Phase Equilibrium and Purification Processes in the Production of

Phase Equilibrium and Purification Processes in the Production of Biofuels and Biocompounds

Research Team:

Antonio J. A. Meirelles – Lab. EXTRAE - FEA/UNICAMP Pedro A. Pessoa Fo. – EPUSP/USP Martín Aznar, M. Alvina Krahenbühl, Roberta Ceriani – FEQ/UNICAMP Mariana Conceição da Costa – FCA/UNICAMP Christianne E. C. Rodrigues, Cintia B. Gonçalves – FZEA/USP Eduardo A. C. Batista - FEA/UNICAMP 37 Graduate Students + 2 Postdoctorates (Simone, Magno, Inês, etc.)

National Collaboration: Luiza Silva – UFPA, Érika Cren – UFMG, Charles Abreu –

UFRJ, Lúcio Cardozo Fo. – UEM, Elias Monteiro Fo. – UFSJ, Adenilson – UFMA,

International Collaboration: Christian Stevens, Roland Verhé – Ghent University,

Belgium; Jérôme Pauly– University of Pau, France; João Coutinho – Aveiro University, Portugal; Rafiqul Gani, Technical University Denmark.

Industrial Collaboration: Santa Adélia Mill, Müller Beverage Company, Desmet

Ballestra (Belgium).

PROJECT GOALS

1.Simulation and Optimization of

Bioethanol Industrial Distillation.

2.Development of Biodiesel

Production by the Ethylic Route

3.Purification and Formulation of

Biocompounds.

Alcoholic

products Specifications

Standards

fixed by

Fuel

( Hydrous/ Anhydrous )

alcoholic content, pH, acidity, conductivity,

density, chloride, sulfate, iron, hydrocarbons ANP

Special/

Neutral

alcoholic content, pH, acidity, conductivity,

density, chloride, sulfate, iron, hydrocarbons, sulfur, copper, sodium, nitrogen, phosphorus,

acetaldehyde, ethyl acetate, methanol,

propanol , isopropanol , butanol , isobutanol , isoamilic alcohol, higher alcohols,

crotonaldehyde , dioxane , ciclohexane , benzene, ethylene glycol, diethylene glycol, acetal

Market

Industrial Distillation of Bioethanol

Bioethanol Distillation 1. Topic frequently investigated in the literature 2. Most works focused on Bioethanol Dehydration (last step

of the concentration process) 3. Oversimplified versions of the process: wine assumed to

be a binary mixture Ethanol + Water; Distillation Equipment as a simple Binary Distillation Column.

4. Minor components are neglected and their role in the distillation of Special Alcoholic Products not considered

Wine Composition

20 Components

Investigating Bioethanol Distillation

in Industrial Scale

1. Samples and Information collected in different sugar mills

2. Simulation of the real industrial equipment using ASPEN PLUS

3. Most important minor components taken into account

Validation Results

Evaluating Performance of Different Industrial Configurations

winecont

eth

productcont

eth

w

w

w

w

F

Total

Factor onPurificati

Heat Integrated Distillation Columns

ALCOHOL-CHEMISTRY requires PURE BIOETHANOL for avoiding damage to catalyst by minor components;

secondary reactions; accumulation of minor components

and final product contamination.

Conventional New Plant 1 New Plant 2 Steam Consumption (SC) (Kg/L) 5.22 3.31 5.22 Number of Trays (NT) 279 144 144 Decrease of SC 36 % 0 % Decrease of NT 48 % 48 % Purification Factor (FTotal) 8250 1092 8804

Patent submission

to INPI

Developing New

Configurations for Distilling

Neutral Alcohol

Developing an ethylic route for biodiesel production

“biodiesel are still among the most prominent alternative biofuels, and there

are still a lot of challenges in the future for research including the use of ethanol instead of methanol” (M. Mittelbach, Eur. J. Lipid Sci. Technol. 2009, 111, 745–746)

Concept: bioethanol used in the entire sequence of biodiesel production,

from the seed (extraction) to the tank.

Problem: Bioethanol accumulates water during biodiesel production, it must

be dehydrated before recycling. 2 Patents submitted to INPI.

Oil Extraction with Ethanol 1. Replacing Hexane as solvent used in the extraction of vegetable oils. 2. Combining the extraction of oils for producing Biodiesel and for edible

use. 3. Recovering Nutraceuticals of high added value (oryzanol, tocopherols,

tocotrienols, phytosterols, etc.) as byproducts or concentrated in the edible oil.

4. The future of the oil industry producing biofuels + food + feed + high added value products.

1. Close to Ethanol boiling point, Vegetable Oils highly

soluble in Bioethanol. 2. Strong acid used in Ion Exchange regeneration can be

also used as the Esterification Catalyst.

0.0

0.2

0.4

0.6

0.8

1.0

1.2

0 200 400 600

Co

nc

TIM

E/C

on

cIN

ITIA

L

time (min)

Soybean OilFFA

Crude Oil must be deacidified for biodiesel production

and for edible use.

Deacidification by Ion Exchange of Crude Oil dissolved in Ethanolic Solutions.

Initial Acidity (FFA)=2.12% Final Acidity=0.23%

Purification of ethylic Biodiesel 1.Phase splitting and decanting:

(biodiesel rich + glycerol rich) phases. 2.Ethanol evaporation, dehydration and

recycling. 3.Glycerol recovery, use as dehydrator

and purification as byproduct. 4.Biodiesel washing and drying. 5.Ethanol as reactant can be fed to the

process as hydrous ethanol and be dehydrated also using glycerol.

Oil Refining and biodiesel purification

Alcoholic and Fatty Biocompounds 1.Purifying and Obtaining Derivatives of High Alcohols (Fusel Oil) by

Computational Simulation Using ASPEN PLUS.

2.Refining of Edible Oils Containing high Levels of Nutraceuticals (-

carotene degraded during refining of Palm Oil can supply the worldwide

requirements of Vitamin A - Mayomol et al., JAOCS, 84, 587-596, 2007).

3.Physicochemical Properties and Solid-Liquid Transitions of Fatty

Systems: Important Information for Formulating Biodiesel Mixtures,

Cosmetics, Pharmaceutical Products and Food Additives.

Flash Point Data of Biodiesel Mixtures

Solid-Liquid Transition and Cloud Point Data

Type 2009/2010 2010/2011 2011/2012

Dissertations,

Theses, etc.

Postdoc 2/0a 3/2 2/2

PhD 19/2 18/3 21/1

MSc 17/4 21/6 16/6

Scientific Initiation 12/5 12/8 7/3

Technical Training 2/1 2/0 3/2

Publications

International

Journals

17 16 23

1.259 Impact Factors (2012) 4.268

Papers in Scientific

Meetings

25 21 19

Human Resource Training and Scientific Production

a x/y: x=total of students in activity, y=total of students that finish their work in the period.

Thank you for your attention

Acknowledgments: