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Energies 2019, 12, x FOR PEER REVIEW Energies 2019, 12, x FOR PEER REVIEW Energies 2019, 12, x FOR PEER REVIEW hEignehrgileisg2n01i9n, 1c2o, 8n0t9ent and requires significant lignin pretreatment before biochemical con8voefr4s1ion. high lignin content and requires significant lignin pretreatment before biochemical conversion. high lignin content and requires significant lignin pretreatment before biochemical conversion. These feedstocks are more appropriate for thermal or thermochemical conversion without any These feedstocks are more appropriate for thermal or thermochemical conversion without any Tphrees-eprfoeecedsstioncgk.sThareelamstocroeluamppnrofpTraiabtle 1foprrothveidrmesatlheorathioeromf coeclhluelmosiceaalncdohnevmeriscieolnlulwosiethtoultiganniny, pre-processing. The last column of Table 1 provides the ratio of cellulose and hemicellulose to lignin, pwraeph-picrohopcmreisastyeinifgno.drTitchaetremlatashtleocaorpltuhpmerromnporoicfahTteampbilrceoac1lecpsosrnionvegirdfsoeiorsnethwaecihtrhaloitguiont oancfeyclelpullruleo-lpsoirscoefceaeenssdisnhtgoe.cmTkh.iceelalustlocoselutmonligofnin, which may indicate the appropriate processing for each lignocellulosic feedstock. wThaibclhe m1 payroivnideicsattheetrhaetiaopopf rcoepllruilaotseeparnodcehsesminicgefllourloesaechtolliignoinc,ewlluhliochsicmfaeyedinsdtoicakt.e the appropriate 3p.rHocyedssrion-gPfrorcesascihnlgigonfoTcerlilgulyocseicrifdeedsstock. 3. Hydro-Processing of Triglycerides 3. Hydro-Processing of Triglycerides In a conventional refinery hydro-processing describes the catalytic processes in which various 3. Hydro-Processing of Triglycerides In a conventional refinery hydro-processing describes the catalytic processes in which various petrIonleaucmondvisetniltliaotneaslrereafcitnweriythhHyd2 arot-eplervocaetesdsintegmdpeesrcartiubreesathnedcparteaslsyutirceptorofocermssetsrainswpohritcahtiovnarfiuoeuls petrolIenuamcdonisvtielnlatitoensarlearecfitnweirtyhhHy2dartoe-plervoacetesdsintegmdpeescrraitbuersetahnedcaptraelysstiucrpertocefossrmestinrawnshpicohrtvaatiroionufsuels paetnrdolheeuamtindgisotill.aTtehsisreisacatcwcoimthpHlis2haetdeltehvraotuedghtetmhepdereastururcetaivnedhpyrdersosugerenatotiofonrmof trhaenhspeaovrtyadtiiosntilfluaetels anpedtrhoeleautimngdoisitl.ilTlahteis irseactcwomithplHis2haetdetlehvraotuegdhtetmhepdereastturruecatinvde phryedssruorgeetnoaftoiormn otrfatnhsephoertaavtiyondifsuteilllsates anindtoheliagthintegrowil.itThhaispipsraocpcroiamteplbisohileindgthproiungt hanthdetdherosturguhctitvhe hnyodnr-odgeestnrautciotinveofhtyhderohgeeanvaytidoinstiollfathese and heating oil. This is accomplished through the destructive hydrogenation of the heavy distillates into lighter with appropriate boiling point and through the non-destructive hydrogenation of the inltigohltigdhistetirllawteitshwahpipchroipmripartoevbeos itlhinegir pqouianltityan[d51t,5h2r]o.uDgehsttrhuectnivoenh-dyedsrtorugcetnivateiohnyodrohgyednraotciroanckoifngthies into lighter with appropriate boiling point and through the non-destructive hydrogenation of the light distillates which improves their quality [51,52]. Destructive hydrogenation or hydrocracking is ligfahvtodreisdtilblaytehsiwghitcehmimpeprraotuvreesst,hheigrhquhaylidtyro[g5e1n,52p]r.eDsseustrreusctainvde hsytrdornogeancaidtiocnatoarlyhsytds raoncdrackaitnaglyisst light distillates which improves their quality [51,52]. Destructive hydrogenation or hydrocracking favored by high temperatures, high hydrogen pressures and strong acid catalysts and catalyst fasvuoprpeodrtbsy(ahluigmhintoe-msipliecraatetus,resisl,ichoi-gahlumhyindoro-pgheonsphreastessur(eSsAPanOd) asntrdonzegolaitceids).cTaytapliycsatlscoanditcioantaslyfostr is favored by high temperatures, high hydrogen pressures and strong acid catalysts and catalyst supports (alumino-silicates, silico-alumino-phosphates (SAPO) and zeolites). Typical conditions for suthpephorytdsr(oaclruamckininog-soilfictahtesp,estirloicleou-amludmisintioll-aptehsoaspreh3a5te0s–4(S3A0 P°CO)ata1n0d0-z2e0o0libteasr).wTiythpiacaslpcaocendvietliocnistyforf supports (alumino-silicates, silico-alumino-phosphates (SAPO) and zeolites). Typical conditions for the hydrocracking of the petroleum distillates are 350–430 °C at 100-200 bar with a space velocity of −1 33 th0e.2h–y2dhrocraancdkinHg2/ofefetdherapteiotrsoloefum800d–i2st0i0ll0atmes /amre 3[502–,543]0.◦ °NCoant-d1e0s0t-r2u0c0tibvaer hwyidthroagespnactieonveilsocciatylleodf the hydrocracking of the petroleum distillates are 350–430 C at 100-200 bar with a space velocity of 0.2–2 h−1 and H2/feed ratios of 800–2000 m3/m3 [52,53]. Non-destructive hydrogenation is called −1 33 0.h2y–d2rhotr−e1antmdeHnt2/afeneddisrafativoosreodf b80y0m–2i0ld00tem3p/mera3t[u5r2e,s5,3m].iNldopnr-edsessutruesctaivnedhcaytdarlyosgtesnoaftimonildisaciadllietyd. 0.2–2 h and H2/feed ratios of 800–2000 m /m [52,53]. Non-destructive hydrogenation is called hydrotreatment and is favored by mild temperatures, mild pressures and catalysts of mild acidity. hyOdfrtohterseeatmhenmtoasntdcoims fmavoonretydpbeys amreildthteesmuplfeidraetdurNesi–,Wm/iAldl2pOr3e,sCsuo–reMsoa/nΑdl2Oca3talnydstNs oi–fMmoi/lΑdla2Oci3d[i5ty2]. hydrotreatment and is favored by mild temperatures, mild pressures and catalysts of mild acidity. Of these the most common types are the sulfided Ni–W/Al2O3, Co–Mo/Αl2O3 and Ni–Mo/Αl2O3 [52] which are also used for the hydrodesulfurization of petroleum distillates [54]. Of these the most common types are the sulfided Ni–W/Al2O3, Co–Mo/Αl2O3 and Ni–Mo/Αl2O3 [52] Of these the most common types are the sulfided Ni–W/Al2O3, Co–Mo/Al2O3 and Ni–Mo/Al2O3 [52] which are also used for the hydrodesulfurization of petroleum distillates [54]. In the biofuel industry hydro-processing describes the chemical reaction of the triglycerides wwhihcihcharaereaalslsoouusseedfforthe hydrodesullffurrizizaatitoionnoof fppetertorloeluemumdidstislltailtleaste[5s4[]5.4]. In the biofuel industry hydro-processing describes the chemical reaction of the triglycerides contained in biomass lipids with H2 for the production of liquid hydrocarbon fuels [55]. H2 saturates InInththeebbioiofufueelliindustry hydro-processiingddeessccrribibeessththeechcehmemiciaclarleraecaticotnioonfothfethtreigtlryigcelyricdeerisdes contained in biomass lipids with H2 for the production of liquid hydrocarbon fuels [55]. H2 saturates the double bonds of the triglycerides and under specific conditions may provide different liquid cocnotnatianinededininbbioiomaassslliipids with H2 for theprroodduucctitoionnoof flilqiuqiudidhyhdyrdorcoacrbaorbnofnuefluse[l5s5[]5. 5H]. Hsa2tsuartautersates 22 the double bonds of the triglycerides and under specific conditions may provide different liquid ftuhelds osubclhe absongdres eonf tdhiestreilg(lyCc1e5–riCd1e8s),agnrdeeundjetr fsupelci(fiCc11c–oCn1d3)itaionnds mgraeyenprnoavpidhethdaiff(eCr5e–nCt 1l0i)q.uOidbvfuioelussly, the double bonds of the triglycerides and under specific conditions may provide different liquid fuels such as green diesel (C15–C18), green jet fuel (C11–C13) and green naphtha (C5–C10). Obviously, tshuechpraosdgurceteionndoiefsleilgh(Ct fu–eCls s),ucghreaesn gjerteefunenl a(Cpht–hCa re)qaunidresgrceoendnitaiponhsthoaf(hCig–hCtem). pOerbavtiuorues,lyh,igh fuels such as green diese1l5 (C158–C18), green jet fue1l1(C11–3 C13) and green naphtha5 (C51–0C10). Obviously, the production of light fuels such as green naphtha requires conditions of high temperature, high pthresspuroreduanctdiosntrofngligahcitdfiuceclastasluycshtsasndgrseuepnpnoartpshthat rperqoumiroetsechoyndrioticornasckoinf gh.iOghn tehmepoethraetruhrea,nd, the production of light fuels such as green naphtha requires conditions of high temperature, high pressure and strong acidic catalysts and supports that promote hydrocracking. On the other hand, thieghprpordesuscutrioenanodf hsteraovnyg garceideinc fcuaetalslysutschanads sgurpeepnordtsietshealtrperqoumiroetsechoyndrioticornacsktihnagt. pOrnomthoeteotmhearinly pressure and strong acidic catalysts and supports that promote hydrocracking. On the other hand, the production of heavy green fuels such as green diesel requires conditions that promote mainly hyadnrdo,ttrheeatpmroendtu,ctailotnhoufgheahvydgrroecernacfkuienlgssmucahyasalgsoreebneduiesedlretoquairelsimcoitneditieoxntsenthtatoprcoamusoetethe the production of heavy green fuels such as green diesel requires conditions that promote mainly hydrotreatment, although hydrocracking may also be used to a limited extent to cause the mainly hydrotreatment, although hydrocracking may also be used to a limited extent to cause the isomerization of the hydrocarbons. In this respect, the conversion of triglycerides into green diesel hydrotreatment, although hydrocracking may also be used to a limited extent to cause the isomerization of the hydrocarbons. In this respect, the conversion of triglycerides into green diesel isomerization of the hydrocarbons. In this respect, the conversion of triglycerides into green diesel requires mild temperatures in the range of 280–450 °C, pressures of 1–5 MPa and solid catalysts of isomerization of the hydrocarbons. In this respect, the conversion of triglycerides into green diesel ◦ maiclidiatyci[d5i6t]y.T[h56e]s.uTlfihdeedsuNlfi–dMedo/NAil–OMo,/CΑol–2OM3o,/CAol–OMoa/nΑdl2NOi3–Wan/dANl Oi–Wca/Ataly2Ost3scmateanltyiostnsedmbeenftoiroened beforearethemostcommonlyused2 c3atalystsalso2for3thehydrotrea2tm3entofthetriglyceridesandan mild acidity [56]. The sulfided Ni–Mo/Αl2O3, Co–Mo/Αl2O3 and Ni–W/Al2O3 catalysts mentioned rerqequuirireessmild tempeerraatutureressininthtehreanragnegoef 2o8f02–84500–45C0, p°Cre,sspurreessuofre1s–5oMf 1P–a5aMndPsaolaidndcastaolyidstscaotfamlyisldts of mild acidity [56]. The sulfided Ni–Mo/Αl2O3, Co–Mo/Αl2O3 and Ni–W/Al2O3 catalysts mentioned requires mild temperatures in the range of 280–450 °C, pressures of 1–5 MPa and solid catalysts of baerfeortheeamreotshtecomomstocnolymumseodnclaytaulsyesdtscaalstoalfyosrttshaelhsoydfororttrheaetmhyedntrotfrtehaetmtriegnlytcoefritdheestarnigdlaynceardidvaenstangde an advantage of the hydro-processing route for green diesel production is that it can be easily before are the most commonly used catalysts also for the hydrotreatment of the triglycerides and an adofvtahnetahgyedrof-ptrhoeceshsyindgroro-purtoecfeosrsginregenroduietseelfporodgurecetinondiisetshealt pitrcoadnubcetieoansiliys atchcaotmiptlicsahnedbine tehaesily accomplished in the existed refinery facilities used for the hydro-processing and hydro- advantage of the hydro-processing route for green diesel production is that it can be easily existed refinery facilities used for the hydro-processing and hydro- desulfurization of the petroleum accomplished in the existed refinery facilities used for the hydro-processing and hydro- desulfurization of the petroleum fractions [55,56]. accomplished in the existed refinery facilities used for the hydro-processing and hydro- fractions [55,56]. desulfurization of the petroleum fractions [55,56]. The hydro-processing of a triglyceride initiates with the saturation of the double bonds of its desulfurization of the petroleum fractions [55,56]. The hydro-processing of a triglyceride initiates with the saturation of the double bonds of its The hydro-processing of a triglyceride initiates with the saturation of the double bonds of its fatty acid chains by hydrogen (hydrogenation) and continues with the removal of oxygen from the The hydro-processing of a triglyceride initiates with the saturation of the double bonds of its fatty acid chains by hydrogen (hydrogenation) and continues with the removal of oxygen from the fatty acid chains by hydrogen (hydrogenation) and continues with the removal of oxygen from the triglyceride molecules, which converts them into saturated hydrocarbons. The reactions causing the fatty acid chains by hydrogen (hydrogenation) and continues with the removal of oxygen from the triglyceride molecules, which converts them into saturated hydrocarbons. The reactions causing triglyceride molecules, which converts them into saturated hydrocarbons. The reactions causing the oxygen removal from the triglyceride molecule are commonly termed as reactions of selective triglyceride molecules, which converts them into saturated hydrocarbons. The reactions causing the the oxygen removal from the triglyceride molecule are commonly termed as reactions of selective oxygen removal from the triglyceride molecule are commonly termed as reactions of selective deoxygenation (SDO) and may be further classified into the reactions of hydrodeoxygenation oxygen removal from the triglyceride molecule are commonly termed as reactions of selective deoxygenation (SDO) and may be further classified into the reactions of hydrodeoxygenation (HDO), deoxygenation (SDO) and may be further classified into the reactions of hydrodeoxygenation (HDO), decarbonylation (deCO) and decarboxylation (deCO2), as shown in the following reactions deoxygenation (SDO) and may be further classified into the reactions of hydrodeoxygenation decarbonylation (deCO) and decarboxylation (deCO2), as shown in the following reactions [55,56]: (HDO), decarbonylation (deCO) and decarboxylation (deCO2), as shown in the following reactions [55,56]: (HDO), decarbonylation (deCO) and decarboxylation (deCO2), as shown in the following reactions [55,56]: 8 of 42 8 of 42 8 of 42 [55,56]: (1) (1) (1) (2) (2) (2) (3) Decarboxylation and decarbonylation are commonly referred as deCOx reactions. In decaDrbeocaxryblaotxiyolnattihoen Oa2nmdoldeecucalersboanryelaretimonoveadreinctohmemfornmlyofreCfOer2rewdhiales indedCeOcaxrbroenaycltaiotinosn. thIne Decarboxylation and decarbonylation are commonly referred as deCOx reactions. In doexcyagrbeonxymlaotlieocnultehse aOr2e mreomleocuvleeds arse CreOmoavned Hin2Oth.eInforbmotohf tChOes2ewdheilCeOinx cdaesceasrbtohneylsaatitounratehde decarboxylation the O2 molecules are removed in the form of CO2 while in decarbonylation the ohxydgreoncamrbolnecpurloesduacreedrheamsovnedCastomCOlesasntdhaHn2tOhe. pInarebnotthfatthyeasceiddcehCaOinx incatsheestrthigelycsaertuidrea.teIdn oxygen molecules are removed as CO and H2O. In both these deCOx cases the saturated hHydDrOoctahrebonxypgreondumcoeldechualsesoanre Crematovmedleesxsctlhuasnivethlye apsaHre2nOt faantdtythaceidsactuhraaitnedinhtyhderotrciagrlbyocenrihdaes. aIn hydrocarbon produced has one C atom less than the parent fatty acid chain in the triglyceride. In HDO the oxygen molecules are removed exclusively as H2O and the saturated hydrocarbon has an HDO the oxygen molecules are removed exclusively as H2O and the saturated hydrocarbon has an (3) (3)PDF Image | Green Diesel: Biomass Feedstocks, Production Technologies
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