WN-020117
Biorefinery in Germany Biorefinery in Germany ––Current StatusCurrent Status
Thomas WillkeFederal Agricultural Research Centre
Institute of Technology and Biosystems EngineeringBundesallee 50, D-38116 Braunschweig
Email: [email protected] - telephone: ++49 (0)531-596-4124
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Outline
Processes, FeedstocksSugar-refinery, starch/sugarOil-mill/biodiesel plant, oil/fatsLignocellulose, wood, straw,…
TechnologiesCell-/substrate-screening, genetic EngineeringFermentation (aerobic, anaerobic)Chemical catalysis (Sugar, Fermentation, Products)Immobilisation Techniques
ExamplesItaconic acid (sugar, oil?)Ethanol (sugar)Palatinit (sugar)
Biotensides (sugar + oil)
1,3-Propanediol (oil)
Catalytic sugar oxidation(sugar)
Biogas (residues,all)
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ProcessesStarch, Sugar
Sucrose
Glucose
Glucose/Fructose
Fructose
Starch-/ Sugar Plants Ethanol
Palatinit
Sugar-Refinery (for example: Südzucker, crop energies)
Fertiliser, Animal feed
Products
Products
Residues
Biogas
ProductsElectricity,
Heat
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Technical polymersexamples
polyoles
dioles, dicarbonicacids
dioles
diamines, dicarbonic acids
monomer
foams, resins, glues, lacquers
flasks, fabricscarpetshigh-performance fibers
CDs, flasks, synthetic glasses
fabrics, carpetsfoils high-performance fibers, cars
use
polyurethane
Trevira®, Sorona®,Corterra®
polyester
Makrolon®polycarbonate
Nylon®, Perlon®
Kevlar®polyamide
namepolymer group
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Polymers: Starting MaterialAcids (accessible from renewable resources)
COOH
HOOC HOOC COOH
itaconicfumaric
2-HP (lactic)
COOHHOOC
succinic
aconiticHOOC
COOHCOOH
3-HP (3-hydroxy propionic)
HO COOH
HOOC
COOH COOH
OH
citric
2-keto-glutaric
HOOC
COOH
O
HOCOOH
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The Tricarbonic-Acid-CyclePotential substrates und products
COOH
COOHCOOH
HO
Citronensäure
COOH
COOHCOOH
cis-Aconitsäure
COOH
COOHCOOHHO
IsocitronensäureCOOH
CH2
COOHO
α-Ketoglutarsäure
COOH
HOOCFumarsäure
COOH
HOOC
HO
Äpfelsäure
COOH
COOH
O
Oxalessigsäure
COOH
COOH
Itaconsäure
Bernsteinsäure
COOH
COOH
glycolysis
sugar Fats/oilglycerol
ACETYL- CoA
(2-Keto-glutarsäure)
Starch
malic
fumaric
succinicIso-citric
cis-aconitic itaconic
Oxal-aceticcitric
ketoglutaric
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Itaconic Acid
sugar, starch(glucose)
itaconic acid
complexing agent
co-monomer,plasticiser
adhesives
Aspergillus terreus(fungi)
paints, lacquers
others
fats, oilglycerol
Yarrowia spp., Candida spp.(yeast)
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Itaconic Acid ProductionFermentation from glucose
0 1 2 3 4 5 6 7 8 9 10 11 12 13 140
20
40
60
80
100
120
140
160
180
200
Glu
cose
[g
/L]
time course[d]
0
10
20
30
40
50
60
70
80
90
100
Itac
onic
aci
d [
g/L
]
itaconic acid
glucose
conditionsbatch(without pH-controll)mineral-saltmedium,P-limitationpH 1,733°C
resultfinal concentration> 80 g/L IAmax. productivity> 1 g/(L·h)Yield: 0,6 g/g = 83% of Theory
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Itaconic Acid Productionother substrates?
0 2 4 6 8 10 12 14 16 18 20 22 240
10
20
30
40
50
60
70
80
Itaco
nic
acid
[g/L
]
time [d]
GlucoseSaccharose
Glycerol
Lactose
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starch, sucrose
immobilisedyeasts or bacteria
(biokatalyst)
sugarbeet
biofuel,chemical feedstock
ethanol
O CH2 CH3H
yeast-cells
x 100
bead surface
wheat
OHOH2C
HO OHO
O
O
OH
OHOH2C
HO OHO
OHOH2C
HO OHO
OH2C
HO OHO O
OHO
HO
O
O
OH
CH2OHOH HO
CH2HO
CH2HO
Immobilisation in BiotechnologyExample: ethanol
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Immobilisation in BiotechnologyTypes & shapes of gel
beadhollow bead
hollow fibresingle cell
fiber
lenstop view
cross section
foilcube particle
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m = motorn = rotations
ufluid = fluid velocityuwire = wire velocity
D = diameter ofthe nozzle
pressure
M
cuttingtool
motor
n
nozzle
D
bead
cuttingwire
liquidjet
cut cylinder
ufluid
uwireor
Bead Production with JetCutterScheme and operation
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cutting tool equipped with23 µm PET fibres
cutting tool with circularstabilization of the wires(48 wires, diameter: 0.1 mm)
JetCutterDetails of the cutting tool
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unsuited adjustmentshigh losses
suited adjustmentsalmost no losses
JetCutteroptimisation of settings for low spray losses
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0 0.2 0.4 0.6 0.8 1 1.2 1.4 1.6 1.8 2bead diameter, mm
0
2
4
6
8
10
12
14di
strib
utio
n de
nsity
, m
m-1
Ca-Alginat
PVA
JetCutterParticle size distribution
bead diameter [mm]
dist
ribut
ion
dens
ity[m
m-1
]
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Ca-alginateØ = 300 µm
Ca-pectinateØ = 500 µm
gelatinØ = 800 µm
chitosanØ = 500 µm
not in true scale!
JetCutterExamples of hydrogel beads
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pilot scaleproduction scale
capacity: up to 1.2 t/d (Ø 1 mm)
JetCutterEquipment
lab scale
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Bioethanol ProductionYeast or bacteria?
50 - 80190 - 2304 - 5bacteriumZymomonas mobilis
10 - 3025 - 700.5 – 1.4yeastSaccharomycescerevisiae
productivity[kg EtOH/(m3·h)]
activity[kg EtOH/(m3 cat·h)]
activity[kg EtOH/(kg BDM·h)]
microorganism
immobilized cellsfree cells
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Ethanol Fermentation: Production PlantConventional or with immobilised cells
nutrientsmolasses
biomassrecycling
conventional fermentation
6 x 200 m3
separator
buffer
ethanol
process design withimmobilised cells
nutrientsmolasses 3 x 60 m3
Separator (smaller)
buffer
ethanol
BMA Braunschweig, capacity: 60,000 litres EtOH / 24 h
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Ethanol-Fermentation: Pilot PlantImmobilised yeast, continously, 3-step
© BMA-Braunschweig
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Palatinose-ProductionExample for immobilisation on an industrial scale
immobilised cellsof
Protaminobacter rubrum
saccharose palatinose
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Palatinose-ProductionBioconversion
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Industrial Production of Palatinose withImmobilised Microorganisms
80,000 tons per year
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sugar
Glucose Gluconsäure
supportedgold catalyst
Production of Sugar AcidsChemical catalysis with gold catalysts
COH
H
HO
H
H
H
OH
OH
OH
C
C
C
C
CH OH2
COOH
H
H
H
H
OH
OH
OH
C
C
C
C
CH OH2
HO
O OH
HH
OH
OH
H
H
CH2OH
O O
H
OH
OH
H
OH
H
CH2OH
Lactobionsäure
milk
starchwood
Lactose
COOH
OH
H
OH
OH
H
H
CH2OH
O O
HH
OH
OH
H
OH
H
CH2OH
T = 40-60°CpH = 7-9
oxygen
Sugar acidsComplexing agentsIngredients for cosmetics,food, pharmaceuticalsFunctional Food
Galactose Galactonsäure
COHO
H
HO
H
H
OH
H
OH
C
C
C
C
CH2OH
HO
COHO
H
HO
H
H
OH
H
OH
C
C
C
C
CH2OH
HOC
HO
H
H
H
OH
C
C
C
C
CH2 OH
HO
C
HO
H
H
H
OH
C
C
C
C
2
HO
HO
H CC OH
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0 2 4 6 8Zeit, min
0
105
2.105
3.105
Sign
al im
UV-
Det
ekto
r
0 2 4 6 8Zeit, min
0
105
2.105
3.105
4.105
5.105
Sign
al im
UV-
Det
ekto
r
0 2 4 6 8Zeit, min
0
5.105
106
Sign
al im
UV-
Det
ekto
r
18 20 22 24 26 28 30
Zeit, min
5.105
106
1,5.106
2.106
2,5.106
Peak
fläch
e im
UV-
Det
ekto
r
Galactonic
Oxidation of MonosaccharidesSelectivity of the gold catalyst (HPLC-data)
COHO
H
HO
H
H
OH
OH
OH
C
C
C
C
CH2OH
H
COHO
H
HO
H
H
OH
OH
OH
C
C
C
C
CH2OH
H
COHO
H
HO
H
H
OH
H
OH
C
C
C
C
CH2OH
HO
COHO
H
HO
H
H
OH
H
OH
C
C
C
C
CH2OH
HO
COHO
H
H
OH
OH
OH
C
C
C
CH2OH
H
COHO
H
H
OH
OH
OH
C
C
C
CH2OH
H
COHO
H
H
OH
H
OH
C
C
C
CH2OH
HO
COHO
H
H
OH
H
OH
C
C
C
CH2OH
HO
Gluconic
Xylonic
Ribonic
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Oxidation of DisaccharidesSelectivity of the gold catalyst
0 2 4 6 8Zeit, min
0
2.105
4.105
6.105
Sign
al im
UV-
Det
ekto
r
18 20 22 24 26 28 30Zeit [min]
0
5
10
15
20
25
30
35
Peak
höhe
UV
[mAb
s]
18 20 22 24 26 28 30Zeit [min]
0
5
10
15
20
25
30
35
Peak
höhe
UV
[mAb
s]
COOH
OH
H
OH
OH
H
H
CH2OH
O O
HH
OH
OH
H
OH
H
CH2OH
O O
HH
OH
OH
H
H
OH
CH2OH COOH
OH
H
OH
OH
H
H
CH2OH
OHH
CH2OH
OOH
H
H
OH
COOH
O H
H
OH
OH
H
H
OH
CH2OH
Lactobionic Maltobionic
Cellobionic
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ProcessesOil mills, Biodiesel Pants
Oils Plants RME (REE), Biodiesel
Glycerol
Fatty acids, fats
Rapeseed meal
1,3-Propanediol
?
Proteins, Animal Feed
Fertiliser
Acroleine1,2-PD + 1,3-PDchemical
biological
Biotensides
MeOH
Rapeseed
Residues
Biogas
Electricity, Heat
Sugar
EtOH
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Biodiesel from RapeseedProduction
RME-productionRapeseed
10 % glycerol
90 % biodiesel
rapeseed cake (6...12 % Öl)
seed
oil mill
oil(40...45 %)
by-products
(55...60 %)
oil
rapeseed meal (1...2 % oil) about 40 % protein
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BiodieselProduction capacity in Germany
Tons per year
Data: UFOP, *estimated
*
50.000140.000 200.000
460.000
730.000
1.100.0001.200.000
1.900.000
2.900.000
0
500.000
1.000.000
1.500.000
2.000.000
2.500.000
3.000.000
1998 1999 2000 2001 2002 2003 2004 2005 2006
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glycerine 80% crude
0
200
400
600
800
1000
12.1
998
06.1
999
12.1
999
06.2
000
12.2
000
06.2
001
12.2
001
06.2
002
12.2
002
06.2
003
12.2
003
06.2
004
12.2
004
06.2
005
12.2
005
pric
e in
bul
k C
FR R
otte
rdam
[€/t]
Price of Raw Glycerol
?2007: < 100 €/t
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Polymers: Starting MaterialsPolyols (accessible from renewable resources)
1,3-propanediol
1,4-butanediol
glycerol
2,3-butanediol
OHHO
HO OH
OH
HOOH
HO OH
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1,3-Propandiol from Glycerol
1,3-propanediol
bacteria, anaerobic
glycerol 10%(byproduct of
biodiesel production)
chemical feedstock
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Possible Products of 1,3-PropanediolApplications...
co-monomers in PTT (= polytrimethyleneterephthalate)
base for carpets (Corterra®)special-textile fibers (Sorona®)
co-monomer in polyestersbinders, adhesives and sealants in industry and housebuilding, lacquers, casting resins
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1,3-Propanediol FermentationStrain NRRL1024 (from culture collection)
conditionsfed-batch(pH-controlled)mineral-saltmedium + YEpH 7.035°C
resultsfinal concentration> 72 g/L 1,3-PDproductivity:> 1.7 gPD/(L·h)
0 10 20 30 40 50 60 700
20
40
60
80
100
conce
ntr
atio
n[g
/L]
time course [h]
glycerol
1,3-propanediol
n-butyrate
acetate
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1,3-Propanediol FermentationStrain IK123 (from screening)
conditionsfed-batch(pH-controlled)mineral-saltmedium + YEpH 7.232°C
resultfinal concentration> 100 g/L 1.3-PDproductivity:> 2 gPD/(L·h)
glycerol
1,3-propanediol
n-butyrate
acetate
0 10 20 30 40 50 60 700
20
40
60
80
100
conce
ntr
atio
n[g
/L]
time course[h]
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1,3-Propandiol-Fermentation: CostsInfluence of nutrients
substitution of YE by PNC (0 €/t)
PNCinstead of
yeast extract
0
500
1000
1500
€ je t1,3-PD
2500
2000
glycerol
glycerol-water
glycerol
yeast extractsalts, NaOH
pharma-glycerol
yeast extractsalts, NaOH
salts, NaOHglycerol
feedstock/mediaenergydirekt fixed costsallocated fixed costsdepreciationROI (20 %)
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Glucose
+
Rapseed oilCandida
bombicola
Sophoroselipid
Production of Hydroxyfatty acids1. Fermentation of the glycolipid
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[Rau, Lang et al., 2001]
Production of hydroxyfatty acids1. Fermentation of the glycolipid
time (h)
Sophoroselipid
Candida bombicola
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Sophoroselipid
300 g/L
GlucoseHydrolysis
17-Hydroxy-oleic acid Hydroxyfatty acid
~ 110 g/L
Sophoroselipid
Production of hydroxyfatty acids2. Hydrolysis
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ProcessesLignocellulose
Glucose
Xylose
Lignin
Lignocellulose Products
Pretreatment
?Products
Products
?
?
Residues, wastewater
Biogas
Electricity, Heat
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Energy from Renewable ResourcesBiogas
feedstock
residuesby-productsfood- andagro-industry, e.g. fats
manure
crops
biogas plant
biogas sulfur removal
reforming
reformingcompression
electricity, heat
motor-CHP
gas boiler
heat
fuel cell
electricity, heat
fuel
liquid storage
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Biogas Plants in Germany
number
Source: German Biogas Association and own Data
year
100 120 139 159 186 274 370 450617
8501050
16501800
2000
25002700
1990 1992 1994 1996 1998 2000 2002 20040
400
800
1200
1600
2000
2400
2800
3200
3600
4000
* estimated
3400*
2006
55 PJ = 2,3 GWh Gaspower
= 0,85 GWh electric power + heat +auxiliary power + losses
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Electricity from Biogasfuel-cell pilot plant located in the FAL
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White Biotechnology in GermanyCompanies in Germany 1 (selection)
Südzucker: Sugar, Palatinose, EthanolDegussa: Amino acidsDow: Plastics, Monomers, SpecialitiesBASF: Vitamins, SpecialitiesCognis: Tensides, Plasticiser, Emulsifiers ...Wacker: Cyclodextrines, Fine Chemicals
Rütgers: Aromatics, Downstream-TechnologiesSymrise: Flavor, Cosmetics, Food-additives
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White Biotechnology in GermanyCompanies in Germany 2 (Selection)
B.R.A.I.N.: Enzymes, Drugs, Bioactives
GeniaLab: Immobilisation Technologies, Starter Cultures, Services
Lipoid: Health& Nutrition, Phospholipids
Codexis/Jülich Fine Chemicals: Enzymes, Chiral synthesis
Direvo: Industrial Enzymes, Biopharmaeuticals
BioSpring: Enzymes, Nucleic acids
Dr. Rieks GmbH: Cosmetics, Food-additives
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Products (> 100 Mio €)by Fermentation
Amino acids: Lysin, Glutamate… (Degussa)
Specialities (BASF, Henkel)
Palatinit (Südzucker)
Riboflavine (Vit B2) (DSM/Roche, BASF)
Cyclodextrines (Wacker)
Organic acids: citric, gluconic… (Jungbunzlauer)
Ethanol (Südzucker/crop energies, Verbio et al.)
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Activities in GermanyResearch & Projects
Research (selected)Linke, ATB-Bornim/Potsdam: Lactic acid, PLA (Pilot Plat)Steinbüchel, Münster: Biopolymere, PolyaminosäurenBornscheuer, Greifswald: Directed Evolution of Industrial EnzymesPeter, Potsdam: Chitin / ChitosanLang, Rau, Braunschweig: Biotenside
FNR-Projects (running)Schwarz, München/Streit, Uni-HH/Liebl, Uni-Göttingen: Enzym. Degrad. of Lignocellulose, NanotechnologyMarc, Creavis/Degussa, Homoserin + Isobutyric Acid>MethylmethacrylateScherzer, BASF/Müller, Fraunhofer-Berlin/Kleinert, Siemens: Tuning of BiopolymersFraunhofer: Cold-Swelling gels, Functionalised Starch, Materials from ModifiedPolysaccharidesFraunhofer-Umsicht: C4-bases Special PolymersMetzger, Oldenburg: Materials from Oils and FatsSchrader, Dechema/Schmidt, Stuttgart. Enz. Lactone-Syntheses, Hydroxylation of Fatty Acids, Drepper, Düsseldorf/Jülich: Lipids from Renewable Resources, Special-oils and Fatty AcidsIn Pipeline: Lignocellulose
Further information: http:\www.fnr.de
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That‘s it...!
Thanks for your kind attention!
Open questions...?
