Palm Fatty Acids Esterification on Heterogeneous Catalysis Prof. Donato Aranda,Ph.D Laboratório Greentec Escola Nacional de Química Federal University Rio de Janeiro Tomar, Bioenergy I March, 2006
Fossil Fuels Fossil Fuels: Greenhouse Effect Fonte: IPCC, 2001
Global Temperature has increased
CO 2 in air
Parcela do Álcool Brazilian Fuels - Consumption 6,6 + 8,8 15,4% VNG 2,4% Pure Ethanol 6,6% Gasoline* 35,3% Diesel 55,7% (42 billions of liters/year) SUBSTITUIÇÃO POR BIODIESEL 2 a 5% 1,1 a 2,8% 20-25% Ethanol ÁLCOOL 8,8% (*) All gasoline in Brazil contains 20-25% ethanol Brazil exports gasoline (11% of production) and imports diesel (6%)
Brazilian Biodiesel Program December/04
Peanut Canola Palm Babassu Castor Soybean, Tallow, Cotton Jatropha Sunflower
Brazilian Biodiesel Program 2005: B2 starts. Mandatory at 2008 All the 2013: B5 mandatory All the country the country LOW FEDERAL TAXES FOR SOCIAL PROJECTS PETROBRAS PURCHASING ALL BIODIESEL PRODUCED WITH SOCIAL SEAL First Bid: : 70 million liters 2005 For 2006: 500 million liters
Agropalma
Vegetable Oil Triglycerides Natural Hydrolysis produces FFA (in all Crude Veg. Oils) H 2 O + Lypases H 3 C-CHCH 2 - CH 2 - CH 2 - CH 2 - CH 2 - CH 2 - CH 2 - CH 2 - CH 2 - CH 2 - CH 2 - CH 2 - CH 2 - CH 2 -COCH 2 O H 3 C-CHCH 2 - CH 2 - CH 2 - CH 2 - CH 2 - CH 2 - CH 2 - CH 2 - CH 2 - CH 2 - CH 2 - CH 2 - CH 2 - CH 2 -COCH O H 3 C-CHCH 2 - CH 2 - CH 2 - CH 2 - CH 2 - CH 2 - CH 2 - CH 2 - CH 2 - CH 2 - CH 2 - CH 2 - CH 2 - CH 2 -COCH 2 O
Palm Fatty Acid Distilatted Fatty Acids extracted in Vegetable Oil Refining PFAD (FFA > 85%) Crude Palm Oil (FFA ~5%) Neutral Oil (FFA < 0.1%)
Agropalma Biodiesel Plant, April/2005 Patent: D. A. G. Aranda and O. A. C. Antunes; PI0301103-8, 2003. D. A. G. Aranda and O. A. C. Antunes, WO2004096962, 2004. BUILT BY DEDINI INDÚSTRIAS DE BASE 10,000 mton/year
Agropalma,, Belém-PA, April/2005 Patent: D. A. G. Aranda and O. A. C. Antunes; PI0301103-8, 2003. D. A. G. Aranda and O. A. C. Antunes, WO2004096962, 2004.
Agropalma,, Belém-PA, April/2005 Patent: D. A. G. Aranda and O. A. C. Antunes; PI0301103-8, 2003. D. A. G. Aranda and O. A. C. Antunes, WO2004096962,
Agropalma s Process Patented by Federal University of Rio de Janeiro
Esterification (Free Fatty Acids) H3C-(CH2)16 (CH2)16-COOH COOH + C2H5OH Cat O / / H3C-(CH2)16 C OCH2CH3 + H2O 100 kg FFA + 16 kg ethanol acid alcohol 110 kg biodiesel + 6 kg water ester water Catalyst = Strong acids
HOMO metanol E= -0,264 ev LUMO acido protonado E= -0,230 ev
The Best Catalyst Heterogeneous Catalyst No soap Reusable Easier separation No neutralizer Niobic Acid (CBMM)
Langmuir-Hinshelwood Hinshelwood-Hougen- Watson Models (-r A ) = k k 1 4 + k + k 2 5 X X A A + k + k 3 6 X X 2 A 2 A Control of Surface Reaction 70 70 60 (a) 1 wt.-% 130 o C 60 (b) 2 wt.% 130 o C 50 50 Conversion / % 40 30 20 Conversion / % 40 30 20 10 0 Niobia HY-340 powder HY Zeolite (SAR = 60) 0 10 20 30 40 50 60 70 Reaction time / min 10 0 Niobia HY-340 powder HY Zeolite (SAR = 60) 0 10 20 30 40 50 60 70 Reaction time / min To be published: Aranda, D.A.G. et al Catalysis Today, 2006
Other Fatty Acid Feedstocks 60 Esterification on Nb-340 Catalyst 55 T = 140 o C 50 Conversion (%) 45 40 35 30 Soybean Tallow Palm 25 20 0 10 20 30 40 50 60 Time (min)
Fatty Acids Molecular Structures
Agropalma Process Patent: D. A. G. Aranda and O. A. C. Antunes; PI0301103-8, 2003. D. A. G. Aranda and O. A. C. Antunes, WO2004096962, 2004.
Agropalma Process
Biodiesel Quality PROPERTIES UNITY EN 14214 AGROPALMA DENSITY, 20ºC kg/m 3 0.86-0.90 0,87 VISCOSITY, 40 C, mm 2 /s 3.5-5.0 4-4.54.5 WATER, MAX. % vol. 0,05 0,000 CONTAMINATION mg/kg 24 15 FLASH POINT, MIN. C 100,0 177 ESTER % 96,5 99,5 DISTILATION; 90% VOL. C -- 350 CARBON RESIDUE. % 0,30 0,01 ASHES, MX. % 0,020 0,001 SULPHUR (*) % 0,001 0,001 Na + K, MAX. mg/kg 5 2 Ca + Mg mg/kg 5 2 P mg/kg 10 1 CORROSION, 3 H, 50 C, MAX. --- 1 1 CETANE --- 51 69 ASPECT --- CLEAN ACIDITY, MAX. mg KOH / g 0,50 0,50 FREE GLYCEROL, MAX. % 0,02 0,001 TOTAL GLYCEROL, MAX. % 0,25 0,00 MONOGLYCERIDES % 0,8 0,01 DIGLYCERIDES % 0,2 0,0 TRIGLYCERIDES % 0,2 0,O METHANOL OR ETHANOL, MAX. % 0,2 0,01 IODINE 120 50 OXIDATION STABILITY 110 C, MIN h 6 72
Esterification Biodiesel: Ethyl or Methyl Diesel - Hydrocarbon H 3 C-CH 2 -CH 2 -CH 2 -CH 2 -CH 2 -CH 2 -CH 2 -CH 2 -CH 2 -CH 2 -CH 2 -CH 2 -CH 2 -CH 2 -CH 3 Biodiesel FAME or FAEE Biodiesel Ethyl Ester H 3 C-CHCH 2 - CH 2 - CH 2 - CH 2 - CH 2 - CH 2 - CH 2 - CH 2 - CH 2 - CH 2 - CH 2 - CH 2 - CH 2 - CH 2 -COC 2 H 5 O Biodiesel Methyl Ester O H 3 C-CHCH 2 - CH 2 - CH 2 - CH 2 - CH 2 - CH 2 - CH 2 - CH 2 - CH 2 - CH 2 - CH 2 - CH 2 - CH 2 - CH 2 -COCH 3
SOAPSTOCK to FFA BIODIESEL New esterification plant in Brazil (Soybean Soapstock) Typically 60% of fatty acids in triglycerides Partially neutralized fatty Acids react with inorganic acid to remove sodium Hydrolysis of Triglycerides FFA > 92% Soybean FFA in Brazil (Soapstock): More than 150,000 mton/y
Conclusions Brazilian Biodiesel Program starts with Residues. Very Cheap Feedstocks (Palm Fatty Acids, Soybean Soapstock, Tallow). About US$ 100-150/ 150/mTon. Total cost of biodiesel from Palm Fatty Acids: About: US$ 0.35-0.40/ 0.40/liter. Esterification Process on Heterogeneous Catalysts Provides Premium Quality Biodiesel from Residues. Hydrolysis of Crude Veg. Oils + Esterification Process is able to convert any type of Fatty Material producing cleaner biodiesel and glycerine.
The use of vegetable oils for engine fuels may seem insignificant today, but such oils may become,, in the course of time, as important as petroleum and the coal-tar products of the present time. Rudolf Diesel, 1912
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