UNIVERSITI PUTRA MALAYSIA

NORHAFIZA BINTI MADEHI

FK 2013 77

JATROPHA CURCAS L. AS POTENTIAL BIO-COAGULANT FOR WASTEWATER TREATMENT

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TREATMENT

By

NORHAFIZA BINTI MADEHI

Thesis Submitted to the school of Graduate Studies, Universiti Putra Malaysia In

Fulfillment of the Requirement for the Degree of Master of Science

February 2013

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Abstract of thesis presented to the Senate of Universiti Putra Malaysia in fulfilment of

the requirement for the degree of Master of Science

JATROPHA CURCAS L. AS POTENTIAL BIO-COAGULANT FOR WASTEWATER

TREATMENT

By

NORHAFIZA BINTI MADEHI

February 2013

Chair: Zurina Zainal Abidin, PhD

Faculty: Engineering

This project aims to investigate the potential use of Jatropha Curcas (JC) as a bio-coagulant

in wastewater treatment. The first objective of this study was to investigate the performance

of JC for its potential use as a bio-coagulant compared to alum. Palm Oil Mill Effluent

(POME) is wastewater generated from the palm oil milling industry. It is a highly polluted

wastewater which contains high Chemical Oxygen Demand (COD), typically averaging from

30,000 to 43,700 mg/L, with Biological Oxygen Demand (BOD), from 20,000 to 30,000

mg/L and Total Suspended Solids (TSS) from 18,000 to 18,500 mg/L. It is acidic in pH

ranging from pH 4.6 to 4.8 and brownish in colour. When freshly discharged, POME has a

temperature of between 80 and 90oC. POME consists of a high volume of liquid waste which

is non-toxic but has an unpleasant odour, and must be treated properly before being

discharged into the environment. The use of inorganic coagulants like alum has led to the

spread of chronic diseases due to the residual content of the coagulants in the treated

wastewater. Thus, this study searched for an alternative using JC plant, a bio-resource.

Coagulation and flocculation methods were used in this study.

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In this study, the optimum condition for synthetic water kaolin treatment was at pH 2, with a

dosage of 120 mg/L, and with 99% turbidity removal. It was found that JC presscake showed

better coagulation performance compared to JC seed coagulant, with 99% turbidity removal

at an optimum pH of 3 and 140 mg/L dosage concentration. JC seeds, on the other hands,

showed the potential to remove about 93% turbidity at the optimum of pH of 3 and with 120

mg/L dosage. Furthermore, the performance of JC as a bio-coagulant was compared to

aluminum sulphate (alum) coagulant. The results showed that alum gave 93% turbidity

removal at optimum pH 5 and with an optimum dosage of 1200mg/L. The treatment of

POME wastewater by using JC presscake as a bio-coagulant was successfully able to reduce

COD with up to 70% in value, 65% of BOD reduction and 88% of TSS removal, whereas

alum coagulant resulted in 59% of COD, 61% of BOD reduction and 71% of TSS removal.

The second objective of this study was to examine the characterization of the composition of

JC seed and JC presscake as potential coagulant agents for wastewater treatment by using

High Performances Liquid Chromatography (HPLC) analysis. The results showed that 18

types of amino acid were detected. The amino acid Lysine was detected to have the highest

composition in JC seed with 24.87%, followed by the amino acid, Cystine, with 21.74% in

composition. JC presscake, on the other hand, had the highest composition for the amino acid

Phenylalanine with 15.34%, followed by the amino acid Cystine with 14.21%.

For the third objective of this study, a final quantitative analysis through HPLC was

conducted. The final treated POME was run through HPLC analysis to detect the presence of

Phorbol-esters. The peaks indicated that there was no Phorbol-ester in the treated wastewater

solution.

As a conclusion, this study has proven that JC presscake has a high potential to be used as a

bio-coagulant for wastewater treatment. The estimated cost for treatment using JC seed was

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RM 0.035 per 1 liter of wastewater treated. JC presscake coagulant is cheaper than JC seed

kernel coagulant if JC presscake coagulant can be directly obtained from the industry’s

extraction process of Jatropha oil.

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Abstrak tesis yang dikemukakan kepada Senat Universiti Putra Malaysia sebagai

memenuhi keperluan untuk Ijazah Master Sains

JATROPHA CURCAS L. SEBAGAI POTENSI BAHAN PENGGENTAL

SEMULAJADI BAGI PERAWATAN AIR SISA

Oleh

NORHAFIZA BINTI MADEHI

Februari 2013

Pengerusi: Zurina Zainal Abidin, PhD

Fakulti: Kejuruteraan

Projek ini bertujuan untuk mengkaji potensi penggunaan tumbuhan Jatropha curcas (JC)

sebagai agen bio-penggental dalam rawatan air sisa. Objektif pertama kajian ini adalah untuk

mengkaji potensi JC untuk digunakan sebagai bio-penggental. Air sisa minyak sawit (POME)

adalah air sisa yang dijana daripada industri pengilangan minyak kelapa sawit. Ia adalah sisa

air yang sangat tercemar yang mengandungi permintaan kimia yang tinggi (COD), biasanya

purata dari 30,000 hingga 43,700 mg / L, permintaan oksigen biokimia (BOD), daripada

20,000 hingga 30,000 mg / L dan jumlah pepejal terampai (TSS) daripada 18,000 hingga

18,500 mg / L. Air sisa ini adalah berasid dan mempunyai pH antara pH 4.6-4.8 dan bewarna

coklat. Air sisa POME yang baru dilepaskan mempunyai suhu antara 80 dan 90oC. Air sisa

POME ini mengandungi jumlah pepejal terampai yang tinggi dan sisa cecair yang bukan

toksik tetapi mempunyai bau yang tidak menyenangkan, dan mesti dirawat dengan sebaiknya

sebelum dilepaskan ke dalam alam sekitar. Penggunaan pengental bukan organik seperti

tawas telah membawa kepada penyebaran penyakit kronik akibat kesan kandungan sisa bagi

bahan penggental dalam air sisa yang dirawat. Oleh itu, kajian ini mencari alternatif

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menggunakan tumbuhan JC sebagai sumber semulajadi. Kaedah penggumpalan dan

penggentalan telah digunakan dalam kajian ini.

Dalam kajian ini, keadaan optimum untuk rawatan air sintetik kaolin adalah pada pH 2,

dengan dos sejumlah 120 mg / L, dan dengan 99% penyingkiran kekeruhan. Ia telah

menunjukkan hampas JC memberikan prestasi sebagai bahan penggentalan yang lebih baik

berbanding dengan penggental benih JC, dengan 99% penyingkiran kekeruhan pada pH

optimum 3 dan 140 mg / L kepekatan dos. Penggental benih JC menunjukkan potensi untuk

menyingkirkan kira-kira 93% kekeruhan akhir air sisa pada optimum pH 3 dan dengan 120

mg / L dos. Seterusnya, prestasi JC sebagai bio-penggental telah dibandingkan dengan

penggental aluminium sulfat (tawas). Hasil kajian menunjukkan bahawa tawas memberikan

93% penyingkiran kekeruhan pada pH optimum 5 dan dengan dos optimum 1200mg / L.

Rawatan air sisa POME dengan menggunakan hampas JC sebagai bio-penggental telah

berjaya mengurangkan COD dengan sehingga 70%, 65% pengurangan BOD dan 88%

penyingkiran TSS, manakala penggental tawas menurunkan 59% COD , 61% pengurangan

BOD dan 71% penyingkiran TSS.

Objektif kedua kajian ini adalah untuk mengkaji komposisi benih JC dan hampas JC yang

dianggap berpotensi sebagai agen penggental untuk pemerawatan air sisa dengan

menggunakan analisis Cecair Kromatografi Berprestasi Tinggi (HPLC). Hasil kajian

menunjukkan bahawa 18 jenis asid amino telah dikesan. Asid amino jenis lisin telah dikesan

mempunyai komposisi tertinggi dalam benih Jatropha curcas dengan 24.87%, diikuti oleh

asid amino jenis cystine dengan komposisi sebanyak 21.74%. hampas JC, dari sudut yang

lain pula mempunyai komposisi tertinggi bagi asid amino jenis Phenylalanine dengan

15.34%, diikuti oleh asid amino jenis cystine, dengan 14.21%.

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Bagi objektif ketiga kajian ini, analisis kuantitatif akhir melalui HPLC telah dijalankan. Air

sisa akhir POME yang telah dirawat telah melalui analisis HPLC untuk mengesan kehadiran

toksik Phorbol-ester. Profil HPLC analisis mendapati bahawa tiada puncak Phorbol-ester

dikesan dalam larutan air sisa yang dirawat.

Kesimpulannya, kajian ini telah membuktikan bahawa hampas JC mempunyai potensi yang

tinggi untuk digunakan sebagai bio-koagulan untuk rawatan air sisa. Anggaran kos untuk

rawatan menggunakan benih JC adalah RM 0.035 setiap 1 liter air sisa dirawat. Penggunaan

hampas JC sebagai agen penggental juga adalah lebih murah daripada penggental jenis benih

JC jika hampas JC boleh diperolehi secara terus daripada proses industri pengeluaran minyak

Jatropha.

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ACKNOWLEDGEMENTS

I would like to express my sincere gratitude to Associate Professor Dr. Zurina Zainal Abidin

for her supervision, constructive criticisms, and her invaluable guidance and encouragement

throughout my study and preparation of this thesis.

My sincere thanks are also addressed to my supervisory committee member, Professor Dr.

Robiah Yunus, for her advice and encouragement during my study.

To my dearest parents, Mr. Madehi Hj Assan and Mdm Mastiah binti Hj. Akoi, thank you so

much for your understanding, support, and endless praying during the period of my study. To

my special friends, Shairy Abu Bakar, Fatin Nordalila and Muhammad Fatah Ibrahim, thank

you for the support given, and being there always for me.

Last but not least, my sincere thanks go to Encik Joha Muhsidi bin Abdul Wahab, Puan

Maslinda binti Abdullah and all the staff in Chemical and Environmental Engineering

Department for their invaluable help. This thesis would not have been completed without the

support from them.

Above all, Alhamdulillah, be praised to Allah swt, the most beneficent, the most gracious and

merciful, who has given me physical and emotional strength as well as comfort to

successfully complete my study.

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APPROVAL SHEET 1

I certify that a Thesis Examination Committee has met on (date) to conduct the final

examination of Norhafiza Binti Madehi thesis entitled “Jatropha curcas As A Potential Bio-

coagulant For Wastewater Treatment” in accordance with the Universities and University

Colleges Act 1971 and the Constitution of the Universiti Putra Malaysia [P.U.(A) 106] 15

March 1998. The committee recommends that the student be awarded the Master Sciences

Biochemical Engineering Degree.

Members of the Thesis Examination Committee were as follows:

Tinia Idaty Mohd. Ghazi, PhD

Faculty of Engineering

Universiti Putra Malaysia

(Chairman)

Wan Azlina Wan Abdul Karim Ghani, PhD

Faculty of Engineering

Universiti Putra Malaysia

(Internal Examiner)

Intan Salwani Ahamad, PhD

Faculty of Engineering

Universiti Putra Malaysia

(Internal Examiner)

Azlina Harun @ Kamaruddin, PhD

Faculty of Engineering

Universiti Sains Malaysia

(External Examiner)

------------------------------------------

ZULKARNAIN ZAINAL, PHD

Professor and Deputy Dean

School of Graduate Studies

Universiti Putra Malaysia

Date:

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Appendix D2

Approval Sheet 2

This thesis was submitted to the Senate of Universiti Putra Malaysia and has been accepted as

fulfillment of the requirement for the degree of Master of Science. The members of the

Supervisory Committee were as follows:

Zurina Zainal Abidin, PhD

Associate Professor

Faculty of Engineeering

Universiti Putra Malaysia

(Chairman)

Robiah Yunus, PhD

Professor

Faculty of Engineeering

Universiti Putra Malaysia

(Member)

-----------------------------------

BUJANG BIN KIM HUAT, PhD

Professor and Dean

School of Graduate Studies

Universiti Putra Malaysia

Date:

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DECLARATION

I declare that the thesis is my original work except for quotations and citations which have

been duly acknowledged. I also declare that it has not been previously, and is not

concurrently, submitted for any other degree at Universiti Putra Malaysia or at any other

institution.

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NORHAFIZA BINTI MADEHI

Date: February 2013

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TABLE OF CONTENTS

Page

ABSTRACT I

ABSTRAK IV

ACKNOWLEDGEMENTS VII

APPROVAL VIII

DECLARATION X

LIST OF TABLES XV

LIST OF FIGURES XVI

LIST OF ABBREVIATIONS XIX

CHAPTER

1 INTRODUCTION 1.1 General Overview 1

1.2 Problem Statement 2

1.3 Research Objectives 4

1.4 Experimental Flow Chart 5

1.4 Organization of Thesis 6

2 LITERATURE REVIEW

2.1 Wastewater 7

2.2 Water Quality 8

2.2.1 Chemical Characterization 9

2.2.2 Physical Characterization 10

2.2.3 Biological Characterization 12

2.3 Coagulation 13

2.3.1 Coagulation Theory and Mechanism 15

2.3.2 Mechanism of Destabilization 15

2.3.2.1 Double-Layer Compression 15

2.3.2.2 Absorption and Charge Neutralization 16

2.3.2.3 The Process of Adsorption and Inter-Particle 16

Bridging

2.4 Factors Affecting Coagulation 17

2.4.1 pH 18

2.4.2 Initial Wastewater Turbidity 18

2.4.3 Types of Coagulant used 18

2.4.3.1 Inorganic Coagulants 18

2.4.3.2 Synthetic Organic Polymer 19

2.4.3.3 Natural Coagulants 20

2.4.4 Coagulant Dosage 22

2.4.5 Rapid Mixing Degree and Conditions 22

2.4.6 Sedimentation time 23

2.5 Jatropha Curcas (JC) 23

2.5.1 Characteristic of Jatropha Curcas (JC) Plant 23

2.5.2 Characteristic of Jatropha Curcas (JC) Seed 26

2.5.3 Jatropha Curcas (JC) as Potential Bio-Coagulant for 29

Wastewater Treatment

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2.6 Palm Oil Mill Effluent Wastewater (POME) 29

2.7 Protein and Amino Acid 32

3 MATERIAL AND METHODOLOGY

3.1 Raw Materials 36

3.2 Initial Characterization of Palm Oil Mill Effluent Wastewater 37

3.3 Preparation of Jatropha Curcas (JC) seed and Jatropha Curcas 38

Presscake Coagulant Agent and Alum Solution

3.3.1 Coagulant Preparation of Jatropha Curcas (JC) Seeds 38

3.3.2 Coagulant Preparation of Jatropha Curcas (JC) 38

after Oil Extraction (Presscake)

3.3.3 Preparation of Alum 39

3.4 Coagulation Experiment for Jatropha Curcas (JC) Seed and 39

Jatropha Curcas (JC) Presscake

3.4.1 Synthetic Kaolin Wastewater 39

3.4.1.1 Effect of Dosage 39

3.4.1.2 Effect of pH 40

3.4.1.3 Effect of Blending Time for Coagulant Extraction 40

3.4.1.4 Effect of Solvent for Coagulant Extraction 40

3.4.2 Palm Oil Mill Effluent Wastewater 41

3.4.2.1 Main Coagulation Experiment 41

3.4.2.1.1 Effect of pH on Jatropha Curcas 42

and Alum

3.4.2.1.2 Effect of Dosage on Jatropha Curcas 42

(JC) and Alum

3.4.2.1.3 Effect of Storage Time 42

3.4.2.1.4 Effect of Storage Condition 42

3.5 Proximate Analysis and Protein Analysis on Jatropha 43

Curcas (JC) Seed

3.6 Quantification of Toxic Phorbol Ester Compound Using High 44

Performances Liquid Chromatography (HPLC)

3.7 Samples Characterization 45

3.8 Experimental Flow Diagram 48

4 RESULTS AND DISCUSSION 4.1 Coagulation Experiment Using Synthetic Kaolin Wastewater 47

4.1.1 Effect of Dosage 47 4.1.2 Effect of pH 50 4.1.3 Effect of Blending Time 52 4.1.4 Effect of Solvent 53

4.1.4.1 Effects of Jatropha Curcas 0.5M NaCl, Jatropha 56 Curcas 0.05M NaOH and Jatropha Curcas

Distilled Water on Coagulation in Synthetic

Wastewater Treatment

4.2 Characterization of Initial Palm Oil Mill Effluent Wastewater 57 4.3 Coagulation Experiment with Palm Oil Mill Effluent 59

Wastewater, Jatropha Curcas (JC) Presscake and Jatropha Seed

Coagulant(Effects on Turbidity Removal)

4.3.1 Effect of Dosage 59

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4.3.2 Effect of pH 63 4.3.3 Effect of Storage Time 65 4.3.4 Effect of Storage Condition 67

4.4 Coagulation Experiment with Palm Oil Mill Effluent 73 Wastewater and Alum

4.4.1 Effect of pH 73 4.4.2 Effect of Dosage 74

4.5 Final Characteristics of Treated Palm Oil Mill Effluent and 75 Comparison with Alum Performances

4.5.1 Final Chemical Oxygen Demand, Biological Oxygen 75 Demand, and Total Suspended Solids Removal Value (mg/L)

4.5.2 Final pH 77

4.5.3 Sedimentation Time 78

4.5.4 Sludge Volume 79 4.6 Proximate Analysis and Protein Analysis on Jatropha Curcas (JC) 80

Presscake and Jatropha Curcas (JC) Seed

4.7 Amino Acid Composition for Jatropha Curcas (JC) Seed and 82 Jatropha Curcas (JC) Presscake Coagulant Extracts

4.8 Quantification of Toxic Phorbol-ester by Using High Performance 86 Liquid Chromatography (HPLC)

5 CONCLUSIONS AND RECOMMENDATIONS 91

5.1 Conclusions 90

5.1 Recommendations 92

REFERENCES 94

APPENDICES 100

PUBLICATION AND AWARD 105

BIODATA OF STUDENT 106

JATROPHA CURCAS L. AS POTENTIAL BIO-COAGULANT FOR WASTEWATER TREATMENTABSTRACTTABLE OF CONTENTSCHAPTERSREFERENCES