Biodiesel Obtaining from Ricinus Seed. Academical Proyect For Promoting Biofuels Use in Mexico

Biodiesel Obtaining from Ricinus Seed Academical Proyect For Promoting Biofuels Use in Mexico Sánchez Daza O.1∗, Amador Ramírez P.2, Reyes Ortega Y.3, Rosas Mendoza S.4, Cervantes De La Rosa A.1, Pineda González A A.1 Facultad de Ingeniería Química, B Universidad Autónoma de Puebla Facultad de Ciencias Qmicas, B Universidad Autónoma de Puebla Instituto de Ciencias B Universidad Autónoma de Puebla Puebla Pue., México, Ciudad Universitaria C P 72570 Groupe Danone, México Abstract Mexico shares a strong responsibility into Latin-America and with the rest of the world as emitter of gases which produce greenhouse effect At present, this responsibility has not a minimum of response in indispensable initiatives and efforts in education, economy, politics, science and technology Meanwhile, the dramatic ecological disequilibrium existing, keeps growing One of the most important contamination source in Mexico is its transport system which uses petroleum derivatives as fuel and, additionally, undergoes a slow modernization process, however, nothing important is appending in order to change this situation Brazil and European Union experiences and an abundant scientific literature have shown the economical and technological feasibility for substituting fossil fuels by other renewable and clean fuels as bioethanol and biodiesel The authors consider as fundamental objective to promote production and use of biofuels in Mexico, for this reason, they are working on the investigation project here presented which is developed in Puebla State (Mexico) searching to take advantage of regional row materials Ricinus seed cultivation could stimulate regional socioeconomic conditions because its water demand is modest, currently the seed grows wildly and some land extension in the region is not active due to high emigration towards United States of America Knowledge about biodiesel obtaining from diverse materials is abundant and international companies market industrial equipment and technology for producing it, nevertheless, the authors consider important to develop in Mexico adequate technology to the specific socioeconomic and natural conditions working the own raw materials Introduction At the present time, there are enough scientific evidences that excessive greenhouse gases (GHG) emissions have produced increasing temperatures worldwide The consequent climate change is been present by intensive and frequent extreme events [17, 18, 19] On the other hand, the global oil production is near to limits that mark the starting of exhaustion [9, 20, 21] Figures and show some analogies and differences between greenhouse emissions from European Union and México: Important participation of the energetic industry in both cases Analogous percentage significance of emissions coming up from transport  Corresponding Author Tel 0052 (222) 29 55 00 Ext 7253 E-mail address: oosdaza@yahoo.com Disproportionate emissions from agriculture and because of deforestation in México High proportion of methane emissions in México, due to an erroneous management of the waste Figure Greenhouse Gas Emissions Mexico Source: PUNE, November 2006 Figure Greenhouse Gas Emissions by Sector European Union Members (EU-15) Source: European Environment Agency, Report No 2006 21% 8% 59% 3% Supply and Energy Use (Without Transport) Transport Agriculture Industrial Processes Waste Management Total Percent 25 9% In Agriculture and Forestry Energy and Process Industries Transport Cement and Metallurgy Industries Waste Management and Others 30 20 15 10 5 Emissions Origin both cases are important GHG emissions from power and heat generation as well as those resulting from transport In order to reduce these GHG emissions and advancing against oil stock diminished, some countries are applying the following policies: • • • • Impulse to the conservation and efficient use of the energy in all scope of the social life (productive and usefulness activities, commercial operations, educative and domestic tasks) Massive financing to investigation and development of renewable and clean energy sources Production of electricity starting of renewable energy sources (solar, wind, hydraulic, biomasa) Impulse to employ biofuels in transportation These general action lines constitute, in the majority of developed countries, public politics slowly instrumented through of governmental entities and/or research and development institutions [1, 13, 16, 24, 25, 28, 36, 39] In Latin America, Brazil stands out for its impulse toward production and use of biofuels (bioethanol and biodisel) [32] Argentina and Uruguay act in a less strong way In Cuba the implementation of renewal energy resources is not relevant; however, it is notable its national educative politics which encourages the energy saving among the population starting of basic levels of the educative system [23, 30] The main renewable energy sources are: hydraulic, solar, wind and biomass The promotion about of the use of these renewable energies actually is very necessary Biomass energy proceeds of organic material which is obtained naturally (biofuels), for instance: forest waste, seeds, grains and farming wastes, organic wastes of industrial or domestic activities Treatment of organic wastes obtaining energy means to recycle materials whose spontaneous degradation could pollute the environment Biodiesel can be obtained from diverse vegetables oils (clean or used) or from animal fats waste [4, 27, 33, 35] Other important fuels as methane, ethane and hydrogen can be also produced beginning with biomass [1, 28] Energetic Renewal in Mexico Mexican Oils (PEMEX: the ninth enterprise in oil production worldwide) has stimulated extraction and export above refinement and petrochemical processes over the last years (Figure and 4) Gas and oil production have been lightly increased but refineries and petrochemical plants almost keep the same Simultaneously, PEMEX has paid taxes to the government by around 37.2% respect to the national incomes from 2001 to 2005 This amount represents 61% above its own incomes due to sales, according to the Bank of Mexico As a consequence, PEMEX has not capacity for reinvesting or developing new projects, furthermore, PEMEX could not participate in developing renewable energy as Petrobras and Shell in Brazil and Holland and other countries respectively Figure Destination of Oil Production Mexico Source: Anuario Estadístico 2004, PEMEX Figure Oil Production Trends Mexico Source: Anuario Estadístico 2004 and Indicators from PEMEX 1800 3500 1600 Barrel Thousands/Day Barrel Thousands/Day 3000 2500 2000 1500 1000 1400 1200 1000 800 Exportation Refinement Petrochemistry 600 400 500 200 1997 1998 1999 2000 2001 2002 2003 2004 2005 1996 2006 1997 1998 1999 Figure Oil Total Stock Mexico Source: Anuario Estadístico 2004, PEMEX 800 60 2001 2002 2003 2004 2005 Figure Perforation Trends Mexico Source: Anuario Estadístico 2004, PEMEX 700 50 600 Oil Well Perforated Equivalent Oil Barrels Thousands of Million 2000 Year Year 40 30 20 500 400 300 200 10 100 1996 1997 1998 1999 2000 2001 Year 2002 2003 2004 2005 1996 1997 1998 1999 2000 2001 2002 2003 2004 2005 Year On the other hand, PEMEX has informed that oil production from “Cantarell” (the most important Mexican oil deposit has represented around 60% of the national oil production) reached its peak in 2006 and the total oil production began to decline (see the end of Figure 3) Possible stock will be not sufficient in order to modifying this trend By searching oil in the Mexican Golf, PEMEX will intend to recover its current production level but there are important financial and technological drawbacks [21] Meanwhile, the interest for exploring and increasing production (Figures and respectively) clearly contrast with the national oil stocks (Figure 5) which have considerably decreased [6] As a result, while oil and energetic policy not change, the country could face difficulties in order to satisfy energy necessities and become us in importers of oil and technologies for renewable energy production To promote use of renewable energy in Mexico, the Senate of the Republic approved in 2004 a resolution for involving energy and environment ministries in designing the necessary studies and projects [15] On the other hand, the energy ministry negotiates financial resources with World Bank and Inter American Development Bank for promoting generation of energy from waste for some places in the country (Querétaro, Chihuahua, León, Guadalajara, Zapopan, Aguascalientes Ciudad Juárez y Puebla) Some official initiatives oriented to promote clean and renewable energy are: • Construction of the hydroelectric “El Cajón” in Nayarit state, the second largest in the country (after of Chicoasén in Chiapas state), with an equivalent capacity up to % respect to the production of the national energy company (CFE) • A generative plant of methane from waste in Monterrey city • Installation of a plant producing biodiesel from jatropha seed in Michoacán state This project is carried out by National University professors supported for the government of the state [35] An important effort to boost biofuels in Mexico was developed in the Center of Studies on Energy in the Instituto Tecnológico de Estudios Superiores of Monterrey, supported by the enterprise Grupo Energéticos S A [35] They built a commercial plant for producing biodiesel form animal fat [35] These few cases indicate that in Mexico does not exist a national plan or policy to stimulate production and use of renewable energy Additionally, national financial support for scientific research has been extremely reduced becoming impossible to forecast a better scenario for the next years For 2007 resources for research would be about 0.35% respect to Gross Domestic Product (GDP) while international institutions recommend 1.5% in order to boost economical growth for countries in developing This is the smaller budget given for investigation in Mexico the last twenty years, the Mexican Academy of Science has said Biodiesel: A Biofuel in Development According to the conclusions of the European Biodiesel Board in 2004 [12]: • Biodiesel and biofuels are today the only viable way for reducing greenhouse gases (GHG) emissions proceeding from transport sector (i e., the sector globally more dependent on imports fossil energy and where CO2 emissions keep rising) • The European Union biodiesel industry is well established and will continue to increase its production Meantime biodiesel is also becoming a world wide reality • There is a need for an international co-operation in order to support the use of biodiesel and biofuels world wide specially in developing countries, where fossil energy use and GHG emission from transport will rise exponentially next years European Union (EU) is the world leader in biodiesel production while Brazil is the first in bio-ethanol production European Biodiesel Board official figures confirm that overall biodiesel production in EU-25 members has markedly increased in the recent years (Figure 7) United States of America is the world second largest biodiesel producer with a production amounted around 250,000 tonnes in 2005 Brazil started a production around 10,000 tonnes per year in 2005 [31] While GHG emission from most sectors could decrease or keep at least stable, CO emissions from transport (21% of the overall GHG emissions in average according to Figures and 2) did not stop growing over last years worldwide The future could be similar because of transport demand keeps rising This last asseveration is another important reason to promote production and use of biofuels creating, simultaneously, an additional outlet for agricultural production and stimulating rural development New employments could also be created 3.5 Figure Biodiesel Production in EU-25 Source: EBB Reports, 2004 and 2006 [11,12] 4500 Figure Yield by Hectare for Different Row Materials 4000 3.0 Biodiesel Thousand Lt/He 3500 Million Tonns/Year 2.5 2.0 1.5 1.0 0.5 0.0 1997 3000 2500 2000 Maize Cotton Hemp Linseed Soybean Mustard Rice Tung Sunflower 10 Peanut 11 Rapeseed 12 Jojoba 13 Ricinus 14 Jatropha 15 Avocado 16 Coconut 17 Palm 18 Coconut Palm 1500 1000 500 1998 1999 2000 2001 2002 2003 2004 2005 2006 Year 10 11 12 13 14 15 16 17 18 Origin Source: http://www.zoetecnocampo.com/Documentos/biodisel.htm (2005) Biodiesel Production from Ricinus Seed 4.1 Justification and Objectives It was written above, Mexico has not designed energetic plans for the future, its capacity as oil producer endangers and its promotion in favour of renewable energy is not significant, in addition, the national financial support for scientific research has been extremely reduced On the other hand, in the last summit meeting on climate change (Nairobi 2006), Mexico was evaluated as first greenhouse transmitter in Latin America and fourteenth world wide For these reasons, there is an urgent necessity for appealing all the possible instances engaging the entire resources and efforts in order to obtain support for promoting renewable energy This is the proposal of the present work The Project embraces to obtain ricinus oil from different ricinus seed types and develop the technology for producing biodiesel that could be used, at the beginning, for the university transport in order to promote it beyond academic spaces Preliminary studies have shown high glyceride content (i e fuel capacity) in ricinus oil and important yield by hectare for the seed cultivation (Figure 8) which demands modest quantities of water Additionally, around the region (Puebla State) ricinus seed currently grows wildly, that means, if ricinus seed cultivation is projected, regional socioeconomic conditions could be stimulated because of some land unsuitable for other agriculturalist products could be used now Furthermore, some land extension in the region is not active due to high emigration towards United States of America 4.2 Preliminary Studies Ricinus shrub belongs to the euforbiaceas family and came up in Africa The warm and moderate climates are propitious for its growth The ricinus seeds produce a 60% of laxative oil out of total weight according to our studies Vegetal oils as ricinus and others, which are used for producing biodiesel (soja, sunflower, palm, rapeseed, etc.), are combinations of fat-acid glycerol esters in different proportion according to the original species The capacity of the oils and fats for producing diesel fuel comes from their molecular structure and their high energy contained The lineal and saturated chains of hydrocarbons are especially good for producing diesel fuel, and the fat acids fulfill this condition Transesterification of the glycerol esters present in vegetable oils, results in a combination of mehyl or ethyl esters [4, 8, 27, 34], depending on which alcohol is used, methanol or ethanol respectively Glicerol (by product of the transesterification) and biodiesel form two immiscible liquid phases that can be separated in a mechanic way In order to obtain high purity products both phases should be refined by separation processes like distillation, evaporation and washing Transesterification to biodiesel can happen faster by using basic or acid homogeneous catalysts [2, 10], some solid and biologic catalysts have also been studied Recent researches have developed a supercritical process without catalyst [7, 25] A critical issue in the biodiesel production happens if some water is present because, reaction could derivate towards an unwanted saponification [5] According to the previous ideas, row material impurities and chemical composition could vary even among vegetable oils elaborated with the same seed but proceeding from different regions On the other hand, specific fat-acid content and natural characteristics of each seed or plant, determine different yield by territorial unit (hectare) Figure shows higher yield for ricinus seeds than well known sources world wide like, soybean, sunflower or rapeseed, nevertheless palm represents the best yield Even though background information for biodiesel obtaining could be located around the world and some countries have developed wide technological experience, search and adaptation of the knowledge are indispensable for developing countries in order to take advantage of the own resources on the specific socioeconomic conditions 4.3 State of The Art Investigation about biodeisel has noticeably been developed, particularly the ten last years The currently contributions could be presented as follows:  Studies around biodiesel production from diverse row materials [4, 33, 35, 38]  Optimization of process variables and reaction kinetics (reaction yield, temperature, different kind of catalysts, etc.) [2, 4, 5, 8, 34]  Fat and vegetal oil characterization (analysis methodologies and determination of physical and chemical properties) [37]  Biodiesel quality as fuel (determination of specifications and standards) [37]  Socioeconomic and agroecological feasibility (characteristics of the land, yield by hectare, genetic modifications, etc.) [3, 22] 4.4 Specific Goals Development of the obtaining process for the ricinus oil (in development) Determination of the chemical composition and quality for the ricinus oil obtained from different varieties of ricinus seeds (in development) Transesterification kinetic studies over different operation conditions (in development) Determination of the chemical composition, physical properties and quality of the biodiesel obtained (in development) Development of the purification system for transesterification products Design and construction of an experimental plant (laboratory scale) for biodiesel production Design and construction of a prototype plant for biodiesel production in short production 4.5 Methodology • Develop process for obtaining ricinus oil by solvent extraction method • Analytic Characterization of the chemical composition for ricinus oil and biodiesel throughout gas chromatographic techniques The principal composition of vegetable oil and biodiesel will be determined using high performance liquid chromatography (HPLC) The chromatographer is equipped with pump mod 600, inyector Rheodyne mod 7725, Photodiode Array detector mod 996 and software Millenium 32 (Waters) A C-18 µ-Bondapack column (Waters) and methanol as a carrier solvent will be used The contents of mono-, di-, and triglycerides remaining in the biodiesel will be also obtained by HPLC following the methodology reported by Holcapek Before using the chromatography method, this will be validated to probe its efficacy • Development of simple techniques in order to determine density (pycnometer) and viscosity (Fenske’s Capillary Viscometer) for ricinus oil and biodiesel • Determination of heat capacities, flame point, number of cetane and oxidation index for biodiesel The heat capacities will be obtained by differential scanning calorimeter (TA Instrument 2010) using the method of ‘‘three steps’’ [4,5] Flame point, number of cetane and oxidation index by combustion calorimetry • Transesterification kinetic study in batch system over different temperatures using basic homogeneous catalysts optimizing mixing operation • Experimental tests for biodiesel purification by distillation, evaporation and washing • Carry out a batch production system for producing biodiesel in laboratory scale • Design and operating tests for a prototype plant in order to produce biodiesel in a short scale Conclusions Because of immoderate use of the traditional energetic resources, the life in the planet is in serious risk of disappearing The needs of energy in the world are growing and must be satisfied, as soon as possible, by clean and renewable sources of energy In order to reach this target, is necessary to invest enough economical resources and work out a great scientific and technologic effort by developing international collaborations Nowadays, many developed countries are impelling an energetic renewal which could contribute to mitigate the ecologic unbalance present Mexico has contributed to the damage of the environment in important form Nevertheless, the measures taken for facing the problem are no significant yet Mexico lacks of a strategy for the medium term, when petroleum era arrives to the end Natural resources in each country vary according to the geography, weather conditions and socioeconomic status, as a result, the strategy for changing the energetic sources could be different Ecological diversity in Mexico enable us to dispose of non-conventional biomass resources for developing renewable fuels that could gradually substitute to the fossil fuels, particularly, those used in the transport sector Preliminary studies realized by the authors show the socioeconomic and technologic possibility to exploit the ricinus shrub, into a sustainability framework, for biodiesel production Biodiesel is a renewable and biodegradable fuel that could substitute to mineral diesel employed in transport now Nowadays the first stage of the present project is advancing Continuation of the further stages is not certain, because of strong restrictions of the national budget intended for investigation sector and due to the limited governmental interest for developing new energy sources In contrast, the authors consider as a priority that Mexico develops in a short term its own technology in order to substitute the fossil fuels gradually, taking advantage of the own raw materials References Aashish Mehta, The Economics and Feasibility of Electricity Generation using Manure Digesters on Small and Mid-size Dairy Farms, Department of Agricultural and Applied Economics Energy Analysis and Policy Program, University of Wisconsin – Madison January, 2002 Adam Karl Khan, Research in Biodiesel Kinetics and Catalyst Development, Department of Chemical Engineering, University of Queensland, Australia, 2002 Altieri, M A., Agroecology: The Science of Natural Resourse Management for Poor Farmers in Marginal Environments, Review, Agiculture, Ecosystems and Environment, 93, 1, 2002 Al-Widyan, M., Al-Shyoukh, A., Experimental Evaluation of the Transesterification of Waste Palm Oil into Biodiesel, Bioresour Technol 85, 253–256, 2002 Anozie, A N., Dzobo, J M., Kinetics of the Hydrolysis of Palm Oil and Palm Kernel Oil, A C S., Published on Web 01/26/2006 British Petroleum Statistical Review of World Energy 2005 Bunyakiat, K., Makmee, S., Sawangkeaw, R., Ngamprasertsith, S., Continuous Production of Biodiesel via Transesterification from Vegetable Oils in Supercritical Methanol, Energy & Fuels, 20, 812, 2006 8 Darnoko, D and Cheryan, M., Kinetics of Palm Oil Transesterification in a Batch Reactor, J of the Ame Oil Chemists' Soc (JAOCS), 77, 12, 2000 Deffeyes, Kenneth S., Beyond Oil: The View from Hubbert’s Peak, Published by Farrar, Straus and Giroux, 2005 10 Di Serio, M., Tesser, R., Dimiccoli, M., Cammarota, F., Nastasi, M., Santacesaria, E., Synthesis of Biodiesel via Homogeneous Lewis Acid Catalyst, Journal of Molecular Catalysis A: Chemical, 239, 111–115, 2005 11 EBB, Annual Biodiesel Production Statistics, April 2006 12 EBB, Biodiesel in Europe and World Wide: Overview and Development Perspectives, June, 2004 13 EBB, Comments to the Commission Consultation on the Revision of the EU Biofuels Directive, July 2006 14 EEA, Greenhouse Gas Emission Trends and Projections in Europe, Report 9, 2006 15 Gaceta Parlamentaria, LIX Legislatura, Senado de la República, Octubre 18, 2005 16 Gerhard Knothe, Robert O Dunn and Marvin O Bagby, Biodiesel: The Use of Vegetable Oils and Their Derivatives as Alternative Diesel Fuels, Oil Chemical Research, National Center for Agricultural Utilization Research, Agricultural Research Service, U.S Department of Agriculture, Peoria, IL 61604, 1997 17 Intergovernmental Panel on Climate Change, Workshop on New Emission Scenarios Meeting Report, Laxenburg, Austria, June–July, 2005 18 Intergovernmental Panel on Climate Change, Contribution of Working Group I to the Third Assessment Report of the Climate Change 2001: The Scientific Basis, Cambridge University Press, Cambridge, United Kingdom and New York, NY, USA, 2001 19 Intergovernmental Panel on Climate Change 12, Meeting Report, Nairobi, November 2006 20 Klare, Michael T., Blood and Oil: The Dangers and Consequences of America's Growing Dependency on Imported Petroleum (The American Empire Project), Owl Books, August 1, 2005 21 Klare, Michael T., El Ocaso de la Era del Petróleo, Published by Fírgoa, Available on http://firgoa.usc.es/drupal, Septiembre13, 2005 22 Meher, L C., Sagar, D V., Naik, S N., Technical Aspects of Biodiesel Production by Transesterification–A Review, Renew Sustain Energy, Rev XX, 1–21, 2004 23 Ministerio de la Industria Básica, Ahorro de Energía La Esperanza del Futuro, Editorial Política, La Habana, Cuba, 2004 24 Multiyear Technical Plan., U S Department of Energy Biomass Program, Available on http://www.eere.energy.gov/biomass/, 2005 25 Nabetani, H., Nakajima, M., Iwamoto, S., Current Research on Biodiesel Fuel in Japan, Asia-Pacific Economic Cooperation, Biomass-Asia Workshop Tokyo, Japan, January 2005 26 PEMEX, Anuario Estadístico 2004 27 Plentz Meneghetti, S M., Meneghetti, M R., Wolf, C R., Silva, E C., Lima G E S., De Lira Silva, R Serra, T M., Cauduro, F., De Oliveira, L G., Biodiesel from Castor Oil: A Comparison of Ethanolysis versus Methanolysis, Energy & Fuels, 20, 2262, 2006 28 Reith, J H., Wijffels, R H., Barten, H., Bio-Methane & Bio-Hydrogen 29 Status and Perspectives of Biological Methane and Hydrogen Production, Dutch Biological Hydrogen Foundation, Energy Research Centre of The Netherlands ECN, Unit Biomass, 2003 30 Somoza Cabrera, J., Desarrollo Sostenible: Un Acercamiento desde la Óptica del Uso de la Energia, Instituto Nacional de Investigaciones Económicas (INIE), Cuba, Abril del 2003 31 32 Soyminas Biodiesel http://www.soyminas.ind.br/ 33 Tashtoush, G., Al-Widyan, M., Al-Jarrah, M., Experimental Study on Evaluation and Optimization of Convertion of Waste Animal Fat into Biodiesel, Energy Conv Manage., 45, 2697–2711, 2004 34 Tesser, R., Di Serio, M., Guida, M., Nastasi, M., Santacesaria, E., Kinetics of Oleic Acid Esterification with Methanol in the Presence of Triglycerides, Ind Eng Chem Res., 44, 7978, 2005 35 Thran, D., Weber, M., Muller Langer, R., Schroder, G., Probst, O., Estudio de Factibilidad GTZ-BID Sobre el Biodiesel como Combustible para el Transporte en México, Tecnológico de Monterrey, Noviembre 2006 36 Una Estrategia de Biocarburantes para España (2005-2010), APPA y PrincewaterhouseCoopers, Junio 2005 37 Vicente, G., Martínez, M., Aracil, J., A Comparative Study of Vegetable Oils for Biodiesel Production in Spain, Energy & Fuels, 20, 394, 2006 38 Vicente, G., Martínez, M., Aracil, J., Esteban, A., Kinetics of Sunflower Oil Methanolysis, Ind Eng Chem Res., 44, 5447, 2005 39 Werner Korbitz (Austrian Biofuels Institute), New Trends in Developing Biodiesel World Wide, Asia Bio-fuels, Singapore, 22-23 April, 2002 10 ... of the obtaining process for the ricinus oil (in development) Determination of the chemical composition and quality for the ricinus oil obtained from different varieties of ricinus seeds (in development)... embraces to obtain ricinus oil from different ricinus seed types and develop the technology for producing biodiesel that could be used, at the beginning, for the university transport in order to... which is obtained naturally (biofuels) , for instance: forest waste, seeds, grains and farming wastes, organic wastes of industrial or domestic activities Treatment of organic wastes obtaining energy