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Innovation in the process of biodiesel synthesis

LITERATURE

Summary of the work made

Different important results have been achieved in biodiesel synthesis:

  1. A system for converting completely vegetable oil into biodiesel in few seconds in mild conditions of temperature and pressure has been developed (see process intensification).

  2. Different heterogeneous catalysts (basic and acid promoting the transesterification reaction have been studied and could be industrially used.

  3. The esterification of free fatty acids promoted by acid exchange resins has been studied in a great detail solving the problem of the resins swelling and deactivating in fixed bed continuous reactors.

  4. The problem of using waste oils as raw material has bee studied and solved.

 

Work

Biodiesel is a fuel safe, renewable, non-toxic, biodegradable and much less contaminant for the environment than conventional diesel fuel. Moreover, it represents a strategic source of energy especially for the countries that have not oilfields. For these reasons, even if the cost of biodiesel is still greater than diesel from petroleum, many governments sustain this production.

Biodiesel is a mixture of fatty acids methyl esters (FAME), normally, obtained in industry by transesterification of vegetable oils with methanol in the presence of alkaline catalysts (NaOH, KOH or related alkoxides). Vegetable oils are composed of tri-glycerides of fatty acids (a mixture of linear fatty acids, with an average number of 18 carbon atoms, and containing in the chain mainly one, but also two or three or none double bonds). The reaction occurs in three successive steps forming progressively di-glycerides, mono-glycerides and glycerol. Glycerol is an important by-product of this process obtained with a yield of about 10% b.w. The only advantage of this most practiced process consists in the mild conditions of temperature (about 60°C) and pressure (atmospheric), while, many drawbacks are present, as: (i) the process requires the use of highly refined oils, i.e., not containing free fatty acids and moisture. This, because, fatty acids react with the catalyst forming soaps that are poorly active in the reaction and form emulsions that strongly prolong the separation time, by settling glycerol from methyl esters. Moisture favors the formation of fatty acids by hydrolysis. Other drawbacks are: the cost of biodiesel is determined for about 85 % by the cost of the feedstock; (ii) the catalyst must be neutralized after the reaction, therefore, cannot be re-used and the salt formed during the neutralization contaminates the glycerol increasing the costs of its purification; (iii) an excess of glycerol is offered in a market that is already saturated. By concluding, to reduce the costs of biodiesel production requires innovation efforts. In particular it is imperative:

  1. To employ less expensive feedstock like unrefined or waste oils (containing free fatty acids), this means to promote both esterification and transesterification;

  2. To improve the actual technology based on the use of homogeneous alkaline catalysts through a better understanding of the reaction mechanism, to develop new biphasic kinetic models and to adopt techniques of process intensification;

  3. To introduce the use of heterogeneous catalysts, possibly finding a catalyst promoting in one step both esterification of free fatty acids and transesterification of tri-glycerides;

  4. To find new remunerative uses for the by-product glycerol (see the appropriate section section in the website).

 

 

Alternative processes for biodiesel production

 

 

 

 

 

Use of corrugated plates heat excharger reactor

 

 

 

 

 

Laboratory Plant

 

 

Literature

Eurochem Engineering has worked hardly, in collaboration with NICL and with different industrial companies, on all the mentioned aspects with relevant results described in several published reviews [1,2], papers and patents devoted to biodiesel synthesis via esterification [3-10], via catalytic transesterification [11-22] and traditional process intensification [23-29].

Reviews on the subject:

  1. E. Santacesaria, G. Martinez Vicente, M. Di Serio, R. Tesser; Main Technologies in biodiesel production: State of the art and future challenges; Catalysis Today: 195 (2012) (1), 2-13

  2. Di Serio, Martino; Tesser, Riccardo; Pengmei, Lu; Santacesaria, Elio. Heterogeneous Catalysts for Biodiesel Production. Energy & Fuels (2008), 22(1), 207-217.

Esterification of free fatty acids in biodiesel synthesis

  1. Tesser, R.; Di Serio, M.; Guida, M.; Nastasi, M.; Santacesaria, E. “Kinetics of Oleic Acid Esterification with Methanol in the Presence of Triglycerides” Industrial & Engineering Chemistry Research (2005), 44(21), 7978-7982.

  2. Santacesaria, E.; Tesser, R.; Di Serio, M.; Guida, M.; Gaetano, D.; Garcia Agreda, A. Kinetics and Mass Transfer of Free Fatty Acids Esterification with Methanol in a Tubular Packed Bed Reactor: A Key Pretreatment in Biodiesel Production. Industrial & Engineering Chemistry Research (2007), 46(15), 5113-5121.

  3. Santacesaria, E.; Tesser, R.; Di Serio, M.; Guida, M.; Gaetano, D.; Garcia Agreda, A.; Cammarota, F. Comparison of Different Reactor Configurations for the Reduction of Free Acidity in Raw Materials for Biodiesel Production. Industrial & Engineering Chemistry Research (2007), 46(25), 8355-8362.

  4. R. Tesser, L.Casale, D. Verde, M. Di Serio, E. Santacesaria “Kinetics of free fatty acids esterification: Batch and loop reactor modelling” Chemical Engineering Journal (2009), 154(1-3), 25-33

  5. R. Tesser, M. Di Serio, L. Casale, G. Carotenuto and E. Santacesaria; Absorption of Water/Methanol Binary System on Ion-Exchange Resins; The Canadian Journal of Chemical Engineering 2010, 88 (6), pp 1044-1053

  6. Riccardo T., Di Serio M., Casale L., Sannino L., Ledda M., Santacesaria E.; Acid exchange resins deactivation in the esterification of free fatty acids; Chemical Engineering Journal 161 (2010) 212–222

  7. Tesser R., Casale L., Verde D., Di Serio M. and Santacesaria E. Kinetics and modeling of fatty acids esterification on acid exchange resins. Chemical Engineering Journal (2010), 157(2-3), 539-550

  8. R. Vitiello, A. Buonerba, R. Tesser, M. Di Serio, A. Grassi, E. Santacesaria; Use of Waste Materials for Biodiesel Production; DGMK Conference Proceedings October 8-10, 2012, Berlin, Germany

Innovative homogeneous and heterogeneous catalysis in biodiesel synthesis via transesterification of tri-glycerides

  1. Di Serio, M.; Tesser, R.; Dimiccoli, M.; Cammarota, F.; Nastasi, M.; Santacesaria, “Synthesis of biodiesel via homogeneous Lewis acid catalyst “Journal of Molecular Catalysis A: Chemical (2005), 239(1-2), 111-115.

  2. Di Serio, M.; Ledda, M.; Cozzolino, M.; Minutillo, G.; Tesser, R.; Santacesaria E. “Transesterification of Soybean Oil to Biodiesel by Using Heterogeneous Basic Catalysts.” Industrial & Engineering Chemistry Research (2006), 45(9), 3009-3014.

  3. M. Cozzolino, R. Tesser, M. Di Serio, M. Ledda, G. Minutillo, E. Santacesaria. “Preparation, characterization and catalytic performances of highly dispersed supported TiO2/SiO2 catalysts in biodiesel production.” Studies in Surface Science and Catalysis (2006), 162 (Scientific Bases for Preparation of Heterogeneous Catalysts), 299-306.

  4. Di Serio, M.; Cozzolino, M.; Giordano, M.; Tesser, R.; Patrono, P.; Santacesaria, E.. From Homogeneous to Heterogeneous Catalysts in Biodiesel Production. Industrial & Engineering Chemistry Research (2007), 46(20), 6379-6384

  5. Santacesaria, E.; Di Serio, M.; Tesser, R.; Casale, L. New technologies in biodiesel production. DGMK Tagungsbericht (2008), 2008-3(Preprints of the DGMK-Conference "Future Feedstocks for Fuels and Chemicals", 2008), 7-18.

  6. Di Serio M., Tesser R., Casale L., A. D’Angelo, M. Trifuoggi and E. Santacesaria; Heterogeneous Catalysis in Biodiesel Production: The Influence of Leaching. Topics in Catalysis (2010), 53 (11-12), 811-819

  7. M. Di Serio, S. Mallardo, G. Carotenuto, R. Tesser, E. Santacesaria; Mg/Al hydrotalcite catalyst for biodiesel production in continuous packed bed reactors; Catalysis Today: 195(2012) (1)54-58

  8. Santacesaria, E.; Di Serio, M.; Tesser, R.. New technologies in biodiesel production. Chimica e l'Industria (Milan, Italy) (2009), 91(5), 126-129

  9. Siano, Dante; Di Serio, Martino; Tesser, Riccardo; Dimiccoli, Marinella; Cammarota, Francesco; Santacesaria, Elio; Siano, Luigi; Nastasi, Mario. “Process for the production of esters from vegetable oils or animal fats.” (in collaboration with Aser S.r.l., Italy) PCT Int. Appl. (2006) WO 2006006033 A1 20060119 Inserire pdf

  10. Siano, Dante; Nastasi, Mario; Santacesaria, Elio; Di Serio, Martino; Tesser, Riccardo; Guida, Maurizio. “Method for forming a packing for resin catalytic packed beds, and so formed packing.” (in collaboration with Aser S.r.l., Italy) PCT Int. Appl. (2006), WO 2006046138 A1 20060504

  11. Siano, Dante; Nastasi, Mario; Santacesaria, Elio; Di Serio, Martino; Tesser, Riccardo; Minutillo, Giuseppe; Ledda, Marianna; Tenore, Teresa; “Transesterification process for producing fatty acid esters from vegetable oils or animal fats using heterogeneous catalysts and aliphatic alcohols.”; (Aser S.r.l., Italy) PCT Int. Appl. (2006), WO 2006050925 A1 20060518

  12. Siano, Dante; Siano, Luigi; Nastasi, Mario; Santacesaria, Elio; Di Serio, Martino; “Method for producing esters from vegetable oils and animal fats by using heterogeneous catalysts.” (Aser S.r.l., Italy). PCT Int. Appl. (2006), WO 2006094986 A1 20060914

Intensification of traditional process catalyzed by NaOH, KOH or related alkoxides

  1. Santacesaria, E.; Di Serio, M.; Tesser, R.; Casale, L.; Verde, D.; Turco, R.; Bertola, A. ; Use of a Corrugated Plates Heat Exchanger Reactor for Obtaining Biodiesel with Very High Productivity Energy & Fuels (2009), 23(10), 5206-5212.

  2. E. Santacesaria, M. Di Serio,R. Tesser, M. Tortorelli, R. Turco, V. Russo; A simple device to test biodiesel process intensification; Chemical Engineering and Processing: Process Intensification; 50(2011)1085-1094.

  3. E. Santacesaria, R. Turco, M. Tortorelli, V. Russo, M. Di Serio, R. Tesser; Biodiesel Process Intensification by Using Static Mixers Tubular Reactors; Industrial & Engineering Chemistry Research 51 (2012) 8777-8787.

  4. E. Santacesaria, M. Di Serio, R. Tesser, R. Turco, M. Tortorelli, V. Russo; Biodiesel Process Intensification in a very simple microchannel device; Chemical Engineering and Processing: Process Intensification 52(2012)47-54.

  5. E. Santacesaria, R. Turco, M. Tortorelli, V. Russo, M. Di Serio, R. Tesser; Biodiesel process intensification: the role of the liquid-liquid interface area in the achievement of a complete conversion in few seconds; Green Process Synthesis. 1(2012) 181-189.

  6. V Russo, R Tesser, M Di Serio, E Santacesaria; A New Kinetic Biphasic Approach to Biodiesel Process Intensification; DGMK Conference Proceedings October 8-10, 2012, Berlin, Germany.

  7. Santacesaria, Elio; Di Serio, Martino; Tesser, Riccardo; Turco, Rosa; Verde Domenico; Casale, Luca; (MYTHEN SpA) “Reactor for Immiscible Liquid Reagents”. (MYTHEN SpA) PCT Int. Appl. (2010) WO 2010073216 (A1)