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Pakistan Journal of Science (Vol. 73 No. 3 September, 2021) EVALUATION OF CEIBA PENTANDRA FOR THE REMOVAL OF RESIDUAL OIL FROM POME(PALM OIL MILL EFFLUENT) BY USING FACTORIAL DESIGN BIOREACTOR M. Afzaal *1, A. Abdullah2, S. Ahmed3*, M. Ibrahim4, J. Khan5, , S.A. Mirza6, A. Aftab7, A. Ahmad8, M.A. Idrees8 and M. A. Ullah9 1 Sustainable Development Study Centre, GC University Lahore, 5400, Pakistan Institute of Marine Biotechnology, Universiti Malaysia Terengganu, 21030 Kuala Terengganu Terengganu, Malaysia 3 Department of Basic Sciences, University of Veterinary and Animal Sciences Lahore, Narowal Campus, 51600, Narowal, Pakistan 4 Department of Biochemistry, Bahauddin Zakariya University, Multan, 60800, Pakistan 5 Department of Chemistry, Khwaja Fareed University of Engineering & Information Technology, 64200, Rahim Yar Khan, Pakistan 6 Department of Botany, GC University Lahore, 5400, Pakistan 6 Research Centre for CO2 Capture (RCCO2.C), Department of Chemical Engineering UniversitiTeknologi PETRONAS, 31750 Tronoh, Perak, Malaysia 8 Department of Pathobiology, University of Veterinary and Animal Sciences Lahore, Narowal Campus, 51600, Narowal, Pakistan 9 Department of Life Sciences, Khwaja Fareed University of Engineering & Information Technology, 64200, Rahim Yar Khan, Pakistan *Corresponding author Email: sarfraz.ahmed@uvas.edu.pk 2 ABSTRACT: Fixed bed column studies were carried out to evaluate the performance of natural Ceiba pentandra (kapok) in removal of residual oil from palm oil mill effluent (POME) under varying flow rate and packing density. A multilevel factorial design based on chemical oxygen demand (COD) and turbidity of the effluent was developed. COD was significantly affected by the effects of flow rates. The maximum packing density and flow rate for maximum COD reduction were observed at 0.08 g/cm3and 5ml/min. COD reductions were observed more than 99% at all packing densities and flow rates. Turbidity reduction ranged from 92.9- 95.8% at all packing densities and flow rates. Fixed bed column designed had been successfully achieved to remove residual oil from palm oil mill effluent (POME) under different packing densities and flow rates. The results suggest that kapok fiber can be used as a low-cost alternative for the removal of residual oil from palm oil mill effluent (POME). Keywords: Ceiba pentandra; Residual oil; Packed-bed column; Factorial design. (Received 12.10.2021 Accepted 27.08.2021) [9]. Typical characteristics of POME have generally been described by[10,11] Different methods have been applied by researchers to treat oily wastewater such as coagulation [8,12,13], adsorption [1,14,4,15], flotation [16,17 18] and membrane filtration [19] Among all the methods, adsorption is an environmental friendly and low-cost method that requires simple technology, and is becoming the method of choice. Different materials had been investigated for the removal of oil such as chitosan [5], barley waste [6], activated carbon[20] and bentonite/organoclay [21].Oil-absorbing material is generally considered as most effective for cleaning up and collecting the spilled oil, and basically they can be divided into three types: inorganic mineral materials, synthetic organic polymers and organic natural materials[22]. Organic natural materials involve many agricultural products like sawdust, cotton fiber, kapok INTRODUCTION Oily water contamination from industries has been a major problem due to the effects on housing wastewater runoff. [1,2]. Palm oil processing is the major oil industry in Malaysia, which annually produces a huge amount of wastewater known as palm oil mill effluent (POME). In 2008, the production of palm oil in Malaysia was individually recorded as 16.3 million tons [3,4] and approximately 2.5–3.5 tons of POME is generated for each ton of crude palm oil produced [5]. POME contains oil, phospholipids and surfactants in the emulsified form for which treatment poses a real problem due to its high stability [6,7,8]. Generally, POME contains as high as 6,000 mg/L of oil, while according to the Malaysian Department of Environment (DOE), the oil discharge limit is 50 mg/L 605 Pakistan Journal of Science (Vol. 73 No. 3 September, 2021) and were measured by colorimetric method in a spectrophotometer at 420 nm (Spectrophotometer DR 5000, HACH, USA) using COD vials (HACH, USA). Turbidity measurements were carried out using DR 2100 P Turbidimeter (HACH, USA). fiber, milkweed, kenaf and straw [22]. Among of those natural materials, kapok or Ceiba pentandra (L.) Gaertn has the advantages over traditional oil-absorbing materials: low cost, biodegradability, intrinsic hydrophobic characteristic and high sorption capacity [23,2]. Kapok fiber has attracted increasing interest as an oil-absorbing material due to its hollow structure and hydrophobic characteristics. Kapok fiber exhibited good water repellency, high oil adsorption capability, and well reusable characteristics, demonstrating its potential as an alternative for application in oil pollution control [22,23,24,25,2]. The main objective of this study was to investigate the applicability of kapok as a natural adsorbent material for the removal of CPO (Crude palm oil effluent) from oil water emulsion as residual oil from POME under continuous condition. Statistical experimental design and analyses: Multilevel factorial design of 16 experimental runs were carried out with all possible combinations of values for each experimental factor (x), packing density and flow rate, at low, medium and high levels (Table 1). Statistical analyses were performed using Statgraphic centurion version 7 (Rockville, USA). COD and turbidity were the evaluated responses. Pareto charts and contour surface responses were constructed to evaluate the interaction that has significant effect on the kapok packed-bed performance, which include the single and quadratic effect. Regression analysis was carried out based on a second-order polynomial equation as described by ( Eq.1) True values of the unknown parameters are represented by the βo, βi, βii, βij coefficients. The analysis of variance (ANOVA) was performed for identification of significant factors at p=0.05 MATERIALS AND METHODS Materials: Raw kapok material collected from Bota, Perak, Malaysia. Fibers were dry, light, fluffy and pale yellow in appearance. Before the experiment, the fibers were cleaned from dust lumps etc. Crude palm oil (CPO) was used as the experimental oil, and was collected from (FELCRA Nasaruddin.Oil Palm Mill). CPO represents the residual oil in POME. Its light yellow colour enable visual observation during oily water emulsion filtration. x x i 1 i 1 y   0    ii xi2    ii xi2    ij xi x j   i j (1) Experimental setup: An acrylic column measuring 2 cm in diameter and 15 cm in length was developed as a fiber packed-bed column. The overall experimental setup was same reported before [2,4]. The initial concentration of CPO and diesel was 4000 mg/L used as residual oil based on 4000 mg/L, oil and grease content in POME [5,7]. Fibers’ performance was analyzed by Chemical Oxygen Demand (COD) and turbidity changes before and after the treatment. Samples for COD and turbidity measurement were collected after the oil breakthrough. COD values (ppm) were measured by colorimetric method in a spectrophotometer at 420 nm (Spectrophotometer DR 5000, HACH, USA) using COD vials (HACH, USA).Turbidity measurements were carried out using DR 2100 P Turbidimeter (HACH, USA). Samples for COD and turbidity measurement were collected after the oil breakthrough. COD values (ppm), RESULTS AND DISCUSSION Effect of packing density and flow rate on chemical oxygen demand and turbidity: Kapok usage for oily water filtration was evaluated based on Chemical oxygen demand (COD) and turbidity. Maximum COD reduction was 99.9 % at flow rate 5ml/min and packing density 0.08 g/cm3 respectively and maximum turbidity reduction was 95.6 % at various flow rate 5ml/min and packing density 0.02 g/cm3 whic suggests a good agreement between experimental and predicted values as shown by table1. Low level of COD and turbidity were attributed to the reduced amount of CPO (crude palm oil) inside oilywater mixtures. This proves the excellent selectivity of kapok for oil over water similar observation was reported by [2]. Table 1. Multilevel Factorial design And Responses For COD[ppm] and Turbidity [NTU] Runs 1 2 3 4 5 Independent vaiable Packing Flow rate density 0.08 5 0.04 15 0.06 10 0.06 5 0.08 20 COD [ppm] Experimental Predicted value value 99.9 99.8125 99.7 99.6175 99.6 99.6975 99.6 99.6675 99.8 99.8125 606 Turbidity [NTU] Experimental Predicted value value 92.9 92.221 94.7 94.139 92.9 93.134 93.5 93.7695 91.8 91.189 Pakistan Journal of Science (Vol. 73 No. 3 September, 2021) 6 7 8 9 10 11 12 13 14 15 16 0.02 0.02 0.02 0.08 0.04 0.02 0.06 0.04 0.04 0.06 0.08 5 15 20 15 10 5 15 20 5 15 10 99.3 99.5 99.5 99.8 99.6 99.4 99.8 99.7 99.5 99.7 99.8 99.3025 99.4825 99.5725 99.8125 99.5575 99.3925 99.7575 99.6775 99.4975 99.7275 99.8125 Statistical experimental design and analyses: The interaction of packing density and flow rate significantly influenced the COD and turbidity. The Pareto chart of COD for packing density and flow rate (Figure 1a) shows that packing density (p< 0.0001) has the most significant positive effect on COD. The Pareto chart of turbidity for packing density and flow rate (Figure 1b) shows that packing density (p< 0.0258) has the negative effect on turbidity. Second-order polynomial equations represent 95.7 95.3 95 91.2 94.9 95.6 92.2 94.2 95.2 92.7 90.7 the COD and turbidity for both variables. COD has the R2of 90.5 % and 93 % for turbidity. The mean absolute error percentage between experimental and predicted values of 0.04% and 0.33%, for COD and turbidity, suggest a good agreement between experimental and predicted values. The inclusions of the quadratic effect are the characteristics that differentiate the response surface designs and screening designs. Standardized Pareto Chart for COD Standardized Pareto Chart for Turbidity A:Packing density + A:Packing density - B:Flow Rate B:Flow Rate AB BB AA AA BB AB 0 2 4 6 Standardized effect 96.079 95.2045 95.236 91.2205 94.441 95.4855 92.8005 94.1495 95.0555 92.811 91.5645 8 10 + - 0 (a) 2 4 6 8 Standardized effect 10 12 (b) Figure 1. Pareto charts for standardized effects of flow rate and packing density on (a) COD and (b) turbidity reduction This quadratic effect causes the COD response surface to have a curved shape, which resembles a hill as shown in (Figure 2a) ` QA 607 Pakistan Journal of Science (Vol. 73 No. 3 September, 2021) Estimated Response Surface 99.8 COD 99.7 99.6 99.5 99.4 99.3 0.02 0.03 0.04 0.05 0.06 0.07 0.08 Packing density COD 99.3-99.36 99.36-99.42 99.42-99.48 99.48-99.54 99.54-99.6 99.6-99.66 99.66-99.72 99.72-99.78 20 99.78-99.84 17 14 99.84-99.9 11 8 99.9-99.96 Flow Rate 5 Turbidity 99.9 Estimated Response Surface 97 96 95 94 93 92 91 0.02 0.03 0.04 0.05 0.06 0.07 0.08 Packing density Turbidity 91.0-91.6 91.6-92.2 92.2-92.8 92.8-93.4 93.4-94.0 94.0-94.6 94.6-95.2 95.2-95.8 20 95.8-96.4 17 14 96.4-97.0 11 8 Flow Rate 97.0-97.6 5 (a) (b) Figure 2. (a) Response surface contour plot for COD (b) Response surface contour plot for turbidity. The maximum COD reduction was predicted achievable at 0.08 g/cm3 packing density and 5 mL/min flow rate which were within the range tested. Based on the regression analyses, the R2 values of 90.5389 for COD not only implied a good agreement between the experimental data and calculated data, but also a better fitness than the model for turbidity (Figure 2b). At lower packing density, the interferer distance inside the kapok column is higher, which increases the size of the effective flow channels as compared to higher packing density. Hence, the availability of pores to entrap the emulsified oil determines the capability of the kapok column to reduce the final turbidity. All of the four packing densities have high percentage of void fractions 95.6%, at 0.08 g/cm3packing density. These small discrepancies of void fraction inside the kapok column may be the main factor behind the insignificant effect of packing density, and flow rate on turbidity. In another studies with much different packing densities of kapok, a filtration efficiency of 99.9% oil removal has been reported [2,25]. However, these experiments were conducted at the different flow rate as compared to our study that applied different packing densities and flow rates. All these results confirmed the superior physicochemical characteristic of kapok for removal of residual oil from POME, and exerted far greater influence on packing density and flow rates in reducing COD and turbidity. excellent capability to reduce COD and turbidity of effluent contaminated with oil. REFERENCES [1] A. Pasila, A biological oil adsorption filter. Marine pollution bulletin,49(2004)1006-1012. [2] A. U. Rahmah, M. A. Abdullah, Evaluation of Malaysian Ceibapentandra (L.) Gaertn.for oily water filtration using factorial design,Desali.266 (2011)51-55. [3] K. Y. Foo, B. H. Hameed. 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