Biodiesel tugas

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    Contents lists available at ScienceDirect Bioresource Technology 101 (2010) 70197024

    Bioresource Technology

    ournal ho!e"age# $$$%elsevier%co!&locate&biortech

    'rouction o bioiesel ro! $inery $aste# *+traction, re-ning an

    transesteri-cation o gra"e see oil Car!en .ar/a ernne, .ar/a 3ess 5a!os, 6ngel

    're 8, 3uan rancisco 5or/gueDe"arta!ento e ngenier/a :u/!ica, nstituto e Tecnolog/as :u/!ica y .eioa!biental, ;niversia e Castillav% Ca!ilo 3os Cela s&n, 1?071 Ciua 5eal, S"ain

    article ino abstract

    >rticle history#5eceive @ 3anuary 2010 5eceive in revise

    or! 2 >"ril 2010 >cce"te 7 >"ril 2010

    Aey$ors#

    ra"e see il

    e+traction 5e-ning

    Transesteri-cation

    Bioiesel

    n regions $ith a large $ine "rouction the usage o their natural $aste to !ae bioiesel can result an interesting alternative%n this $or, ierent !ethos o e+traction, re-ning an transesteri-cation o gra"e see oil $ere assaye% T$o techniEues o

    oil e+traction $ere co!"are# solvent e+traction an "ressing% T$o conventional transesteri-cations o the re-ne oil $ere

    carrie out using !ethanol an bioethanol, being the !ethyl an ethyl ester contents higher than 97 $t%F% inally, several in

    situ transesteri-cations $ere one% n situ transesteri-cation i not reach either the oil yiel e+traction or the alyl ester

    contents but the obtaine bioiesel ha better o+iation stability in co!"arison $ith the conventional "rocess%

    2010 *lsevier =t% >ll rights reserve%

    1% ntrouction

    n recent years, the biouels interest has been rene$e% This act is ue torecent technological avances to ensure a goo agricultural "rouction an itssubseEuent conversion in the !ost suitable energetic !anner $ith littleecono!ic invest!ent% Thus, agricultural $aste use as uel is co!"etitive$ith ossil sources, o"ening a ne$ o""ortunity or the use o rene$ableresources available globally an !ore "articularly at the regional level%

    ten, the vegetable oils investigate or their suitability as bioiesel arethose $hich occur abunantly in a s"eci-c area% Gorl gra"es "rouction $asover H7 !illion !etric tons in 200I, $ith S"ain, rance an taly being the!aor $orl gra"e "roucers "roviing al!ost hal o the total "rouction%.ore than 20F o gra"e "rouction ty"ically beco!es $aste uring $ine"rouction% ra"e see oil is obtaine ro! the sees let ollo$ing "ressing

    o the uice ro! gra"es or $ine !aing an bioethanol is obtaine ro! byngel%'ereLucl!%es (6% 're)%

    09H0

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    C%.% ern

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    ne et al% & Bioresource Technology 101 (2010) 7019

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    ra$ !aterials or bioiesel "rouction are vegetable oils $ith a high"ro"ortion o unsaturate atty aci !ainly !onounsaturate ones as oleicaci (5a!os et al%, 2009)%The re-ning "rocess involves a co!"lete series o treat!ents to !ae the oilsuitable or bioiesel "rouction, !ainly by re!oval o non I9 oil "ress$ith a ca"acity o in"ut !aterial o I@ g&h% The yiel o the "rocess $ase+"resse as the !ass o oil e+tracte ro! 100 g o rie gra"e see%

    The oil e+traction using solvents $as evelo"e using both a So+ther!(erhart S'C) an a So+hlet a""aratus% >n o"ti!iation o the e+tractionti!e using the So+hlet a""aratus $as carrie out% n 2? h, the !a+i!u! oil

    e+traction yiel $as achieve% >n e+traction ti!e o H h $as chosen%

    The re-ning o gra"e see oil $as carrie out in a 200 != our!erican il Che!ist Society (>CS Ce @gilent Technologies Series 1100 N'=C $ith a uorescence etector(Ther!o.* sa!"le at as"eci-e rate an ra$ing it uner vacuu! through a $ire !esh -lter screen%C'' is then e-ne as the lo$est te!"erature at $hich 20 != o sa!"lesaely "asses through the -lter $ithin H0 s% >n auto!atic tester S= '' Is$as use to carry out the eter!ination o the C''%

    Ther!al analytical !ethos such as suba!bient ierential scanningcalori!eter (DSC) $ere successully a""lie to neat "etroiesel an engine

    oils% DSC analyses $ere conucte in a ierential scanning calori!eter!oel DSC :100 o T>% The

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    ne et al% & Bioresource Technology 101 (2010) 7019

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    Test

    Solvent See !oisture il yiel +iation

    ($t%F) ($t%F) stability (h)

    1

    Ne+ane 1017%I 4

    2

    Ne+anea 1017%1 ?

    ? Ne+ane 2%I 1@%4 ?%@

    4

    Ne+anea 2%I 1@ ?

    I

    >cetone 2%I 14%I ter centriugation (1I !in, 4 C an 2000 r"!), soa"s $erese"arate ro! the oil "hase% inally, the $ater content in the oil $as re!oveby eva"oration uner vacuu! conitions% De$a+ing $as not inclue in there-ning "rocess ue to the atty aci "ro-le o gra"e see oil i not"resente long chain saturate !ethyl esters% Table ? sho$s ey Euality"ara!eters that $ere !easure or gra"e see oil beore an ater re-ning"rocess% >ter the alali re-ning "rocess, the vegetable oil reache $atercontent less than I00 ""! an the aci value $as less than 0%I !g AN&g,Euantities that $ill guarantee a goo Euality or the bioiesel% The oil lossater re-ning "rocess $as aroun ? $t%F%

    >s it $as co!!ente beore, the alali re-ning can re!ove the "ossible

    "hos"haties "resent in the oil% n Table ?, the "hos"horous content or ra$gra"e see oil $as ?%@ ""! belo$ the li!it o 4 ""! establishe in ;Q*

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    YCatalystZ(Q)

    Te!"% Ti!e .ethyl il e+traction +iation

    (C) (h) ester yiel ($t%F) stability (h)

    ($t%F)

    QaN (0%1) ?I 1H @9%? @%4 22%I

    QaN (0%1) I0 1H @7%0 7%H 20%2

    AN (0%1) ?I 10 91%1 H%4 2?%I

    AN (0%4) I0 10 9I%I 10%0 21%ICN?A(0%1)

    I0 10 9?%2 10%? 20%0

    CN?A(0%1)

    I0 10a @9%I I%9 2@%0

    >""eni+ >% Su""le!entary ata

    'bioiesel

    ' in situ bioiesel .ethyl ester +iation stability

    (F) (F)a ($t%F) (h)

    100 0 97%@ ?%0H

    97 ? 97%7 ?%HH

    9? 7 97%I 4%49

    @9 11 97%? I%2I

    @0 20 9H%9 7%12

    0 100 9?%2 20

    or ethyl esters are belo$ those o their corres"oning !ethyl esters (Anotheet al%, 200I)% ra"e see oil obtaine in this $or, consiste o u" H@ $t%F olinoleic aci% The .' o !ethyl linoleate is 4?%1C co!"are $ith .' oethyl linoleateIH%72C(Anothe an Dunn, 2009)% These co!"ouns !ayirectly inuence clou "oint, C'' an other col o$ "ro"erties% naition, DSC eter!ination $as "eror!e to !ethyl an ethyl esters(Su""le!entary .aterial ig% 2)% Dunn (1999) e+tene the a""licability o

    DSC in !easuring col o$ "ro"erties o !ethyl ester% Co!"letions o !eltte!"eratures ro! DSC !eltin curves $ere use to "reict crystalliationte!"eratures o >.*S% Both bioiesel !et the stanar s"eci-cation ;Q*ntio+iant an anti"rolierative "ro"erties o a tocotrienolrich raction ro!gra"e sees% oo Che!istry 114, 1?@H1?90%Cre$s, C%, Nough, '%, o$ar, 3%, Brereton, '%, =ees, .%, uiet, S%, Ginel!ann, G%, 200H%

    :uantitation o the !ain constituents o so!e authentic gra"e see oils o ierent origin% 3ournal o>gricultural an oo Che!istry I4, H2H1H2HI%Do!ingue, N%, QWe, .%3%, =e!a, 3%.%, 1994% *ny!atic "retreat!ent to enhance oil e+traction ro!ruits an oilsees# a revie$% oo Che!istry 49, 2712@H%Dunn, 5%%, 1999% Ther!al analysis o alternative iesel uels ro! vegetable oils% 3ournal o the>!erican il Che!ists Society 7H, 10911I%ernaneceite I4, I?I7%uil co!"rehensive evaluation o the !elting "oints o atty acis anesters eter!ine by ierential scanning calori!etry% 3ournal o the >!erican il Che!ists Society@H, @4?@IH%

    Anothe, %, er"en, 3%O%, Arahl, 3%, 200I% The Bioiesel Nanboo% >CS 'ress, Cha!"aign, llinois%

    =ee, %, 3ohnson, =%>%, Na!!on, *%%, 199I% ;se o branche 10?4, 2?7242%

    =uEue%, 1999% Bioiesel "rouction# a revie$% Bioresource Technology 70, 11I%

    .aier, T%, Schieber, >%, Aa!!erer, D%, Carle, 5%, 2009% 5esiues o gra"e (Oitis viniera =%) see oil"rouction as a valuable source o "henolic antio+iants% oo Che!istry 112, II1II9%

    .artinello, .%, Necer, %, 'ra!"aro, .%C%, 2007% ra"e see oil eacii-cation by !olecularistillation# analysis o o"erative variables inuence using the res"onse surace !ethoology% 3ournal ooo *ngineering @1, H0H4%.ittelbach, .%, 2009% *uro"ean "ers"ective% n# 2n nternational Congress on Bioiesel%

    .olero U!e, >%, 'ereyra =U"e, C%, .art/ne e la ssa, *%, 199H% 5ecovery o gra"e see oil byliEui an su"ercritical carbon io+ie e+traction# a co!"arison $ith conventional solvent e+traction%The Che!ical *ngineering 3ournal H1, 2272?1%

    .uho"ahyay, .%, 2000% Qatural *+tracts ;sing Su"ercritical Carbon Dio+ie% C5C 'ress, ;niteStates%Qya!, A%=%, Tan, C%'%, =ai, %.%, =ong, A%, Che .an, X%B%, 2009% 'hysicoche!ical "ro"erties an

    bioactive co!"ouns o selecte see oils% =GT oo Scie nce an Technology 42, 1?9H140?%

    'assos, C%'%, Silva, 5%.%, Da Silva, %>%, Coi!bra, .%>%, 2009% *nhance!ent o the su"ercritical uie+traction o gra"e see oil by using eny!atically "retreate see% 3ournal o Su"ercritical lui 4@,22I229%5a!os, .%3%, ernne, C%.%, Casas, >%, 5or/gue, =%, 're, 6%, 2009% nuence o atty acico!"osition o ra$ !ate rials on bioiesel "ro"erties% Bioresource Technology 100, 2H12H@%

    5onhe, %, 1971% *+tracciUn el aceite e granilla e uva% rasas y >ceites 22, ?9?400%

    Xoon, S%N%, Ai!, S%A%, Shin, .%%, Ai!, A%N%, 19@I% Co!"arative stuy o "hysical !ethos or li"io+iation !easure!ent% 3ournal o the >!erican il Che!ists Society H@, 14@714@9%