European International Journal of Science and Technology

Vol. 2 No. 2

March 2013

ETHYL BIODIESEL: MICROWAVE IRRADIATION AIDING ETHANOLYSIS OF WASTE COOKING OIL

Sandro L. Barbosa,a, Sa!"o E. O. M"randa,a S#an$%" I. K$%"n,b Gabr"%$a R. H&r#ado,% Adr"ano C. M. Baron",' and M"(&%$ ). Dabdo&bd

Department of Pharmacy - Biochemistry, Universidade Federal dos Vales do Jequitinhonha e ucuri, !" da #l$ria, 1%& 'entro, Diamantina, #, '(P, Bra)il, '(P *+1,,-,,,e - mail. sandro"/ar/osa0ufv1m"edu and savio2eom0hotmail"com 3 'orrespondin4 author" 5el". 677-*%-*7*212*8- fa9. 677-*%-*7*212*8Department of #eneral and :nor4anic 'hemistry, :nstitute of 'hemistry, ;<o Paulo ;tate University = U>(;P, !" Prof" Francisco De4ni s?n, @uitandinha, Araraquara, ;P, Bra)il, '(P 18%,,-+,,- ( - mail. stanlei0iq"unesp"/r Department of 'hemistry and Pharmacy, Universidade Federal do ato #rosso do ;ul, 'idade UniversitBria, 'ampo #rande, ;, Bra)il, '(P &+,&,-+,,(-mail. 4a/ihurt0yahoo"com and adriano0nin"ufms"/r Department of 'hemistry, Faculdade de Filosofia, 'iCncias e Detras de !i/eir<o Preto, University of ;<o Paulo, Av" Bandeirantes *+,,, onte Ale4re, '(P 18,8,-+,1, !i/eir<o Preto, ;P, Bra)il(-mail. mi41oda/0usp"com"/r
d e /

Abs#ra'# We de cri!e a "ethodology to produce !iodie el of e#cellent $uality fro" %a te coo&ing oil' Na() cataly t and ethanol' !y accelerating the tran e terification reaction %ith "icro%a*e irradiation fro" an un"odified hou ehold "icro%a*e o%en. The re ulting Wa te +oo&ing (il Ethyl E ter %ere e*aluated according to the phy ical and che"ical propertie de"anded !y regulatory tandard for !iodie el ' and a !rief di cu ion of the "eaning and cope of the e $uality control para"eter directly related to !iodie el i al o pre ented. ,ey%ord - Ethylic .iodie el/ Wa te +oo&ing (il/ Micro%a*e Irradiation/ .iotechnology/ 0uality +ontrol/ .iofuel. *. In#rod&'#"on :n 1%+E, !udolf Diesel introduced the first diesel en4ine, Fhich had efficiency in the order of 2EG" 5he fuel initially utili)ed Fas petroleum, folloFed in 1+,, /y ve4eta/le oils, /ut /ecause of economic reasons, mainly their hi4h cost and loF availa/ility compared to petroleum, plant-derived oils Fere eventually a/andoned as fuels H1-*I"
211

European International Journal of Science and Technology ISSN- 230123433

%%%.ce&info.org.u&5EIJST

5he difference /etFeen fossil diesel and ve4eta/le oils is mainly in the molecular Fei4ht of these tFo compounds, and also in the hi4her viscosity and density of ve4eta/le oil compared to the mineral product" Fossil diesel consists of hydrocar/ons Fith an avera4e num/er of 18 car/ons, Fhereas ve4eta/le oils consist of 4lycerol triesters Jthe product of condensation /etFeen 4lycerol and lon4-chain fatty acidsK" 5he side chains of these fatty acids have 1,-car/on atoms in the less-common, to 1% in the more-a/undant types" 5he molecular Fei4ht of ve4eta/le oils is appro9imately three times hi4her than that of fossil fuel H*,8I" 5he transesterification of ve4eta/le oils such as soy/ean or sunfloFer, and of animal fats or other tri4lycerides usin4 methanol or ethanol /reaLs doFn tri4lyceride molecules, producin4 a mi9ture of methyl or ethyl esters of the correspondin4 lon4-chain fatty acids, Fith 4lycerol as a co-product" 5he transesterification reaction occurs /etFeen the tri4lycerides and an alcohol in the presence of catalysts such as acids, alLalis, or en)ymes JlipasesK H7-%I" 5he molecular Fei4ht of these monoesters is similar to the molecular Fei4ht of fossil diesel" 5he similarities in /oth molecular Fei4ht and physical?chemical properties, such as loFer viscosity and density, have stimulated the use of these esters in compression i4nition en4ines as su/stitutes for fossil diesel, instead of ve4eta/le oils in natura H8,+I" Biodiesel fuel has the folloFin4 characteristics. it is virtually free of sulfur and aromatic compounds, has a cetane num/er equivalent to or hi4her than that of fossil diesel fuel, has an avera4e o9y4en content of appro9imately 11G, and has similar viscosity to, and a hi4her flash point than conventional fossil fuels" :n economic terms, /iodiesel fuel noF occupies a specific marLet niche in the a4ricultural sector" :ts production cost is relatively hi4her than that of commercial fossil diesel, /ut Fill decrease si4nificantly Fith increased production and use on a lar4er scale, or Fhen used cooLin4 oil or animal fats are utili)ed as raF materials H+I" Biodiesel fuel is a domestic and Mlocally producedN reneFa/le fuel, /iode4rada/le, non-to9ic, and has loF emission profiles, thus /ein4 environmentally friendly" :t is defined as the mono alLyl esters of lon4-chain fatty acids" 5o /e used as a fuel, /iodiesel must meet quality standards, i"e", A;5 DE&71 in the U;A, and (> 18218 in (urope H1,,11I" 5hese specifications prescri/e the required properties of /iodiesel fuel /lend stocL JB1,,K for middle distillate fuels at the time and place of delivery" 5he stated requirements may /e applied at other points in the production and distri/ution system, as a4reed /etFeen the purchaser and the supplier" 5he /iodiesel specifications must include mono-alLyl esters of lon4-chain fatty acids derived from ve4eta/le oils and animal fats, and must under4o chemical analysis for flash point, methanol, Fater and sediment, Linematic viscosity, sulfated ash, o9idation sta/ility, sulfur, copper strip corrosion, cetane num/er, cloud point, acid num/er, car/on residue, total and free 4lycerin, phosphorus, reducedpressure distillation temperature, atmospheric-equivalent temperature, com/ined calcium and ma4nesium, and com/ined sodium and ma4nesium H1,,11I" :n Bra)il, /iodiesel quality is controlled accordin4 to specifications esta/lished /y A>P !e4ulation >o & JA>P, Bra)ilian #overnment Petroleum, >atural #as and Biofuels A4encyK H12I" :ts physical and chemical parameters, similar to chemical analysis of /iodiesel in the U;A and (urope, are analy)ed folloFin4 protocols covered /y international 4uidelines, mainly from the American ;ociety for 5estin4 and aterials JA;5 K, :nternational Or4ani)ation for ;tandardi)ation J:;OK, and?or (uropean 'ommittee for ;tandardi)ation J'(>K" Biodiesel fuels, Fhen approved /y A>P !e4ulation &, can /e /lended in any concentration Fith petroleum-/ased diesel fuels to /e used in e9istin4 diesel en4ines Fith little or no modification" Blends of /iodiesel fuel Fith petroleum-/ased diesel fuel, esta/lished /y !e4ulation &, are desi4nated BP, Fhere P represents the percent /y volume of /iodiesel fuel in the /lend H12I" :n addition to the ecolo4ical and ener4y advanta4es of /iodiesel fuel, Fe emphasi)e its technical and economic /enefits /ased on the folloFin4 considerations. 1" 5he use of ethyl /iodiesel fuel increases en4ine dura/ility, and /ecause of its hi4h lu/ricatin4 poFer, the fuel consumption, i4nition, and poFer of the en4ine remain unchan4ed"
212

European International Journal of Science and Technology

Vol. 2 No. 2

March 2013

2" Biodiesel fuel is particularly interestin4 for countries Fith lar4e rural areas, alloFin4 lar4e-scale production of ve4eta/le oils at loF cost" Qith increased area planted for oil-producin4 crops, the output can /e increased, and costs consequently reduced" Biodiesel production Fill also mean increasin4 industrial activity, Fith the creation of neF 1o/s" *" Biodiesel fuel production promotes studies of additional ne4lected, underutili)ed, and une9ploited nonfood oil plant species for /iofuel production and8" Biodiesel promotes reduction in emissions of pollutant 4ases /y the partial or total replacement of fossil diesel" +. Ma#%r"a$ and M%#,ods 5he e9perimental procedure descri/ed here is 4eneric and typical" +.*. Ma#%r"a$s: 5he la/oratory e9periment required an unmodified household microFave oven J287, #R)?7E, QK, a Litasato flasL, a separation funnel, round-/ottomed flasLs, and a distillation system" :n this e9periment, Faste cooLin4 oil JQ'OK Fas collected from restaurants, residences, hotels, etc, and Fas supplied /y the Diamantina 'ity Rall" +.+. M%#,ods: For the production of Qaste 'ooLin4 Oil (thyl (sters JQ'O((sK /iodiesel, transesterification reactions Fere performed employin4 Q'O, under normal pressure and microFave irradiation H1*I" 5he reaction pro4ress and the complete transformation of mono-, di-, and tri4lycerides in ve4eta/le oil into monoalLylesters Fas monitored usin4 5hin Dayer 'hromato4raphy J5D'K JFi4ure 1K and /y Rydro4en >uclear a4netic !esonance ;pectroscopy J1R > !K JFi4ure 2K" 5D' e9periments Fere performed usin4 silica-4el coated aluminum foils from ercL, prepared usin4 tFo drops of acetic acid in 1, mD of a solution of a +7.7 mi9ture of he9ane.ethyl acetate H18I, and samples Fere taLen every 2, s for 2 min, durin4 the reaction pro4ress" 5he relevant si4nals chosen for inte4ration in 1R > ! e9periments are caused /y the protons attached to the 4lycerol moiety of mono-, di-, or triacyl4lycerols in Q'O J8"1 ppm and 8"* ppmK and the si4nal of the S-methylene protons present in all esters derived from tri4lycerides J2"* ppm, tripletK, as Fell as the triplet at 2"E& ppm and quartet at 8"1, ppm indicate ethyl ester J='O2'R2'R*K formation" 2"2"1" Production of /iodiesel mediated /y microFave J QK irradiation 5he cooLin4 oil ? Anhydrous ethyl alcohol J++,*GK? >aOR ratios used in the reactions Fere 1,, mD ? %, mD ? 1"1, 4 respectively" :n this e9perimental procedure, the Q'O JFi4ure *K Fas first filtered throu4h silica-4el E, mesh J1,",, 4K to eliminate free fatty acids, polymeric su/stances, and Fater JFi4ure 8K" 5he Q'O had an acid value of ,"8, m4 TOR and ,",2G Fater content prior to /ase-cataly)ed transesterification" %, mD of ethanol, previously treated Fith 1"1, 4 >aOR, Fas transferred to a /eaLer containin4 1,, mD of the filtered oil" 5his mi9ture Fas irradiated in the Q oven for * min at 7E, Q, and 1, mD of distilled Fater Fas added to help the su/sequent separation process" 5he resultin4 mi9ture Fas transferred to a separation funnel and alloFed to cool, Fhere it separated into Q'O((s Jupper phaseK and 4lycerin JloFer phaseK JFi4ure 7K" After the separation of the phases, the /iodiesel Fas Fashed Fith successive additions of 17G /y volume of distilled Fater under moderate a4itation until neutral pR, and dried over anhydrous 4;O8 JFi4ure EK"5he 4lycerin phase Fas neutrali)ed and sli4htly acidified Fith sulfuric acid under stirrin4, filtered, and transferred to a separation funnel, Fhere it a4ain formed tFo phases, the neF upper layer containin4 free
21*

European International Journal of Science and Technology ISSN- 230123433

%%%.ce&info.org.u&5EIJST

fatty acids and some Q'O((s" 5he loFer 4lycerin phase Fas neutrali)ed Fith a concentrated solution of sodium hydro9ide, and Fater and residual ethanol Fere removed /y distillation" Upon coolin4 to room temperature, sodium sulfate precipitated and Fas filtered and recrystalli)ed from /oilin4 Fater, filtered a4ain, Fashed Fith cold Fater, and dried in an oven at %, U' for tFo hours" 5he M/roFn 4lycerinN o/tained Fas purified /y distillation under hi4h vacuum JV 1, mmR4K in the presence of activated charcoal" 2"2"1" 'haracteri)ation and @uality 'ontrol of Biodiesel Fuel 5he sample of Q'O((s Fas sent to the 'enter for onitorin4 and !esearch of the @uality of Fuels, Biofuels, 'rude Oil and Derivatives = '( P(@', Araraquara, ;<o Paulo, ;P, Bra)il, for fuel characteri)ation" 5he sample Fas tested to determine the /iodiesel fuel physical and chemical properties, accordin4 to A;5 , (>, and?or >B! ;tandard ethods, covered /y A>P !e4ulation &" 5a/le 1 summari)es the ;tandard ethods used, as Fell as the specification limits recommended /y the !e4ulation" 5he ;tandard ethods include several physical and chemical parameters such as relative density JA;5 D8,72K, o9idative sta/ility J(> 18112K, flash point JA;5 D+*K, Linematic viscosity JA;5 D887K, car/on residue JA;5 D87*,K, copper corrosiveness JA;5 D1*,K, cold filter plu44in4 point JA;5 DE*&1K, total acid num/er JA;5 DEE8K, iodine value J(> 18111K, and Fater content JA;5 DE*,8K" Also, mass percenta4es of mono-, di-, and tri4lycerides JA;5 DE7%8K, free and total 4lycerin JA;5 DE7%8K, methyl or ethyl esters J(> 181,*K, and methanol or ethanol J(> 1811,K Fere determined /y #as 'hromato4raphy Fith Flame :oni)ation Detector J#'-F:DK" 5he elemental content of /iodiesel J>a, T, 'a, 4, and P, >B! 1777*K Fas also analy)ed /y :nductively 'oupled Plasma = Optical (mission ;pectrometry J:'P-O(;K, Fhile total sulfur J;, accordin4 to A;5 D82+8K Fas analy)ed /y ener4ydispersive P-ray fluorescence spectrometry J(DPK" 5he instruments employed in these analyses Fere an automatic densimeter JAnton Paar #m/R, model D A87,,K, a !ancimatW J etrohm :on Analysis, model %&*K, a PensLy- artens closed cup automatic flash point tester JPetrotest :nstruments #m/R, model P A 8K, an automated Linematic viscosity measurin4 system J5anaLa ;cientific Dimited, model ATV-2,2K, a micro car/on residue tester J5anaLa ;cientific Dimited, model A'!- *K, a copper strip corrosion tarnish tester JPetrotest :nstruments #m/RK, a cold filter plu44in4 point tester J5anaLa ;cientific Dimited, model AFP-1,2K, an automatic potentiometric titrator JT( (lectronics, model A5-7,,>2K, a coulometric Tarl Fischer titrator J etrohm :on Analysis, model &7EK, a 4as chromato4raph Fith flame ioni)ation detector J;himad)u 'orporation, model #'-2,1,K coupled to a '5' 'om/i PAD headspace and liquid in1ector system J;himad)u 'orporation, model AO'-7,,,K, an ener4y dispersive P-ray fluorescence spectrometer J;himad)u 'orporation, model (DP-%,,K, and an inductively coupled plasma optical emission spectrometer J5hermo ;cientific, model i'AP E*,, DuoK" 2"2"1"1" !elative Density 0 2, X' JA;5 D8,72K. !elative density Fas also measured Fith an automatic oscillatin4 U-tu/e densimeter and tFo inte4rated Pt 1,, platinum thermometers JDTD tracea/leK Fith a stated accuracy of 7"1,-E 4"cm-*" 5he temperature of the densimeter Fas re4ulated to Y,",,1 T Fith a solidstate thermostat" 5he densimeter Fas cali/rated daily Fith /oth dry air and /i-distilled de4assed Fater" 2"2"1"2" Qater 'ontent JA;5 DE*,8K. 5his test method determines the sum of free Fater in /iodiesel /y 'oulometric Tarl Fischer 5itration" 2"2"1"*" Flash Point JA;5 D+*K. 5his requirement ensures that the methanol or ethanol used in production is completely removed from the /iodiesel fuel, /ecause of /oth fire-safety concerns and the corrosive nature of alcohol"
218

European International Journal of Science and Technology

Vol. 2 No. 2

March 2013

2"2"1"8" O9idative ;ta/ility 0 11, X' J(> 18112K. 5he duration of the induction period is a measure of its resistance to o9idation" 5he (> 18112 method is /ased on the fact that in o9idated oils or fats, volatiles are formed at the end of the induction period" 5he o9idative sta/ility of the /iodiesel samples Fas evaluated at temperatures of 1,, and 1,7 U' and air floF of 2, D"h-1" :n this method, the o9idation is induced /y the passa4e of a constant air floF throu4h the sample that is Lept under constant temperature" 5he volatile products of the reaction, Fhich Fere /loFn off Fith the air, Fere collected in distilled or deioni)ed Fater and measured /y the chan4e in electrical conductivity of these liquids" Durin4 the course of the reaction, due to an increase in the conductivity, a curve is draFn from Fhich the induction period is inferred" 5he most si4nificant and undesira/le insta/ility chan4e in liquid fuel Fith time is the formation of solids, also termed filtera/le sediments" Durin4 lon4-term stora4e, o9idation due to contact Fith air Jauto9idationK is a le4itimate concern Fith respect to maintainin4 fuel /iodiesel quality" 2"2"1"7" Tinematic Viscosity 0 8, X' JA;5 D887K. Adequate viscosity is required for lu/rication and to prevent leaLa4e in metal?metal seals, /ut viscosity must not /e so hi4h as to cause sei)ure of parts, particularly under loF-temperature conditions" Ri4h-viscosity fuel can also cause hi4her in1ection pressures, leadin4 to increased Fear and shorter equipment life" 2"2"1"E" 'ar/on !esidue JA;5 D87*,K. 5his test provides an estimate of the car/on-depositin4 tendencies of a fuel, and is desi4ned to prevent the formation of deposits in the com/ustion cham/er" :n /iodiesel samples, hi4h levels of 4lycerides are e9pected to contri/ute to en4ine deposit formation and hence to a hi4her car/on residue" 2"2"1"&" 'opper 'orrosiveness, * h 0 7, X' JA;5 D1*,K. 'orrosion is of concern /ecause of potential dama4e to copper components of fuel systems, /ut also /ecause dissolved copper can cataly)e o9idation reactions, leadin4 to the formation of deposits and corrosive free acids" 5his requirement mirrors the A;5 D+&7 requirement for conventional petrol-diesel, and is desi4ned to ensure that /iodiesel is equally compati/le Fith and resistant to o9idation /y copper" 2"2"1"%" 'old Filter Plu44in4 Point JA;5 DE*&1K. 5he most important practical disadvanta4e of /iodiesel is that it has a hi4her pour cold filter plu44in4 point than mineral diesel oil" 5he cold filter plu44in4 point measures the temperature at Fhich paraffin or, in the case of /iodiesel, ester structures, crystalli)e /efore in1ection, there/y /locLin4 the filter" 5he ensuin4 lacL of fuel can result in en4ine failure, mainly in cool to cold temperatures" 5he raF materials used in the manufacture of /iodiesel influence the cold filter plu44in4 point" :n the case of rapeseed oil methyl ester this occurs at =12U ', and for palm oil at 617U '" 2"2"1"+" 5otal Acid >um/er JA;5 DEE8K. 5his test measures the presence of corrosive free fatty acids and o9idation products /y Potentiometric 5itration" 5he total acid num/er or acid value is the total amount of potassium hydro9ide necessary to neutrali)e the free acids in a /iodiesel sample" 5his can /e further improved /y controllin4 the transesterification, cleanin4, and dryin4 processes" Ri4h acid values in the feedstocL indicate an unrefined or poorly refined product oil source due to poor process control, such as ethanol carryover, and could also cause de4radation of ru//er parts in older en4ines, resultin4 in filter clo44in4" 2"2"1"1," :odine Value J(> 18111K. 5he iodine value is the amount of iodine, measured in 4rams, a/sor/ed /y 1,, 4 of a 4iven sample" 5he :odine value Jor :odine num/erK is commonly used as a measure of the chemical sta/ility of different /iodiesel fuels a4ainst the o9idation descri/ed a/ove" 5he :odine value is
217

European International Journal of Science and Technology ISSN- 230123433

%%%.ce&info.org.u&5EIJST

determined /y measurin4 the num/er of dou/le /onds in the mi9ture of fatty acid chains in the fuel /y introducin4 iodine into 1,, 4 of the sample /ein4 tested, and measurin4 hoF many 4rams of iodine are a/sor/ed" :odine a/sorption occurs at dou/le-/ond positions - thus a hi4her iodine value num/er indicates a hi4her quantity of dou/le /onds in the sample, 4reater potential to polymeri)e, and hence loFer sta/ility" 2"2"1"11" ono-, Di-, and 5ri4lycerides and Free and 5otal #lycerin JA;5 DE7%8K. A 4as chromato4raphy test method. Free #lycerin, Fhich is a /y-product of the transesterification process, causes in1ector deposits, Fhich can clo4 the fuel system" Free #lycerin can cause fuel separation and materials compati/ility pro/lems" :t can also /uild up in the /ottom of stora4e and fuel tanLs" 5otal #lycerin includes the sum of free 4lycerin and mono-, di-, and tri-4lycerides, all reported as mass percent 4lycerin" 5his measures the level of free 4lycerin plus any unreacted oil or fats Jmono-, di- or tri4lyceridesK in the /iodiesel" 5he unreacted 4lycerides have much hi4her /oilin4 points than /iodiesel or conventional diesel fuel, Fhich can lead to in1ector en4ine deposits and may adversely affect cold-Feather operation" A>P !e4ulation & does not set a standard limit for mono-, di-, and tri4lyceride content in the final product" RoFever, the (uropean /iodiesel standard recommends that the mono-, di-, and tri4lyceride content should not e9ceed ,"2, ,"2, and ,"%, respectively" Of all the individual standard methods that cover /iodiesel analysis, pro/a/ly the most important Fith re4ard to monitorin4 the actual refinin4 process is A;5 DE7%8" :deally, the level of free 4lycerin and any unreacted mono-, di-, or tri4lycerides in /iodiesel Fill indicate hoF efficiently the transesterification reaction is proceedin4" All the ve4eta/le oil Fill react Fith the methanol or ethanol and Fill /e converted to the methyl or ethyl ester" Analy)in4 the sample usin4 this method Fill indicate if there are any unreacted tri4lycerides as Fell as any traces of free 4lycerin in the final product" A;5 DE7%8 descri/es a method for quantitatively determinin4 free and total 4lycerin in methyl or ethyl esters J/iodieselK /y #' usin4 flame ioni)ation detection JF:DK technolo4y" 5he detection ran4e in this method is ,",,7 to ,",7 mass G for free 4lycerin and ,",7 to ,"7 mass G for total 4lycerin" 5he sample is first derived Fith a silylatin4 a4ent and then in1ected into an open tu/ular #' column pacLed Fith 7G phenylpolydimethylsilo9ane" 'ali/ration is achieved Fith tFo internal standards J/utanetriol and tricaprinK and four reference materials" ono-, di-, and tri4lycerides are determined /y comparison Fith mono-olein, di-olein, and tri-olein, respectively" 'onversion factors are then applied to the results for mono-, di-, and tri4lycerides to calculate the sampleZs /onded 4lycerin content" 5he total 4lycerin is the sum of the free and /onded 4lycerin" 2"2"1"12" ethanol or (thanol J(> 1811,K. onitorin4 residual methanol or ethanol in B1,, is a matter of safety, since even small amounts of this material can loFer the flash point" oreover, residual alcohol can affect fuel pumps, seals, and elastomers, and result in poor com/ustion properties" A>P !e4ulation & sets a standard limit for methanol or ethanol content in the final product as ,"2, mass G, ma9imum" Of all the individual standard methods that cover /iodiesel analysis, pro/a/ly one of the most important concerns (> 1811," 5his standard method descri/es a method for quantitatively determinin4 residual methanol or ethanol content in /iodiesel /y 4as chromato4raphy usin4 flame ioni)ation detection technolo4y and coupled Fith a headspace system" (ither polar or non-polar columns are alloFed" (> 1811, can /e applied to mi9tures containin4 ,",1 to ,"7G methanol or ethanol" 5he /iodiesel sample is heated in a sealed vial at %, U', and after attainin4 equili/rium, a defined amount of the 4as phase is in1ected into the #' in an open tu/ular column pacLed Fith a polyethylene 4lycol stationary phase" ;ince the /iodiesel matri9 can influence the equili/rium /etFeen the methanol or ethanol concentrations in the liquid and 4as phases, cali/ration standards must /e prepared in methanol- or ethanol-free /iodiesel" 5he (> 1811, /iodiesel standard recommends preparation of a cali/ration curve containin4 ,",1, ,"1, and ,"7 mass G methanol or ethanol in /iodiesel" An internal standard should alFays /e used Fhen applyin4 manual headspace in1ection" Qhen
21E

European International Journal of Science and Technology

Vol. 2 No. 2

March 2013

usin4 a headspace auto sampler, an internal standard is not necessary, /ut is recommended to increase the relia/ility of the results" 7 [D of 2-propanol is added to each standard and /iodiesel sample" 2"2"1"1*" ethyl or (thyl (sters J(> 181,*K. 5his method provides verification that the ester content in /iodiesel is 4reater than +E"7 mass G, Fhile also alloFin4 the characteri)ation of the fatty acid methyl esters JFA (K composition" 5he ester content and linolenic acid methyl ester content are quantified /y internal cali/ration Fith methyl heptadecanoate" An accurate characteri)ation of fatty acid methyl esters JFA (K in /iodiesel is essential for a more accurate calculation of the cetane inde9" 5he cetane num/er of /iodiesel depends on the distri/ution of fatty acids in the ori4inal oil" 2"2"1"18" ;odium and Potassium J>B! 1777*K. etals that are covered include Ba, 'a, 4, >a, T, and ;n, althou4h ;, P, and 'l can /e present in com/ined form" An application to /iodiesel is o/viously determinin4 residual >a or T from the catalyst" 5he presence of metals in the /iodiesel can cause opera/ility pro/lems due to formation of deposits and poisonin4 of emission-control devices, or can cataly)e reactions that cause undesired products" 5he metals of interest include sodium J>aK and potassium JTK, used as catalysts in /iodiesel production" Fuel-in1ection equipment manufacturers have proposed to limit the content of >a and T Jcom/inedK to 7 ppm each" etals Fere analy)ed via >B! 1777* /y inductively coupled plasma optical emission spectroscopy J:'P-O(;K confi4ured Fith dual vieF, for Fhich the reported detection limits for >a and T in /iodiesel after dilution Fith Lerosene are ,",E J>a 7%+"7+2 nm, radial vieFK and ,"18 JT &E+"%+E nm, a9ial vieFK [4 L4=1" *"1"17" 'alcium and a4nesium J>B! 1777*K. 'alcium and ma4nesium are of concern /ecause of soap formation" 5hey may also /e found in animal fats as a result of contact Fith non-lipid material" 5he metals of interest include ma4nesium J 4K and calcium J'aK, used in adsor/ents for purifyin4 /iodiesel" Fuelin1ection equipment manufacturers have proposed to limit the content of 4 and 'a Jcom/inedK to 7 ppm each" >B! 1777* calls for analy)in4 'a and 4 /y :'P-O(;" 'a is determined at 822"E&* nm and 4 at 2&+"77* nm" Other Favelen4ths are accepta/le if they are free from interference" etals Fere analy)ed via >B! 1777* /y inductively coupled plasma optical emission spectroscopy J:'P-O(;K confi4ured Fith dual vieF, for Fhich the reported detection limits for 'a and 4 in /iodiesel after dilution Fith Lerosene are ,",1 J'a *17"%%& nm, radial vieFK and ,",E J 4 2&+"77* nm, a9ial vieFK [4 L4=1" 2"2"1"1E" Phosphorus J>B! 1777*K. 5his element can /e carried over from ve4eta/le oils, for e9ample, from phospholipids present in all ve4eta/le oils or 4lucosinolates in rapeseed-/ased /iodiesel" :t must /e ensured that phosphorus is not found in MalternativeN /iodiesel sources, such as used fryin4 oils or animal fats, Fhich can come into contact Fith e9traneous materials containin4 this element" 5he intent of this requirement is to protect e9haust catalysts, Fhich are /ecomin4 more and more common on diesel equipment" 5races of phosphorus, resultin4 from phospholipids, can remain in ve4eta/le oils after refinin4" Phosphorus can poison catalysts used for reduction of e9haust emissions" Phosphorus JPK Fas analy)ed accordin4 to >B! 1777*, /y inductively coupled plasma optical emission spectroscopy J:'P-O(;K confi4ured Fith dual vieF, for Fhich the reported detection limits for P in /iodiesel after dilution Fith Lerosene are ,",7 JP 1&%"&EE nm, a9ial vieFK [4 L4=1" 2"2"1"1&" ;ulfur Jaccordin4 to A;5 D82+8K. ;ulfur, liLe phosphorus, is a potential catalyst poison and is carried over from ve4eta/le oils, for e9ample, from phospholipids present in all ve4eta/le oils or 4lucosinolates in rapeseed-/ased /iodiesel" ost /iodiesel fuels inherently contain little or no sulfur, e9cept possi/ly in rapeseed oil" 5he specification is important to shoF that /iodiesel Fill not ne4atively affect
21&

European International Journal of f Science and Technology ISSN- 230123433

%%%.ce& %%%.ce&info.org.u&5EIJST

automotive catalyst systems" ;ulfur is covered cov /y A;5 D787* and (> 2,%%8, ,%%8, Fhich determine sulfur content /y UV fluorescence of the sample samp durin4 its com/ustion and /y Favelen4th Favelen4th-dispersive P-ray fluorescence spectrometry JQDPK, DPK, respectively" respec As an alternative method, A;5 D82+ D82+8 calls for sulfur analyses /y ener4y-dispersive P-ray ray spectroscopy spectro J(DPK, as performed on petrol-diesel diesel fuel" fu -. R%s&$#s and D"s'&ss"on :n the present study, ethyl hyl /iodiesel fuels Fere successfully synthesi)ed ed from Fast Faste cooLin4 oil" All the Faste cooLin4 oil present Fas consumed consume durin4 the reaction process, producin4 ducin4 Q'O Q'O((s and 4lycerin J(quation 1K" (quation 1

5he process developed here Fas conducted co at normal pressure and microFave icroFave irra irradiation for * min" 5he transesterification reaction Fas also studied stu /y reflu9, /ut the reaction time e Fas appro appro9imately 12, min" 5herefore, more ener4y Fould ld /e used in i this process than the ener4y e9pended 9pended dur durin4 the * min of microFave irradiation" Qhile apprisin4 the effect ect of the >aOR >a catalyst amount on Q'O((s production, seven s e9periments Fere conducted Fith different t concentrations concentratio J,G, ,"7G, ,"&7G, ,"%,G, ,"+,G, ,G, 1",,G, 1"1,GK of >aOR, and each e9periment Fas repeated ated five times" time :n all e9periments, an ethanol? oil il ratio of %, mD. 1,, mD Fas used" 5he reaction pro4ress Fas monitored monito usin4 5hin Dayer 'hromato4raphy 4raphy J5D' J5D'K and 1R > ! ;pectroscopy" As e9pected, no o product appeared a Fith ,G catalyst" 'atalyst st concentra concentrations hi4her than 1"1,G adversely affected Q'O((s O((s production, produc resultin4 in soap formation and d a loFer ester est yield" 5he optimum yield J+%GK %GK of Q'O((s Q' Fas 4ained at an ethanol?oil il molar rat ratio of &.1" Ri4her proportions Ja/ove &.1K of ethanol anol had an adverse effect on Q'O((s production" uction" At eth ethanol-to-oil molar ratios 4reater than %, mD of ethanol. anol. 1,, 1, mD of oil, separation of esters s from 4lycerol 4lyce Fas difficult" Unreacted ethanol, Fhen present, sent, can suppress su the 4ravity decantation so o that the a apparent yield of Q'O((s decreases, /ecause traces races of 4lycerol 4lyc may remain in the /iodiesel phase ase H17,1E H17,1EI" -.*. C,ara'#%r".a#"on and /&a$"#0 a$"#0 Con#ro$ Con#ro o1 WCOEEs. 5he sample of Q'O((s Fas tested to determine dete the /iodiesel fuel quality accordin4 cordin4 to A A;5 , (>, and?or >B! ;tandard ethods esta/lished lished /y A>P A !e4ulation &" 5a/le 1 shoFs the specifica specification limits of the standard methods and the sample ple results o/tained o/ for each requirement"

European International Journal of Science and Technology

Vol. 2 No. 2

March 2013

5a/le 1" Biodiesel Fuel Physicochemical Properties of Qaste 'ooLin4 Oil (thyl (sters JQ'O((sK" Physical and Properties 'hemical Units L4?m* m4?L4 ;tandard ethod A;5 D8,72 A;5 DE*,8 A;5 D+* (> 18112 ;pecification Dimits !esults A>P !e4ulation & %7,", = +,,", 7,,", 1,,", E", %&+"8 *+&"E %E", 1"7 8"8 ,", 1A - 1", ,",+% %&"% ,"%, ,"7, ,"*, ,",1 ,"2, ,",1+ +&"8 1"& ,"1 ,"7 *+",

!elative Density 0 2, X' Qater 'ontent, ma9"

Flash Point, min" X' O9idative ;ta/ility 0 11,h X', min Tinematic Viscosity 0 8,mm2?s X'

A;5 *", = E", D887 A;5 ,",7, 'ar/on !esidue, ma9 mass G D87*, A;5 1", 'opper 'orrosiveness, * h0 7, X', ma9 D1*, A;5 1+", 'old Filter Plu44in4 Point,X' ma9 DE*&1 m4 TOR?4 A;5 ,"7, 5otal Acid >um/er, ma9 DEE8 :odine Value 4?1,,4 (> 18111 >A3 ono4lycerides >A3 Di4lycerides >A3 A;5 5ri4lycerides >A3 mass G DE7%8 Free #lycerin, ma9 ,",2 5otal #lycerin, ma9 ,"27 ethanol or (thanol, ma9 mass G (> 1811, ,"2, ethyl or (thyl (sters, min mass G (> 181,* +E"7 7", ;odium 6 Potassium, ma9 m4?L4 7", 'alcium 6 a4nesium,m4?L4 >B! 177* ma9 Phosphorus, ma9 m4?L4 1,", accordin4 to 5otal ;ulfur, ma9 m4?L4 A;5 7,", D82+8
3 >A = not applica/le

*"1"1" !elative Density 0 2, X' JA;5 D8,72K. !elative densities out of the ran4e can also indicate the presence of contaminants, and cause an incorrect in1ection amount of fuel in the cham/er" 5he relative density of /iodiesel is typically %%,", L4?m*, si4nificantly hi4her than typical petrodiesel, Fhich ran4es from %8,", to %E,", L4?m*"
21+

European International Journal of Science and Technology ISSN- 230123433

%%%.ce&info.org.u&5EIJST

*"1"2" Qater 'ontent JA;5 DE*,8K. Free Fater is undesira/le /ecause it may promote micro/ial 4roFth and corrode fuel-system components, causin4 e9cessive Fear in fuel-in1ection equipment" 5he Q'O((s met the specification of 7,,", m4?L4 ma9imum" *"1"*" Flash Point JA;5 D+*K. 5he flash point for the /iodiesel met the specification of 1,,", X' minimum" 5his requirement ensures that the alcohol used in preparation is completely removed from the final /iodiesel" *"1"8" O9idative ;ta/ility 0 11, X' J(> 18112K. 5he o9idative sta/ility of the /iodiesel did not meet the specification of E h, minimum" RoFever, the /iodiesel sample Fas tested Fithout any added antio9idant" *"1"7" Tinematic Viscosity 0 8, X' JA;5 specification of *", to E", mm2?s" *"1"E" 'ar/on !esidue JA;5 ma9imum" D887K. 5he Linematic viscosity for the /iodiesel met the

D87*,K. 5he /iodiesel samples tested met this requirement of ,",7 mass G,

*"1"&" 'opper 'orrosiveness, * h 0 7, X' JA;5 D1*,K. 5he /iodiesel samples e9hi/ited a 1A sli4ht tarnish, therefore easily meetin4 the standard requirement of 1",, ma9imum" *"1"%" 'old Filter Plu44in4 Point JA;5 DE*&1K. 5he cold filter plu44in4 point of used cooLin4 oil occurs at - 1", U ', Fhich meets the specification limits of 1+", X', ma9imum" *"1"+" 5otal Acid >um/er JA;5 ma9imum limit of ,"7 m4 TOR?4" DEE8K. 5he /iodiesel sample tested shoFed acid levels /eloF the

*"1"1," :odine Value J(> 18111K. A>P !e4ulation & does not set a standard limit for iodine value in the final product" *"1"11" ono-, Di-, and 5ri4lycerides and Free and 5otal #lycerin JA;5 DE7%8K. A>P !e4ulation & does not set a standard limit for mono-, di-, and tri4lyceride content in the final product" RoFever, the (uropean /iodiesel standard recommends that the mono-, di-, and tri4lyceride content should not e9ceed ,"2, ,"2, and ,"%, respectively" 5he /iodiesel sample met the free and total 4lycerin requirements of ,",2 and ,"27 mass G ma9imum, respectively" *"1"12" ethanol or (thanol J(> 1811,K. 5he /iodiesel sample met the methanol or ethanol requirements of ,"2, mass G ma9imum" *"1"1*" ethyl or (thyl (sters J(> 181,*K. 5he /iodiesel sample met the specification for FA ( content"

*"1"18" ;odium and Potassium J>B! 1777*K. 5he com/ined >a and T contents met this requirement" *"1"17" 'alcium and requirement" a4nesium J>B! 1777*K. 5he com/ined 'a and 4 contents did meet this

*"1"1E" Phosphorus J>B! 1777*K. 5he P content did meet this requirement"
22,

European International Journal of Science and Technology

Vol. 2 No. 2

March 2013

*"1"1&" ;ulfur Jaccordin4 to A;5 D82+8K. FolloFin4 this methodolo4y, Fe found that the ; content did meet this requirement and note its applica/ility to /iodiesel neat fuels"

2. Con'$&s"on Qe descri/ed a methodolo4y for the production of ethyl /iodiesel fuel JQaste 'ooLin4 Oil (thyl (sters = Q'O((sK usin4 microFave irradiation from an unmodified household microFave oFen" 5he e9cellent quality of the /iodiesel produced in this Fay from Faste cooLin4 oil Fas comproved /y the systematic determination of its several physical and chemical properties, folloFin4 standard methods of analysis, in particular those esta/lished /y A;5 , and the A>P !e4ulation & in Bra)il"

3. A'4no5$%d(6%n#s 5he authors thanL the A4Cncia >acional do Petr$leo, #Bs >atural e Biocom/ust\veis = A>P, FAP( :#, and FU>DU>(;P for financial support, alon4 Fith 'AP(; and '>Pq for the provision of felloFships, and also '( P(@' J'entro de onitoramento e Pesquisa na @ualidade de 'om/ust\veis, Petr$leo e DerivadosK for offerin4 its infrastructure and staff for the development of the characteri)ation and quality control of the /iodiesel fuel"

7. R%1%r%n'%s H1I D" Bryant, !udolf Diesel - pioneer of a4e of poFer, ;cience 18% J1+E7K, pp" 211" H2I D" Bryant, !udolf Diesel and his rational en4ine, ;cientific American 221 J1+E+K, pp" 1,%" H*I ("#" ;hay, Diesel fuel from ve4eta/le oils. ;tatus and opportunities, Biomass and Bioener4y 8 J1++*K, pp" 22&-282" H8I F" a, "A" Ranna, Biodiesel production. a revieF, Bioresource 5echnolo4y &, J1+++K, pp" 1-17" H7I ]" ]esilo4lu, :mmo/ili)ed lipase-cataly)ed ethanolysis of sunfloFer oil, Journal of the American Oil 'hemists ;ociety %1 J2,,8K, pp" 17&-1E," HEI "J" #off, >";" Bauer, ;" Dopes, Q"!" ;utterlin, #":" ;uppes, Acid-'ataly)ed Alcoholysis of ;oy/ean Oil, Journal of the American Oil 'hemists ;ociety %1 J2,,8K, pp" 817-82," H&I ]"]esilo4lu, :" Tilic, Dipase-cataly)ed esterification of 4lycerol and oleic acid, Journal of the American Oil 'hemists ;ociety %1 J2,,8K, pp" 2%1-2%8" H%I A" Rsu, T"'" Jones, 5"A" Fo4lia, Q">" armer, 'ontinuous Production of (thyl (sters of #rease Usin4 an :mmo/ili)ed Dipase, Journal of the American Oil 'hemists ;ociety %1 J2,,8K, pp" &8+-&72" H+I Q" T^r/it), Biodiesel production in (urope and >orth America, an encoura4in4 prospect, !eneFa/le (ner4y 1E J1+++K, pp" 1,&%-1,%*" H1,I American ;ociety for 5estin4 and aterials, A;5 :nternational ;tandards QorldFide, Annual BooL of A;5 ;tandards, Vol" ,7",8", Qest 'onshohocLen, PA, 2,,%, DE&71" H11I (uropean 'ommittee for ;tandardi)ation, :';. &7"1E,"2, = Diquid fuels, Brussels, Bel4ium, 2,,*, (> 18218" H12I A4Cncia >acional do Petr$leo, #Bs >atural e Biocom/ust\veis JBra)ilK, !e4ulation >o" & J2,,%K, DiBrio Oficial da Uni<o JedK, #overno do Brasil. Bras\lia" H1*I ;" ;iler- arinLovic, A" 5omasevic, 5ransesterification of sunfloFer in situ, Fuel && J1++%K, pp" 1*%+1*+1" H18I " Taieda, 5" ;amuLaFa, 5" atsumoto, T" Ban, A" Tondo, ]" ;himada, R" >oda, F" >omoto, T" OhtsuLa, (" :)umoto, R" FuLuda, Biodiesel fuel production from plant oil cataly)ed /y !hi)opus ory)ae
221

European International Journal of Science and Technology ISSN- 230123433

%%%.ce&info.org.u&5EIJST

lipase in a Fater-containin4 system Fithout an or4anic solvent, Journal of Bioscience and Bioen4ineerin4 %% J1+++K, pp" E2&-E*1" H17I >" Usta, Use of to/acco seed oil methyl ester in a tur/ochar4ed indirect in1ection diesel en4ine, Biomass Bioener4y 2% J2,,7K, pp" &&-%E" H1EI U" !ashid, F" AnFar, B"!" oser, ;" Ashraf, Production of sunfloFer oil methyl esters /y optimi)ed alLali-cataly)ed methanolysis, Biomass Bioener4y *2 J2,,%K, pp" 12,2-12,7

222