to several countries annually such as Singapore
Taiwan and Japan (Singhal et ai 2008) Approximately 7 tonnes of sago pith waste has been
produced daily from a single sago starch processing mill (Bujang et ai 1996) Sago industries
consume about 30 000 L of water to process one tonne of sago and the liquid residue were
released as wastewater (Banu et ai 2006) The sago residues were released into nearby
streams together with wastewater as sago effluent which can lead to serious environmental
problems and affect aquatic life (Awg-Adeni et ai 2010)
Sago effluent contains high biochemical oxygen demand (BOD) and chemical oxygen demand
(COD) (Awg-Adeni et ai 2010) The effluent also contains high total suspended solid (TSS)
(Rashid et ai 2010) and acidic in nature with high organic matter unpleasant odour and
irritating colour (Ayyasamy et ai 2008) One of the treatments that has been applied onto the
sago effluent was using a hybrid reactor on-site waste treatment with very short retention
periods which combines both fixed-film and up-flow anaerobic sludge blanket systems (Banu
et ai 2006) The sago effluent was treated by the hybrid reactor for the reduction of COD
(Banu et ai 2006) The hybrid reactor system is a combination of suspended-film and fixedshy
film growth processes (Shannon et ai 2002) Sago effluent was also utilised as an additional
carbon in anaerobic digesters for the production of biogas (Abd-Aziz 2002) Other application
of biomass produced from the treated sago effluent was as a supplement for prawn feed in
aquaculture industries (Vickineswary et at 1997)
Activated sludge process is a wastewater treatment process which utilising bacteria and
microorganism to degrade suspended and dissolved organic matter via aerobic or anaerobic
oxidation (Gerardi 2006) It is a process in which a mixture of sewage and activated sludge
are agitated and aerated The sludge residue from activated sludge process can be easily
removed from the water through simple sedimentation Other treatment method such as
anaerobic digestion of sago effluent seems to be costly and difficult to maintain the system
(Ganczarczyk 1983) As an alternative aerobic digestion was introduced via activated sludge
proce s to treat sago effluent This treatment has more advantage as it utilises aerobic
microbes which grow faster than anaerobic microbes and consist of a simple process only
(Ganczarczyk 1983) In this study the sago biomass generated from the activated sludge was
chemically treated to produce sago biochar
Nowadays biochars are being prepared manually for various applications Biochars were
usually applied in environmental management such as soil improvement waste management
climate change mitigation and energy production (Lehmann and Joseph 2009) Biochar is a
carbon rich product obtained from biomass that undergo thermal decomposition with little or
absence of air at elevated temperature via pyrolysis (Lehmann and Joseph 2009) Pyrolysis is
a thermo-chemical process in which organic material is converted into a carbon rich solid
which is char and volatile matter by heating in the absence of oxygen (Demirbas and Arin
2002) A higher amount of volatile matter released during pyrolysis of biomass produces
2
biochars with lower densities and higher porosities (Vassilev et at 2009) The various
functional groups on the surface of biochar such as C=O S=O and -OH influence the sorption
of adsorbate by the nature of their surface charge and by the availability of 1t electron
(Lehmann and Joseph 2009) Pyrolysis process is regularly used for biochar production as the
technique is relatively simple and inexpensive and allows considerable flexibility in both the
type and quality of the biomass feedstock (Laird et at 2009) Microwave pyrolysis is the
latest technology used to pyrolyse biomass Microwave pyrolysis offers more advantages over
conventional heated pyrolysis due to unifonn and efficient heating (Miura et at 2004)
Biochar has also been used as a precursor for the production of activated carbon Activated
carbon is effective and used in various applications such as in water treatment for drinking
water metal extraction and heterogeneous catalysts (Azargohar and Dalai 2006) However
the usage of commercial activated carbon is limited due to its higher preparation cost (Rao et
at 2009) Several studies reported on the utilisation of agricultural wastes for the production
of low cost activated carbon such as palm oil miH shells (Nik et at 2006) groundnut shells
(Malik et at 2007) physic nut wastes (Pechyen et at 2007) hulls of rice and wheat (Qiu et
at 2008 Rao et at 2009) and palm oil empty fruit bunch (Wahi et at 2009) However there
are no studies reported on the production of activated carbon from sago processing waste
either from sago pith or sago effluent
3
12 Problem statements
Mass production of agricultural waste has become an issue to the government and
environmentalists due to illegal disposal into the jungles or the rivers which destroy the
ecosystem Sago industries generate significant amount of wastes annually either as sago pith
or sago effluent Practically direct waste disposal to the rivers brings harmful effect to the
aquatic life This study was conducted to produce some value added products from the sago
effluent Limited reserve land for agricultural waste disposal leads to the transformation of the
waste into value added products Therefore there is a need to overcome the environmental
problem caused by the disposal of sago waste In this study the sago effluent was treated via
activated sludge process to produce biomass which then transformed into biochars and applied
for various applications The production of value added products from sago waste will provide
economical solution for waste management in sago industries
4
l
LIST OF ABBREVIATIONS
AN
ASTM
B1S
BOD
CAC
cBOD
CHN
COD
DCM
FAAS
FTlR
MCM
M41S
nBOD
NMR
NPK
POMS
SAC
SBA
SBC
SBM
SEM
TLC
Ammoniacal nitrogen
American society for testing and materials
Biochar impregnated silica
Biochemical oxygen demand
Commercia~ activated carbon
Carbonaceous biochemical oxygen demand
Carbon hydrogen nitrogen
Chemical oxygen demand
Dichloromethane
Flame atomic absorption spectrometer
Fourier transfonn infrared
Mobil catalytic material
Mesoporous silicate 41
Nitrogeneous biochemical oxygen demand
Nuclear magnetic resonance
Nitrogen phosphorous potassium
Palm oil mill sludge
Sago activated carbon
Santa barbara amorphous
Sago biochar
Sago biomass
Scanning electron microscope
Thin layer chromathography
xvii
TSS Total suspended solid
XRD X-Ray diffractometer
xviii
LIST OF SYMBOLS
degc Degree celsius
U max Maximum vibration
8 Chemical shift
xix
CHAPTER
INTRODUCTION
11 Research background
Sarawak is currently one of the world largest exporters of sago products About 25 000 - 40
000 tonnes of sago products were exported to several countries annually such as Singapore
Taiwan and Japan (Singhal et ai 2008) Approximately 7 tonnes of sago pith waste has been
produced daily from a single sago starch processing mill (Bujang et ai 1996) Sago industries
consume about 30 000 L of water to process one tonne of sago and the liquid residue were
released as wastewater (Banu et ai 2006) The sago residues were released into nearby
streams together with wastewater as sago effluent which can lead to serious environmental
problems and affect aquatic life (Awg-Adeni et ai 2010)
Sago effluent contains high biochemical oxygen demand (BOD) and chemical oxygen demand
(COD) (Awg-Adeni et ai 2010) The effluent also contains high total suspended solid (TSS)
(Rashid et ai 2010) and acidic in nature with high organic matter unpleasant odour and
irritating colour (Ayyasamy et ai 2008) One of the treatments that has been applied onto the
sago effluent was using a hybrid reactor on-site waste treatment with very short retention
periods which combines both fixed-film and up-flow anaerobic sludge blanket systems (Banu
et ai 2006) The sago effluent was treated by the hybrid reactor for the reduction of COD
(Banu et ai 2006) The hybrid reactor system is a combination of suspended-film and fixedshy
film growth processes (Shannon et ai 2002) Sago effluent was also utilised as an additional
carbon in anaerobic digesters for the production of biogas (Abd-Aziz 2002) Other application
of biomass produced from the treated sago effluent was as a supplement for prawn feed in
aquaculture industries (Vickineswary et at 1997)
Activated sludge process is a wastewater treatment process which utilising bacteria and
microorganism to degrade suspended and dissolved organic matter via aerobic or anaerobic
oxidation (Gerardi 2006) It is a process in which a mixture of sewage and activated sludge
are agitated and aerated The sludge residue from activated sludge process can be easily
removed from the water through simple sedimentation Other treatment method such as
anaerobic digestion of sago effluent seems to be costly and difficult to maintain the system
(Ganczarczyk 1983) As an alternative aerobic digestion was introduced via activated sludge
proce s to treat sago effluent This treatment has more advantage as it utilises aerobic
microbes which grow faster than anaerobic microbes and consist of a simple process only
(Ganczarczyk 1983) In this study the sago biomass generated from the activated sludge was
chemically treated to produce sago biochar
Nowadays biochars are being prepared manually for various applications Biochars were
usually applied in environmental management such as soil improvement waste management
climate change mitigation and energy production (Lehmann and Joseph 2009) Biochar is a
carbon rich product obtained from biomass that undergo thermal decomposition with little or
absence of air at elevated temperature via pyrolysis (Lehmann and Joseph 2009) Pyrolysis is
a thermo-chemical process in which organic material is converted into a carbon rich solid
which is char and volatile matter by heating in the absence of oxygen (Demirbas and Arin
2002) A higher amount of volatile matter released during pyrolysis of biomass produces
2
biochars with lower densities and higher porosities (Vassilev et at 2009) The various
functional groups on the surface of biochar such as C=O S=O and -OH influence the sorption
of adsorbate by the nature of their surface charge and by the availability of 1t electron
(Lehmann and Joseph 2009) Pyrolysis process is regularly used for biochar production as the
technique is relatively simple and inexpensive and allows considerable flexibility in both the
type and quality of the biomass feedstock (Laird et at 2009) Microwave pyrolysis is the
latest technology used to pyrolyse biomass Microwave pyrolysis offers more advantages over
conventional heated pyrolysis due to unifonn and efficient heating (Miura et at 2004)
Biochar has also been used as a precursor for the production of activated carbon Activated
carbon is effective and used in various applications such as in water treatment for drinking
water metal extraction and heterogeneous catalysts (Azargohar and Dalai 2006) However
the usage of commercial activated carbon is limited due to its higher preparation cost (Rao et
at 2009) Several studies reported on the utilisation of agricultural wastes for the production
of low cost activated carbon such as palm oil miH shells (Nik et at 2006) groundnut shells
(Malik et at 2007) physic nut wastes (Pechyen et at 2007) hulls of rice and wheat (Qiu et
at 2008 Rao et at 2009) and palm oil empty fruit bunch (Wahi et at 2009) However there
are no studies reported on the production of activated carbon from sago processing waste
either from sago pith or sago effluent
3
12 Problem statements
Mass production of agricultural waste has become an issue to the government and
environmentalists due to illegal disposal into the jungles or the rivers which destroy the
ecosystem Sago industries generate significant amount of wastes annually either as sago pith
or sago effluent Practically direct waste disposal to the rivers brings harmful effect to the
aquatic life This study was conducted to produce some value added products from the sago
effluent Limited reserve land for agricultural waste disposal leads to the transformation of the
waste into value added products Therefore there is a need to overcome the environmental
problem caused by the disposal of sago waste In this study the sago effluent was treated via
activated sludge process to produce biomass which then transformed into biochars and applied
for various applications The production of value added products from sago waste will provide
economical solution for waste management in sago industries
4
TSS Total suspended solid
XRD X-Ray diffractometer
xviii
LIST OF SYMBOLS
degc Degree celsius
U max Maximum vibration
8 Chemical shift
xix
CHAPTER
INTRODUCTION
11 Research background
Sarawak is currently one of the world largest exporters of sago products About 25 000 - 40
000 tonnes of sago products were exported to several countries annually such as Singapore
Taiwan and Japan (Singhal et ai 2008) Approximately 7 tonnes of sago pith waste has been
produced daily from a single sago starch processing mill (Bujang et ai 1996) Sago industries
consume about 30 000 L of water to process one tonne of sago and the liquid residue were
released as wastewater (Banu et ai 2006) The sago residues were released into nearby
streams together with wastewater as sago effluent which can lead to serious environmental
problems and affect aquatic life (Awg-Adeni et ai 2010)
Sago effluent contains high biochemical oxygen demand (BOD) and chemical oxygen demand
(COD) (Awg-Adeni et ai 2010) The effluent also contains high total suspended solid (TSS)
(Rashid et ai 2010) and acidic in nature with high organic matter unpleasant odour and
irritating colour (Ayyasamy et ai 2008) One of the treatments that has been applied onto the
sago effluent was using a hybrid reactor on-site waste treatment with very short retention
periods which combines both fixed-film and up-flow anaerobic sludge blanket systems (Banu
et ai 2006) The sago effluent was treated by the hybrid reactor for the reduction of COD
(Banu et ai 2006) The hybrid reactor system is a combination of suspended-film and fixedshy
film growth processes (Shannon et ai 2002) Sago effluent was also utilised as an additional
carbon in anaerobic digesters for the production of biogas (Abd-Aziz 2002) Other application
of biomass produced from the treated sago effluent was as a supplement for prawn feed in
aquaculture industries (Vickineswary et at 1997)
Activated sludge process is a wastewater treatment process which utilising bacteria and
microorganism to degrade suspended and dissolved organic matter via aerobic or anaerobic
oxidation (Gerardi 2006) It is a process in which a mixture of sewage and activated sludge
are agitated and aerated The sludge residue from activated sludge process can be easily
removed from the water through simple sedimentation Other treatment method such as
anaerobic digestion of sago effluent seems to be costly and difficult to maintain the system
(Ganczarczyk 1983) As an alternative aerobic digestion was introduced via activated sludge
proce s to treat sago effluent This treatment has more advantage as it utilises aerobic
microbes which grow faster than anaerobic microbes and consist of a simple process only
(Ganczarczyk 1983) In this study the sago biomass generated from the activated sludge was
chemically treated to produce sago biochar
Nowadays biochars are being prepared manually for various applications Biochars were
usually applied in environmental management such as soil improvement waste management
climate change mitigation and energy production (Lehmann and Joseph 2009) Biochar is a
carbon rich product obtained from biomass that undergo thermal decomposition with little or
absence of air at elevated temperature via pyrolysis (Lehmann and Joseph 2009) Pyrolysis is
a thermo-chemical process in which organic material is converted into a carbon rich solid
which is char and volatile matter by heating in the absence of oxygen (Demirbas and Arin
2002) A higher amount of volatile matter released during pyrolysis of biomass produces
2
biochars with lower densities and higher porosities (Vassilev et at 2009) The various
functional groups on the surface of biochar such as C=O S=O and -OH influence the sorption
of adsorbate by the nature of their surface charge and by the availability of 1t electron
(Lehmann and Joseph 2009) Pyrolysis process is regularly used for biochar production as the
technique is relatively simple and inexpensive and allows considerable flexibility in both the
type and quality of the biomass feedstock (Laird et at 2009) Microwave pyrolysis is the
latest technology used to pyrolyse biomass Microwave pyrolysis offers more advantages over
conventional heated pyrolysis due to unifonn and efficient heating (Miura et at 2004)
Biochar has also been used as a precursor for the production of activated carbon Activated
carbon is effective and used in various applications such as in water treatment for drinking
water metal extraction and heterogeneous catalysts (Azargohar and Dalai 2006) However
the usage of commercial activated carbon is limited due to its higher preparation cost (Rao et
at 2009) Several studies reported on the utilisation of agricultural wastes for the production
of low cost activated carbon such as palm oil miH shells (Nik et at 2006) groundnut shells
(Malik et at 2007) physic nut wastes (Pechyen et at 2007) hulls of rice and wheat (Qiu et
at 2008 Rao et at 2009) and palm oil empty fruit bunch (Wahi et at 2009) However there
are no studies reported on the production of activated carbon from sago processing waste
either from sago pith or sago effluent
3
12 Problem statements
Mass production of agricultural waste has become an issue to the government and
environmentalists due to illegal disposal into the jungles or the rivers which destroy the
ecosystem Sago industries generate significant amount of wastes annually either as sago pith
or sago effluent Practically direct waste disposal to the rivers brings harmful effect to the
aquatic life This study was conducted to produce some value added products from the sago
effluent Limited reserve land for agricultural waste disposal leads to the transformation of the
waste into value added products Therefore there is a need to overcome the environmental
problem caused by the disposal of sago waste In this study the sago effluent was treated via
activated sludge process to produce biomass which then transformed into biochars and applied
for various applications The production of value added products from sago waste will provide
economical solution for waste management in sago industries
4
LIST OF SYMBOLS
degc Degree celsius
U max Maximum vibration
8 Chemical shift
xix
CHAPTER
INTRODUCTION
11 Research background
Sarawak is currently one of the world largest exporters of sago products About 25 000 - 40
000 tonnes of sago products were exported to several countries annually such as Singapore
Taiwan and Japan (Singhal et ai 2008) Approximately 7 tonnes of sago pith waste has been
produced daily from a single sago starch processing mill (Bujang et ai 1996) Sago industries
consume about 30 000 L of water to process one tonne of sago and the liquid residue were
released as wastewater (Banu et ai 2006) The sago residues were released into nearby
streams together with wastewater as sago effluent which can lead to serious environmental
problems and affect aquatic life (Awg-Adeni et ai 2010)
Sago effluent contains high biochemical oxygen demand (BOD) and chemical oxygen demand
(COD) (Awg-Adeni et ai 2010) The effluent also contains high total suspended solid (TSS)
(Rashid et ai 2010) and acidic in nature with high organic matter unpleasant odour and
irritating colour (Ayyasamy et ai 2008) One of the treatments that has been applied onto the
sago effluent was using a hybrid reactor on-site waste treatment with very short retention
periods which combines both fixed-film and up-flow anaerobic sludge blanket systems (Banu
et ai 2006) The sago effluent was treated by the hybrid reactor for the reduction of COD
(Banu et ai 2006) The hybrid reactor system is a combination of suspended-film and fixedshy
film growth processes (Shannon et ai 2002) Sago effluent was also utilised as an additional
carbon in anaerobic digesters for the production of biogas (Abd-Aziz 2002) Other application
of biomass produced from the treated sago effluent was as a supplement for prawn feed in
aquaculture industries (Vickineswary et at 1997)
Activated sludge process is a wastewater treatment process which utilising bacteria and
microorganism to degrade suspended and dissolved organic matter via aerobic or anaerobic
oxidation (Gerardi 2006) It is a process in which a mixture of sewage and activated sludge
are agitated and aerated The sludge residue from activated sludge process can be easily
removed from the water through simple sedimentation Other treatment method such as
anaerobic digestion of sago effluent seems to be costly and difficult to maintain the system
(Ganczarczyk 1983) As an alternative aerobic digestion was introduced via activated sludge
proce s to treat sago effluent This treatment has more advantage as it utilises aerobic
microbes which grow faster than anaerobic microbes and consist of a simple process only
(Ganczarczyk 1983) In this study the sago biomass generated from the activated sludge was
chemically treated to produce sago biochar
Nowadays biochars are being prepared manually for various applications Biochars were
usually applied in environmental management such as soil improvement waste management
climate change mitigation and energy production (Lehmann and Joseph 2009) Biochar is a
carbon rich product obtained from biomass that undergo thermal decomposition with little or
absence of air at elevated temperature via pyrolysis (Lehmann and Joseph 2009) Pyrolysis is
a thermo-chemical process in which organic material is converted into a carbon rich solid
which is char and volatile matter by heating in the absence of oxygen (Demirbas and Arin
2002) A higher amount of volatile matter released during pyrolysis of biomass produces
2
biochars with lower densities and higher porosities (Vassilev et at 2009) The various
functional groups on the surface of biochar such as C=O S=O and -OH influence the sorption
of adsorbate by the nature of their surface charge and by the availability of 1t electron
(Lehmann and Joseph 2009) Pyrolysis process is regularly used for biochar production as the
technique is relatively simple and inexpensive and allows considerable flexibility in both the
type and quality of the biomass feedstock (Laird et at 2009) Microwave pyrolysis is the
latest technology used to pyrolyse biomass Microwave pyrolysis offers more advantages over
conventional heated pyrolysis due to unifonn and efficient heating (Miura et at 2004)
Biochar has also been used as a precursor for the production of activated carbon Activated
carbon is effective and used in various applications such as in water treatment for drinking
water metal extraction and heterogeneous catalysts (Azargohar and Dalai 2006) However
the usage of commercial activated carbon is limited due to its higher preparation cost (Rao et
at 2009) Several studies reported on the utilisation of agricultural wastes for the production
of low cost activated carbon such as palm oil miH shells (Nik et at 2006) groundnut shells
(Malik et at 2007) physic nut wastes (Pechyen et at 2007) hulls of rice and wheat (Qiu et
at 2008 Rao et at 2009) and palm oil empty fruit bunch (Wahi et at 2009) However there
are no studies reported on the production of activated carbon from sago processing waste
either from sago pith or sago effluent
3
12 Problem statements
Mass production of agricultural waste has become an issue to the government and
environmentalists due to illegal disposal into the jungles or the rivers which destroy the
ecosystem Sago industries generate significant amount of wastes annually either as sago pith
or sago effluent Practically direct waste disposal to the rivers brings harmful effect to the
aquatic life This study was conducted to produce some value added products from the sago
effluent Limited reserve land for agricultural waste disposal leads to the transformation of the
waste into value added products Therefore there is a need to overcome the environmental
problem caused by the disposal of sago waste In this study the sago effluent was treated via
activated sludge process to produce biomass which then transformed into biochars and applied
for various applications The production of value added products from sago waste will provide
economical solution for waste management in sago industries
4
CHAPTER
INTRODUCTION
11 Research background
Sarawak is currently one of the world largest exporters of sago products About 25 000 - 40
000 tonnes of sago products were exported to several countries annually such as Singapore
Taiwan and Japan (Singhal et ai 2008) Approximately 7 tonnes of sago pith waste has been
produced daily from a single sago starch processing mill (Bujang et ai 1996) Sago industries
consume about 30 000 L of water to process one tonne of sago and the liquid residue were
released as wastewater (Banu et ai 2006) The sago residues were released into nearby
streams together with wastewater as sago effluent which can lead to serious environmental
problems and affect aquatic life (Awg-Adeni et ai 2010)
Sago effluent contains high biochemical oxygen demand (BOD) and chemical oxygen demand
(COD) (Awg-Adeni et ai 2010) The effluent also contains high total suspended solid (TSS)
(Rashid et ai 2010) and acidic in nature with high organic matter unpleasant odour and
irritating colour (Ayyasamy et ai 2008) One of the treatments that has been applied onto the
sago effluent was using a hybrid reactor on-site waste treatment with very short retention
periods which combines both fixed-film and up-flow anaerobic sludge blanket systems (Banu
et ai 2006) The sago effluent was treated by the hybrid reactor for the reduction of COD
(Banu et ai 2006) The hybrid reactor system is a combination of suspended-film and fixedshy
film growth processes (Shannon et ai 2002) Sago effluent was also utilised as an additional
carbon in anaerobic digesters for the production of biogas (Abd-Aziz 2002) Other application
of biomass produced from the treated sago effluent was as a supplement for prawn feed in
aquaculture industries (Vickineswary et at 1997)
Activated sludge process is a wastewater treatment process which utilising bacteria and
microorganism to degrade suspended and dissolved organic matter via aerobic or anaerobic
oxidation (Gerardi 2006) It is a process in which a mixture of sewage and activated sludge
are agitated and aerated The sludge residue from activated sludge process can be easily
removed from the water through simple sedimentation Other treatment method such as
anaerobic digestion of sago effluent seems to be costly and difficult to maintain the system
(Ganczarczyk 1983) As an alternative aerobic digestion was introduced via activated sludge
proce s to treat sago effluent This treatment has more advantage as it utilises aerobic
microbes which grow faster than anaerobic microbes and consist of a simple process only
(Ganczarczyk 1983) In this study the sago biomass generated from the activated sludge was
chemically treated to produce sago biochar
Nowadays biochars are being prepared manually for various applications Biochars were
usually applied in environmental management such as soil improvement waste management
climate change mitigation and energy production (Lehmann and Joseph 2009) Biochar is a
carbon rich product obtained from biomass that undergo thermal decomposition with little or
absence of air at elevated temperature via pyrolysis (Lehmann and Joseph 2009) Pyrolysis is
a thermo-chemical process in which organic material is converted into a carbon rich solid
which is char and volatile matter by heating in the absence of oxygen (Demirbas and Arin
2002) A higher amount of volatile matter released during pyrolysis of biomass produces
2
biochars with lower densities and higher porosities (Vassilev et at 2009) The various
functional groups on the surface of biochar such as C=O S=O and -OH influence the sorption
of adsorbate by the nature of their surface charge and by the availability of 1t electron
(Lehmann and Joseph 2009) Pyrolysis process is regularly used for biochar production as the
technique is relatively simple and inexpensive and allows considerable flexibility in both the
type and quality of the biomass feedstock (Laird et at 2009) Microwave pyrolysis is the
latest technology used to pyrolyse biomass Microwave pyrolysis offers more advantages over
conventional heated pyrolysis due to unifonn and efficient heating (Miura et at 2004)
Biochar has also been used as a precursor for the production of activated carbon Activated
carbon is effective and used in various applications such as in water treatment for drinking
water metal extraction and heterogeneous catalysts (Azargohar and Dalai 2006) However
the usage of commercial activated carbon is limited due to its higher preparation cost (Rao et
at 2009) Several studies reported on the utilisation of agricultural wastes for the production
of low cost activated carbon such as palm oil miH shells (Nik et at 2006) groundnut shells
(Malik et at 2007) physic nut wastes (Pechyen et at 2007) hulls of rice and wheat (Qiu et
at 2008 Rao et at 2009) and palm oil empty fruit bunch (Wahi et at 2009) However there
are no studies reported on the production of activated carbon from sago processing waste
either from sago pith or sago effluent
3
12 Problem statements
Mass production of agricultural waste has become an issue to the government and
environmentalists due to illegal disposal into the jungles or the rivers which destroy the
ecosystem Sago industries generate significant amount of wastes annually either as sago pith
or sago effluent Practically direct waste disposal to the rivers brings harmful effect to the
aquatic life This study was conducted to produce some value added products from the sago
effluent Limited reserve land for agricultural waste disposal leads to the transformation of the
waste into value added products Therefore there is a need to overcome the environmental
problem caused by the disposal of sago waste In this study the sago effluent was treated via
activated sludge process to produce biomass which then transformed into biochars and applied
for various applications The production of value added products from sago waste will provide
economical solution for waste management in sago industries
4
carbon in anaerobic digesters for the production of biogas (Abd-Aziz 2002) Other application
of biomass produced from the treated sago effluent was as a supplement for prawn feed in
aquaculture industries (Vickineswary et at 1997)
Activated sludge process is a wastewater treatment process which utilising bacteria and
microorganism to degrade suspended and dissolved organic matter via aerobic or anaerobic
oxidation (Gerardi 2006) It is a process in which a mixture of sewage and activated sludge
are agitated and aerated The sludge residue from activated sludge process can be easily
removed from the water through simple sedimentation Other treatment method such as
anaerobic digestion of sago effluent seems to be costly and difficult to maintain the system
(Ganczarczyk 1983) As an alternative aerobic digestion was introduced via activated sludge
proce s to treat sago effluent This treatment has more advantage as it utilises aerobic
microbes which grow faster than anaerobic microbes and consist of a simple process only
(Ganczarczyk 1983) In this study the sago biomass generated from the activated sludge was
chemically treated to produce sago biochar
Nowadays biochars are being prepared manually for various applications Biochars were
usually applied in environmental management such as soil improvement waste management
climate change mitigation and energy production (Lehmann and Joseph 2009) Biochar is a
carbon rich product obtained from biomass that undergo thermal decomposition with little or
absence of air at elevated temperature via pyrolysis (Lehmann and Joseph 2009) Pyrolysis is
a thermo-chemical process in which organic material is converted into a carbon rich solid
which is char and volatile matter by heating in the absence of oxygen (Demirbas and Arin
2002) A higher amount of volatile matter released during pyrolysis of biomass produces
2
biochars with lower densities and higher porosities (Vassilev et at 2009) The various
functional groups on the surface of biochar such as C=O S=O and -OH influence the sorption
of adsorbate by the nature of their surface charge and by the availability of 1t electron
(Lehmann and Joseph 2009) Pyrolysis process is regularly used for biochar production as the
technique is relatively simple and inexpensive and allows considerable flexibility in both the
type and quality of the biomass feedstock (Laird et at 2009) Microwave pyrolysis is the
latest technology used to pyrolyse biomass Microwave pyrolysis offers more advantages over
conventional heated pyrolysis due to unifonn and efficient heating (Miura et at 2004)
Biochar has also been used as a precursor for the production of activated carbon Activated
carbon is effective and used in various applications such as in water treatment for drinking
water metal extraction and heterogeneous catalysts (Azargohar and Dalai 2006) However
the usage of commercial activated carbon is limited due to its higher preparation cost (Rao et
at 2009) Several studies reported on the utilisation of agricultural wastes for the production
of low cost activated carbon such as palm oil miH shells (Nik et at 2006) groundnut shells
(Malik et at 2007) physic nut wastes (Pechyen et at 2007) hulls of rice and wheat (Qiu et
at 2008 Rao et at 2009) and palm oil empty fruit bunch (Wahi et at 2009) However there
are no studies reported on the production of activated carbon from sago processing waste
either from sago pith or sago effluent
3
12 Problem statements
Mass production of agricultural waste has become an issue to the government and
environmentalists due to illegal disposal into the jungles or the rivers which destroy the
ecosystem Sago industries generate significant amount of wastes annually either as sago pith
or sago effluent Practically direct waste disposal to the rivers brings harmful effect to the
aquatic life This study was conducted to produce some value added products from the sago
effluent Limited reserve land for agricultural waste disposal leads to the transformation of the
waste into value added products Therefore there is a need to overcome the environmental
problem caused by the disposal of sago waste In this study the sago effluent was treated via
activated sludge process to produce biomass which then transformed into biochars and applied
for various applications The production of value added products from sago waste will provide
economical solution for waste management in sago industries
4
biochars with lower densities and higher porosities (Vassilev et at 2009) The various
functional groups on the surface of biochar such as C=O S=O and -OH influence the sorption
of adsorbate by the nature of their surface charge and by the availability of 1t electron
(Lehmann and Joseph 2009) Pyrolysis process is regularly used for biochar production as the
technique is relatively simple and inexpensive and allows considerable flexibility in both the
type and quality of the biomass feedstock (Laird et at 2009) Microwave pyrolysis is the
latest technology used to pyrolyse biomass Microwave pyrolysis offers more advantages over
conventional heated pyrolysis due to unifonn and efficient heating (Miura et at 2004)
Biochar has also been used as a precursor for the production of activated carbon Activated
carbon is effective and used in various applications such as in water treatment for drinking
water metal extraction and heterogeneous catalysts (Azargohar and Dalai 2006) However
the usage of commercial activated carbon is limited due to its higher preparation cost (Rao et
at 2009) Several studies reported on the utilisation of agricultural wastes for the production
of low cost activated carbon such as palm oil miH shells (Nik et at 2006) groundnut shells
(Malik et at 2007) physic nut wastes (Pechyen et at 2007) hulls of rice and wheat (Qiu et
at 2008 Rao et at 2009) and palm oil empty fruit bunch (Wahi et at 2009) However there
are no studies reported on the production of activated carbon from sago processing waste
either from sago pith or sago effluent
3
12 Problem statements
Mass production of agricultural waste has become an issue to the government and
environmentalists due to illegal disposal into the jungles or the rivers which destroy the
ecosystem Sago industries generate significant amount of wastes annually either as sago pith
or sago effluent Practically direct waste disposal to the rivers brings harmful effect to the
aquatic life This study was conducted to produce some value added products from the sago
effluent Limited reserve land for agricultural waste disposal leads to the transformation of the
waste into value added products Therefore there is a need to overcome the environmental
problem caused by the disposal of sago waste In this study the sago effluent was treated via
activated sludge process to produce biomass which then transformed into biochars and applied
for various applications The production of value added products from sago waste will provide
economical solution for waste management in sago industries
4
12 Problem statements
Mass production of agricultural waste has become an issue to the government and
environmentalists due to illegal disposal into the jungles or the rivers which destroy the
ecosystem Sago industries generate significant amount of wastes annually either as sago pith
or sago effluent Practically direct waste disposal to the rivers brings harmful effect to the
aquatic life This study was conducted to produce some value added products from the sago
effluent Limited reserve land for agricultural waste disposal leads to the transformation of the
waste into value added products Therefore there is a need to overcome the environmental
problem caused by the disposal of sago waste In this study the sago effluent was treated via
activated sludge process to produce biomass which then transformed into biochars and applied
for various applications The production of value added products from sago waste will provide
economical solution for waste management in sago industries
4