The Effects of Trans-Esterification of Castor Seed Oil Using Ethanol, Methanol and their Blends on the Properties and Yields of Biodiesel

Transcription

1 Inernaional Journal of Engineering and echnology Volume 2 No. 10, Ocober, 2012 he Effecs of rans-eserificaion of Casor Seed Using Ehanol, Mehanol and heir Blends on he Properies and s of Efeovbokhan, Vincen Enoniemonria 1, Ayoola Ayodeji 1, Anawe Paul Apeye Lucky 2,Oeri Ogheneofego 1 1 Deparmen of Chemical Engineering, Covenan Universiy, Km 10 Idi-Iroko Road, Canaan Land, Oa, Nigeria. 2 Deparmen of Peroleum Engineering, Covenan Universiy, Km 10 Idi-Iroko Road, Canaan Land, Oa, Nigeria. ABSRAC he effecs of ehanol, mehanol and heir blends a differen percenage mixures on he properies and yields of biodiesel a varied rans-eserificaion imes and emperaures using sodium hydroxide as a base caalys have been invesigaed. A 70 o C, he opimum yields were: for ehanol 88.4%, 94.2%, 94.8%, and 95.2% and for mehanol, 90.6%, 95.6%, 96.0%, and 96.4% a 1 hour, 2 hours, 3 hours and 4 hours respecively. he biodiesel yields increased as ime of reacion progressed for boh solvens bu he yields obained from mehanol were generally higher han hose from ehanol. A mixure of boh solvens a 50% each produced he overall highes of biodiesel yield of 98.6% a 70 o C and in 4 hours compared o eiher solven used alone a he same ime and emperaure. he properies such as densiies, viscosiies, flash poins and pour poins of he biodiesels esed were found o conform o ASM sandards. he average values were as follows: densiies a, were , and g/cm 3 ; viscosiies (a 40 o C) were cS, cS and cS; flash poins were o C, o C and o C while for pour poins hey were o C, o C and -6 o C for ehyl, mehyl and ehyl/mehyl biodiesel respecively. Keywords: rans-eserificaion, Casor oil, Solvens blends, yields, Effec of emperaure and ime. 1. INRODUCION Mos of he world s energy needs are supplied hrough fossil fuel sources (peroleum, coal and naural gas). [1] Wih he curren environmenal concerns posed by fossil fuels and heir limied availabiliy, he search for alernaive energy such as hydroelecriciy, biomass, wind, nuclear, geohermal, hydrogen and solar energy is on he rise. And biodiesel has araced keen aenion from numerous researchers all around he world as a possible source of alernaive and renewable energy o replace or complemen pero-diesel. is renewable and does no conribue o global warming due o is closed carbon cycle. [2] I is non-oxic, biodegradable and an excellen subsiue for peroleum based diesel fuel. [3] can be produced by he reacion (ranseserificaion) of a vegeable oil or animal fa wih a low molecular weigh alcohol in he presence of a srong acid or base as caalys, his produces a mixure of fay acid alkyl esers (biodiesel) and glycerol. [1] Alhough, Alkali caalyzed rans-eserificaion has been mos frequenly [4, 5] used indusrially, mainly due o is fas reacion rae. he direc use of vegeable oils in fuel engines is problemaic. Due o heir high viscosiy (abou imes higher han diesel fuel) and low volailiy, hey do no burn compleely and form deposis in he fuel injecor of diesel engines. [6] here were problems of coking, carbon deposis due o incomplee combusion, oil ring sicking, hickening, lower volailiies, incorrec vapourizaion characerisics, lubricaing problems and high viscosiy. [1] his is why vegeable oils have o undergo rans-eserificaion process o overcome hese problems and o make hem useable and compaible wih diesel engines. Mos oil bearing seeds can serve as feedsock for biodiesel producion. Some of which include casor, jaropha, soybean, canola, wase vegeable oil, ec. rans-eserificaion involves he conversion of he oils o heir alkyl esers by reacion wih alcohol. And i has been he mos commonly used mehod for he producion of biodiesel. Ehanol and mehanol have been he common alcohols used in he rans-eserificaion of hese oils o biodiesel in he presence a base or an acid caalys. Unforunaely, no much research has been conduced a invesigaing he combined effec of boh alcohols in he rans-eserificaion of vegeable oils ino biodiesel. Differen vegeable oils especially hose common o a paricular localiy have been used. Rapeseed oil for insance, is he predominan feedsock for biodiesel producion in he European Union (EU) while soybean oil is predominan in he Unied Saes [7] and Canada. However, he use of oils from edible food crops for he producion of biodiesel is discouraged as shorages may arise in he long run. Developing counries like Nigeria canno afford o use edible oils o produce biodiesel as i would lead o acue food shorages. his is because larger populaion of her rural dwellers is mere subsisence farmers ha sill depend on hoe and culass raher han mechanized farming. Nigeria is blessed wih a hos of non-edible oils such as rubber seed, jaropha and casor oils which should be exploied. Hence casor oil was chosen as feedsock because i is non-edible and would 1734

2 Inernaional Journal of Engineering and echnology (IJE) Volume 2 No. 10, Ocober, 2012 no compee wih food crops alleviaing concerns abou food shorages ha may arise from he producion of biodiesel from food crops. he oil conen of casor seed has been found o be beween 46-55% by weigh [8] and is relaively high compared o soybean (20%) and rapeseed (40%). [9] Casor seed (Ricinus communi) is a species ha belongs o he Euphorbiaceae family. he common names are casor oil plan, and Palma Chrisi. I has is origin in Africa bu can be found in ropical and subropical counries of he world. he casor plan is droughresisan and can hrive in arid condiions. [10] I is nonedible as i conains ricin, a poisonous proein subsance. [11] Casor oil also known as or ricinus oil conains approximaely 90% of ricinoleic acid, [12] which makes he oil o be readily solubiliy in alcohol a room emperaure. [13,14] Whereas, oher vegeable oils have differen composiions of fay acids and are usually insoluble in alcohol a room emperaures, casor oil dissolves easily in alcohol, eher, glacial aceic acid, chloroform, carbon [8, 15] sulfide, and benzene. Casor oil is viscous, pale yellow, non-volaile and non-drying oil wih mild odour and a bland ase. [9, 11] I has a boiling poin of 313 C and has a densiy of 961 kg/m 3. [16] he casor biodiesel has very ineresing properies (very low cloud and pour poins) ha show ha his fuel is very suiable for use in exreme low emperaures (e.g. winer). 2. MEHODOLOGY 2.1 Insrumen used: Anon paar densiy meer DMA 38, hermosaic viscosiy bah, Auomaed Pensky- Marens closed cup flash poin eser, poin bah, 2.2 Apparaus used: Ho plae magneic sirrer, reor sands, buree, pipee, 500mL separaing funnel, condensaion uni, hermomeer, 50mL measuring cylinder, 500mL hree-neck fla boom flask, 250mL and 500mL beakers, 250ml conical flask and waer hose, were provided by he Deparmen of Chemical Engineering, Covenan Universiy, Oa Nigeria. 2.3 Reagens used: Casor oil, ehanol, mehanol, hydrochloric acid, sodium hydroxide pelles, were purchased from Angos Nigeria Limied, Lagos sae, Nigeria. he disilled waer was provided by Chemical Engineering Deparmen, Covenan Universiy, Oa Nigeria. All experimens were carried ou in he Chemical Engineering laboraory, Covenan Universiy, Oa, Nigeria. 2.4 Procedure Experimenal Se-up he 500mL hree-neck fla boom flask (he reacor) was se-up wih he middle opening (or neck) carrying a reflux condensaion uni, one of he wo side arms carried he hermomeer and he second side arm carried a ground sopper which served as feed poin o he reacor. he seup was mouned on he ho plae magneic sirrer. he condenser was in-urn conneced o a ap for in- and ouflow of cold waer o preven loss of alcohol during he rans-eserificaion reacions rans-eserificaion of he Casor his was divided in o hree pars namely; ranseserificaion of he oil using ehanol, mehanol and hen a combinaion of he wo alcohols a predeermined raios. 46.5g of ehanol (absolue) and 50.0g of he oil were firs measured in wo separae beakers ha have been previously washed and dried. 0.5g (1% by weigh) of he caalys (pure poassium hydroxide) was weighed and dissolved in he ehanol and he resulan soluion was hen charged ino he reacor and pre-warmed. he sirrer speed was se o 4rps (revoluion per second) and he oil which was also pre-warmed in a separae beaker was carefully added o he sodium ehoxide in he reacor and was hen subjeced o heaing a differen emperaures and varied imes of rans-eserificaion reacions. A he end of he reacion, he reacion mixure was poured ino a separaing funnel and lef o sand for approximaely 24hours, his was o allow for disinc phase separaion. he phases were hen separaed o recover he biodiesel for furher purificaion and drying. he above procedure was repeaed bu insead of ehanol, mehanol and a combinaion of ehanol-mehanol mixures were used. 3. RESULS AND DISCUSSION OF RESULS 3.1 Effec of emperaure and ime on rans-eserificaion reacions were carried ou a varying emperaures of 55 o C, 60 o C, 65 o C and 70 o C using mehanol and ehanol and a combinaion of he wo alcohols. Figures 3.1, 3.2 and 3.3 illusrae he effec of emperaure on he yield of biodiesel. For ranseserificaion wih ehanol he yield of biodiesel progressively increased wih emperaure as he ime was held consan. A consan ime of 1 hour, he biodiesel yield was 64% a 55 o C, 80% a 60 o C, 86% a 65 o C, and 88.4% a 70 o C. he biodiesel yield also increased as he ime of reacion increased a he same emperaures invesigaed. A consan ime of 2 hours, he biodiesel yield was 75% a 55 o C, 85.6% a 60 o C, 89.6% a 65 o C, and 94.2% a 70 o C. Furhermore, a consan ime of 3 hours, he biodiesel yield was 88.4% a 55 o C, 89.6% a 60 o C, 92% a 65 o C, and 94.8% a 70 o C whereas, a consan ime of 4 hours, he biodiesel yield was 85.2% a 55 o C, 91.8% a 60 o C, 94% a 65 o C, and 95.2% a 70 o C. Exacly he same rend was also observed for ranseserificaion of casor oil wih mehanol excep ha he 1735

3 Inernaional Journal of Engineering and echnology (IJE) Volume 2 No. 10, Ocober, 2012 bio-diesel yields generally were higher for mehanol han wih ehanol a he same reacion imes and emperaures considered. he highes percenage yield of biodiesel was 96.2% wih mehanol rans-eserificaion compared o 95.2% obained from ehanol rans-eserificaion in 4 hours and a 70 o C. he converse is rue when ranseserificaion imes were varied and emperaures kep consan. For he ehanol-mehanol blends differen percenage raios, 0-100, 30-70, 40-60, 50-50, 60-40, and were used for he rans-eserificaion reacions. he opimum reacion condiions of 4 hours and emperaure of 70 o C were used. Figure 3.4 and able 3.9 show he yield of biodiesel from heir various blends used. he yield of biodiesel increased progressively from 96.4%, a 0:100 ehanol: mehanol blend, reaching a maximum of 99.6%, a 50:50 ehanol: mehanol blend before i began o decrease seadily o a value of 95.2% a 100:0 ehanol: mehanol blend. his gives an indicaion ha blending of alcohols resuls in higher biodiesel yield. From ables 3.1 o 3.9, he densiies of bio-diesel a range from g/cm 3 which conform o ASM sandard of g/cm 3. he densiies of he biodiesel produced from ehanol were wihin he range of wih an average value of , he biodiesel produced from mehanol had densiy values wihin he range wih an average value of while he biodiesel produced from he ehanol-mehanol blend had densiy values wihin he range From he resuls, i is clear ha he densiy produced from he ehanol-mehanol blend had he lowes densiy. Viscosiy values (a 40 o C) of all he biodiesel produced were wihin he range cS which conform o ASM sandard of cS. he viscosiy of he biodiesel produced form ehanol was wihin he range cS wih an average value of cS, while ha of he biodiesel produced from mehanol was wihin he range cS wih an average value of cS and he viscosiy of he biodiesel produced from he ehanol-mehanol blend was wihin he range cS wih an average value of cS. poin values of he biodiesel was wihin he range o C which conform o ASM sandard (>130 o C). he flash poin of he biodiesel produced form ehanol was wihin he range o C wih an average value of o C, he flash poin of he biodiesel produced from mehanol was wihin he range o C wih an average value of o C while he flash poin of he biodiesel produced from he ehanol-mehanol blend was wihin he range o C wih an average value of o C. poin values of he biodiesel were wihin he range -6-0 o C which also conform o ASM sandard. he pour poin of he biodiesel produced from ehanol was wihin he range -6-0 o C wih an average value of o C, while he pour poin of he biodiesel produced from mehanol was wihin he range -3-0 o C wih an average value of o C and he pour poin of he biodiesel produced from he ehanol-mehanol blend was - 6 o C. 4. CONCLUSION he rae of rans-eserificaion of casor oil increased wih reacion ime and emperaure. Higher yields were obained from he rans-eserificaion of casor oil wih mehanol compared o ehanol. However, is ranseserificaion wih blends of ehanol and mehanol gave higher yields compared o he yields obained from boh alcohols used alone. Equal percenage blend of 50: 50, ehanol: mehanol, gave he highes yield of 99.6%. he pour poin, flash poin, densiy a and viscosiy a 40 o C of he biodiesel produced were wihin he allowable limis se by he American Sociey for esing and Maerials (ASM) making casor oil a suiable feedsock for high qualiy biodiesel. he use of biodiesel as fuel provides useful soluions o various environmenal problems and will go a long way o amelioraing impending energy crises. I is renewable in naure, biodegradable, and will reduce emissions of green house gases. he use of casor oil as biodiesel feed sock should be grealy encourage because i is a non-edible crop and would no compee wih acreage dedicaed for food crops. REFERENCES [1] L.C. Meher, D. Vidya Sagar, S.N. Naik, echnical aspecs of biodiesel producion by ranseserificaion - a review, Cenre for Rural Developmen and echnology, Indian Insiue of echnology Delhi, India. [2] J. Sheehan, V. Camobreco, J. Duffield, M. Graboski, and H. Shapouri, Life cycle invenory of biodiesel andperoleum diesel for use in an urban bus, final repor for U.S. Dep. of Energy s Office of Fuel Developmen and he U.S. Dep. of Agriculure s Office of Energy, by he Naional Renewable Energy Laboraory, NREL SR (May 1998). [3] (Harun e al., 2006). Harun, M., M. Ali and I. Musafa Environmenally Friendly Diesel for Pakisan. Environ.Monior, 6: [4] Ayhan Demirbas, Producion from Vegeable s via Caalyic and Non-caalyic Supercriical Mehanol ranseserificaion Mehods, Deparmen of Chemical Engineering, Selcuk Universiy, Konya, urkey. [5] Freedman B, Buerfield RO, Pryde EH. ranseserificaion kineics of soybean oil. J Am Chem Soc ;63(10): [6] Demirbas A. fuels from vegeable oils via caalyic and non-caalyic supercriical alcohol ranseserificaions and oher mehods: a survey. Energy Convers Manage 2003; 44:

4 Inernaional Journal of Engineering and echnology (IJE) Volume 2 No. 10, Ocober, 2012 [7] Kinas, J.A..Producion of s from Muliple Feed socks and Properies of s and /Diesel Blends.Final Repor. Naional Renewable Energy Laboraory. (2003). [8] Dan Anderson, Derek Maserson, Bill McDonald and Larry Sullivan, Indusrial Plan Design and Engineering: Pracical Experience, Crown Iron Works Company, Minneapolis, USA. [9] D.S. Ogunniyi, Casor oil: A vial indusrial raw maerial, Deparmen of Chemisry, Universiy of Ilorin, Ilorin, Nigeria [10] Caye M. Drapcho, Nghiem Phu Nhuan, erry H. alker, Biofuels Engineering Process echnology [11] Marer A. D., Casor: Markes, Uilizaion and Prospecs, ropical Produc Insiue, G152, p , [12] Belrão, N. E. M. Informações sobre o, em Especial Feio com o Óleo de Mamona Comunicado écnico (12/2003), EMBRAPA. [13] Carmen Leonor Barajas Forero, from casor oil: a promising fuel for cold weaher, Deparmen of Hydraulic, Fluids and hermal Sciences, Francisco de Paula Sanander Universiy, Columbia. [14] Mohammed H. Chakrabari and Rafiq Ahmad, ranseserificaion Sudies on Casor as a Firs Sep owards Is Use in Producion, Deparmen of Environmenal Engineering, NED Universiy of echnology, Pakisan. [15] Carmen Leonor Barajas Forero, from casor oil: a promising fuel for cold weaher; Deparmen of Hydraulic, Fluids and hermal Sciences Francisco de Paula Sanander Universiy Avenida Gran Colombia No.12E-96 Cucua (Colombia) clbarajas@bari.ufps.edu.co [16] Nivea De Lima Da Silva*, Cesar Baisella, Rubens Maciel Filho., Maria Regina Wolf Deerminaion of Casor Molecular Weigh by Vapour Pressure Osmomery echnique, Laboraory of Separaion Process Developmen, School of Chemical Engineering, Brazil. able 3.1: Resuls of rans-eserificaion wih Ehanol 55 o C Raw maerials Condiions Producs Properies Casor Ehanol Densiy a Viscosi y a 40 o C A A A A able 3.2: Resuls of rans-eserificaion wih Ehanol 60 o C Raw Maerials Condiions Producs Properies Casor Ehanol Densiy a Viscosiy a 40 o C A A A A able 3.3: Resuls of ranseserificaion wih Ehanol 65 o C Raw maerials Condiions Producs properies Casor Ehanol Densiy a Viscosi y a 40 o C 1737

5 Inernaional Journal of Engineering and echnology (IJE) Volume 2 No. 10, Ocober, 2012 A A A A able 3.4: Resuls of ranseserificaion wih Ehanol 70 o C Raw maerials Condiions Producs properies Casor Ehanol Biodiese l Densiy a Viscosi y a 40 o C A A A A Casor able 3.5: Resuls of rans-eserificaion wih Mehanol 55 o C Raw maerials Condiions Producs properies NaO Densiy a Viscosiy a Mehanol H 40 o C B B B B Casor able 3.6: Resuls of rans-eserificaion wih Mehanol 60 o C Raw maerials Condiions Producs properies Mehanol NaO H Biodiese l Densiy a Viscosiy a 40 o C B B B B able 3.7: Resuls of rans-eserificaion wih Mehanol 65 o C Raw maerials Condiions Producs properies Casor Mehano Densiy Viscosiy a 1738

6 Inernaional Journal of Engineering and echnology (IJE) Volume 2 No. 10, Ocober, 2012 l a 40 o C B B B B able 3.8: Resuls of rans-eserificaion wih Mehanol 70 o C Caso r Raw maerials Condiions Producs properies Mehanol Densiy a Viscosiy a 40 o C B B B B Casor able 3.9: Resuls of rans-eserificaion wih Mehanol 70 o C Raw maerials Condiions Producs properies Flas Densiy Viscosi h NaO Biodie Biodies a y a Poin Ehanol Mehanol H sel el 40 o C C C C C C C C Poin 1739

7 Inernaional Journal of Engineering and echnology (IJE) Volume 2 No. 10, Ocober, hr 2hrs 3hrs 4hrs Reacion emperaure ( o C) Fig.3.1: Ehyl bio-diesel yield a varied reacion emperaures and fixed imes hr 2hrs 3hrs 4hrs Reacion emperaure ( o C) Fig.3.2: Mehyl bio-diesel yield a varied reacion emperaures and fixed imes 1740

8 % biodiesel yield % biodiesel yield Inernaional Journal of Engineering and echnology (IJE) Volume 2 No. 10, Ocober, % biodiesel yield a 55 deg C % biodiesel yield a 60 deg C % biodiesel yield a 65 deg C % biodiesel yield a 70 deg C ime of reacion Fig.3.3: Ehyl bio-diesel yield a varied reacion imes and fixed emperaures % biodiesel yield a 55 deg C % biodiesel yield a 60 deg C % biodiesel yield a 65 deg C % biodiesel yield a 70 deg C ime of reacion Fig.3.4: Mehyl bio-diesel yield a varied reacion imes and fixed emperaures 1741

9 Inernaional Journal of Engineering and echnology (IJE) Volume 2 No. 10, Ocober, 2012 Fig.3.5: Effec of Ehanol: Mehanol Blend on Percenage Bio-Diesel a 70 o c and 4 Hours Reacion ime 1742