Pyrolysis of tall oil-derived fatty and resin acid mixtures

In e na ional Schola ly Resea ch Ne wo k ISRN Renewable Ene gy Volume 2012, A icle ID 409157, 8pages doi:10.5402/2012/409157 Resea ch A icle Py olysis o Tall Oil-De i ed Fa y and Resin Acid Mix u es Hanna Lappi1and Raimo Al´ en2 1Kannus Resea ch Uni , Finnish Fo es Resea ch Ins i u e, Silm¨ aj¨ a en ie 2, 69100 Kannus, Finland 2Labo a o y o Applied Chemis y, Depa men o Chemis y, Uni e si y o Jy ¨ askyl¨ a, P.O. Box 35, FI-40014, Finland Co espondence should be add essed o Hanna Lappi, [email p o ec ed] Recei ed 4 Ap il 2012; Accep ed 23 May 2012 Academic Edi o s: M. Ga cia-Pe ez and A. S oppa o Copy igh © 2012 H. Lappi and R. Al´ en. This is an open access a icle dis ibu ed unde he C ea i e Commons A ibu ion License, which pe mi s un es ic ed use, dis ibu ion, and ep oduc ion in any medium, p o ided he o iginal wo k is p ope ly ci ed. Neu alised mix u es o all oil-de i ed a y acids and esin acids we e sepa a ely py olysed (a 750◦C o 20 s) by py olysis gas ch o- ma og aphy wi h mass-selec i e and lame ionisa ion de ec ion (Py-GC/MSD/FID) o cla i y hei he mochemical beha iou . The py olysa e o a y acid sal s cha ac e is ically con ained high amoun s o unsa u a ed alipha ic hyd oca bons and mino amoun s o monoa oma ics, whe eas he py olysis o esin acid sal s mainly esul ed in he o ma ion o a oma ics wi h up o h ee benzene ings and only in e y low amoun s o alipha ic hyd oca bons. The da a ob ained a e use ul when conside ing he sui abili y o a ious all oil p oduc s con aining a y and esin acid ac ions o he p oduc ion o bio uels and chemicals ia py olysis. 1. In oduc ion Bo h a y acid and esin acid (i.e., icyclic di e penoids) componen s occu in he ini ial oleo esin ac ion o coni - e ous wood species [1]. In he k a pulping indus y, all oil soap, con aining mainly he sodium sal s o hese acids, is emo ed by skimming om he spen cooking liquo “black liquo ” du ing i s e apo a ion be o e combus ion in a eco e y u nace o p oduce ene gy and eco e he ino ganic cooking chemicals [2]. T adi ionally, he a y and esin acids a e libe a ed by adding sulphu ic acid o yield c ude all oil (CTO, he a e age yield is in he ange o 30 o 50 kg on−1 o pulp), which is hen pu i ied and ac iona ed by acuum dis illa ion. The main ac ions and hei mass p opo ions a e ligh oil (10% o 15%), a y acids (20% o 40%), osin (25% o 35%), and pi ch esidue (20% o 30%). Va ious comme cial a y acid p oduc s om all oil (TOFA) a e a ailable [3]. In gene al, monoenoic oleic (C18:1) and dienoic linoleic (C18:2) acids a e common in mos TOFA p oduc s, al hough du ing k a pulping, he o iginal dienoic and ienoic a y acids wi h cis con igu a ion a e pa ly isome ised o acids wi h conjuga ed double bonds wi h mainly cis- ans con igu a ion [4]. On he o he hand, du ing k a pulping as well as du ing he acidula ion o all oil soap, a gene al shi o a y acid composi ion owa ds a lowe deg ee o unsa u a ion has been epo ed [5]. The p edomina ing esin acids in comme cial all oil osin (TOR) a e he abie ane- and pima ane- ype di e penoids (Figu e 1). The p incipal change in his ac ion occu ing du ing k a pulping is he pa ial con e sion o le opima ic acid in o abie ic acid. Fu he mo e, du ing all oil dis illa ion, some double-bond isome isa ion o bo h abie ane- and pima ane- ype acids, disp opo iona ion o abie adienoic acids, and dehyd ogena ion o abie adienoic and dehyd oabie ic acids ake place [6]. Howe e , he dominan eac ions esponsible o he losses o o iginal esin acids include deca boxyla ion oge he wi h he dehyd a ion and polyme isa ion o all acid ypes. Du ing he las wo decades, a ious common ege able oils ha e a oused conside able in e es as po en ial sou ces o bio uels [8–10]. The go e ning idea has been o p o- duce py oly ically hyd oca bon- ich mix u es esembling pe oleum. In ou ea lie in es iga ions, he he mochemical beha iou o common a y acid (C18,C 18:1,andC 18:2) sodium sal s [11], ege able oil (palm, oli e, apeseed and cas o oils) soaps [12], and CTO soap [13] was cla i ied unde py oly ic condi ions. O he comme cial p ocesses o con e sion o ege able oils in o liquid uels include, o example, anses e i ica ion and hyd op ocessing o p oduce, espec i ely, a y acid es e s and linea hyd oca bons [14–16]. Howe e , one o he main d awbacks o hyd op ocessing is ha i mus be 2ISRN Renewable Ene gy Isopima ic acid COOH Pima ic acid COOH Sanda acopima ic acid COOH Dehyd oabie ic acid COOH Abie ic acid COOH Neoabie ic acid COOH Le opima ic acid COOH Palus ic acid COOH Figu e 1: Chemical s uc u es o he mos common esin acids [7]. conduc ed unde high p essu e. In addi ion, con en ional hyd op ocesses a e usually qui e expensi e (la ge eac o s and comp esso s, cos s o ecycle o bo h eed and hyd ogen, as well as cos o shu down and o eplace and/o egene a e deac i a ed ca alys ) [17]. Addi ional inefficiencies a e due o ecycle o eed because o low con e sions as well as o impu i ies con aining sulphu , ni ogen, me als, and a oma ics. Commonly p ac iced anses e i ica ion has some d aw- backs including he equi emen o a la ge amoun o alcohol, ypically me hanol, which is usually de i ed om na u al gas o o he ossil uel sou ces [14,18]. The o ma ion o a low alue by-p oduc in he o m o glyce ol is also a p oblem, a leas un il he e a e enough acili ies o i s e ining. Addi ionally, he hea ing alues a e lowe han hose o con en ional diesel uels. The analysis pe o med by U.S. Depa men o Ene gy [19] concludes ha he p oduc ion o hyd oca bon mo o uels om biomass ia he py olysis ou e is economically a ac i e. The cos becomes e en mo e a ou able i he acili y can be closely associa ed wi h an exis ing pe oleum e ine y. Fas py olysis is a simple, efficien (high he mal efficiency), low ossil uel inpu , and inexpensi e echnology [20,21]. The by-p oduc s o cha and gas can be used wi hin he p ocess o p o ide p ocess hea equi emen s [22]. In his way, he e a e no was e s eams o he han om lue gas and ash. Themainobjec i eo hiss udywas oob ainmo e de ailed da a on he he mochemical eac ions aking place du ing he py olysis o he main componen s in all oil- de i ed p oduc s. Fo his pu pose, neu alised ac ions o TOFA and TOR we e selec ed. Ou en a i e indings [13] indica ed ha due o he ema kable o ma ion o complica ed a oma ics, esin acids would ha e, o example, anega i eeffec on he quali y o he p oduc du ing p oduc ion o diesel- ype bio uels. This s udy was based on ea lie indings [11] ha , when py olysing soaps (i.e., as sodium sal s o acids) ins ead o using ee acids as eeds ocks, py olysis can be con olled mo e eadily. This also means ha , o example, in he case o all oil-based eeds ocks, py olysis can be applied di ec ly o all oil soap and no ex e nal sulphu ic acid is needed o acidula ion. 2. Expe imen al 2.1. Chemicals and Tall Oil Samples. The compounds used as in e nal s anda ds in he gas ch oma og aphic (GC) analysis o he ex ac i es we e heneicosanoic acid (99%, Sigma) and be ulinol (≥98%, Sigma). The ex e nal s anda d used in he quan i a i e py olysis expe imen s was adaman ane (>99%, Fluka) in benzene (>99%, Fluka). Sol en s used in he sample p epa a ion o he ex ac i es we e analy ical g ade ace one (BDH), me hyl e -bu yl e he (MTBE) (Lab- Scan), and analy ical g ade py idine (BDH). The silyla ion eagen s bis( ime hylsilyl) i luo oace amide (BSTFA) and ime hylchlo osilane (TMCS) we e om Regis Technolo- gies. The chemicals used in he de e mina ion o saponi i- ca ion alues we e po assium hyd oxide (≥85%, Riedel de Ha¨ en), sodium hyd oxide (≥99%, Fluka), hyd ochlo ic acid (≥37%, Riedel de Ha¨ en), dena u ed alcohol BA (99.5 w-%, Al ia), and phenolph halein (Me ck). Wa e was ob ained om a Millipo e Milli-Q wa e sys em. TOFA con aining abou 1.4% unsaponi iables and TOR con aining abou 3.5% unsaponi iables we e he p oduc s o Fo chem Oy. 2.2. Analysis o Tall Oil Acid Mix u es. Fo he analysis o ex ac i e cons i uen s, he samples we e dilu ed in ace one (0.5 mg mL−1) and de i a ised o GC wi h a mix u e o BSTFA and TMCS (99 : 1, esp.). De i a isa ion o samples was pe o med by keeping hem a 70◦C o one hou . Quan- i a i e analysis o he indi idual compounds was ca ied ISRN Renewable Ene gy 3 ou on an Agilen 6850 Se ies GC Sys em wi h an Equi y- 5(30m ×0.32 mm, ilm hickness 0.25 μm) column. The injec o empe a u e was 290◦C and he de ec o empe a- u e was 300◦C. The GC o en empe a u e p og amme was 1.5 min a 100◦C, ollowed by an inc ease o 6◦Cmin −1 o 180◦C, 10 min a 180◦C, an inc ease o 4◦Cmin −1 o 290◦C, and 20 min a 290◦C. Quali a i e analysis o he indi idual componen s was pe o med wi h an Agilen 6890 Se ies GC Sys em equipped wi h a 7683 injec o and an Agilen 5973 mass selec i e de ec o (MSD). The capilla y column used was an HP-5MS (30 m ×0.32 mm, ilm hickness 0.25 μm) and he GC o en empe a u e p og amme was he same as ha used in he quan i a i e analyses. Saponi ica ion alues o he acid mix u es we e de e - mined acco ding o he TAPPI s anda d T621 cm-01. 2.3. Py olysis Expe imen s. TOFA and TOR we e bo h saponi ied wi h sodium hyd oxide ( he amoun was 1.5 imes he equi alen amoun ) p io o py olysis. Soap samples we e py olysed in qua z ubes a a hea ing a e o 1000◦Cs −1 using a CDS Py op obe 1000 hea ed- ilamen py olyse coupled o an HP 5890 II gas ch oma og aph (Py-GC). The column was a ZB-5HT capilla y GC column (30 m × 0.25 mm, ilm hickness 0.25 μm). De ec ion was ca ied ou wi h ei he an HP 5972 mass selec i e de ec o (MSD, quali- a i e analyses) o an HP 5890 GC/ lame ionisa ion de ec ion (FID quan i a i e analyses). The sample size o quali a i e analysis was abou 3 mg and o quan i a i e analysis abou 1 mg. The Py-GC in e ace empe a u e was 250◦Cand he injec o empe a u e 280◦C. Py olysis pa ame e s we e chosen acco ding o he esul s o p e ious esea ch [12,13]. In each expe imen , he py olysis empe a u e was 750◦Cand he empe a u e was kep cons an o 20 s. The GC o en empe a u e was 5 min a 35◦C, an inc ease o 5◦Cmin −1 o 125◦C, 3◦Cmin −1 o 285◦C, 5◦Cmin −1 o 380◦C, and inally 5 min a 360◦C. Helium was used as he ca ie gas and as an ine a mosphe e in he py olysis in e ace. The ca ie gas low a e was kep a 1 mL min−1du ing he gas ch oma og aphic analysis. Due o he mul iplici y o py olysis p oduc s, he iden- i ica ion o all cons i uen s in py olysa es appea ed o be impossible only by he e en ion ime wi h espec o some in e nal s anda ds. Fo his eason, a p ope in e p e a ion o he mass spec a o he py olysis p oduc s was based on a comme cial da abase, Wiley 7n, oge he wi h he ecogni ion o agmen a ion pa e ns as well as ou ea lie esul s [11–13]. Only quali y ma ches o abo e 85% we e included. The calib a ion cu e o quan i a i e de e mina ion o he py olysis p oduc s was de e mined by he py olysis o adaman ane dissol ed in benzene. The calib a ion was pe o med using a simila me hod o ha used by Bocchini e al. [23] when adding he in e nal s anda d o py olysis. Solu ions o adaman ane in he 40 o 110 μgmL −1 ange we e ca e ully added o a qua z capilla y ube, which was immedia ely inse ed in o he Py-GC in e ace. A e an equilib a ion pe iod o 30 s, py olysis was pe o med. Six diffe en concen a ions we e py olysed using he same pa ame e s as o he samples. Two eplica es we e made o each concen a ion. The co ela ion coefficien (R2)o he calib a ion cu e ob ained was 0.990. Due o he mul i ude o peaks in he ege able oil py olysa es, adaman ane was only used as an ex e nal s anda d. This quan i ica ion was used o calcula e he p oduc yields. 3. Resul s and Discussion 3.1. Raw Ma e ials. The o al amoun s o a y acids and esin acids de ec ed in TOFA we e abou 94% and 3%, espec i ely. Values we e sligh ly diffe en om hose gi en by he manu ac u e (97% and 1.7%, esp.), which was p obably due o ou inaccu a e compound quan i ica ion (i.e., in all cases, he esponse ac o s used be ween he GC peak a eas de i ed om he in e nal s anda ds and compounds we e equal o 1) and a ac ha no all peaks ( he amoun o uniden i ied peaks was abou 3%, Table 1) could be iden i ied. Due o double-bond ea angemen s, ou diffe en isome s o conjuga ed C18:2 acids we e ound. The main a y acid componen s we e unsa u a ed linoleic (C18:2), oleic (C18:1), and linolenic (C18:3) acids. The composi ion o esin acids in TOR diffe ed signi i- can ly om ha in CTO, indica ing a ious decomposi ion and isome isa ion eac ions du ing dis illa ion [24]. Fo his eason, he amoun o uniden i ied peaks (mainly a ious esin acid de i a i es) was also ela i ely high (abou 10% o he o al peak a eas, Table 1). The o al amoun s o a y acids and esin acids de ec ed in TOR we e abou 3% and 86%, espec i ely. These alues diffe ed om hose gi en by he manu ac u e (92% and 3.5%), p obably because o he limi a ion o he analysis me hod men ioned abo e. The main esin acid componen s we e abie ane- ype acids, abie ic, dehyd oabie ic, and palus ic acids. 3.2. Py olysis o Soap Mix u es. All he py olysa es con ained signi ican amoun s o highly ola ile p oduc s ma ked as “C3–C5compounds” in Figu e 2, p ima ily co esponding o bo h alkenes and alkanes. Howe e , due o he low esolu ion o hese nume ous low-molecula -mass compounds, hei p ope iden i ica ion was no possible wi h he appa a us used. The py olysis o neu alised TOFA esul ed in a high amoun o unsa u a ed alipha ic hyd oca bons (Figu es 2 and 3,Table 2), al hough some a oma ics wi h one benzene ing we e also o med (Figu e 2,Table 3). The mos p omi- nen ac ions we e alkenes (C6–C12) and alkadienes (C11, C12 and C17) oge he wi h benzene and me hylbenzene. The alkadienes can be conside ed ep esen a i es o he ypical eac ion p oduc s de i ed, o example, om oleic acid (C18:1). Due o he lowe dissocia ion ene gies o allyl bonds, he p esence o he double bond in he alkyl chain a ou s he homoly ic C–C clea age a he allyl posi ion a he han he homoly ic C–C clea age adjacen o he ca boxylic g oup [25]. Fo his eason, a ela i ely signi ican amoun o 1- undecene was o med om oleic acid. The addi ional double bonds in he alkyl chain (c ., linoleic (C18:2) and linolenic (C18:3) acids) a ou ed cyclisa ion and a oma isa ion, hus 4ISRN Renewable Ene gy 0 5 10 15 20 25 30 35 To al TIC a ea (%) TOFA TOR C3-C5 compounds A oma ics Alipha ic hyd oca bons One benzene ing Two benzene ings Th ee benzene ings Phenolics and o he oxygen con . Alkanes Alkenes Dienes Cyclic hyd oca bons Oxygen con aining compounds Te penes and e penoids Cycloalkanes Cycloalkenes Ke ones O he oxygen con . Te penes, con . oxygen Te penes, no oxygen O he iden i ied Figu e 2: Pe cen age o he TIC peak a eas o a ious py olysis p oduc s g oups and he s anda d de ia ion o he esul s. 10 8 6 4 2 0 TIC a ea (a.u.) 02040 Re en ion ime (min) A A A A A A AA A A AA A AAA x x x x x x xx x x xx x xx xxx xxx o o o oooooo N A oma ics, one benzene ing n-alk-1-enes and o he alkenes n-alkanes Dienes Te penes and e penoids, including esin acids and s e oids Naph henes Numbe o ca bon a oms A x o T N 3–17 3–5 2-nonadecanone 6 7 8 8 9 9 10 11 11 12 13 14 15 16 16 17 ×105 Figu e 3: The main p oduc s o med in he py olysis expe imen s (750◦C and 20 s) wi h neu alised TOFA. Numbe s indica e he amoun o ca bon a oms in a molecule. Table 1: Composi ion o o al ex ac i es (% o he o al). TOFA TOR Fo mula Fa y acids Palmi ic acid 0.1 ∗C16H32O2 Ma ga ic acid 0.1 C17H34O2 17:0 an eiso 0.1 C17H34O2 Linolenic acid 8.5 C18H30O2 Linoleic acid 48.1 C18H32O2 Oleic acid 24.6 C18H34O2 S ea ic acid 3.5 ∗C18H36O2 18:2 (conjuga ed) 0.8 C18H32O2 18:2 (conjuga ed) 1.8 C18H32O2 18:2 (conjuga ed) 2.4 C18H32O2 18:3 (conjuga ed) 0.9 C18H30O2 10-Nonadecenoic acid 1.1 C19H36O2 Nonadecanoic acid 0.2 C19H38O2 Eicosa ienoic acid 1.2 C20H34O2 Eicosadienoic acid 0.2 C20H36O2 Eicosenoic acid 0.2 C20H38O2 A achidic acid 0.2 0.4 C20H40O2 Behenic acid 2.2 C22H44O2 Lignose ic acid 0.5 C24H48O2 94.0 3.1 Resin acids Secohyd oabie ic acid ∗C20H30O2 8,15-Isopima idien-18-oic acid ∗1.3 C20H30O2 8,15-Pima adien-18-oic acid 1.8 1.1 C20H30O2 Pima ic acid 1.0 3.3 C20H30O2 Sanda acopima ic acid 0.1 1.2 C20H30O2 Isopima ic acid 0.1 4.3 C20H30O2 Palus ic acid 10.6 C20H30O2 Dihyd oabie ic acid 0.5 C20H32O2 Le opima ic acid 0.3 C20H30O2 Dehyd oabie ic acid 21.4 C20H28O2 Abie ic acid 36.2 C20H30O2 Abie a e aenoic acid 1.0 C21H28O2 Neoabie ic acid 1.7 C20H30O2 Isodehyd oabie ic acid ∗C20H30O2 Hyd oxydehyd oabie ic acid 1.2 C20H28O3 Uniden i ied hyd oxy esin acid 1.4 C20H30O3 Dihyd oxydehyd oabie ic acid 0.3 C20H28O4 Hyd oxy-7-oxodehyd oabie ic acid 0.4 C20H26O4 3.0 86.2 Unknown 3.0 10.7 ∗ T aces o he compound de ec ed in quali a i e analysis, no enough o he quan i ica ion. Abb e ia ions: TOFA: neu alised all oil a y acid mix u e and TOR: neu alised all oil esin acid mix u e. explaining a conside able amoun (abou 13% o he o al compounds, Figu es 2and 3)o a oma icsde ec edin he TOFA py olysa e. The amoun o a ious uniden i ied compounds was abou 29% o he o al compounds. ISRN Renewable Ene gy 5 Table 2: Classi ica ionao alipha ic py olysis p oduc s (including hei o mula) om he all oil s udies. n−Alk-1-enes and o he alkenes 1-Hexene C6H12 1-Hep ene C7H14 1-Oc ene and o he oc enesbC8H16 1-Noneneband o he nonenesbC9H18 1-Deceneband o he decenesbC10H20 1-Undecene and o he undecenesbC11H22 1-Dodecene and o he dodecenesbC12H24 1-T ideceneband o he idecenesbC13H26 1-Te adeceneband o he e adecenesbC14H28 1-Pen adecenebC15H30 1-HexadecenebC16H32 1-Hep adecenebC17H34 Alkanes Hep ane C7H16 Oc ane C8H18 NonanebC9H20 DecanebC10H22 Undecane C11H24 DodecanebC12H26 T idecane C13H28 Te adecanebC14H30 Pen adecanebC15H32 Dienes 2-Me hyl-2,3-hexadiene C7H12 2,5-Dime hyl-2,4-hexadienecC8H14 1,3-Oc adienebC8H14 1,3-NonadienebC9H16 1,4-Undecadieneband 2,4-undecadienebC11H20 2,4-DodecadienebC12H22 1,9-Te adecadienebC14H26 1,15-HexadecadienebC16H30 6,8-Hep adecadienebC17H32 Cycloalkanes Bu ylcyclopen anebC9H18 Nonylcyclopen anebC14H28 NonylcyclohexanebC15H30 Cycloalkenes Me hylcyclopen adienecC6H8 1-Me hyl-1,4-cyclohexadiene C7H10 3-E henylcyclopen enebC7H10 5,6-Dime hyl-1,3-cyclohexadienecand C8H12 1,5-dime hyl-1,4-cyclohexadienec 1,3,8-p-Men ha iene C10H14 1,4-Dime hyldihyd oazulenecC12H14 Te penes and e penoids α-Te pinenecC10H16 Δ3-Ca enecC10H16 LimonenecC10H16 ChamazulenecC14H16 1,4-dime hyl-7-(1-me hyle hyl)azulenecC15H18 S igmas an-3,5-diencC29H48 Te penes and e penoids con aining oxygen Bo neolcC10H18O 1-Me hyloes a-1,3,5(10)- ien-18-no -17-ke onecC18H22O Ke ones 2-DodecanonebC12H24O 2-NonadecanonebC19H38O Table 2: Con inued. O he Oxygen con aining compounds 10,12-HexadecadienalbC16H28O 9,12,15-Oc adeca ien-1-olbC18H32O O he s 1,4-Bis(me hylene)cyclohexanecC8H12 5-Dodecen-7-ynebC12H20 1-(2-Me hyl-1-p openyl)-7-(1-p opynyl)- icyclohexanecC8H12 1-HexadecynebC16H30 Hexae hylidenecyclohexanecC18H24 10-Deme hylsqualenecC19H48 aCompounds a e lis ed wi hin each subs ance g oup acco ding o hei GC e en ion imes. bOnly in he py olysa e o neu alised TOFA. cOnly in he py olysa e o neu alised TOR. 14 12 10 8 6 4 2 0 TIC a ea (a.u.) 0 20406080 Re en ion ime (min) ×105 A A AA A A A A A A A A A A A A A2 A2 A2 A2 A2 A2 A2 A2 A2 A3 A3 T T T T N N A oma ics, one benzene ing A oma ics, wo benzene ings A oma ics, h ee benzene ings Dienes Te penes and e penoids, including esin acids and s e oids Naph henes Numbe o ca bon a oms A2 A A3 T N 6–8 67 8 3–5 Figu e 4:Themainp oduc s o medin hepy olysisexpe imen s (750◦C and 20 s) wi h neu alised TOR. Numbe s indica e he amoun o ca bon a oms in a molecule. The main compounds in he py olysa e om he neu- alised TOR cha ac e is ically comp ised a ious a oma ics wi h one o h ee benzene ings, while a lowe amoun o alipha ic hyd oca bons could clea ly be de ec ed (Figu es 2 and 4, Tables 2and 3). In his case, he po ion o unknown py olysis p oduc s was e y high (app ox., 44%). Howe e , i could be assumed (based also on MS spec a) ha a la ge po ion o hese uniden i ied compounds consis o a wide ange o polya oma ic hyd oca bon de i a i es. Fo example, i has been ound ea lie [26] ha he mos abundan esin acid-de i ed py olysis p oduc s a e naph halene de i a i es. Mo eo e , py olysis expe imen s wi h abie ic acid [27] indica ed ha besides agmen a ion and deca boxyla ion eac ions, dehyd ogena ion is o impo ance, sugges ing 6ISRN Renewable Ene gy Table 3: Classi ica ionao a oma ic py olysis p oduc s (including hei o mula) om he all oil s udies. A oma ics, one benzene ing Benzene C6H6 Toluene C7H8 E hylbenzene C8H10 S y ene C8H8 o-Xylene and p-xylenecC8H10 CumenecC8H12 P openylbenzene C9H12 IsocumenebC9H12 o-E hyl oluene and m-e hyl oluene C9H12 α-Me hyls y olcC9H10 m-Vinyl oluenebC9H10 2-Isop opyl oluene C10H14 IndanebC9H10 Indene C9H8 1,2-Die hylbenzenecC10H14 m-P opyl oluenecand o-p opyl oluenebC10H14 Bu ylbenzenebC10H14 β-Dime hyls y ene C10H12 2,5-Dime hyls y enecC10H12 p-Me hylcumenecC10H14 o-Allyl oluenecC10H12 2-Bu enylbenzene C10H12 α,p-Dime hyls y enecC10H12 p-E hylcumenecC11H16 2-Phenyl-2-pen ene C11H14 2,4-Dime hylcumenecC11H16 1-Me hylindenebC10H10 o-Isop opyl-α-me hyls y enecC12H16 Phenop enecC10H10 Pen ylbenzenebC11H16 1,2-Dihyd onaph halenebC10H10 p-Isobu yl oluenebC11H16 3-Phenyl-2-pen enecC11H14 1,1-Dime hylindene C11H12 T ime hyl(1-me hyle hyl)benzenecC12H18 2,3-Dihyd o-1,1,6- ime hylindenecC12H16 1,4-Dime hyl e alincC12H16 1,3-Dime hylindenecand 4,7-dime hylindenecC11H12 1,2-Die hyl-3,4-dime hylbenzenecC12H18 HexylbenzenebC12H18 (1-Me hylbu a-1,3-dienyl)benzenecC11H12 1,2-Dihyd o-3-me hylnaph halenecC11H12 1,1,3-T ime hylindenecC12H14 β,2,4,6-Te ame hyls y enecC12H16 1,1,6-T ime hyl e alincC13H18 1-Phenyl-1,3-hexadienecC12H14 Hep ylbenzenebC13H20 o-Hexyl oluenebC13H20 (2,4,6-T ime hylphenyl)allenecC12H14 1,1-Dime hyl-3- inylindancC13H16 Oc ylbenzenebC14H22 3-E hyl-1-(1-me hyle hyl)indenecC14H18 NonylbenzenebC15H24 DecylbenzenebC16H26 Me hyl-1-me hyleneoc ahyd ophenan h enecC16H20 UndecylbenzenebC17H28 4,8-Die hyl-1,5-dime hyldicyclopen a[a,d]benzenecC18H26 Table 3: Con inued. A oma ics, wo benzene ings Naph halene C10H8 α-Me hylnaph halene and β-me hylnaph halene C11H10 1,3-Dime hylnaph halene and C12H12 2,6-dime hylnaph halenec 1-E hylnaph halenecC12H12 2-E henylnaph halenecC12H10 2-(1-Me hyle hyl)naph halenecC13H14 1,4,5-T ime hylnaph halenecC13H14 1,2,3,4-Te ame hylnaph halenecC14H16 1-Me hyl-7-(1-me hyle hyl)naph halenecC14H16 4,4-Dime hyl-1,1-biphenylcC14H14 1,6-Dime hyl-4-(1-me hyle hyl)naph halenecC15H18 9,10-Dihyd o-1-me hylphenan h enecC15H16 1,1-Diphenyl-1,3-pen adienecC17H16 Bis(1-me hyle hyl)-1,1-biphenylcC18H22 9-Bu yl-1,2,3,4- e ahyd oan h acenecC18H22 A oma ics, h ee benzene ings 1-Me hyl-phenan h enecC15H12 2,3,5-T ime hylphenan h enecC17H16 1-Me hyl-7-(1-me hyle hyl)phenan h enecC18H18 Me hyl-n-p opylphenan h enecC18H18 Phenolics and o he oxygen con aining a oma ics PhenolbC6H6O 2-Me hylphenolcC7H8O 2,5-Dime hylphenolcC8H10O 1-(2,4-Dime hylphenyl)e hanonecC10H12O 4-(1-Me hyle hyl)benzeneme hanolcC10H14O 2,3-Dihyd o-3,3-dime hylinden-1-olcC11H14O 1-(1,1-Biphenyl)-4-yl-e hanonecC14H12O Isoma u nincC16H14O3 aCompounds a e lis ed wi hin each subs ance g oup acco ding o hei GC e en ion imes. bOnly in he py olysa e o neu alised TOFA. cOnly in he py olysa e o neu alised TOR. he mochemical s abili y o he decahyd ophenan h ene ing s uc u e. In he py olysis o neu alised TOR, as was also he case wi h neu alised TOFA, no signi ican amoun s o phenolics we e o med. The o al amoun o py olysis p oduc s eco e ed om labo a o y-scale py olyse s is no mally a he low, e en hough hese p oduc s can be conside ed o e lec well he main chemis y in ol ed. In ou expe imen s, quan i a i e analyses indica ed ha he de ec able amoun s o lique iable p oduc s we e (exp essed as % o he ini ial d y solids) 1.4% om neu alised TOFA and 1.1 om neu alised TOR. 4. Conclusions The main indings om his s udy can be summa ised as ollows. (i) The composi ion o all oil soap has a clea effec on he composi ion o py olysis p oduc s o igina ing om i . The cha ac e is ic agmen a ion pa e ns o his eeds ock ma e ial can be de ec ed. The effec s ISRN Renewable Ene gy 7 o he main cons i uen s in he aw ma e ial on he dis ibu ion o py olysis p oduc s a e ypically seen. (ii) Resin-acid-con aining soaps mainly esul in he p onounced o ma ion o a oma ics du ing py olysis, whe eas alipha ic unsa u a ed and sa u a ed hyd o- ca bons can be p incipally ob ained om a y acid- con aining soaps. (iii) When conside ing he possible all oil-based p o- duc ion o enewable diesel, wi h espec o p oduc quali y (i.e., he need o low con en s o a oma ics and oxygen-con aining compounds), a y-acid- ich ac ions seem o be mo e sui able eeds ocks han esin-acid- ich ac ions. Acknowledgmen s The au ho s g a e ully acknowledge inancial suppo om he Finnish Minis y o Educa ion, wi hin he amewo k o he In e na ional Doc o al P og amme in Pulp and Pape Science and Technology (PaPSaT). Special hanks a e due o Ms. Ma ia Luh ala o he skil ul assis ance wi h he analy ical wo k. The au ho s wish o hank Fo chem Oy om Finland o kindly p o iding he samples. Re e ences [1] B. 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