biodieselcomposition gerhardknothe 2012 08

Biodiesel Composition and Fuel Properties Gerhard Knothe USDA / ARS / NCAUR Peoria, IL 61604 U.S.A. E-mail: gerhard.knothe@ars.usda.gov It All Began With… … the Diesel Engine Diesel’s Vision: Develop an engine more efficient than the steam engine, but … Rudolf Diesel did not originally investigate vegetable oils as fuel. Rather… Diesel’s first engine The Original Demonstration in the Words of Rudolf Diesel “At the Paris Exhibition in 1900 there was shown by the Otto Company a small Diesel engine, which, at the request of the French Government, ran on Arachide (earth-nut or pea-nut) oil, and worked so smoothly that only very few people were aware of it. The engine was constructed for using mineral oil, and was then worked on vegetable oil without any alterations being made. R. Diesel, The Diesel Oil-Engine, Engineering 93:395–406 (1912). Chem. Abstr. 6:1984 (1912). The Original Demonstration in the Words of Rudolf Diesel The French Government at the time thought of testing the applicability to power production of the Arachide, or earth-nut, which grows in considerable quantities in their African colonies, and which can be easily cultivated there, because in this way the colonies could be supplied with power and industry from their own resources, without being compelled to buy and import coal or liquid fuel.” Diesel, R., The Diesel Oil-Engine, Engineering 93:395–406 (1912). Chem. Abstr. 6:1984 (1912). Vegetable Oils as Alternative Fuel for Energy Independence: Not a New Concept ● 1920’s-1940’s: Many European countries interested in vegetable oils as fuels for their African colonies in order to provide a local energy source. ● Also interest in Brazil, China, India. ● A.W. Baker and R.L. Sweigert, Proc. Oil & Gas Power Meeting of the ASME :40-48 (1947): “The United States is one of the countries in the world fortunate enough to have large supplies of petroleum, which its inhabitants have not always used wisely. With a possible diminishing supply of oil accompanied by an increase in consumption, the study of substitute fuels becomes of some importance. Vegetable oils loom as a possibility for engines of the compression-ignition type.” The First Report on Biodiesel Belgian Patent 422,877 (1937): Procédé de transformation d’huiles végétales en vue de leur utilisation comme carburants. An Extensive Report on Biodiesel “Old” Research: First Cetane Number Determination for Biodiesel Bulletin Agricole du Congo Belge, Vol. 33, p. 3-90 (1942) : (Potential) Sources of Biodiesel • Vegetable oils • Classical (edible) commodity oils (palm, rapeseed / canola, soybean, etc.) • “Alternative” (inedible) oils (jatropha, karanja, pennycress, etc.) • Animal fats • Used cooking oils • “Alternative” feedstocks • Algae • Variety of feedstocks with considerably varying fatty acid profiles • Fuel properties vary considerably Why biodiesel and not the neat oil? CH 2 -OOCR 1 R ׳OOCR 1 CH 2 OH | Catalyst | CH-OOCR 2 + 3 R ׳OH → R ׳OOCR 2 + CHOH | | CH 2 -OOCR 3 R ׳OOCR 3 CH 2 OH Vegetable Oil Alcohol Vegetable Oil Alkyl Esters Glycerol (Triacylglycerol) (Biodiesel) Viscosity! 27-35 mm 2 /sec 4-5 mm 2 /sec Kinematic viscosity of petrodiesel fuels usually ≈ 1.8-3.0 mm 2 /sec. [...]... Test method Limits Ester content EN 14103 96.5 min oC Density; 15 EN ISO 3675, 12185 860-900 oC Viscosity, 40 EN ISO 3104, ISO 3105 3.5-5.0 Flash point EN ISO 2719, 3679 101 min Sulfur content EN ISO 2084 6, 2088 4 10.0 max Carbon residue (10% dist res.) EN ISO 10370 0.30 max Cetane number EN ISO 5165 51 min Sulfated ash ISO 3987 0.02 max Water content EN ISO 12937 500 max Total contamination EN 12662 24... content EN 14105 0.80 max Diglyceride content EN 14105 0.20 max Triglyceride content EN 14105 0.20 max Free glycerine EN 14105, 14106 0.02 max Total glycerine EN 14105 0.25max Alkali metals (Na + K) EN 14 108, 14109, 14538 5.0 max Earth alkali metals (Ca + Mg) prEN 14538 5.0 max Phosphorus content EN 14107 4.0 max Units % (m/m) kg/m3 mm2/s oC mg/kg % (m/m) % (m/m) mg/kg mg/kg h mg KOH / g g iodine /100g... al et M hy et M hy lP od D ad H ex ec ec an an e e e at et M So y B hy io lO di le es as e el 0.0 B Brake-Specific Emission Rate, g/hp-hr 3.0 G Knothe, C.A Sharp, T.W Ryan III, Energy & Fuels 20, 403- 408 (2006) 10 0 -10 -20 -30 -40 -50 -60 -70 -80 Hexadecane Dodecane Me soyate Me oleate Me palmitate Me laurate NOx PM Change in NOx and PM vs petrodiesel Change in Exhaust Emissions Relative to Base Fuel