Innovative Uses of Glycerol from Biodiesel Plants December 13, 2011 NH Atlanta Hotel, Brussels, Belgium
Introduction on Glycerol as co-product from biodiesel plants
Dr. Ir. Wim De Greyt, R&D Manager Desmet Ballestra Group, Zaventem, Belgium
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Innovative Uses of Glycerol from Biodiesel Plants December 13, 2011 NH Atlanta Hotel, Brussels, Belgium
GENERAL OUTLINE OF THE PRESENTATION
1. GENERAL ASPECTS - Production, Market, Applications 2. GLYCEROL AS CO-PRODUCT OF BIODIESEL PROCESS - Current biodiesel market - Factors affecting crude glycerol composition 3. GLYCEROL REFINING 4. SECOND GENERATION BIODIESEL - New feedstocks/new technologies - How will it affect glycerol industry
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Innovative Uses of Glycerol from Biodiesel Plants December 13, 2011 NH Atlanta Hotel, Brussels, Belgium
GLYCEROL : SOME CHARACTERISTICS
C3H8O3 (92,09 g/mole)
Propane-1,2,3-triol Glycerin, glycerine
Density : 1.261 kg/l
Colorless, odorless, hygroscopic Viscous and non - liquid Slight sweet taste
Innovative Uses of Glycerol from Biodiesel Plants December 13, 2011 NH Atlanta Hotel, Brussels, Belgium
Glycerol Production
SYNTHETIC ROUTE
Produced from propylene Epichlorohydrin process; Not applied anymore (not economical)
NATURAL ROUTE
Obtained as co-product from oils and fats processing; Traditionally obtained from Soap production and Fat Splitting Currently mostly obtained from biodiesel production; Varying quality and production volumes
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Innovative Uses of Glycerol from Biodiesel Plants December 13, 2011 NH Atlanta Hotel, Brussels, Belgium
Glycerol as co-product from oils and fats processing
SOAP PRODUCTION FAT SPLITTING
BIODIESEL PRODUCTION
SWEET WATER
CRUDE GLYCEROL
Glycerol Refining
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Innovative Uses of Glycerol from Biodiesel Plants December 13, 2011 NH Atlanta Hotel, Brussels, Belgium
Earlier Glycerol industry (< 2004)
MARKET APPLICATIONS
Stable market (production,price) 1 Mio ton/yr (mainly USA) Mostly from soap production/fat splitting Limited synthetic glycerol
Food products (humectant,) Personal care products Oral care products (tooth paste) Tobacco & pharmaceuticals
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Innovative Uses of Glycerol from Biodiesel Plants December 13, 2011 NH Atlanta Hotel, Brussels, Belgium
Glycerol industry after biodiesel boom (> 2004)
* CRUDE GLYCEROL PRODUCTION MORE THAN DOUBLED
- More than 1 Mio ton extra crude glycerol from biodiesel industry;
* VERY VOLATILE MARKET
- Pricing strongly dependent on supply; - Growing supply due to growing biodiesel demand; - Global oversupply crisis;
* URGENT NEED TO FIND NEW APPLICATIONS
- Necessary expansion in glycerol refining capacity is delayed; - Especially need for new uses of crude, unrefined glycerol
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Innovative Uses of Glycerol from Biodiesel Plants December 13, 2011 NH Atlanta Hotel, Brussels, Belgium
New potential uses of (crude) glycerol
* ANIMAL FEED INGREDIENT
- Crude glycerol can be used in cattle and poultry feed; - Replacement of corn - Global oversupply crisis;
* POSSIBLE BUILDING BLOCK FOR MANY COMPOUNDS
- Epichlorohydrin production (Solvay) - 1,3 propanediol - Hydrogen, methanol, GTBE, .. Required glycerol quality ?
* GLYCEROL AS ENERGY SOURCE
- Feedstock for biomethanisation plants; - Direct use as fuel (Calorific value : 19 25 MJ/kg, depending on purity)
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Innovative Uses of Glycerol from Biodiesel Plants December 13, 2011 NH Atlanta Hotel, Brussels, Belgium
Biodiesel Production Process
Biodiesel production in Europe
10 9 8 7 Million ton 6 5 4 3 2 1 0 Year 2002 2003 2004 2005 2006 2007 2008
9,1 7,75 5,7 4,9 3,2 1,06 1,4 1,9
9,5
2009
2010
Source : European Biodiesel Board
* 9.5 Mio tons biodiesel produced in 2010 in EU-27 * World production :Approx. 15 Mio tons
1.5 Mio ton crude glycerol
Innovative Uses of Glycerol from Biodiesel Plants December 13, 2011 NH Atlanta Hotel, Brussels, Belgium
First Generation Biodiesel
* FEEDSTOCKS
- Triglyceride oils; - Rapeseed, soybean, palm oil; * PRODUCTION PROCESS
FIRST GENERATION BIODIESEL PROCESS
- Continuous process; - 60C/atm. pressure/2-3 hr; - Catalyst
* CATALYST
- Mostly homogeneous catalysts (NaOH,KOH, NaOMe,KOMe) - Heterogeneous catalysts (limited industrial application)
Triglyceride 1000 kg Methanol 100 kg Glycerol 100 kg Biodiesel 1000 kg
* BY-PRODUCT : GLYCEROL
- 10% of biodiesel production
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Innovative Uses of Glycerol from Biodiesel Plants December 13, 2011 NH Atlanta Hotel, Brussels, Belgium
Biodiesel Production Process
REACTOR 1 REACTOR 2 REACTOR 3 BIODIESEL, GLYCERINE & METHANOL (to glycerine separation)
FEEDSTOCK
METHANOL & CATALYST
* Multistage process
METHANOL & CATALYST METHANOL & CATALYST
* Sequential addition of catalyst and methanol * Recycling of glycerol phase to first reactor to save catalyst
CRUDE GLYCERINE (to purification) GLYCERINE & CATALYST
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Innovative Uses of Glycerol from Biodiesel Plants December 13, 2011 NH Atlanta Hotel, Brussels, Belgium
Glycerol purification
METHANOL VAPOR BIODIESEL, GLYCERINE & METHANOL Water + citric acid
EVAPORATOR
CENTRIFUGE
CRUDE BIODIESEL (to biodiesel purification)
CRUDE GLYCERINE (from no. 1 transesterification reactor)
GLYCERINE TANK
CRUDE GLYCERINE (to glycerine purification)
* Crude biodiesel is first flashed (partial methanol removal) and then washed
with citric acid (catalyst inactivation)
* Heavy phase (water, methanol,glycerol, soaps, traces biodiesel,.) is blended in glycerine tank with crude glycerol from reactor 1
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Innovative Uses of Glycerol from Biodiesel Plants December 13, 2011 NH Atlanta Hotel, Brussels, Belgium
Glycerol purification
CRUDE GLYCERINE
Hydrochloric or sulfuric acid (for soaps conversion)
REACTOR
DECANTER
FFA (to acid esterification)
PURIFIED GLYCERINE
Caustic (pH correction) REACTOR
EVAPORATOR
DRYER
CRUDE GLYCERINE (80-85% purity)
METHANOL
WATER
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Innovative Uses of Glycerol from Biodiesel Plants December 13, 2011 NH Atlanta Hotel, Brussels, Belgium
Crude Glycerol from biodiesel production
Crude Glycerol color can vary depending on feedstock/process
* M.O.N.G. = Matter Organic Non Glycerine
- Biodiesel, Fatty Matter, FFA,. - Biodiesel production losses (has to be as low as possible)
* Salts content and type
- Depending on type and amount of catalyst (K- or Na-salts) - Depending on acid for catalyst inactivation (chlorides or sulphates) - No salts when a heterogeneous (solid) catalyst is used
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Innovative Uses of Glycerol from Biodiesel Plants December 13, 2011 NH Atlanta Hotel, Brussels, Belgium
Glycerol Refining
Required quality technical applications
Required quality edible applications
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Innovative Uses of Glycerol from Biodiesel Plants December 13, 2011 NH Atlanta Hotel, Brussels, Belgium
Glycerol Refining
Salt boxes
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Innovative Uses of Glycerol from Biodiesel Plants December 13, 2011 NH Atlanta Hotel, Brussels, Belgium
Pharma-grade Glycerol Refining Process
To bleaching (activated carbon)
Pharma grade glycerol Quality specs Purity : min. 99.7% Color : max. 5 APHA Ash : max. 0.01% Water : max. 0.2 %
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Complex Distillation
Innovative Uses of Glycerol from Biodiesel Plants December 13, 2011 NH Atlanta Hotel, Brussels, Belgium
Distilled Glycerol Refining Process
Dewatering Preconcentration
Salt boxes
Distillation
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Innovative Uses of Glycerol from Biodiesel Plants December 13, 2011 NH Atlanta Hotel, Brussels, Belgium
Biodiesel Industry in 2020
Biodiesel production will increase, but to which volume ?
OECD forecast : 40 Mio tons in 2020
Global biodiesel production forecast
40 Mio tons
MAIN ISSUES/UNCERTANTIES
- Policy measures supporting biofuels - Availability of new feedstocks - Sustainability criteria
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- Development of second generation (lignocellulosic) biofuels - Evolution of diesel fleet
Source : OECD Agricultural Outlook
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Innovative Uses of Glycerol from Biodiesel Plants December 13, 2011 NH Atlanta Hotel, Brussels, Belgium
Second generation biodiesel
= Biodiesel (FAME) produced from more sustainable feedstocks by a more sustainable technology
Second Generation Feedstocks
* High FFA feedstocks (like Palm FAD,)
* Technical (non-edible) oils (e.g. Jatroph) * Waste oils (e.g. Cat. 1 tallow) Second Generation Technology
* Advanced acid esterification processes
Less useful glycerol per ton biofuel
More pure glycerol
* Solid catalysts (chemical/enzymes)
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Innovative Uses of Glycerol from Biodiesel Plants December 13, 2011 NH Atlanta Hotel, Brussels, Belgium
Second generation biofuel
= Biofuel (non-FAME) produced from sustainable feedstocks (oils/fats or lignocellulosic biomass)
Biofuels from Ligno-cellulosic biomass not expected next decade Second generation biofuel from oils and fats (hydrotreating process)
Branched alkanes (no FAME) No glycerol as co-product High cetane number Low cloud point
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Innovative Uses of Glycerol from Biodiesel Plants December 13, 2011 NH Atlanta Hotel, Brussels, Belgium
CONCLUSIONS
First generation biodiesel boom created a glycerol problem Glycerol is an interesting building block for mainly different applications. Current oversupply can be an opportunity Glycerine production will always be largely dependent on the biodiesel industry. Growth of biodiesel industry is highly uncertain and dependent on a number of unpredictable external factors Glycerine market will remain volatile on short-mid term
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De Smet Ballestra Group
THANK YOU FOR YOUR ATTENTION !!!
Science behind technology !
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