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Current Status
Thomas Willke
Federal Agricultural Research Centre
Institute of Technology and Biosystems Engineering
Bundesallee 50, D-38116 Braunschweig
Email: thomas.willke@fal.de - telephone: ++49 (0)531-596-4124
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Outline
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Processes
Starch, Sugar
Biogas
Glucose/Fructose Products
Electricity,
Heat Fructose Products
Palatinit
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Technical polymers
examples
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Polymers: Starting Material
Acids (accessible from renewable resources)
COOH
fumaric
itaconic
HOOC O
HOOC HOOC COOH
2-keto-glutaric
OH COOH
HOOC
citric succinic
COOH COOH
HOOC COOH
HO COOH COOH
COOH COOH
HOOC
cis-Aconitsäure
cis-aconitic itaconic
Itaconsäure
fumaric
Fumarsäure
COOH
COOH
COOH
HO COOH
COOH COOH Isocitronensäure
Iso-citric
Bernsteinsäure
succinic CH2
O COOH
α-Ketoglutarsäure
ketoglutaric
(2-Keto-glutarsäure) TW-020117
Itaconic Acid
sugar, starch
(glucose) complexing agent
Aspergillus terreus
(fungi)
co-monomer,
plasticiser
itaconic acid
paints, lacquers
Yarrowia spp., Candida spp.
(yeast)
others
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Itaconic Acid Production
Fermentation from glucose
200 100
conditions
180 90 batch
(without pH-
160 itaconic acid 80
controll)
140 70 mineral-salt
120 60
P-limitation
100 50 pH 1,7
33°C
80 40
60 30
result
40 20 Î final concentration
glucose > 80 g/L IA
20 10
Î max. productivity
0 0 > 1 g/(L·h)
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14
Î Yield: 0,6 g/g =
time course[d] 83% of Theory
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Itaconic Acid Production
other substrates?
80
70 Glucose
Saccharose
60
Itaconic acid [g/L]
50
Glycerol
40
30
20
10
Lactose
0
0 2 4 6 8 10 12 14 16 18 20 22 24
time [d]
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Immobilisation in Biotechnology
Example: ethanol
biofuel,
chemical feedstock
bead surface
yeast-cells
wheat
x 100
sugarbeet
HO CH2
O HO CH2
HO
O
O HOH2C O HO HO
OH CH2OH
OH
O
HO OH
O
O
OH H O CH2 CH3
HOH2C O H2C O HOH2C O
O
immobilised
O
HO OH
O
HO OH HO OH O
cube particle
foil
lens
hollow bead bead top view
cross section
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Bead Production with JetCutter
Scheme and operation
pressure
cutting nozzle
tool
motor D
cut cylinder
bead
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JetCutter
optimisation of settings for low spray losses
suited adjustments
Æ almost no losses
unsuited adjustments
Æ high losses
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JetCutter
Particle size distribution
-1] -1
[mmmm 14
12
Ca-Alginat
density,
10
distribution density
6
distribution
PVA
4
0
0 0.2 0.4 0.6 0.8 1 1.2 1.4 1.6 1.8 2
beaddiameter
bead diameter, mm
[mm]
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JetCutter
Examples of hydrogel beads
Ca-alginate Ca-pectinate
Ø = 300 µm Ø = 500 µm
gelatin chitosan
Ø = 800 µm Ø = 500 µm
lab scale
production scale
pilot scale capacity: up to 1.2 t/d (Ø 1 mm)
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Bioethanol Production
Yeast or bacteria?
yeast
Saccharomyces 0.5 – 1.4 25 - 70 10 - 30
cerevisiae
bacterium
4-5 190 - 230 50 - 80
Zymomonas mobilis
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Ethanol Fermentation: Production Plant
Conventional or with immobilised cells
conventional fermentation biomass
recycling
separator
nutrients
6 x 200 m3
molasses
ethanol
buffer
Separator
(smaller)
process design with
ethanol
immobilised cells
buffer
nutrients
molasses 3 x 60 m3
BMA Braunschweig, capacity: 60,000 litres EtOH / 24 h
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Ethanol-Fermentation: Pilot Plant
Immobilised yeast, continously, 3-step
© BMA-Braunschweig
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Palatinose-Production
Example for immobilisation on an industrial scale
immobilised cells
of
Protaminobacter rubrum
saccharose palatinose
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Palatinose-Production
Bioconversion
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Industrial Production of Palatinose with
Immobilised Microorganisms
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Production of Sugar Acids
Chemical catalysis with gold catalysts
sugar
milk T = 40-60°C
pH = 7-9
Sugar acids
Complexing agents
starch Ingredients for cosmetics,
food, pharmaceuticals
wood oxygen HO O Functional Food
C
H C OH
HO C H
Galactose C HO
Galactonsäure
H C OH HO C H
CH 2OH
O OH CH2OH
H
HO C H H C OH H OH
CH2 OH OH H
O O H CH2OH OH H COOH
OH CH2 OH
OH H H OH HO C H OH O O
COOH
H OH H H OH
H OH H C OH H H H C OH
H O
Lactose supported H OH HO C H
C CH 2 OH Lactobionsäure H C OH
H
HO
C
C
OH
H
gold catalyst H C OH
H
H
C
C
OH
OH
Glucose Gluconsäure CH2OH
CH2OH
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Oxidation of Monosaccharides
Selectivity of the gold catalyst (HPLC-data)
2,5.106 106
2.106
Peakfläche im UV-Detektor
HO O
HO O C
Signal im UV-Detektor
C H C OH
1,5.106 H C OH Gluconic Galactonic HO C H
HO C H 5.105 HO C H
6 H C OH
10 H C OH
H C OH
CH2 OH
CH2 OH
5.105
0
18 20 22 24 26 28 30 0 2 4 6 8
Zeit, min
Zeit, min
3.105 5.105
4.105
Signal im UV-Detektor
Signal im UV-Detektor
HO O
2.105 C
HO O
Xylonic 3.105
H C OH C
HO C H H C OH
Ribonic
H C OH 2.105 H C OH
105
CH2 OH H C OH
105 CH2 OH
0 0
0 2 4 6 8 0 2 4 6 8
Zeit, min Zeit, min
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Oxidation of Disaccharides
Selectivity of the gold catalyst
35 35
30 30
Lactobionic Maltobionic
Peakhöhe UV [mAbs]
Peakhöhe UV [mAbs]
25 25
20 CH2OH 20
H OH
CH2OH CH2OH
15 CH2OH OH H COOH 15
H O H H OH
OH O O
OH H OH H COOH
10 H OH 10 O
OH H OH
H H
5 5 H OH H OH
H OH
0 0
18 20 22 24 26 28 30 18 20 22 24 26 28 30
Zeit [min] Zeit [min]
6.105
Cellobionic
Signal im UV-Detektor
4.105
CH2OH
H OH
CH2OH OH H COOH
.
2 10 5 H O O
OH H H OH
OH H
H OH
0
0 2 4 6 8
Zeit, min TW-020117
Processes
Oil mills, Biodiesel Pants
MeOH EtOH
Fertiliser
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Biodiesel from Rapeseed
Production
RME-production
Rapeseed
10 % glycerol
oil by-products
rapeseed cake (6...12 % Öl)
(55...60 %)
oil mill
rapeseed meal (1...2 % oil)
about 40 % protein TW-020117
Biodiesel
Production capacity in Germany
2.500.000
1.900.000
2.000.000
1.500.000 1.200.000
1.100.000
1.000.000 730.000
460.000
500.000 140.000 200.000
50.000
0
1998 1999 2000 2001 2002 2003 2004 2005 2006
0
200
400
600
800
1000
12.1998
06.1999
12.1999
06.2000
12.2000
06.2001
Price of Raw Glycerol
12.2001
06.2002
12.2002
glycerine 80% crude
06.2003
12.2003
06.2004
12.2004
06.2005
?
12.2005
2007: < 100 €/t
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Polymers: Starting Materials
Polyols (accessible from renewable resources)
1,3-propanediol
HO OH
2,3-butanediol
1,4-butanediol
HO OH HO
OH
HO OH
OH glycerol
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1,3-Propandiol from Glycerol
1,3-propanediol
glycerol 10%
(byproduct of
biodiesel production)
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Possible Products of 1,3-Propanediol
Applications...
Î co-monomers in PTT (=
polytrimethyleneterephthalate)
¾ base for carpets (Corterra®)
¾ special-textile fibers (Sorona®)
Î co-monomer in polyesters
¾ binders, adhesives and sealants in industry and
housebuilding, lacquers, casting resins
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1,3-Propanediol Fermentation
Strain NRRL1024 (from culture collection)
100
conditions
concentration [g/L]
fed-batch
80 1,3-propanediol
(pH-controlled)
mineral-salt
medium + YE
60 pH 7.0
glycerol
35°C
40
results
n-butyrate Î final concentration
20 > 72 g/L 1,3-PD
Î productivity:
acetate > 1.7 gPD/(L·h)
0
0 10 20 30 40 50 60 70
time course [h]
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1,3-Propanediol Fermentation
Strain IK123 (from screening)
100
1,3-propanediol conditions
concentration [g/L]
fed-batch
80 (pH-controlled)
mineral-salt
medium + YE
60 pH 7.2
glycerol 32°C
40
result
n-butyrate Î final concentration
20 > 100 g/L 1.3-PD
Î productivity:
acetate
> 2 gPD/(L·h)
0
0 10 20 30 40 50 60 70
time course[h]
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1,3-Propandiol-Fermentation: Costs
Influence of nutrients
2500
€ je t
1,3-PD
2000 ROI (20 %)
depreciation
allocated fixed costs
1500
salts, NaOH direkt fixed costs
yeast extract energy
feedstock/media
1000
500
salts, NaOH
glycerol yeast extract salts, NaOH
glycerol glycerol
0
pharma- glycerol- PNC
glycerol water instead of
yeast extract
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Production of Hydroxyfatty acids
1. Fermentation of the glycolipid
Sophoroselipid
Glucose
+
Rapseed oil
Candida
bombicola
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Production of hydroxyfatty acids
1. Fermentation of the glycolipid
Sophoroselipid
time (h)
Candida bombicola
Sophoroselipid
Sophoroselipid
300 g/L
Hydrolysis Glucose
17-Hydroxy-oleic
acid Hydroxyfatty acid
~ 110 g/L
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Processes
Lignocellulose
Pretreatment
Lignocellulose
? Glucose Products
Xylose Products
Lignin Products
? Residues,
wastewater
? Biogas
Electricity,
Heat
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Energy from Renewable Resources
Biogas
gas boiler
feedstock
crops heat
reforming
compression electricity, heat
biogas plant
residues
by-products liquid storage
food- and
agro-industry, e.g. fats
fuel
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Biogas Plants in Germany
number 55 PJ = 2,3 GWh Gaspower
4000
= 0,85 GWh electric power + heat +
3600 auxiliary power + losses 3400*
3200
2800 2700
2500
2400
2000
2000 1800
1650
1600
1200 1050
850
800 617
370 450
400 186
274
100 120 139 159
0
1990 1992 1994 1996 1998 2000 2002 2004 2006
year * estimated
Source: German Biogas Association and own Data
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Electricity from Biogas
fuel-cell pilot plant located in the FAL
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White Biotechnology in Germany
Companies in Germany 1 (selection)
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White Biotechnology in Germany
Companies in Germany 2 (Selection)
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Products (> 100 Mio €)
by Fermentation
Î Palatinit (Südzucker)
Î Cyclodextrines (Wacker)
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Activities in Germany
Research & Projects
Research (selected)
Î Linke, ATB-Bornim/Potsdam: Lactic acid, PLA (Pilot Plat)
Î Steinbüchel, Münster: Biopolymere, Polyaminosäuren
Î Bornscheuer, Greifswald: Directed Evolution of Industrial Enzymes
Î Peter, Potsdam: Chitin / Chitosan
Î Lang, Rau, Braunschweig: Biotenside
FNR-Projects (running)
Î Schwarz, München/Streit, Uni-HH/Liebl, Uni-Göttingen: Enzym. Degrad. of Lignocellulose,
Nanotechnology
Î Marc, Creavis/Degussa, Homoserin + Isobutyric Acid>Methylmethacrylate
Î Scherzer, BASF/Müller, Fraunhofer-Berlin/Kleinert, Siemens: Tuning of Biopolymers
Î Fraunhofer: Cold-Swelling gels, Functionalised Starch, Materials from Modified
Polysaccharides
Î Fraunhofer-Umsicht: C4-bases Special Polymers
Î Metzger, Oldenburg: Materials from Oils and Fats
Î Schrader, Dechema/Schmidt, Stuttgart. Enz. Lactone-Syntheses, Hydroxylation of Fatty Acids,
Î Drepper, Düsseldorf/Jülich: Lipids from Renewable Resources, Special-oils and Fatty Acids
Î In Pipeline: Lignocellulose
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That‘s it...!
Open questions...?
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