PRODUCTION OF BIODIESEL FROM HIGH ACIDIC RAW MATERIALS Design and development of an heterogeneous catalytic process

PRODUCTION OF BIODIESEL FROM HIGH ACIDIC RAW MATERIALS Design and development of an heterogeneous catalytic process INDEX Why biodiesel from High Acidic Raw Materials? How can we make biodiesel? Our proposal The results Discussion Achievements Glosary FA = Fatty Acid FFA = Free Fatty Acid FAME = Fatty Acid Methyl Ester TG = Triglycerides DG = Diglycerides MG = Monoglycerides Aknowledgements

PRODUCTION OF BIODIESEL FROM HIGH ACIDIC RAW MATERIALS Design and development of an heterogeneous catalytic process Why biodiesel from High Acidic Raw Materials? Waste oils Animal fats Tomorrow Today The first question, we should answer is why we should produce biodiesel from high acidic raw materials. Today, the production of biodiesel from vegetable oils is well-known. This way of production requires extensive cultivation areas only for biodiesel production which leads to less food to fulfill population needs. The production of biodiesel from waste oils and animal fats, fatty acid-rich raw materials, will decrease the use of cultivation areas for biodiesel production and, at the same time, valorizate a harmful residues. This technology has a social and enviromental benefit. Requires extensive cultivation areas Less food for Population needs

PRODUCTION OF BIODIESEL FROM HIGH ACIDIC RAW MATERIALS Design and development of an heterogeneous catalytic process How can we make biodiesel? Alkaline Transesterification Homogeneous KOH KOH Developed Tecnology Triglycerides Methanol FAME Glycerine Vegetable oils How is biodiesel produced nowadays? On one hand, starting from vegetable oils, that consist mainly of triglycerides, an alkaline transesterification is normally performed. This homogeneus reaction takes place in alkaline media, in the presence of KOH as catalyst. Triglycerides react with mehtanol to produce FAMEs, which is biodiesel, and glycerine as a subproduct. On the other hand, the production of biodiesel from animal fats and waste oils, fatty acid-rich raw materials, consists of an acidic esterification in the presence of sulphuric acid as catalyst. Fatty acids react with methanol to produce FAME and water, that should be removed from reaction media to favour the reaction towards the product of our interest. The use of sulphuric acid as catalyst has many drawbacks: because of its corrosive nature, the handling and storage of this product is always problematic. The final product must be neutralized before commercialization as biodiesel. The above reasons make the process expensive and not adequate from an enviromental standpoint. Therefore, an innovative heterogeneous catalytic process is, more than ever, required to overcome the mentioned drawbacks. Acidic Esterification Homogeneous Sulphuric acid Drawbacks Fatty Acids Methanol FAME Water Animal Fats Waste Oils

PRODUCTION OF BIODIESEL FROM HIGH ACIDIC RAW MATERIALS Design and development of an heterogeneous catalytic process Our proposal: the Process Catalysts Lewatit GF-101 Amberlyst 39wet Column Our proposal is an heterogeneus catalytic process, using the sulphonic resins Lewatit GF-101 and Amberlyst 39wet as catalyst, in substitution of sulphuric acid. In this pictures we can see the laboratory-scale pilot plant, where raw materials and methanol are mixed in the stirred tank. A HPLC pump drives the mixture through this column, filled of the sulphonic resin. Finally, the mixture is returned to the Stirred Tank. Stirred Tank Pump “Heterogeneous Catalytic Process”

PRODUCTION OF BIODIESEL FROM HIGH ACIDIC RAW MATERIALS Design and development of an heterogeneous catalytic process Our proposal: Raw materials ANIMAL FATS “Yellow Grease”. Acidity ~ 15%. Proteins and Phospholipids Physical extraction Fe, P and S catalyst poisons regulated by EN14214 OLEINEs Neutralized soapstock. Acidity ~ 75% Proteins, Phospholipids, Glycerids Neutralizing FFA with NaOH and acidification Na > 1% The raw materials used were: Animal Fats, known as “Yellow Grease”, are extracted from animal tissues by melting and centrifugation. For this reason, fatty acids could be contaminated with proteins and phospholipids. Iron, phosphorus and sulphur can act as catalyst poisons. This raw material did not flow easily because of its low melting point. Animal fats often clogged pipes, becoming a problem. Oleines are a subproduct of oil industry. An alkali (NaOH or KOH) is added to vegetable oil to precipitate soaps. This soaps are separated from triglycerides and neutralized to produce fatty acids. The neutralized soapstock is highly acidic and contains proteins, phospolipids, some glycerids and sodium or potassium. Metal cations may poison the active centres of catalysts. Deodorization is a process to remove fatty acids from vegetable oils. These compounds are responsible of bad odours. The process is a distillation with steam. Highly-pure-fatty acid subproduct is obtained with 75% acidity. DEODORIZATION DISTILLATE Acidity ~ 75% Esentially Free Fatty Acids Distillation of FFA with steam

PRODUCTION OF BIODIESEL FROM HIGH ACIDIC RAW MATERIALS Design and development of an heterogeneous catalytic process The results: Diluted oleine 15% w/w in sunflower oil 1 2 3 4 5 6 -10 10 20 30 40 50 60 70 80 90 100 Esterification Yield (%) Time (hours)  Low Esterification Yield (%)  Production of Triglycerides Results, Using diluted oleine 15% w/w in sunflower oil as raw material, the results show a very low esterification yield. The chromatogram in the bottom-left corner shows an increase in triglycerides in the esterified product. Therefore, fatty acids react preferably with monoglycerides and diglyceridos rather than methanol. Initial DG FA TG Esterified FAME

PRODUCTION OF BIODIESEL FROM HIGH ACIDIC RAW MATERIALS Design and development of an heterogeneous catalytic process The results: Diluted deodorization distillate 30% w/w in sunflower oil 1 2 3 4 5 6 7 8 -10 10 20 30 40 50 60 70 80 90 100 Time (hours) Esterification Yield (%) High Esterification Yield (%)  Production of Triglycerides Initial Using diluted deodorization distillte 30% w/w in sunflower oil, results show a strong increase in Esterification Yield, but again the production of triglyceridos from mono and diglycerides is significant. Only fatty acid methyl esthers can be used for biodiesel. FA MG DG TG Esterified FAME

PRODUCTION OF BIODIESEL FROM HIGH ACIDIC RAW MATERIALS Design and development of an heterogeneous catalytic process The results: Non diluted oleine 75% free fatty acids 10 20 30 40 50 60 70 80 90 100 1 2 3 4 5 6 7 8 9 11 12 Methyl ester (%) Esterification Yield (%) 10% Free acidity Triglycerides Destillation Final 1% p/p FFA EU14214 Esterification Yield (%) Using non diluted olive oleine as raw material, 75% free fatty acids, the results show a strong increase in yield in the first two hours of reaction. The main products are FAMEs (87%) with some triglycerides. However, a residual 10% free fatty acid content is remained, and does not decrease with time. A final destillation should be performed to comply with the EU14214 european regulation for biodiesel specifications. Time in hours High Esterification Yield (%) High FAME Yield (%)

PRODUCTION OF BIODIESEL FROM HIGH ACIDIC RAW MATERIALS Design and development of an heterogeneous catalytic process Discussion: Three phase heterogeneous process FA + Sunflower oil (TG) Methanol Catalyst FA FA + Methanol FAME Oil Phase Water Phase Why Fatty-Acid-Methyl-Esther Yields are higher in case of non diluted raw material. The explanation is the three phase heterogeneus nature of the process. Three phases: FA, methanol and catalyst must be put in contact and they are not miscible. Using diluted raw material, FA are more miscible in sunflower oil (glycerides) than in methanol, so FA finally react with mono and diglycerides to produce triglycerides. Using non diluted acidic raw materials, in abscence of glycerides, FA concentration in methanol is higher, so the evolution to FAME on the surface of catalyst is favoured, as can be seen in the right side of the picture. DILUTED RAW MATERIAL NON DILUTED FA = Fatty Acid FAME = Fatty Acid Methyl Ester TG = Triglycerides

PRODUCTION OF BIODIESEL FROM HIGH ACIDIC RAW MATERIALS Design and development of an heterogeneous catalytic process Achievements The production of biodiesel from non diluted oil industry wastes, in good yield, that commits with european legislation EU14214 Removal and valorization of a problematic waste A new process for biodiesel production from high acidic raw materials, more friendly from an enviromental , safety and economic standpoint To resume, three main achievements have been reached: The production of biodiesel from non diluted oil industry acidic wastes, in good yield, that commits with EU14214 The removal and valorization of a problematic waste The design and development of an innovative process for production of biodiesel from high acidic raw materials, more respectful with enviroment, in a safer and more profitable technology.

PRODUCTION OF BIODIESEL FROM HIGH ACIDIC RAW MATERIALS Design and development of an heterogeneous catalytic process Acknowledgements Analysis and Characterization of products To resume, three main achievements have been reached: The production of biodiesel from non diluted oil industry acidic wastes, in good yield, that commits with EU14214 The removal and valorization of a problematic waste The design and development of an innovative process for production of biodiesel from high acidic raw materials, more respectful with enviroment, in a safer and more profitable technology. Design and construction of the Bench-Scale plant Project suported under the program CIT-120000-2009-035 by Ministery of Science and Innovation

PRODUCTION OF BIODIESEL FROM HIGH ACIDIC RAW MATERIALS Design and development of an heterogeneous catalytic process Thank you very much for your attention To resume, three main achievements have been reached: The production of biodiesel from non diluted oil industry acidic wastes, in good yield, that commits with EU14214 The removal and valorization of a problematic waste The design and development of an innovative process for production of biodiesel from high acidic raw materials, more respectful with enviroment, in a safer and more profitable technology.

PRODUCTION OF BIODIESEL FROM HIGH ACIDIC RAW MATERIALS Design and development of an heterogeneous catalytic process http://www.vancebioenergy.com/product_biodiesel_en14214.php Annex: EU14214 Biodiesel Specifications   Property Unit Test Method Specification Ester content % (m/m) EN 14103-03 96.5 min Density at 15°C kg/m3 EN ISO 12185-96 860 – 900 Kinematic viscosity at 40°C mm2/s EN ISO 3104-94 3.5 – 5.0 Flash point °C EN ISO 2719-02 101 min Sulfur content mg/kg EN ISO 20846-04 10 max Carbon residue (on 10% distillation residue) EN ISO 10370-93 0.3 max Cetane Number – EN ISO 5165 51 min Sulfated ash content ISO 3987-94 0.02 max Water content EN ISO 12937-00 500 max Total Contamination EN 12662-98 24 max Copper Strip Corrosion (3 hours at 50°C) Rating EN ISO 2160-98 Class 1 max Oxidation stability , 110°C (accelerated oxidation) hours EN 14112-03 6 min Acid value mg KOH/g EN 14104-03 0.5 max Iodine value g iodine/100g EN 14111-03 120 max Linolenic acid methyl ester 12 max Polyunsaturated (>= 4 Double bonds) methyl ester EN 14103 1 max Methanol content EN 14110-03 0.2 max Monoglyceride content EN 14105-03 0.8 max Diglyceride content Triglyceride content Free glycerine Total glycerine 0.25 max Group I metals (Na + K) EN 14108/9 5 max Group II metals (Ca + Mg) EN 14538 Phosphorus content EN 14107 4 max Cold Filter Plugging Point EN 116 +15 max