PRODUCTION OF BIO-DIESEL FROM WASTE COOKING OIL BY USING HOMOGENEOUS CATALYST

Int. J. Chem. Sci.: 12(3), 2014, 941-951 ISSN 0972-768X www.sadgurupublicatins.cm PRODUCTION OF BIO-DIESEL FROM WASTE COOKING OIL BY USING HOMOGENEOUS CATALYST ALI MOHAMMED SALEH * and KAVITA KULKARNI Department f Chemical Engineering, Bharati Vidyapeeth Deemed University, Cllege f Engineering, PUNE (M.S.) INDIA * Authr fr crrespndence; E-mail: kskulkarni@bvucep.edu.in; Ph.: 020-24107391; Fax: 020-24372998 ABSTRACT Waste cking il (WCO) was used as bi-diesel feedstck. WCO with methanl was heated at different temperature with the help f cnventinal mechanical stirrer. Ptassium hydrxide (KOH) and sdium hydrxide (NaOH) was used as catalyst. The effect f different peratinal parameters such as, catalyst lading, reactin temperature, and reactin time were evaluated. Frm the results, it was clear that the bi-diesel fuel prduced frm waste cking il (WCO) was within the recmmended standards f bidiesel fuel. The trans-esterificatin reactin using ptassium hydrxide (KOH) catalyst was mre effective than sdium hydrxide (NaOH) catalyst fr the higher yields cnversin. With ptassium hydrxide 0.4 wt. %, yield was 94.4% and cnversin was 97.76% at 60 C, in three hurs reactin time. Key wrds: Bi-diesel, Waste cking il, Trans-esterificatin reactin, Hmgeneus catalyst. INTRODUCTION With the increase in ppulatin, there has been cnsistent demand in every arena fr fuel. Human life is largely dependent n material things. These material things are prduced and transprted with the help f fuel driven mediums, but fuel is largely amassed in very few cuntries f the wrld especially middle-east cuntries. With the grwth f the ecnmy and cnsumptin, the gvernments f many cuntries f the wrld are striving hard t find an alternative t the fssil fuel, which is slw & gradually depleting. Mrever, the fssil fuel leads t pllutin and bad effects n human health. Keeping this int mind, bi-diesel wuld be natural chice fr cuntries largely dependent n imprt s as t utilize the natural resurces in the ptimum manner fr ther basic needs. 1 An alternative fuel fr diesel engines and fr heating il burners culd be vegetable il. Fr engines designed t burn petrl, diesel fuel, vegetable ils has high viscsity must be lwered t run these engines and

942 A. M. Saleh and K. Kulkarni: Prductin f Bidiesel frm. heating il burners; therwise will face many prblems (A) Starter prblem (B) Incmplete cmbustin (C) Carbn build up n the pistn (D) Engines kncking (E) Damage the engines 2. When the mn-alkyl esters f fatty acids derived frm vegetable ils r animal ils, it is called Bidiesel. Bi-diesel was synthesized frm edible (Veg r animal) ils and nn edible (Veg r animal) ils 3. Fr bi-diesel prductin edible vegetable ils such as canla, sybean, sun flwer and crn were used and culd be used as diesel substitutes 4,5. Bidiesel was prduced frm the nn-edible il f Karanja by trans-esterificatin f the waste karanja il with methanl in the presence f NaOH as catalyst. In this reactin, cnversin f bidiesel was 92%. Waste cking il (WCO) is cheaper than edible vegetable il s can be used fr bidiesel prductin 6. Waste cking il frm restaurants was used t reduce the cst f feedstck t prduce bidiesel. By use f base catalyst cnversin was 95%. Effect f different variables such as methanl-t-il rati, acid-t-il rati, reactin temperature was studied fr acid catalyzed pretreatment f crude Jatrpha il 7,8. When the feedstck has high free fatty acid t prduce bidiesel with less acid value tw steps had been fllwed in which first was acid catalyst fr ester-factin and secnd step was base catalyst fr trans-esterificatin 9. The prductin f bidiesel was studied frm waste cking il feed stck in ultrasund cavitatin, cnventinal mechanical stirrer, alchl and different catalysts weight (0.5%, 0.75% and 1%). High yield (94.2%) was btained frm waste cking il thrugh ultrasund cavitatin 10. Different aspects such as ptimizatin f methanl fr trans-esterificatin, design parameters were studied using waste cking il as feed stck 11-13. In this wrk, experiments were carried ut fr the bidiesel prductin frm waste cking il (WCO) using cnventinal trans-esterificatin prcesses. Waste cking il (WCO) cntains high FFA cntent, s that alkali transesterificatin was emplyed using methanl and (KOH & NaOH) catalysts. This wrk aims t evaluate the effect f different perating parameters n the methyl ester yield. Materials and methds EXPERIMENTAL 15 Liters waste cking il (WCO) frm Ruby Hall Clinic, Pune, was cllected. Ptassium hydrxide (KOH), sdium hydrxide (NaOH) flakes and methanl (AR Grade) were used. The mixture was stirred at the cnstant speed fr all experiments. All experiments f trans-esterificatin reactin were carried ut in a 2 Liters rund-bttm flask endwed with a water-cled reflux cndenser. Heating mantle with cnventinal mechanical stirrer methd was used fr heating the mixture in the flask. Equipment Trans-esterificatin experiments were carried ut in a 2 Liters three-necked (first ne fr therm well and secnd fr stpper third fr stirrer) batch reactr. With a cnventinal

Int. J. Chem. Sci.: 12(3), 2014 943 mechanical stirrer, a thermcuple cnnected t a heater plate, and tw necks, ne is stpper t remve samples and t feed the raw materials such as (waste cking il, catalyst and methanl) and anther fr the thermmeter (therm well), respectively. The experimental set-up is shwn in Fig. 1. Experimental prcedure Fig. 1: Experimental set-up fr bi-diesel prductin The trans-esterificatin reactin was carried ut in 2 Liters reactin flask with mechanical stirrer, thermmeter, stpper and heating mantle. The trans-esterificatin prcess was studied fr catalyst (0.4 wt. %, 0.7 wt. % and 1.0 wt. % KOH), at a reactin time (1-3 h) at 50, 60, 70 and 80 ± 2 C and at atmspheric pressure. Feed was made free frm water, as any water r misture in the system will cnsume sme f the catalyst and slw the trans-esterificatin reactin. Hence, Feed (WCO) was preheated after cllectin at 110 ± 2 C in rder t ensure n water in the waste cking il (WCO). Waste cking il (WCO) sample was weighed carefully n weighing machine. The sample was fund t be 400 ml waste cking il (WCO), 100 ml methanl and 0.4 wt. % f KOH. The same was fllwed fr NaOH. The mixture was heated up t 60 ± 2 C with cntinuus agitatin fr 3 hr. The reactin mixture was feculent. The prduct was kept in the separating funnel fr 12 hrs. Tw phases having a different density were frmed as a result f trans-esterificatin. Upper layer cnsisted f bi-diesel, alchl and sap and dwn layer cnsisted f glycerin, excess alchl, catalyst, impurities and traces f unreacted il. Tw layers were separated and measured. Purificatin f upper layer was dne i.e. alchl was remved by heating mixture at 80 C and washed with warm distillated water three times.

944 A. M. Saleh and K. Kulkarni: Prductin f Bidiesel frm. RESULTS AND DISCUSSION A base catalyst was studied fr 0.4 wt. %, 0.7 wt. % and 1 wt. % KOH and same fr NaOH. Figure 2 and 4 shwed the effect f base catalyst n the yield. The maximum yield was btained fr waste cking il (WCO) at 0.4 wt. % f catalyst. Trans-esterificatin reactin culd nt ccur prperly with an insufficient amunt f a base catalyst was prved during experimentatin. Yield was slightly decreased abve 0.4% f catalyst. Mass transfer became mre imprtant at higher cncentratins. The temperature effect n the yield was studied fr 50 C, 60 C, 70 C and 80 C at atmspheric pressure. The maximum yield was achieved at a temperature f 60 C fr waste cking il (WCO). Frm the result shwn in the Table 1, the maximum yield was 94.4% and cnversin was 97.76% at 60 C and 0.4 wt. % KOH cncentratin. Table 1: Yield and cnversin f bi-diesel prduced frm waste cking il by using KOH catalyst Sample N. Temperature ( C) Catalyst (wt. %) Yield (%) Cnversin (%) 1 50 0.4 94.38 97.02 2 50 0.7 88.8 91.06 3 50 1.0 86.4 88.08 4 60 0.4 94.4 97.76 5 60 0.7 93.1 96.27 6 60 1.0 87.3 90.3 7 70 0.4 90 91.8 8 70 0.7 87.39 91 9 70 1.0 86.5 88 10 80 0.4 90.9 91.05 11 80 0.7 87.8 89.5 12 80 1.0 86.5 88.8 Similarly frm Table 2, the maximum yield 93.45% and cnversin 96.47% was btained at 60 C and 0.4 wt. % NaOH cncentratins. Frm Figures 2-5, it can be cncluded that by using KOH catalyst, the bi-diesel yield and cnversin was greater than the NaOH catalyst. The suitable perating cnditins were btained at 60 C reactin temperature, 3 hr

Int. J. Chem. Sci.: 12(3), 2014 945 reactin time and 0.4 wt. % KOH catalyst cncentratins. Methyl ester cnversin was gd as the temperature was increased. The perating temperature fr reactin was higher than that f biling pint f methanl s the alchl was evaprated and thus resulted in fewer yields. Table 2: Yield and cnversin f bi-diesel prduced frm waste cking il by using NaOH catalyst Sample N. Temperature ( C) Catalyst (wt. %) Yield (%) Cnversin (%) 1 50 0.4 90.17 94.04 2 50 0.7 80.68 82.12 3 50 1.0 82.09 85.09 4 60 0.4 93.45 96.47 5 60 0.7 86.6 89.57 6 60 1.0 86.4 88.08 7 70 0.4 91.4 96.27 8 70 0.7 89.9 92.55 9 70 1.0 84.02 85.09 10 80 0.4 89.8 92.5 11 80 0.7 88.3 91.05 12 80 1.0 84.5 87.4 Bidiesel yield (%) 96 94 92 90 88 50 C 60C 70 C 80 C 86 0.4 0.5 0.6 0.7 0.8 0.9 1.0 KOH Cnc. (wt. %) Fig. 2: Effect f KOH catalyst n bi-diesel yield

946 A. M. Saleh and K. Kulkarni: Prductin f Bidiesel frm. Cnversin (%) 98 96 94 92 90 50 C 60C 70 C 80 C 88 0.4 0.5 0.6 0.7 0.8 0.9 1.0 KOH Cnc. (wt. %) Fig. 3: Effect f KOH catalyst n cnversin Bidiesel yield (%) 94 92 90 88 86 84 82 80 0.4 0.5 0.6 0.7 0.8 0.9 1.0 NaOH Cnc. (wt. %) 50 C 60C 70 C 80 C Fig. 4: Effect f NaOH catalyst n bi-diesel yield Cnversin (%) 98 96 94 92 90 88 86 84 82 0.4 0.5 0.6 0.7 0.8 0.9 1.0 NaOH Cnc. (wt. %) 50 C 60C 70 C 80 C Fig. 5: Effect f NaOH catalyst n cnversin

Int. J. Chem. Sci.: 12(3), 2014 947 In Table 6, it is shwn that elemental cntent f methyl ester (bi-diesel) fuel prduced frm waste cking il was different than this elemental cntent fr petrl, diesel fuel. These differences in elemental cntents between bi-diesel and the petrl diesel cause difference in the characteristics. The Grss Calrific Value (GCV) f petrl diesel fuel accrding t Indian standard is 10000 cal/g and in experimental study it was fund 9870 cal/g fr bi-diesel. Presence f the elements Ca, Mg, K and Na in less amunt fr bi-diesel than cnventinal diesel fuel, therefre the effect f bi-diesel n engine will be less than the effect f cnventinal diesel. Table 3: Yield and cnversin f bi-diesel prduced frm waste cking il by using 0.4 wt. % KOH catalyst at 60 C Sample N. Time (Hr) Yield (%) Cnversin (%) 1 3 94.4 97.76 2 2 92.3 93.2 3 1 93.48 95.53 Table 4: Yield and cnversin f bi-diesel prduced frm waste cking il by using 0.4 wt. % NaOH catalyst at 60 0 C Sample N. Time (Hr) Yield (%) Cnversin (%) 1 3 93.45 96.47 2 2 90.2 94 3 1 91.5 95.2 Table 5: Prperties f methyl ester frm waste cking il Sample Clud pint ( C) ASTM D2500 Test jar methd Pur pint ( C) ASTM D7683 Test jar methd Flash pint ( C) Pensky Marten flash pint apparatus Viscsity (cp) Brkfield DVII + Pr viscmeter 1 11-3 126 6.3 2 10-2 130 7.49 3 10-4 140 6.36 4 4-3 145 4.77 Cnt

948 A. M. Saleh and K. Kulkarni: Prductin f Bidiesel frm. Sample Clud pint ( C) ASTM D2500 Test jar methd Pur pint ( C) ASTM D7683 Test jar methd Flash pint ( C) Pensky Marten flash pint apparatus Viscsity (cp) Brkfield DVII + Pr viscmeter 5 5-1 128 4.92 6 6-1 120 5.01 7 0-4 108 4.58 8 4-2 98 4.43 9 12-2 123 4.74 Table 6: Elemental analysis f methyl ester frm waste cking il S. N. Test descriptin Test result fr sample 1 Test methd 1 Aluminium cntent ppm 0.5 ASTM D 4737-10 2 Antimny cntent ppm < 0.1 ASTM D 6595-11 3 Barium cntent ppm < 0.1 ASTM D 6595-11 4 Brn cntent ppm < 0.1 ASTM D 6595-11 5 Cadmium cntent ppm < 0.1 ASTM D 6595-11 6 Calcium cntent ppm 4.5 ASTM D 6595-11 7 Chrmium cntent ppm 0.2 ASTM D 6595-11 8 cpper cntent ppm 8.6 ASTM D 6595-11 9 Irn cntent ppm 0.4 ASTM D 6595-11 10 Lead cntent ppm 11.5 ASTM D 6595-11 11 Magnesium cntent ppm 0.3 ASTM D 6595-11 12 Manganese cntent ppm < 0.1 ASTM D 6595-11 13 Mlybdenum cntent ppm 2.1 ASTM D 6595-11 14 Nickel cntent ppm 0.1 ASTM D 6595-11 15 Phsphrus cntent ppm < 0.1 ASTM D 6595-11 16 Ptassium cntent ppm 146 ASTM D 6595-11 17 Silicn cntent ppm 4.1 ASTM D 6595-11 Cnt

Int. J. Chem. Sci.: 12(3), 2014 949 S. N. Test descriptin Test result fr sample 1 Test methd 18 Silver cntent ppm < 0.1 ASTM D 6595-11 19 Sdium cntent ppm 5.3 ASTM D 6595-11 20 Tin cntent ppm < 0.1 ASTM D 6595-11 21 Titanium cntent ppm < 0.1 ASTM D 6595-11 22 Vanadium cntent ppm < 0.1 ASTM D 6595-11 23 Zinc cntent ppm 13 ASTM D 6595-11 24 Grss calrific value cal/g 9870 IS 1448(P6)2013 Bidiesel yield (%) 94.5 94.0 93.5 93.0 92.5 92.0 91.5 91.0 90.5 90.0 1.0 1.5 2.0 2.5 3.0 Time (hr) KHO (0.4 wt.) NaOH (0.4 wt.) Fig. 6: Effect f time n yield at 60 C 98 Cnversin (%) 97 96 95 94 KHO (0.4 wt.) NaOH (0.4 wt.) 93 1.0 1.5 2.0 2.5 3.0 Time (hr) Fig. 7: Effect f time n cnversin at 60 C

950 A. M. Saleh and K. Kulkarni: Prductin f Bidiesel frm. CONCLUSION Results shwed that using KOH catalyst the bi-diesel yield and cnversin btained was greater than the NaOH catalyst. With ptassium hydrxide reactin, less sap frmatin was btained than sdium hydrxide. The suitable perating cnditins were btained at 60 C reactin temperature, 3 hr reactin time and 0.4 wt. % KOH cncentratins. Reductin in the reactin time was effected n the bi-diesel characteristic such as viscsity and specific gravity as present slight unreacted raw materials (WCO). Als, it was cncluded that increasing the catalyst cncentratin bi-diesel yield was reduced due t the frmatin f sap. Bi-diesel characteristics like viscsity, flash pint, clud pint, specific gravity, grss calrific value, elemental analysis and pur pint were cmparable t diesel. REFERENCES 1. C. L. Petersn DLR, Emissins Tests with an On-Rad Vehicle Fueled with Methyl and Ethyl Esters f Rapeseed Oil, in ASAE Internatinal Winter Meeting, Paper N. 946532 (1994). 2. W. Xu, L. Ga, S. Wang and G. Xia, Bidiesel Prductin in a Membrane Reactr using MCM-41 Supprted Slid Acid Catalyst, Bi-resurce Technlgy, 159, 286-291 (2014). 3. Z. Al-Hamamre and J. Yamin, Parametric Study f the Alkali Catalyzed Transesterificatin f Waste Frying Oil fr Bidiesel Prductin, Energy Cnversin and Management, 79, 246-254 (2014). 4. A. Dhar, R. Kevin and A. K. Agarwal, Prductin f Bidiesel frm High-FFA Neem Oil and its Perfrmance, Emissin and Cmbustin Characterizatin in a Single Cylinder DICI Engine, J. Fuel Prc. Technl., 97, 118-129 (2012). 5. B. Freedman, E. H. Pryde and T. L. Munts, Variables Affecting the Yields f Fatty Esters frm Transesterified Vegetable Oils, J. Am. Oil Chem. Sc., 61(10), 1638-1643 (1984). 6. H. J. Yadav, P. P. Rathd and S. S. Arvind, Bidiesel Preparatin Frm Karanja Oil : An Overview, Int. J. Adv. Engg. Res. Studies, 1(3), 42-46 (2012). 7. M. Canakci and J. Van Gerpen, Bidiesel Prductin Frm Oils and Fats with High Free Fatty Acids, J. American Sc. Agri. Eng., 44(6), 1429-1436 (2001).

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