Antonio J A Meirelles Laboratory of Extraction Applied Thermodynamics and Equilibrium EXTRAE School of Food Engineering FEA University of Campinas UNICAMP São Paulo Brazil ID: 798472
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Slide1
Ethylic biodiesel: the bottlenecks for process optimization
Antonio J. A. Meirelles Laboratory of Extraction, Applied Thermodynamics and Equilibrium (EXTRAE) School of Food Engineering (FEA)University of Campinas (UNICAMP), São Paulo, BrazilCo-workers: E. Batista, F. Batista, C. Rodrigues, C. Gonçalves. L. Bessa, M. Ferreira, M. Cuevas, T. Deboni, T. Porcina, S. Shiozawa.
Slide2TopicsSources of fatty compounds for biodiesel production.
Biodiesel nowadays: methanol vs. ethanol.An ethylic route for biodiesel production: extraction, refining, trans/esterification, purification and ethanol recovery.
Slide3Vegetable Oils in the World,
Million metric tons, 14/15 (USDA, 2015)
Source
Energy ratio
Microalgae
0.35 - 1.24
Palm
1.64 - 4.90
Soybean
0.61 - 2.41
Rapeseed
0.91 - 3.00 Sunflower0.46 - 3.20
Biodiesel in
the
World Million m3 USA Germany Brazil Argentina
Brazil: 4
th
Soybean Oil,
<<< 5
th
Palm
Oil, 3
rd
in Biodiesel, 2
nd
in Bioethanol.
Slide4A controversial subject
Agro-ecological zoning by EMBRAPA on the deforested area of Amazon (2007=13.94% of the Legal Amazon region): 29.7 million ha appropriate for agricultural cultivation of oil palm (5,87% of the Legal Amazon region). (Embrapa, 2010) The area investigated by EMBRAPA is composed of 80% of degraded and abandoned pastures.Cultivation expansion restricted to the already deforested region according to the images collected before 2008.
2007:
10.92 million ha
used worldwide for oil palm cultivation
(
C. Carter et al. Eur. J. Lipid Sci. Technol. 109 (2007) 307–314)
. Malaysia + Indonesia= (4+5) million ha cultivation of Palm
(Homma, 2011)
.
Indonesia: deforestation related to the expansion of oil palm cultivation
(Becker, CONFINS, 2010).
Slide5Agribusiness based on Palm Oil/Palm Biodiesel is similar to that based on Sugar/BioethanolOil palm trees/Palm oil: high productivity per hectare.Palm Oil/Palm Biodiesel Agribusiness uses cogeneration based on palm tree residues. The ratio bioenergy generated/fossil energy used Sugar Cane Bioethanol
(World Watch Institute).EMBRAPA: new varieties adapted to Brazilian savannah (irrigation) and richer in unsaturated fatty acids
(Embrapa, 13/10/2010, 23/05/2011).Researches on Hydrolysis of lignocellulosic residues from palm tree (empty fruit bunches and palm press fiber): coupling production of palm oil biodiesel and bioethanol
(Gutiérrez et al., Bioresource Technology, 2009).
Slide6FAEE X FAME GHG gains
GHG Emission“fatty acid methyl esters .. .are still among the most prominent alternative biofuels, and there are still a lot of challenges …including the use of ethanol instead of methanol” (M. Mittelbach
, Editorial, Eur. J. Lipid Sci. Technol. 2009, 111, 745–746).
How to develop a feasible
route for
ETHYLIC BIODIESEL?
Our Approach:
i
)
bioethanol can be used in the entire sequence of biodiesel production, from the seed (oil extraction) to the
tank
; ii) the main bottleneck is concentrated in the purification steps and recovery, in a anhydrous form, of bioethanol used in excess.Distillery (CD2) X Sugar + Bioethanol (JP2)
Slide7Oil Extraction with EthanolReplacing hexane as
solvent: extraction of oils for Biodiesel and for edible purposes.Recovering Nutraceuticals of high added value (oryzanol, tocopherols, phytosterols, etc.) as byproducts or concentrated in the edible oil.Future of the oil industry biofuels + food + feed + high added value products.
Extraction Yield (%)
Soybean Oil
Temperature
(°C)
Nitrogen Solubility Index (%)
Food
Research
International62 (2014) 662-670
Slide8Oil Deacidification
By LLE with EthanolBy Ion Exchange
Breakthrough Curves
○
Soybean Oil
■
Free Fatty Acids
▲
Rice Bran Oil■ Free Fatty Acids
Slide9Solubility of anhydrous ethanol in palm oil at 45
oC25 mass% 86 mol%Ethanol/oil mol ratio = 6.14
Slide10Close to Ethanol boiling point, Vegetable Oils highly soluble in Bioethanol.Strong acid used in Ion Exchange regeneration can be also used as the Esterification Catalyst.
Slide11Process development based on experimental studies and computer simulation (Aspen Plus)
Simulation requires suitable methods for the calculation and prediction of properties, especially phase equilibrium and reaction kinetics.Process Simulation and Catalysis
Slide12Biodiesel reaction is a Two-Phase reversible reaction
How the presence of two phases affects the reaction velocity? POSSIBLE MASS TRANSFER INFLUENCE♦, TAG; ■, DAG; ▲, MAG ×, Biodiesel; ○, GlycerolReaction Kinetics at 338,15 KTime (min)Concentration (mole/L)
Palm
Oil Conversion to Biodiesel
(▲) 308 K; (●) 323K; (■)
338
K
.
Time (min)
Conversion (%)
Slide13LLE for
Oil-FFA-Solvent: UNIFAC Parameters readjustment Databank with 102 commercial fatty systems360 (2013) 379– 391
Slide14LLE for
TAG_Corn+DAG+MAG+Ethyl linoleate+Ethanol at 303.15 K:●, experimental; ─ NRTL; ∙∙∙∙∙∙ UNIFAC_LLE; --- ,UNIFAC_Readjust.
LLE for HOSO+DAG+MAG+ethyl
oleate+oleic acid+ethanol at T = 303.15 K: ●, experimental; - - - -
, UNIFAC-LLE; ∙∙∙∙∙∙, UNIFAC-Readjust.
Fluid
Phase
Equilibria
, 404 (2015), 32-41
JCT, 89 (2015), 148-158
Slide15Purification of Ethylic BiodieselPhase splitting and decanting: (biodiesel rich + glycerol rich) phases.Ethanol evaporation, dehydration and recycling.
Biodiesel washing and drying.Main Problem: Ethanol RecyclingAnhydrous bioethanol contains 0.5 m% Water.Without dehydration bioethanol recycle accumulates water.Ethanol Dehydration3 Industrial Techniques: Extractive Distillation with EG, Azeotropic Distillation with CH, Molecular Sieve.Not the best solution: expensive in comparison to Methanol dehydration (no Azeotropy)Biodiesel Purification + Ethanol Recovery
Slide16Anhydrous Bioethanol
Hydrated Bioethanol
Water
Ethanol Dehydration with Ethylene Glycol
Almost 1/3 of the Brazilian Production
Industrial Installations for 300 to 1.000 m
3
/day
Slide17Ethanol Dehydration GLYCEROL´s EFFECT on Ethanol + Water VLE similar to the observed for Ethylene Glycol
Slide18Process for ethylic biodiesel
Byproduct GLYCEROL used for dehydrating Bioethanol to be recycled;
Ethanol as new reactant can be fed to the process as hydrous ethanol and be dehydrated also using glycerol.
Glycerol recycles around 10 times in the installation, being withdrawn before harmful effects can occur.
Two Brazilian patents (INPI) for
deacidifying
vegetable
oils and
for producing biodiesel
.
Slide19Molar Ratio Ethanol/Oi
lBiodiesel Loss, %■ Kg Steam/L Biodiesel Oil Conversion/ %
Molar Ratio Ethanol/Oil
Time/ h
Concentration/ mole/L
Biodiesel
Ethanol
Glycerol
TAG
DAG
MAG
60 oC E/O=6:1Concentration/ mole/LTime/ h■Biodiesel Ethanol Oleic/Linoleic Acids 60 oC E/A=15:1Aspen Simulation
Slide20CONCLUSION
P
ossibilities
to integrate the production of biofuels and edible oils have been researched and developed in the case of
ethylic
biodiesel.
Thank you for
your attention
Acknowledgments: