(1)I hereby declared that the work embodied in this report is the result of the original research and has not been submitted for a higher degree to any universities or institutions

Tekspenuh

(1)I hereby declared that the work embodied in this report is the result of the original research and has not been submitted for a higher degree to any universities or institutions.. ______________________ Student Name: NUR HANISAH BINTI MASARUDIN Date:. I certify that the report of this final year students entitled “the use of chemically modified cellulose for adsorption of copper ions” by Nur Hanisah Binti Masarudin, matric number F15A0146 has been examined and all the corrections recommended by examiners has been done for the degree of Applied Science (Bioindustrial Technology) with Honours, Faculty of Bioengineering and Technology, University Malaysia Kelantan. Approved by:. _____________________ Supervisor Name: DR. ASANAH BT RADHI Date:. i. FYP FBKT. DECLARATION.

(2) First and foremost, my full thank to Allah S.W.T for giving an opportunity to me in aspect mental and health to finished my Final Year Project. I would like to thank my supervisor, Dr. Asanah Bt Radhi for sharing her knowledge and expertise in this study and also giving me an opportunity to do a research on the topic that was of great importance to me. Her passion in teaching me to do my final year project was the valuable thing and I really appreciate what she has done to me. Her guidance has made me to finish my (FYP) and I really grateful was having such sporting, kind-hearted supervisor like Dr. Asanah. I also would like to express my gratitude towards the lab assistance, Ms Syahirah, Mr Muhammad, for letting me to do a research in the Material Science laboratory. By their provision and guidance in the lab, I can handle the experiment correctly without doing any mistakes. The most appreciation also gives to Mr Rohanif who has helped me a lot regarding the uses of Atomic Adsorption Spectrometer (AAS). Without him, I cannot obtain the result for my FYP project. Special thanks also to my friends, especially my partners under same supervisor for always giving me a support moral, encourages me to do the research. They also have provided me all the needed in order to complete my research and thesis writing. Undoubtedly, none of this could not happen without my family especially my mother who always concern about me and giving me moral support to stay focus in studying.. ii. FYP FBKT. ACKNOWLEGEMENT.

(3) OF COPPER IONS. ABSTRACT. The current research was carry out to produce a cost effective biosorbent and to study the biosorption process involved in the adsorption of heavy metal such as copper using treated cellulose. Commercial cellulose and extracted cellulose from pineapple leaf were undergoing alkaline treatment with 5% NaOH. The operational parameters such as temperature, contact time, mass of the adsorbent, and agitation speed were fixed. The samples were then prepared in different pH solutions which were pH 6.2, 7.4, 9.2 and 11.5. In this case, Atomic Absorption Spectrophotometer (AAS) was used to analyse the adsorption efficiency of the adsorbent. The results of the adsorption showed that the commercial cellulose has a great efficiency in removal of copper ion compared to extracted cellulose. The removal of copper ions for commercial cellulose is higher as the pH increase. The result differ for the extracted cellulose due to the some error while doing the research. The characteristic commercial cellulose and extracted cellulose were carried out by using FTIR, TGA and XRD.. iii. FYP FBKT. THE USE OF CHEMICALLY MODIFIED CELLULOSE FOR ADSORPTION.

(4) ABSTRAK. Kajian semasa dijalankan untuk menghasilkan bioserap kos efektif dan untuk mengkaji proses bioserap yang terlibat dalam penjerapan logam berat seperti tembaga menggunakan selulosa yang dirawat. Selulosa komersial dan selulosa yang diekstrak menjalani rawatan alkali dengan 5% NaOH. Parameter operasi seperti suhu, masa hubungan, jisim adsorben, dan kelajuan agitasi telah ditetapkan. Kesemua sampel disediakan dalam larutan pH yang berbeza iaitu pH 6.2, 7.4, 9.2, dan 11.5 Dalam kes ini, Spektrofotometer Penyerapan Atom (AAS) digunakan untuk menganalisis kecekapan penjerapan penyerap. Hasil penjerapan menunjukkan bahawa selulosa komersial mempunyai kecekapan yang tinggi dalam penghapusan ion tembaga berbanding selulosa yang diekstrak. Pengyingkiran ion temabaga bagi selulosa komersial tinggi jika pH itu tinggi. Keputusan untuk selulosa yang diekstrak berbeza disebabkan ada ralat ketika penyelidikan dilakukan. Ciri-ciri untuk selulosa komersial dan selulosa yang diekstrak dilakukan dengan menggunakan FTIR, TGA dan XRD.. iv. FYP FBKT. PENGGUNAAN SELULOSA TERUBAH KIMIA UNTUK PENYERAPAN ION TEMBAGA.

(5) PAGE DECLARATION. i. ACKNOWLEDGEMENT. ii. ABSTRACT. iii. ABSTRAK. iv v-vii. TABLE OF CONTENT LIST OF FIGURE. viii. LIST OF TABLE. viii. LIST OF ABBREVIATION. ix. LIST OF SYMBOL. x. CHAPTER 1: INTRODUCTION 1.1 Background of study. 1-2. 1.2 Problem statement. 3. 1.3 Objective. 4. 1.4 Scope of study. 4. 1.5 Significant of study. 4-5. CHAPTER 2: LITERATURE REVIEW 2.1 Pineapple leaf. 6. 2.1 Cellulose. 6-7. v. FYP FBKT. TABLE OF CONTENT.

(6) 7-8. 2.2.2 Swelling of cellulose. 9-10. 2.2.3 Modification of cellulose for adsorbent 2.3 Adsorption. 11 11-12. 2.4 Heavy metal. 12. 2.5 Technique to remove heavy metal. 13. CHAPTER 3: MATERIALS AND METHOD 3.1 Research flowchart. 14-15. 3.2 Materials. 15. 3.3 Method 3.3.1 Sample preparation. 15-16. 3.3.2 Cellulose extraction from pineapple leaf 3.3.2.1 Alkali treatment. 16. 3.3.2.2 Bleaching. 16. 3.3.3 Surface modification 3.3.3.1 Alkali saponification. 17. 3.3.4 Solution preparation 3.3.4.1 Preparation of 1000ppm Cu2+ solution. 17. 3.3.4.2 Preparation of 10ppm Cu2+. 17. 3.3.4.3 Preparation copper solution with differences pH. 18. 3.3.5 Adsorption of cellulose sample in Cu2+ aqueous solution. 18. vi. FYP FBKT. 2.2.1 Structure of cellulose.

(7) 18-19. 3.3.7 Characterization of extracted cellulose and commercial cellulose 3.3.7.1 FTIR. 19. 3.3.7.2 XRD. 20. 3.3.7.3 TGA. 20. CHAPTER 4: RESULT AND DISCUSSION 4.1 Removal efficiency at different pH. 22-23. 4.2 Characterization of commercial cellulose and extracted cellulose 4.2.1 FTIR. 24-26. 4.2.2 XRD. 26-28. 4.2.3 TGA. 28-29. CHAPTER 5: CONCLUSION AND RECOMMENDATION 5.1 Conclusion. 30. 5.2 Recommendation. 31. 32-34. REFERENCE. 35. APPENDIX. vii. FYP FBKT. 3.3.6 Absorption analysis.

(8) Page 2.1. Molecular structure of cellulose. 7. 2.2. Schematic diagram of Na-cellulose I structure. 8. 2.3. Patterns of hydrogen bonds in cellulose I and cellulose II. 9. 3.1. Research flowchart. 15. 4.1. Adsorption of copper ion at different pH. 22. 4.2. FTIR Spectra of commercial cellulose and extracted cellulose. 24. 4.3. XRD pattern for commercial cellulose and extracted cellulose. 26. 4.4. TGA curve of commercial cellulose and extracted cellulose. 28. LIST OF TABLE. Page 4.1. Group frequency of absorption band of cellulosic sample. 23. 4.2. The crystallinity of commercial cellulose and extracted cellulose. 25. viii. FYP FBKT. LIST OF FIGURE.

(9) C6H10O5. Molecular formula of cellulose. H. Hydrogen element. AGU. Anhydroglucopyranose unit. IR. Infrared spectroscopy. NMR. Nuclear magnetic resonance. NaOH. Sodium hydroxide. CH3COOH. Acetic acid. NaClO2. Sodium chlorite. CuSO4. Copper sulphate. dH20. Distilled water. Cu2+. Copper ion. FTIR. Fourier-transform infrared spectroscopy. XRD. X-ray Diffraction. TGA. Thermogravimetric analysis. AAS. Atomic Absorption Spectrophotometer. ix. FYP FBKT. LIST OF ABBREVIATIONS.

(10) wt %. Weight percentage. L. Litre. ml. Milli litre. g. Gram. kV. Kilo voltan. mA. Milli ampere. 𝜆. Lambda. Ǻ. Angstrom unit. Crl. Crystallinity index. I002. Peak intensity corresponding to crystalline. Iam. Peak intensity of the amorphous fraction. x. FYP FBKT. LIST OF SYMBOL.

(11) INTRODUCTION. 1.1. Background of study. Industries are largely using plant fibres for many applications from numerous resources. In the middle of 20th century, synthetic fibres rose up extremely whilst natural fibres industries fall its market shares.In 2009, publicizing of material and natural fibre is considered as international year of natural fibre (IYNF), which is highly contributory to agriculture, farmers, environment as well as market demands. On the basis of compound annual growth rate of 3.3%, it is predicted to cross over 3.3 billion pounds. The cell wall is complexity of polysaccharide network that contribute to the protection and stability of the plant. It is one of the first layers of abiotic as well as biotic stimuli perception. A controlled remodeling of the primary cell wall is mandatory for the plant for its growth adaptation to environmental stresses. Cellulose is the primary component in a plant cell walls. It is synthesized by plasma membrane-localized cellulose synthases moving along cortical microtubule tracks (Cristopher et al., 2017). Cellulose also can be found in certain bacteria such as in prokaryote bacteria. The function of cell wall in this bacteria is to protect the cell from the internal turgor pressure. Cellulose is one of the most widely used natural substances and has become one of the most important commercial raw materials. Cellulose for industrial use is mainly obtained from wood pulp. 1. FYP FBKT. CHAPTER 1.

(12) major component of plant matter. The cellulose is the major constituent of paper, paperboard and card stock. Cellulose also the main ingredient of textiles made from cotton, linen, and other plant fibers. It can be turned into rayon, an important fiber that has been used for textiles since the beginning of the 20th century. The properties of cellulose are it has no taste, odorless, insoluble in water and most organic solvents, and it easy to degrade. Cellulose is one type of polymer which it can be broken down chemically into its glucose units by treating it with concentrated mineral acids at high temperature. Cellulose is a straight chain polymer unlike starch, no coiling or branching occurs, and the molecule adopts an extended and rather stiff rod-like conformation, aided by the equatorial conformation of the glucose residues. The adsorption process is widely used by various researchers for the removal of heavy metals from waste streams and active carbon is often used as adsorbent. Despite its abundance use in the wastewater and water treatment industry, activated carbon is still an expensive material. In recent years, the need for a safe and economical method for the removal of heavy metals from polluted waters has necessitated research interest toward the production of low cost alternatives to commercially available activated carbon. Therefore, there is an urgent need that all possible sources of agro-based inexpensive adsorbents should be explored and their feasibility for the removal of heavy metals should be studied in detail (Hegazi, 2013). The use of cellulose as adsorbent have been studied as it cheap and the most abundant agricultural waste.. 2. FYP FBKT. and cotton. The kraft process is the process used to separate cellulose from lignin, another.

(13) Problem statement. Copper in particular is natural elements predominantly used in chemical process industries. Copper is a very common substance that occurs intrinsically in the environment and spreads through natural phenomena, which is extensively utilized by electrical industries, in fungicides, and in antifouling paints. There is evidence to suggest that copper may be carcinogenic to humans and can cause damage to a variety of aquatic life (Ng et al., 2002). Among the ionic species of copper, Cu (II) ions can have alarming effects in aqueous solution, attaching easily to organic and inorganic matter based on solution pH (Wan et al., 2010). Excessive release of heavy metals into the environment due to industrialization and urbanization has posed a great problem worldwide. Unlike organic pollutants, the majority of which are susceptible to biological degradation, heavy metal ions do not degrade into harmless end products. The technique that have been used from the researchers to remove the copper ions from the solution widely investigated such as by ion exchange and filtration. Nowadays, the use of activated carbon as adsorbent in order to remove heavy metal from the solution is widely used. The use of activated carbon as adsorbent has its limitation factor which encourage to use the cellulose as adsorbent. This is because the activated carbon is more expensive compare to cellulose which is modified and act as adsorbent. The cellulose can easily obtained from the waste material that is generated and it is the most abundant agriculture waste in the world.. 3. FYP FBKT. 1.2.

(14) Objective. The objective of this research: . To prepare an extractive cellulose from pineapple leaf and pure cellulose for adsorption of copper. . To determine the adsorbent efficiency of extractive cellulose and pure cellulose at different pH. . To characterize the functional group, thermal properties, and crystallinity of cellulose. 1.4. Scope of study. Pineapple leaves are used as a source for extracting cellulose. Pineapple leaves rich in cellulose content are higher than other raw materials. The pineapple leaves are selected because of its availability to get in the market as well as the higher cellulose content. The cellulose is undergone process to become as adsorbent for removal of copper ion in solution.. 1.5. Significant of study. The finding of this study is the use of cellulose not only use to synthesis of new materials but also as adsorbent in order to remove heavy metal such as copper ion in 4. FYP FBKT. 1.3.

(15) carbon as it have its limitation to act as adsorbent. The use of cellulose as adsorbent of heavy metal will not harm environment as it is environmental friendly.. 5. FYP FBKT. solution. The cellulose as adsorbent can replaced the activated carbon as the activated.

(16) LITERATURE REVIEW. 2.1. Pineapple Leaf. Pineapple or its scientific name Ananas comosusvar comosus is the most significant representative of the Bromeliaceae and is plant and grown throughout subtropical and tropical regions worldwide for local international export and local consumption (Ventura et al., 2009). Pineapple is one of the most familiar tropical fruits largely grown around the world for its fruits. Pineapple leaves, the major part of the plant that is currently unused needs global attention for its commercial exploitation. After fruit harvesting, the leaves are often being disposed by burning or decompose. This happened because of the ignorance from farmers communities regarding the existence of commercial uses of pineapple leaves (Anbia et al., 2015). One of the waste materials in agriculture sector is pineapple leaf, which is widely cultivated in Asia. Pineapple is one of the most essential tropical fruits in the world (Arib et al., 2004). The pineapple leaf consists of 70-82% of holocellulose, 5-12% of lignin, and 1.1 % of ash.. 2.2. Cellulose. Cellulose is a natural occurring linear polymer of anhydroglucose which can be found abundantly on earth (Kester and Fennema, 1986). The cellulose it is a fibrous, water 6. FYP FBKT. CHAPTER 2.

(17) stalks, or trunks of plants (Kohn, 2014). Elemental composition of cellulose was first discovered by Payen in 1838 which is the empirical formula of C6H10O5 whereby he found the composition of 6.2 % H and 44.4 % C in an elemental analysis of cellulose (Payen, 1842; Krassig and Schurz, 1986).The limitation of cellulose as a biomaterial is the cellulose is not biodegradable because in the human body it lack of the digestive enzyme which is cellulase to digest the cellulose.. 2.2.1. Structure of cellulose. At the molecular level, cellulose is a simple linear polymer consist of the Danhydroglucopyranose (AGU) unit associated with β- (1,4) -glycosidic bonds formed between carbon 1 and carbon 4 glucose adjacent (Kester and Fennema, 1986) as shown in Figure 2.1. In solid state, the AGU unit is rotated 180º with respect to each other due to β-linkage constraints. Each of the AGU units comprises of three hydroxyl groups at carbon 2, 3 and 6 positions. The hydroxyl group on carbon 1 from both ends of the molecule is an aldehydes group that has a reduction feature. Conversely, the hydroxyl group at carbon 4 on the other end of the chain consists of alcohol borne hydroxyl group constituent and thus is known as a non-reducing end (Staudinger, 1932). In cellulose plant fibers, cellulose is present in amorphous states and also crystalline phase through inter-hydrogen bonds and intra-molecular molecules; therefore the cellulose does not melt before the thermal decline (Fengel and Wegner, 1989). The parallel cellulose is parallel to each other in the fibers, surrounded by a hemicellulose and lignin matrix. Additionally, cellulose has its feature such as good mechanical properties, biodegradability and low density (Zimmerman, Pohler and Schwaller, 2005).. 7. FYP FBKT. insoluble and tough material which mostly can be found in the cell walls, stem, mainly in.

(18) which are type I, II, III, IV and V. However, only type I illustrate the best mechanical characteristic. In addition, cellulose I have been found to have a parallel chain orientation while cellulose II was an anti-parallel chain. Through the analysis from the nuclear magnetic resonance (NMR) and infrared spectroscopy (IR) found that, the AGU ring exists in the pyranose ring form adopts the 4C1-chair conformation which constitutes the lowest energy conformation, thus are thermodynamically more stable (Michell and Higgins, 1965).. Figure 2.1: Molecular structure of cellulose reducing (right) and non-reducing (left) end groups. At equatorial positions at AGU, the three hydroxyl groups present which is a secondary hydroxyl group in carbon 2 and 3 with a major hydroxyl group at a carbon 6 position, influences the cellulose reaction and chemical feature (Kadla and Gilbert, 2000). In addition, cellulose hydroxyl groups also play a significant role in cellulose solubility, and β-glycosyl cellulose cell networks are susceptible to hydrolysis as shown in figure 2.2. Cellulose is insoluble in water and ordinary organic solvents due to the formation of strong intra- and inter-molecular hydrogen bonds. (Bono, et al., 2009). Therefore hydrogen bonding network presence have to be broken in order to dissolve cellulose.. 8. FYP FBKT. Based on Iversen and Lennholm (1995), there are a few categories of celluloses,.

(19) Swelling of cellulose. Alkaline cellulose is an important swelling complex formed after treatment with NaOH as it enhances cellulose reactivity in the direction of chemical reactions compared with untreated cellulose (Fengel and Wegener, 1989). This means that the etherifying or esterifying reagent is able to penetrate the cellulose structure easier and thereby replacing the hydroxyl group of the anhydrous glucose unit becomes easier.. Figure 2.2: Schematic diagram of Na-cellulose I structure (Fink, Walenta and Mann, 1995). NaOH treatment of cellulose yields the pure cellulose modification I and II as well as mixtures of cellulose I and II which depends upon the concentration of the NaOH solution.. 9. FYP FBKT. 2.2.2.

(20) (b). Figure 2.3 Patterns of hydrogen bonds in (a) cellulose I and (b) cellulose II (Fink, Walenta & Mann, 1995). Cellulose II seen to have more hydrogen bonds, which contribute to additional chain stability and therefore thermodynamically more stable than cellulose I (O’Sullivan, 1997). Besides, due to higher cross-linking density and inter-molecular, cellulose II is less reactive compare to cellulose I (Kolpack and Blackwell, 1976). As shown in figure 2.3 (b), all the hydroxyls position lead to the formation of intra- and inter-molecular hydrogen bonds within the cellulose II unit cell structure. Krassig (1993) reported the reduction of inter-fibrillar surfaces that can be accessed by cellulose II due to its low reactivity when density and hydrogen bonding increased.. 10. FYP FBKT. (a).

(21) Modification of cellulose for adsorbent. The use of cellulose as a basis for the new absorbent design lies largely in its high abundance, low cost and relative convenience where it can be chemically modified (William, 2008). Generally, chemically modified cellulose exhibits higher adsorption capacity for numerous aquatic pollutants compare to non-modified form. Many chemicals was for cellulose modification including minerals and organic acids, fuels, oxidizing agents, organic compounds (Hokkanen, 2016). The approach to modification of cellulose has been based on the grafting of suitable polymer exchange to the cellulose back bone followed by fictionalizations or direct chemical modification approach (Low, 2004; Tashiro, 1982; Maekawa, 1984).. 2.3. Adsorption. Adsorption is the deposition of molecular species to the surface. The adsorbent defined as the molecular species absorbed on the surface and adsorbate defined as surfaces where adsorption is in effect. .The common example of adsorbents are metal, clay, silica gel, and colloids. Thus, adsorption is a surface phenomenon. Adsorption can be categorized into two which are physical and chemical adsorption. The phenomenon of physical adsorption is involves the weak Van der Waal forces by means of which on a solid surface get adsorbed by the gas molecule. The characteristics of this physical adsorption are there is no specificity as any gas can be adsorbed onto the surface, in nature this adsorption is irreversible and is dependent on. 11. FYP FBKT. 2.2.3.

(22) thus the adsorption of gas molecules increase. Conversely, the decrease in the pressure will cause the removal of gas molecules from the solid surface. Besides, the increase in temperature will increase the physical adsorption. The chemical adsorption involvement of chemical bonds between the gas molecules and the adsorbent surface. The characteristics of this adsorption are it is an exothermic process and the process is accompanied by the increase in the temperature. It occurs slowly at low temperature and occurs at a higher rate with increase in pressure. Just as in case of physical adsorption, chemical adsorption is directly proportional to surface area and thus increases with increase in surface area.. 2.4. Heavy metal. The pollution of heavy metal has become one of the most serious environmental issues today. The treatment of heavy metals is one of the special concern due to their persistence and recalcitrance in the environment (Fenglian, 2010). Heavy metals such as chromium, cadmium, copper, arsenic, lead, mercury, nickel, and zinc are major pollutants of freshwater reservoirs due to properties such as it not biodegradable, toxic, and persistent properties. Industrial growth is a major source of heavy metals that introduce such pollutants into the different segments of the environment including water, soil, air, and biosphere. Heavy metals can be absorbed easily by and vegetables fish because of their high solubility in aquatic environments. Therefore, they can gather in the human body through the food chain. Various methods have been developed and used for water and wastewater treatment to decrease heavy metal concentrations (Azimi, 2017). 12. FYP FBKT. temperature and pressure. As the pressure increase, it decreases the volume of gas and.

(23) Technique to remove heavy metal. The most common method used for the adsoprtion of metal ions from wastewater is precipitation but this is ineffective at low ion concentrations. Other processes employed include electrolysis, membrane processes, ion exchange, filtration and evaporative recovery. These are very costly especially for small commercial problems and have operating problems, such as sensitivity to acid and salt condition, limited flow-rates, and fouling (Aderhold et al. 1996). One such method is adsorption. Adsorption techniques are relatively simple where the sorbent concentrates the target particle onto its surface. Industrial sorbents include activated carbon and silica gel (Aderhold et al., 1996). Biosorption is where both animal and plant derived material are used to detect metal ions from aqueous solution (Williams and Edyvean 1997). Metal sequestration involves a number of mechanisms including chelation, ion exchange, adsorption by physical forces and ion entrapment. Chemical groups that are best suited for sequestration of metal ions are polysaccharides, proteins and phosphate groups with carboxyls, hydroxyls and sulphates. Thus the biosorbent potential of any biological biosorbent depends on its morphological structure and chemical make-up (Volesky and Holan 1995). Most commonly, microbial, fungal and microalgal biomasses have been investigated (see Volesky and Holan 1995 for a list). Marine micro and macro-algae are gaining increasing attention as they are rich sources of biological material which can accumulate metal ions as well as being relatively cheap to process (Zhou et al. 1998). Living cultures of Cladophora have a high removal efficiency, being able to concentrate cadmium and remove between 86-96% of the added cadmium over 48h (Sobhan and Sternberg 1999).. 13. FYP FBKT. 2.5.

(24) MATERIALS AND METHOD. 3.1. Research Flowchart. PREPARATION OF SAMPLE (The sample were dried and ground). CELLULOSE EXTRACTION (The pineapple leaf were undergone alkali treatment and bleaching). ADSORBENT TESTING (Tested in different pH 6, 7, 9, 11). ADSORPTION MEASUREMENT (Atomic Absorption Spectrophotometer) 14. FYP FBKT. CHAPTER 3.

(25) FTIR. TGA. XRD. Figure 3.1: Research Flowchart. 3.2. Materials. In this study, the main material that used for the experiment were commercial cellulose, extracted cellulose, sodium hydroxide (NaOH), acetic acid (CH3COOH), sodium chlorite (NaClO2), copper sulphate powder (CuSO4), and distilled water (dH20).. 3.3. Method. 3.3.1 Sample preparation. The commercial cellulose was obtained from the chemical store in the lab. The raw material which is pineapple leaf was collected from Ayer Lanas, Kelantan. The pineapple leaf was dried in an oven at 90 °C for 48 hours in order to reduce the moisture 15. FYP FBKT. CHARACTERIZATON OF COMMERCIAL CELLULOSE AND EXTRACTED CELLULOSE.

(26) was ground and sieve (450 μm).. 3.3.2 Cellulose extraction from pineapple leaf. 3.3.2.1 Alkali treatment. The 90 g of dried pineapple leaf was treated with 4 wt % of sodium hydroxide aqueous solution for 6 hours. The black slurry obtained was filtered and the solid materials which is extracted cellulose was washed several times with distilled water. After that, the sample was dried at 60 º C for 24 hours in an oven.. 3.3.2.2 Bleaching process. 20 g of free extractive powder was mixed with 650 mL of distilled water, 5 mL of acetic acid and 6 g of sodium chlorite and was heated on heating plate for 1 h at 75 º C. This treatment was repeated twice until the sample became white. Then, the mixture was allowed to cool and was filtered using distilled water. The bleached fibers were dried at 60 º C for 24 h in an oven.. 16. FYP FBKT. content of the sample and to prevent the growth of microorganism. After that, the samples.

(27) 3.3.3.1 Alkali saponification. The 10 g of extracted cellulose and pure cellulose were added to 100 ml of 5 % NaOH solution and mixed for 4 hours at room temperature.. 3.3.4 Solution preparation. 3.3.4.1 Preparation of 1000ppm Cu2+ solution. Approximately, 2.5117g of copper sulphate was weighted and put in the volumetric flask containing 1L distilled water. The mixture was mixed thoroughly until the copper sulphate was fully dissolved.. 3.3.4.2 Preparation of 10ppm Cu2+ solution. In order to acquire 10ppm Cu2+, 2.5 ml of the stock solution was added into 250ml volumetric flask. Then, distilled water was added until it reaches calibration mark.. 17. FYP FBKT. 3.3.3 Surface modification.

(28) Six difference copper solutions with difference pH of 7, 9, 11, and one with original pH of copper solution were prepared. The pH of copper solution was adjusted accordingly to desired pH by using a few drops of NaOH.. 3.3.5 Adsorption of cellulose sample in Cu2+ aqueous solution. The adsorption of the metal ion was investigated by adding 1 g of commercial cellulose and extracted cellulose sample into each conical flask that contains 25 ml of Cu2+. Then, the conical flasks were placed in the orbital shaker for one hour at 100 rpm under room temperature. After 1 h, the solution were filtered by using filter paper and syringe filter. Then, the samples were placed into 15ml falcon tube for the dilution process.. 3.3.6 Absorption analysis. The entire samples was analysed by using Atomic Absorption Spectroscopy machine. Each of the samples were analysed and the result was obtained. In order to check out the impact of pH on copper biosorption utilizing commercial cellulose and extracted cellulose as the biosorbent, tests were led by altering the pH from 6 to 11. The percentage of removal was calculated by using Equation (3.1) below. 18. FYP FBKT. 3.3.4.3 Preparation copper solution with differences pH.

(29) 𝐶𝑖−𝐶𝑓 𝑐𝑓. × 100. (3.1). In Equation 3.1, Ci and Cf are the initial and final concentration of Cu2+ (mg/L) in aqueous solution, respectively.. 3.3.7 Characterization of extracted cellulose and commercial cellulose. The extracted cellulose and commercial cellulose were characterized by using FTIR, XRD and TGA.. 3.3.7.1 FTIR. The functional group of the samples were determined by using FTIR spectroscopy. The sample data was calculated by using Thermo Scientific model Nicolet I S10 spectrometer. The sample data was calculated in the spectrometer in the range 4005000 cm-1.. 19. FYP FBKT. 𝐸 (%) =.

(30) The XRD pattern of the samples were obtained by using X-Ray diffractometer equipped with CUKα radiation is 𝜆= 1.5406Ǻ in the range 2θ range 5 º - 50 º at 2 º per min. The operating voltage is 45 kV and current is 30 mA.. 3.3.7.3 TGA. The thermogravimetric analysis was performed to determine the thermal decomposition of the samples. The thermal stability data was collected on a Perkin Elmer TGA 7. The samples were burned under temperature ranging 25 º - 550 º at a heating rate of 10 K per min under a nitrogen gas flow 20 cm3 min-1.. 20. FYP FBKT. 3.3.7.2 XRD.

(31) RESULT AND DISCUSSION. Based on this research, the pH has been pinpointed as one of the significant parameter in controlling the adsorption of heavy metal. As indicated by a few authors, pH varieties could modify the accessibility and qualities of metal ions in solution and also changing the chemical status of the functional groups in charge of biosorption. The measurement of adsorption was carried out by using AAS. The characterization of extracted cellulose and commercial cellulose were carried in order to determine its functional group, crystallinity and thermal decomposition of the sample by using FTIR, XRD and TGA respectively.. 21. FYP FBKT. CHAPTER 4.

(32) Removal efficiency at different pH. Removal efficiency at different pH 150 Extracted Cellulose. 89 %. Percentage of removal (%). 100. 85 %. 44 %. 50. Commercial Cellulose. 55 % 9.45 %. - 10 %. 0 6. 7. 8. 9. 10. 11. 12. -50 -100. - 120 %. -150 -200. - 179 %. pH Figure 4.1: Adsorption of copper ion at different pH. Figure 4.1 showed that the adsorption of copper ions for the commercial cellulose and the extracted cellulose. The adsorption of copper ion for the commercial cellulose and extracted cellulose can be seen in different pH which are at pH 6.2, 7.4, 9.2 and 11.5. The removal efficiency of commercial cellulose at pH 6.2, 7.4, 9.2 and 11.5 are 89 %, 85 %, 55 % and -10 % were observed respectively. Meanwhile the removal efficiency of extracted cellulose at pH 6.2, 7.4, 9.2 and 11.5 are 44 %, 9.45 %, -120 % and -179 % respectively. The removal efficiency of commercial cellulose is higher than the extracted cellulose. From the figure above seen that the ability for commercial cellulose to remove the copper ions from the solution is high at pH 6.2 and low as the pH is increase which is at pH 11.5. The extracted cellulose showed the same result same as the commercial cellulose which is the ability to remove the copper ions from the solution is high at pH 22. FYP FBKT. 4.1.

(33) remove the copper ions from the solution is low compare to commercial cellulose. This is because the dosage use to remove the copper ions from the solution is not adequate. Hence, the efficiency removal of copper ions from the solution obviously low. The effect of pH is related with the adsorption of the copper ions in a solution. The fact of this can be explained by the competition of hydrogen ions H+ and the metal ions occupying the available adsorption site. At lower pH, the adsorption sites are saturated by H+ and when the pH increase, the sorption sites becomes available and the adsorption of copper ions increase. At the higher pH, the copper precipitated and positive charged ions compete with the remaining Cu2+ (Abbar et al., 2017). The increase the pH effect the removal efficiency of heavy metals from solution. As the pH increase, the removal efficiency of copper ions from solution also increase.. 23. FYP FBKT. 6.2 and the ability to remove is low as the pH increase but the efficiency in order to.

(34) Characterization of commercial cellulose and extracted cellulose. 4.2.1. FTIR. The sample of FITR analysis were scanned and obtained in with the spectral range from 4000-5000 cm-1. The figure 4.1 showed the FTIR spectra of commercial cellulose and extracted cellulose.. Commercial cellulose Extracted cellulose 200. Transmittance %. 3331. 2917. 1644 1031. 100. 3300. 1589. 2382. 1032. 0. 4000. 2000 -1. Wavenumber (cm ). Figure 4.2: IR spectra of commercialized cellulose and extracted cellulose. Fourier transform infrared spectroscopy (FTIR) allows the characterization of a chemical structure by identifying the functional groups present in each sample (Santos et al., 2015). 24. FYP FBKT. 4.2.

(35) cellulose and extracted cellulose. The absorption band for extracted cellulose are at ~ 3331, ~2917, ~1644, and ~1031 were almost identical to commercial cellulose which are at ~3300, ~2382, ~1589, and ~1032 which show that there is no change in the functional group. Furthermore, the commercial cellulose and extracted cellulose show a broad band between the region 3200 to 3700 cm. -1. which indicate to the hydrogen bond (O-H). stretching vibration. O-H stretching vibration indicates as the bending vibration of water molecules. The spectrum of commercial cellulose is sharpest in the spectrum region of O-H stretching vibration at ~ 3300 meanwhile for extracted cellulose at ~3331. Besides that, the commercial cellulose show the sharpest peak at ~1032 meanwhile for extracted cellulose at ~ 1031. This indicate to the stretching vibration of C-O-C pyranose ring (antisymmetric in phase ring) of cellulose molecules.. Table 4.1 Group frequency of absorption band of cellulosic sample Primary polymer. Control. Vibration mode. peak ( cm -1) Commercial cellulose. Functional group. 3200-3700. Stretch. O-H. ~2382. Stretch. C-H. ~1589. Water absorb from cellulose. O-H. ~1032. Stretch. C-O. 25. FYP FBKT. Figure 4.1 illustrate there is slightly changed the absorption band for commercial.

(36) cellulose. 3200-3700. Stretch. O-H. ~2917. Stretch. C-H. ~1644. Water absorb from cellulose. O-H. ~1031. Stretch. C-O. 4.2.2 XRD. Commercial Cellulose Extracted Cellulose. 4000. Intensity (a.u). 3000. 2000. 1000. 0 30. 60. 90. 2  ( ). Figure 4.3: XRD pattern for commercial cellulose and extracted cellulose. 26. FYP FBKT. Extracted.

(37) XRD pattern is the most crystalline and has the sharpest peak which is at 2θ = 22.6° compare to extracted cellulose which is at 2θ = 21.43°. Extracted cellulose has crystalline and amorphous region made it low crystalline compare to commercial cellulose. The extracted cellulose in not pure may cause by the presence of the residue such as lignin, ash and other residue which is not completely removed during the extraction and bleaching process. Based on the areas under the diffraction curve, the application of the surface method for the calculation of crystallinity index for each sample pattern was calculated by using EVA software using the Segal’s method.. CI ( % ) = 100 × (I002 − Iam)/ I002. (4.1). The intensity value of the 002 crystalline peak (I002) and the height of minimum (Iam) were used in the Crl calculation (Segal’s method). Table 4.2 showed the crystallinity index of commercial cellulose and extracted cellulose. The crystallinity of the sample depend on the crystallinity index. As shown in table 4.2, the crystallinity of the commercial cellulose is the highest compare to extracted cellulose which is 78.1 % and 33.8 % respectively. From the observation, it showed that the crystallinity of the commercial cellulose is higher than the extracted cellulose.. 27. FYP FBKT. The crystallinity of sample was characterized by XRD. The commercial cellulose.

(38) CRYSTALLINITY INDEX ( % ). Commercial cellulose. 78.1. Extracted cellulose. 33.8. TGA. Commercial Cellulose Extracted Cellulose 100. 80. Weight percentage %. 4.2.3. SAMPLE. 60. 40. 20. 0 100. 200. 300. 400. 500. Temperature (°C). Figure 4.4: TGA curve of commercial cellulose and extracted cellulose. 28. FYP FBKT. Table 4.2: The crystallinity index of commercial cellulose and extracted cellulose.

(39) of the weight of the substance is recorded as a function of temperature. In figure 4.3, it shows the thermogravimetric analysis for commercial cellulose and extracted cellulose. In all cases, an initial weight loss on the fibers occurs in range 35 – 150 º, due to the evaporation of adsorbed and bound water (Flauzino Neto et al., 2013). Degradation of hemicellulose and cellulose starts at temperature 220 and 250 º respectively, while lignin degrades at lower temperature, 200 º C (Moran, Alvarez, Cyras, & Vazquez, 2008). At higher temperature, lignin is more heat resistant than hemicellulose and cellulose due to its low degradation rate. The weight loss between 200 and 300 º C is mainly due to hemicelluloses decomposition and the parallel show decomposition of lignin, while the weight loss between 250 and 500 º C is attributed to cellulose loss ( 250 – 300 º C) and lignin ( 200 – 500 º C) decomposition (Nanda et al., 2013). At temperatures higher than 400 º C, there is oxidation and breakdown of the charred residue to lower molecular weight gaseous product (Moran et al., 2008). In this study, the samples had small amount of weight loss at the temperature below than 40 º C. By the comparison of the extracted and commercial cellulose, it was observed that the commercial cellulose had no weight loss in the range between 100 – 300 º C meanwhile the extracted cellulose show the continues weight loss in 50 – 150 º C. The extracted cellulose started to decompose at high temperature which is at 230 – 350 º C but for the commercial cellulose the decompose started at temperature range 310 – 360 º C. At temperature which is higher than 360 º C, the weight loss of the both cellulose samples decrease as the temperature increase. The weight loss of the cellulose sample is due to decomposition and dehydration of the sample.. 29. FYP FBKT. The sample were heated under the nitrogen gas at control flow rate. The change.

(40) CONCLUSION AND RECOMMENDATION. 5.1. CONCLUSION. As a conclusion, the extracted cellulose was successfully extracted from pineapple leaf according to extraction process and to act as adsorbent for the removal of copper ions from solution. The surface modification of extracted cellulose and commercial cellulose can enhance the percentage removal of heavy metal because it can increase the copper bonding with the active sites on the adsorbent surface. The pH play an important role in removing heavy metal. The characterization of the samples in term of its functional group, crystallinity, and thermal decomposition were done by using FTIR, XRD and TGA respectively. The commercial cellulose and extracted cellulose can be adsorbent for the removal of heavy metal.. 30. FYP FBKT. CHAPTER 5.

(41) RECOMMENDATION. For the recommendation part, the use of scanning electron to observe the morphology of the cellulose samples can be done to further the research about the adsorption process. The other parameter such as temperature, contact time, agitation time and the different amount of dosage of cellulose use also can be applied in order to observe the removal efficiency of heavy metal. Other heavy metal such as zinc, cadmium, and lead also can be one of the example of heavy metal that can be removed by the cellulose.. 31. FYP FBKT. 5.2.

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(45) APPENDIX A: Alkali treatment. APPENDIX B: Bleaching process 35. FYP FBKT. APPENDIX.

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