TECHNOLOGICAL CHALLENGES FOR THE …

1 Universidad de C rdoba (Espa a) TECHNOLOGICAL CHALLENGES FOR THE production OF biodiesel IN ARID LANDS Diego LunaDepartamento de Qu mica Org nica, Universidad de C rdoba, Campus de Rabanales, Edificio. Marie Curie, E-14014 C rdoba, Spain. Green Catalyst, Campus de Rabanales, E-14014 C rdoba, FOR BIOFUELS AND biodiesel IN ARID LANDS (BIO3) Friday, November 26, 2010 Universidad de C rdoba (Espa a)Hexadecane (also called cetane) is an alkane hydrocabon with the chemical formula C16H34, a chain of 16 carbon atomsMolecular formulaC16H34 Molar g/molMelting point18 C, 291 K, 64 FBoiling point287 C, 560 K, 549 FSolubility in waterInsolubleFlash point135 CAutoignition temperature201 CTriglyceride molecule modelFriday, November 26, 2010 Universidad de C rdoba (Espa a)Conventional Transesterification process of triglyceride moleculesBiodiesel typically comprises of fatty acid (chains C14 C22) esters of short-chain alcohols, mainly methanol Three molecules of fatty acid methyl esters (FAME) and one molecule of glycerol are generated for every molecule Friday, November 26, 2010 Universidad de C rdoba (Espa a)

2 Strengths and weaknesses of the available different methods for the production of the mixtures of methyl esters of fatty acids that constitute FAME, the conventional Temperature/ C Economic charges Improvements Basic reactionN a O H , KOH60 Low Available technologyAcid reactionH2SO455 - 120 LowDo not form soapssupercritical alcohol -239-385 Medium Uses no catalyste n z y m a t i c processLipases45 -55 HighLow level of wastesFriday, November 26, 2010 Universidad de C rdoba (Espa a)Pilot scale material balance for Jatropha oil transesterification using NaOH (1 %) as catalyst Friday, November 26, 2010 Universidad de C rdoba (Espa a)Lurgi Transesterification , November 26, 2010 National Sustainable Agriculture Information is the national sustainable agriculture information service operated by the National Center for Appropriate Technology, through a grant from the Rural Business-Cooperative Service, Department of Agriculture.

3 These organizations do not recommend or endorse products, companies, or individuals. NCAT has offices in Fayetteville, Arkansas ( Box 3657, Fayetteville, AR 72702), Butte, Montana, and Davis, CaliforniaBy David Ryan, Energy SpecialistDecember 2004 NCAT 2004 biodiesel - A PrimerAbstract: This publication is an introduction to biodiesel productionWashing BiodieselUnwashed biodiesel will not meet ASTM (American Society of Testing and Materials) standards. For more information about ASTM standards, and testing and specifications for biodiesel and other diesel fuels, see Resources. Remember, equipment and engine manufacturers only warranty their equipment and engines for their material and manufacturer defects. Fuel manufacturers (in this case, you) assume responsibility for any damage caused by the fuel. Washing biodiesel is easy to do, and requires only water and de C rdoba (Espa a)Friday, November 26, 2010 Universidad de C rdoba (Espa a)Processes of Dehydration (1), Oxidation (2) and Polymerization (3), undertaken by the residual glycerol in the biodiesel , inside the engines working at higher , November 26, 2010 Universidad de C rdoba (Espa a)Polymer deposition resulting from a use of biodi sel with an inadequate oxidation resulting from soap deposition (bio-diesel with an excessively high alkaline or alkaline earth content).

4 Friday, November 26, 2010 Universidad de C rdoba (Espa a)Friday, November 26, 2010 Universidad de C rdoba (Espa a) production of high-quality biofuel from vegetable oils through removal of oxygen in triglyceride molecules by overall hydrotreatment in conventional , November 26, 2010 Universidad de C rdoba (Espa a)Composition of the high-quality biofuels obtained from vegetable oils through the hydroprocessing routes to transportation fuels in conventional biogasoline hydrobiodiesel (or H- biodiesel ) Friday, November 26, 2010 Universidad de C rdoba (Espa a)DMC-BIOD is a patented biofuel (Notari and Rivetti, 2004) that integrates the glycerine as glycerol carbonate, in a process that can be developed by enzymatic technology (Su et al, 2007) obtained by crossed transesterification reaction of a triglyceride with dimethyl carbonate, obtaining a mix of three moles of FAMEs and one mole of glyceryl carbonate (GC).

5 Friday, November 26, 2010 Universidad de C rdoba (Espa a)Gliperol is a biofuel patented by the Industrial Chemistry Research Institute of Varsow (Poland), (Kije!ski et al, 2004), consisting of a mixture of three moles of FAME or FAEE and a mole of triacetin, that can be obtained by the cross transesterification of ethyl acetate and the corresponding triglycerides in an enzymatic catalyzed process (Modi et al., 2007).Friday, November 26, 2010 Universidad de C rdoba (Espa a)Ecodiesel , is a biofuel which incorporates the glycerol as monoglyceride, produced by enzymatic technology and patented by the University of Cordoba (Luna et al, 2007). It is composed of two moles of ethyl esters of fatty acids (FAEE) and a mole of monoglyceride ( MG).Friday, November 26, 2010 Universidad de C rdoba (Espa a). (TRIOLEIN) (TG !!>DG) [MW: TG " 3/2 DG]CH3-(CH2)7-CH=CH- (CH2)7-COO-CH2 CH3-(CH2)7-CH=CH-(CH2)7-COO-CH2 # k1 #CH3-(CH2)7-CH=CH- (CH2)7-COO-CH !

6 !>CH3-(CH2)7-CH=CH-(CH2)7-COO-CH # #CH3-(CH2)7-CH=CH- (CH2)7-COO-CH2 + CH2OH CH3-(CH2)7-CH=CH-(CH2)7-COOCH2CH3 (FAEE) (DG !!>MG) [MW: DG " 1/2 MG]CH3-(CH2)7-CH=CH- (CH2)7-COO-CH2 CH2OH # k2 #CH3-(CH2)7-CH=CH- (CH2)7-COO-CH !!>CH3-(CH2)7-CH=CH-(CH2)7-COO-CH # # CH2OH + CH2OH 2 CH3-(CH2)7-CH=CH-(CH2)7-COOCH2CH3 (FAEE)Friday, November 26, 2010 Universidad de C rdoba (Espa a)Fuel properties of mineral diesel, Jatropha biodiesel , Jatropha DieselJatropha BiodieselJatropha OilDensity(kg/m3) 840 1 Kinematic Viscosity at 40 C (cst) Point ( C)6 1 3 14 1 Flash Point ( C) 71 3191229 4 Conradson Carbon Residue (%,w/w) Content (%, w/w) 0.

7 Value (MJ/kg) (%, w/w) < No. 48-5651-5223-41 Carbon (%, w/w) (%, w/w) (%, w/w) , November 26, 2010 Universidad de C rdoba (Espa a)Propertiessoybean oilFAMEaFAMEbFAEEcDiesel Specific gravity (g cm-3) (40oC, cSt or m2/s) point (oC) point (oC) point (oC)27411017917074 Boiling point (oC)357366347273191 Cetane (%wt) of combustion (KJ/Kg) FAME stands for fatty acid methyl esters from soybean oilb FAME stands for fatty acid methyl esters from rapeseed oilC FAEE stands for fatty acid ethyl esters from rapeseed oil Physico-chemical properties of soybean oil, biodiesel (B100) obtained from soybean oil and rapeseed oil and No. 2 diesel (D2) (Peterson and Reece, 1996).Friday, November 26, 2010. Kinematic viscosity values, ! (cSt or mm2/s) at 40 C of various representative biodiesel blends as well as commercial diesel and Oil/AlcoholFAEMG+DGTGY ieldConv.!1 Sunflower / / / (1:1)e (8:2)e catalyst NaOHbHomogeneous catalyst KOHcFree PPLdSynthetic biodiesel blendeBlend of commercial diesel and biodiesel with viscosity, $ = cSt.

8 (Caballero, V., et al., 2009; Process Biochem. 44, 334 342) Friday, November 26, 2010. Influence of lipase (from Termomyces lanuginosus) amount in conversion and kinematic viscosity, of reactions carried out at oil/ethanol volume ratio 12 and pH near to 12, and 20 C of reaction , C., et al. 2010; Cost Action CM0903 (UBIOCHEM), 1st Workshop, 13-15 May, C rdoba (Spain). Friday, November 26, 2010. Figure 9. Influence of water content in conversion and kinematic viscosity of reactions carried out with g of lipase (from Termomyces lanuginosus), at oil/ethanol volume ratio 12 and pH near to 12, and 20 C of reaction , November 26, 2010. Friday, November 26, 2010. Friday, November 26, 2010. Friday, November 26, 2010. ! Regarding the introduction of renewable energies, in most cases we find today with an uncomfortable truth: currently available technologies require an excessive amount of water Therefore, in the absence of a major TECHNOLOGICAL advancement in these technologies is predictable a scenario in which the availability of water would be a real limiting factor in the production of biofuels in arid lands, more important even that those due to the own production of crops where are obtained the corresponding raw materials.

9 " In this future scenery, nonirrigated vegetable oils could offer an increasingly integration within crude-petrol refineries for fuels blending after hydrotreating in flows of hydrogen with conventional catalysts. In this way introducing fuels based upon feedstocks other than petroleum will be smooth and gradual, providing a production of the same commodities currently demanded but considering their renewable character are now named Hidrobiodiesel, biogasoline and bioLPG, respectively. Concluding remarks" The logistical problems associated with the transport of the oils and fats, for its treatment in conventional refineries, can also to be decisive to indicate it s processing in a specific plant for develop the transesterification process. In these cases, the biofuel plant can be considered as an additional treatment to that required by any energetical seed, after the oil extraction to be transformed in biofuel.

10 However, in water-poor regions will be required use any of the processes that integrate the glycerine into the biofuel, because these technologies hardly need water to , November 26, 2010. ! Among the three alternative technologies currently available for the synthesis of new biofuels that integrate the glycerine, those which is based on the selective production of monoglycerides is technologically the simplest and less demanding in water and energy because ethanol, the reagent used in this case, is clearly much less expensive and easier to obtain than diethyl carbonate or methyl acetate, which are the reagents used by the other alternative technologies. ! This technology that integrates glycerine as monoglyceride, can also be applied to a very small production scale and with a minimal investment, compared with current oil refineries, so that it could be installed in areas close to where crops are produced (the biofuel plant is become actually in an additional treatment after the oil extraction of crops)