Valorisation of side-stream products (SSRP) obtained WP 2: Optimisation of oil-rich crops primary processing Deliverable D 2.2 Valorisation of side-stream products (SSRP) obtained during refining of vegetable oils dr. ir. Camelia Echim Prof. dr. ir. Roland Verhé Prof. dr. ir. Christian Stevens ~Workshop Foggia, 23-26th April, 2009~

Vegetable oils composition: Sterols (free, esterified) FFA Tocopherols, tocotrienols Minor compounds Color pigments Glycerides Squalene, phosholipids, metals etc. abbbbbbb Foggia 23-26 th April 2009

Refining process of vegetable oils (NBD) (RBD) Foggia 23-26 th April 2009

Deodorizer distillates Typical composition of the SSRPs Compounds (%) Soapstock Acid oil Deodorizer distillates Spent bleaching earth RBD NBD Water 32-67 <1-3 - FFA 10-28 39-79 80-90 30-60 10-13 Acylglycerols 12-13 18-30 <1-14 5-12 up to 30 Phospholipids 5-9 traces Unsaponifiable matter <1 <1-4 5-10 25-33 Foggia 23-26 th April 2009

Deodorizer distillates Applications of the SSRPs Soapstock Acid oil Deodorizer distillates Spent bleaching earth Source of free fatty acids Food additives Disposed: Incineration Land filling Low-grade oil Pharmaceutical industry Medium grade soap products Cosmetics Oleochemicals Animal feed Foggia 23-26 th April 2009

Production of biodiesel/biofuel from SSRPs Foggia 23-26 th April 2009

Estimates for the production of SSRPs Oil crop Crude Oil production* (mil. t/year 2007) FFA (%) Side stream refining products FAD** Soapstock*** Acid oil# Palm (PO) 36.84 4.0-5.0 1.77-1.84 - Soybean (SBO) 35.26 0.5-1.0 0.11-0.21 0.30-0.60 0.15-0.30 Rapeseed (RSO) 18.36 0.06-0.12 0.16-0.32 0.08-0.16 Sunflower (SFO) 11.10 2.0-3.0 0.20-0.30 0.18-0.28 0.09-0.14 Total 101.56 7.0-10.0 2.14-2.47 0.64-1.20 0.32-0.60 *Source: Malaysian Palm Oil, 2007 **DD=1.2 x FFA of crude oil (Vries RJ, 1984) #AO=1.7 x FFA of crude oil (Vries RJ, 1984) *** SS= 2 x AO PO=100%RBD SBO, RSO= 50%RBD+50%NBD SFO=75%RBD+25%NBD Foggia 23-26th April 2009

Biodiesel production scheme for soapstock (SS) and acid oil (AO) Chemically or enzymatically catalysed processes Incomplete conversion => -pre-treatment soap-splitting and/or hydrolysis or drying/filtration or transesterification -post-treatment distillation SOAPSTOCK (FFA, acylglycerol, etc) Drying and/or filtration Hydrolysis Soap-splitting (AO) Transesterification Hydrolysis Esterification Esterification Esterification Distillation Distillation BIODIESEL BIODIESEL BIODIESEL via direct conversion via hydrolysis route via soap-splitting route EN14214: YES NOT NOT YES

Biodiesel production scheme for acid oil (AO) via acylglycerol route Chemically catalysed process or non-catalytic process Incomplete conversion => -post-treatment distillation EN14214: YES

Biodiesel production scheme for deodorizer distillates by direct conversion Chemically or enzymatically catalysed process Incomplete conversion => -pre-treatment hydrolysis -post-treatment transesterification or distillation EN14214: YES YES NOT

Biodiesel production scheme for deodorizer distillate via acylglycerol route Enzymatically catalysed process or non-catalytic process Incomplete conversion => -post-treatment distillation EN14214: YES NOT

Case study 1 FACT (Fatty Acid Conversion Technology)* STAND ALONE PROCESS For high acidity feedstocks (fatty acid distillates) Chemically catalysed process (heterogenesous catalyst, 90°C, 3.5 bar) To produce biofuels To produce biodiesel according to EN14214 by distillation of FAME *F. Soragna, Desmet Ballestra Group (2008, 2009)

Case study 2 FACT (Fatty Acid Conversion Technology)* INTEGRATED PROCESS For medium/high acidity feedstocks Chemically catalysed process (heterogenesous catalyst, 90°C, 3.5 bar) Integrated transesterification step To produce biofuels To produce biodiesel according to EN14214 *F. Soragna, Desmet Ballestra Group (2008, 2009)

References: Vries RJ (1984) Utilization of Malaysian Palm oil and Palm Kernel Oil for fatty acids and derivatives. J. Am. Oil Chem. Soc, 61 (2): 404-407. Malaysian Palm Oil. Fact sheets (2007). Malaysian Palm Oil Council and Malaysian Palm Oil Board: 2-63. EN 14214:2003. Automotive Fuels - Fatty Acid Methyl Esters (FAME) for Diesel Engines - Requirements and Test Methods. Soragna F. (2008) Alternative routes to process low quality raw materials to produce biodiesel. Biofuel. 3 rd Annual meeting 28-30 October, Berlin. Soragna F. (2009) New Desmet Ballestra FACT (Fatty Acids Conversion Technology), personal communication. Foggia 23-26 th April 2009

Conclusions There are multiple routes to converting the SSRPs to biodiesel, some of which have found industrial application and others have a scientific value. There is a general trend to pre-treat the soapstock before converting it to FAME, either by acidulation, in order to generate AO (soap-splitting route) or by hydrolysis of neutral oil (hydrolysis route). Starting from deodorizer distillate two processes (direct conversion or via acylglycerols route) are shown to produce biodiesel. Pre-treatment of the feedstock or post-treatment of the final biodiesel is often required in order to meet the quality specifications. Using a combination of technologies, low-value lipid resources are converted into biodiesel that complies with the EU and ASTM specifications.

Thank you for your attention!! Foggia 23-26th April 2009