www.senecagreen.com Universidad de Córdoba BIODIVERSITY FOR BIOFUELS AND BIODIESEL IN ARID LANDS (BIO3) TECHNOLOGICAL CHALLENGES FOR THE PRODUCTION OF BIODIESEL IN ARID LANDS Diego Luna Departamento de Química Orgánica, Universidad de Córdoba, Campus de Rabanales, Edificio. Marie Curie, E-14014 Córdoba, Spain. (qo1lumad@uco.es) Seneca Green Catalyst, Campus de Rabanales, E-14014 Córdoba, Spain.
Hexadecane (also called cetane) is an alkane hydrocabon with the chemical formula C 16 H 34, a chain of 16 carbon atoms Molecular formula C 16 H 34 Molar mass 226.44 g/mol Melting point 18 C, 291 K, 64 F Boiling point 287 C, 560 K, 549 F Solubility in water Insoluble Flash point 135 C Autoignition temperature 201 C Triglyceride molecule model
Conventional Transesterification process of triglyceride molecules Biodiesel 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
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 biodiesel. Technology Basic reaction A c i d reaction supercritical alcohol e n z y m a t i c process Catalys t N a O H, KOH Working Temperature/ C Economi c Improvements charges 60 Low Available technology H 2 SO 4 55-120 Low Do not form soaps - 239-385 Medium Uses no catalyst Lipases 45-55 High Low level of wastes
Pilot scale material balance for Jatropha oil transesterification using NaOH (1 %) as catalyst
Lurgi Transesterification Process.
ATTRA is the national sustainable agriculture information service operated by the National Center for Appropriate Technology, through a grant from the Rural Business- Cooperative Service, U.S. Department of Agriculture. These organizations do not recommend or endorse products, companies, or individuals. NCAT has offices in Fayetteville, Arkansas (P.O. Box 3657, Fayetteville, AR 72702), Butte, Montana, and Davis, California National Sustainable Agriculture Information Service www.attra.ncat.org By David Ryan, P.E. NCAT Energy Specialist December 2004 NCAT 2004 Biodiesel - A Primer Abstract: This publication is an introduction to biodiesel production Washing Biodiesel Unwashed 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 time.
Processes of Dehydration (1), Oxidation (2) and Polymerization (3), undertaken by the residual glycerol in the biodiesel, inside the engines working at higher temperatures.
Damage resulting from soap deposition (bio-diesel with an excessively high alkaline or alkaline earth content). Polymer deposition resulting from a use of biodiésel with an inadequate oxidation stability.
Production of high-quality biofuel from vegetable oils through removal of oxygen in triglyceride molecules by overall hydrotreatment in conventional refineries.
Composition of the high-quality biofuels obtained from vegetable oils through the hydroprocessing routes to transportation fuels in conventional refineries. biolpg biogasoline hydrobiodiesel (or H-biodiesel)
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).
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).
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).
. Universidad de Córdoba (TRIOLEIN) (TG!!>DG) [MW: TG " 3/2 DG] CH 3 -(CH 2 -CH=CH- (CH 2 -COO-CH 2 CH 3 -(CH 2 -CH=CH-(CH 2 -COO-CH 2 # k 1 # CH 3 -(CH 2 -CH=CH- (CH 2 -COO-CH!!>CH 3 -(CH 2 -CH=CH-(CH 2 -COO-CH # # CH 3 -(CH 2 -CH=CH- (CH 2 -COO-CH 2 + CH 2 OH CH 3 -(CH 2 -CH=CH-(CH 2 -COOCH 2 CH 3 (FAEE) CH 3 -(CH 2 -CH=CH- (CH 2 -COO-CH 2 (DG!!>MG) [MW: DG " 1/2 MG] CH 2 OH # k 2 # CH 3 -(CH 2 -CH=CH- (CH 2 -COO-CH!!>CH 3 -(CH 2 -CH=CH-(CH 2 -COO-CH # # CH 2 OH + CH 2 OH
Fuel properties of mineral diesel, Jatropha biodiesel, Jatropha oil. Property Mineral Diesel Jatropha Biodiesel Density(kg/m 3 ) 840±1.732 879 917±1 Jatropha Oil Kinematic Viscosity at 40 ºC (cst) 2.44±0.27 4.84 35.98±1.3 Pour Point (ºC) 6±1 3±1 4±1 Flash Point (ºC1±3 191 229±4 Conradson Carbon Residue (%,w/ w) 0.1±0.0 0.01 0.8±0.1 Ash Content (%, w/w) 0.01±0.0 0. 013 0.03±0.0 Calorific Value (MJ/kg) 45.343 38.5 39.071 Sulphur (%, w/w) 0.25 <0.001 0.0 Cetane No. 48-56 51-52 23-41 Carbon (%, w/w) 86.83 77.1 76.11 Hydrogen (%, w/w) 12.72 11.81 10.52 Oxygen (%, w/w) 1.19 10.97 11.06
Physico-chemical properties of soybean oil, biodiesel (B100) obtained from soybean oil and rapeseed oil and No. 2 diesel (D2) (Peterson and Reece, 1996). Properties soybean oil FAME a FAME b FAEE c Diesel Specific gravity (g cm -3 ) 0.920 0.86 0.8802 0.876 0.8495 Viscosity (40 o C, cst or m 2 /s) 46.68 6.2 5.65 6.11 2.98 Cloud point ( o C) 2-2.2 0-2 -12 Pour point ( o C) 0-9.4-15 -10-18 Flash point ( o C) 274 110 179 170 74 Boiling point ( o C) 357 366 347 273 191 Cetane number 48.0 54.8 61.8 59.7 49.2 Sulphur (%wt) 0.022 0.031 0.012 0.012 0.036 Heat of combustion (KJ/Kg) 40.4 40.6 40.54 40.51 45.42 a FAME stands for fatty acid methyl esters from soybean oil b FAME stands for fatty acid methyl esters from rapeseed oil C FAEE stands for fatty acid ethyl esters from rapeseed oil
Kinematic viscosity values,! (cst or mm2/s) at 40 ºC of various representative biodiesel blends as well as commercial diesel and biodiesel. Nº Oil/Alcohol FAE MG TG Yield Conv.!. 1 Sunflower oil - +DG - 100 - - 31.9 2 Commercial Diesel - - - - - 3.1 3 Commercial Biodiesel - - - - - 2.9 4 Used /MeOH a 95.7 4.3-95.7 100.0 3.9 5 Sunflower / EtOH b 94.8 5.2-94.8 100.0 6.6 6 Sunflower /EtOH c 55.7 44.2-55.7 100.0 6.9 7 Sunflower / EtOH 61.3 38.7-61.3 100.0 4.1 8 Sunflower /1-PrOH 62.0 35.8-62.0 100.0 9.2 9 Sunflower /2-prOH 33.9 55.6 10.8 33.9 89.5 12.9 10 Sunflower /EtOH 44.3 33.6 22.1 45.3 77.9 19.6 11 Used/EtOH 54.3 41.2 4.5 54.3 95.5 23.4 12 Used/EtOH 51.4 40.9 7.7 51.4 92.3 24.5 13 Used/EtOH 66.0 31.0 3.0 66.0 100.0 19.7 14 Sunflower /EtOH 58.4 41.6-58.4 100.0 15.0 15 Sunflower / EtOH 60.8 39.2-60.8 100.0 5.4 16 Sunflower /EtOH 26.5 53.4 20.1 26.5 76.6 20.7 17 Sunflower /EtOH d 13.4 84.6 2.0 13.4 98.0 24.5 18 Used/MetOH 71.9 28.1-71.9 100.0 13.1 19 Diesel/biodiesel (1:1) e B50 - - - - - 6.4 20 Diesel/biodiesel (8:2) e B20 - - - - - 4.2 (Caballero, V., et al., 2009; Process Biochem. 44, 334 342) a Homogeneous catalyst NaOH b Homogeneous catalyst KOH c Free PPL d Synthetic biodiesel blend e Blend of commercial diesel and biodiesel with viscosity, $ = 13.1 cst.
. Influence of lipase (from Termomyces lanuginosus) amount in conversion and kinematic viscosity, of reactions carried out at oil/ethanol volume ratio 12/3.5 and ph near to 12, and 20 ºC of reaction temperature. Verdugo, C., et al. 2010; Cost Action CM0903 (UBIOCHEM), 1st Workshop, 13-15 May, Córdoba (Spain).
. Figure 9. Influence of water content in conversion and kinematic viscosity of reactions carried out with 0.03 g of lipase (from Termomyces lanuginosus), at oil/ ethanol volume ratio 12/3.5 and ph near to 12, and 20 ºC of reaction temperature.
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. Concluding remarks! 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. " 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. " 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. 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 operate.
.! 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), so that it become clearly more competitive than the hydrotreating technology for biofuel production in semi-desert areas of low productivity and geographically dispersed, where logistical problems are particularly limiting. The development and maturation of these new technologies, that produce biofuels applicable to diesel engines that not generate unwieldy waste glycerine and which in turn requires its total elimination in the biodiesel, with a high cost in water and energy, it is expected to boost up the use of biofuels, and thus create a scenery to get opportunities for small and medium enterprises for producing biofuels in very diverse geographical areas, including semi-desert areas, where being possible the cultivation of plants suitable for its transformation "in situ" into biofuels, so that agriculture can play an increasingly important role through the production of new crops capable of supplying to industrial and energy sectors that now are completely dependent on petroleum.
Acknowledgments Prof. J. M. Marinas Prof. J. M. Campelo Prof. A. A. Romero Prof. F. M. Bautista Assistant Prof. R. Luque Dr. J. M. Hidalgo Dr. C. Verdugo Dra. V. Caballero Prof. J. Berbel Prof. E.D. Sancho Dr. A. Posadillo mosque and City of Cordoba
Acknowledgments European Capital of Culture Prof. J. M. Marinas Prof. J. M. Campelo Prof. A. A. Romero Prof. F. M. Bautista Assistant Prof. R. Luque Dr. J. M. Hidalgo Dr. C. Verdugo Dra. V. Caballero Prof. J. Berbel Prof. E.D. Sancho Dr. A. Posadillo mosque and City of Cordoba
(farmlands on the outskirts of Cordoba planted with sunflower) MANY THANKS FOR YOUR KIND ATTENTION qo1lumad@uco.es