UNIVERSITI PUTRA MALAYSIA JATROPHA CURCAS L. AS POTENTIAL BIO-COAGULANT FOR WASTEWATER TREATMENT NORHAFIZA BINTI MADEHI FK 2013 77
JATROPHA CURCAS L. AS POTENTIAL BIO-COAGULANT FOR WASTEWATER 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
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 Chair: Zurina Zainal Abidin, PhD Faculty: Engineering By NORHAFIZA BINTI MADEHI February 2013 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 90 o C. 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. I
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 II
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. III
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 Pengerusi: Zurina Zainal Abidin, PhD Fakulti: Kejuruteraan Oleh NORHAFIZA BINTI MADEHI Februari 2013 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 90 o C. 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 IV
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%. V
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. VI
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. VII
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 Biocoagulant 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: VIII
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: IX
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. ----------------------------------------- NORHAFIZA BINTI MADEHI Date: February 2013 X
TABLE OF CONTENTS Page ABSTRACT ABSTRAK ACKNOWLEDGEMENTS APPROVAL DECLARATION LIST OF TABLES LIST OF FIGURES LIST OF ABBREVIATIONS 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 I IV VII VIII X XV XVI XIX 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 XI
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 XII
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 XIII