1 wp 2: optimisation of oil-rich crops primary processing deliverable d 2.2 valorisation of...
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WP 2: Optimisation of oil-rich crops primary processing WP 2: Optimisation of oil-rich crops primary processing Deliverable D 2.2Deliverable D 2.2
Valorisation of side-stream products (SSRP) Valorisation of side-stream products (SSRP) obtained obtained
during refining of vegetable oilsduring refining of vegetable oils
dr. ir. Camelia EchimProf. dr. ir. Roland Verhé
Prof. dr. ir. Christian Stevens
~~Workshop Foggia, Workshop Foggia, 23-26th April, 2009April, 2009~~
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Sterols (free, esterified) Sterols (free, esterified)
Tocopherols, tocotrienolsTocopherols, tocotrienols
Color pigmentsColor pigments
Squalene, phosholipids, Squalene, phosholipids,
metals etc.metals etc.
Vegetable oils composition:Vegetable oils composition:
Minor Minor compoundscompounds
FFAFFA
GlyceridesGlycerides
Foggia 23-26 th April 2009
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Refining process of vegetable oils Refining process of vegetable oils
Foggia 23-26 th April 2009
(NBD) (RBD)
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TypicalTypical compositioncomposition of the SSRPsof 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 traces
Foggia 23-26 th April 2009
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ApplicationsApplications of the SSRPs 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 Oleochemicals
Animal feed Animal feed Animal feed
Foggia 23-26 th April 2009
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Foggia 23-26 th April 2009
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Estimates for the production of SSRPs
Oil cropCrude Oil
production*
(mil. t/year 2007)
FFA (%) Side stream refining products(mil. t/year 2007)
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 0.5-1.0 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
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SOAPSTOCK (FFA, acylglycerol, etc)
SOAPSTOCK (FFA, acylglycerol, etc)
Esterification
Distillation
BIODIESELBIODIESEL
Drying and/or filtration
Transesterification
Esterification Esterification
BIODIESELBIODIESEL BIODIESELBIODIESEL
Hydrolysis
Soap-splitting (AO)
Distillation
Hydrolysis
via direct conversion via soap-splitting route via hydrolysis route
Chemically or enzymatically catalysed processes
Incomplete conversion =>
-pre-treatment soap-splitting and/or hydrolysis or drying/filtration or transesterification
-post-treatment distillation
EN14214: YES NOT NOT YES
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Chemically catalysed process or non-catalytic process
Incomplete conversion =>
-post-treatment distillation
EN14214: YES
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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
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Biodiesel production scheme for deodorizer distillate via acylglycerol route
Enzymatically catalysed process or non-catalytic process
Incomplete conversion =>
-post-treatment distillation
EN14214: YES NOT
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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)
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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)
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1. 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.
2. Malaysian Palm Oil. Fact sheets (2007). Malaysian Palm Oil Council and Malaysian Palm Oil Board: 2-63.
3. EN 14214:2003. Automotive Fuels - Fatty Acid Methyl Esters (FAME) for Diesel Engines - Requirements and Test Methods.
4. Soragna F. (2008) Alternative routes to process low quality raw materials to produce biodiesel. Biofuel. 3 rd Annual meeting 28-30 October, Berlin.
5. Soragna F. (2009) New Desmet Ballestra FACT (Fatty Acids Conversion Technology), personal communication.
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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.
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16Foggia 23-26th April 2009