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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.

16Foggia 23-26th April 2009