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Upgrading of byUpgrading of by--products from products from biodieselbiodiesel and sugar industry by and sugar industry by bioconversion and chemical bioconversion and chemical catalysiscatalysis

Thomas WillkeFederal Agricultural Research Centre

Institute of Technology and Biosystems EngineeringBundesallee 50, D-38116 Braunschweig

Email: thomas.willke@fal.de - telephone: ++49 (0)531-596-4124

ExCo59, Golden, USA

25 April 2007

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BiorefineryChain links

Biomass

Transport

Pretreatment

Separation

Separation, Purification

Conversion

Products, Energy

Transport

Market

Storage, Conservation, Availability?

Storage, Conservation?

Added value

?

Energy Demand, Biomass/Energy Losses

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Some Important Steps in Biorefineries

è Pretreatment, Conservation, SeparationØPhysical, mechanical (destructure, milling, sieving)Ø (Thermo)chemical (heat, acid, base, …)ØBiological (enzymes, microorganisms)ØCombination of all

è ConversionØBiotechnological (bacteria, fungi, enzymes)ØChemical-catalytic (e.g. noble-metal-catalysis)Ø (Thermo)chemical (pressure, heat, …)ØCombination of all

The whole process combines physical, chemicaland biotechnological steps

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Biorefineries in GermanyExisting

Starch

Ethanol, ProductsOil

Biodiesel, Glycerol

Biogas

Sugar

Ethanol, Products

Ligno-cellulose

Residueswaste streams

Just starting with biogas (energy maize)

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Biorefinery in GermanyThe main problem: costs

Cost reduction in Biorefinery

è Transportation efficiencyØEnergy-density of feedstock and productsØ Infrastructure, distances

è More efficient processesØBiocatalysts, chemical catalystsØProductivityØProduct concentration

è Cheaper and more efficient feedstocksØAgricultural/industrial residuesØLignocelluloseØAdditional use of wase water/-air

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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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Top 12 Platform Chemicals From Biomass

è 1,4-Succinic, fumaric and malic acidsè 2,5-Furan dicarboxylic acidè 3-Hydroxypropionic acidè Aspartic acidè Glucaric acidè Glutamic acidè Itaconic acidè Levulinic acidè 3-Hydroxybutyrolactoneè Glycerol (1,3-propanediol)è Sorbitolè Xylitol/arabinitol

Source: Top Value Added Chemicals From Biomass, PNNL & NREL, 2004

Ethanol ?

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starch, sucrose

immobilisedyeasts or bacteria

(biokatalyst)

sugarbeet

biofuel,chemical feedstock

ethanol

O CH2 CH3H

yeast-cells inside

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

CH2OHOHHO

CH2HO

CH2HO

Immobilisation in BiotechnologyExample: ethanol-production with immobilised yeasts

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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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Animation of the Cutting Process

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unsuited adjustmentsà high losses

suited adjustmentsà almost no losses

JetCutteroptimisation of settings for low spray losses

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Bioethanol ProductionAdvantage of immobilisation

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

immobilised 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, continuously, 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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Itaconic Acid ProductionThe process

Itaconic acid

Fungi, aerobicYeast, aerobic

glycerol 10%(byproduct of

biodiesel production)

chemical feedstock

Sugar

or

?

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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

conditionsn batch

(without pH-controll)

n mineral-saltmedium,P-limitation

n pH 1,7n 33°C

resultè final concentration

> 80 g/L IAè max. productivity

> 1 g/(L·h)è 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

conditionsn batch

(without pH-controll)

n mineral-saltmedium,P-limitation

n pH 1,7n 33°C

Result (for Glucose)è final concentration

> 80 g/L IAè max. productivity

> 1 g/(L·h)è Yield: 0,6 g/g =

83% of Theory

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sugar

Glucose Gluconsäure

supportedgold catalyst

Innovative TechnologiesChemical catalysis with gold catalysts

COH

H

HO

H

H

H

OH

OH

OH

C

C

C

C

CHOH2

COOH

H

H

H

H

OH

OH

OH

C

C

C

C

CHOH2

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

CH2 OH

HO

COHO

H

HO

H

H

OH

H

OH

C

C

C

C

CH2 OH

HO

C

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

Sig

nal i

m U

V-D

ete

ktor

0 2 4 6 8Zeit, min

0

105

2.105

3.105

4.105

5.105

Sig

nal

im U

V-D

etek

tor

0 2 4 6 8Zeit, min

0

5.105

106

Sig

nal i

m U

V-D

ete

ktor

18 20 22 24 26 28 30

Zeit, min

5.105

106

1,5.106

2.106

2,5.106

Pea

kflä

che

im U

V-D

ete

ktor

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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ProcessesOil mill, biodiesel plant

Rapeseed 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

Sugar

EtOH

Biogas

Electricity, Heat

Sunflower

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Biodiesel from RapeseedProduction

RME-productionRapeseed

10 % glycerol

90 % biodiesel

rapeseed cake (6...12 % oil)

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

pri

ce in

bu

lk C

FR

Ro

tter

dam

[€/

t]

Price of Raw Glycerol

?2007: < 100 €/t

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1,3-Propandiol from Glycerol

1,3-propanediol

bacteria, anaerobic

glycerol 10%(byproduct of

biodiesel production)

chemical feedstock

(polymers)

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1,3-Propanediol FermentationStrain NRRL1024 (from culture collection)

conditionsn fed-batch

(pH-controlled)n mineral-salt

medium + YEn pH 7.0n 35°C

resultsè final concentration

> 72 g/L 1,3 -PDè productivity:

> 1.7 gPD/(L·h)

0 10 20 30 40 50 60 700

20

40

60

80

100

conce

ntr

ation

[g/L

]

time course [h]

glycerol

1,3-propanediol

n-butyrate

acetate

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1,3-Propanediol FermentationStrain IK123 (from screening)

conditionsn fed-batch

(pH-controlled)n mineral-salt

medium + YEn pH 7.2n 32°C

resultè final concentration

> 100 g/L 1.3-PDè productivity:

> 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: Cost ReductionInfluence of glycerol and nutrients price

substitution ofyeast extract

0

500

1000

1500

€ per 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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Processes in FutureLignocellulose

Glucose

Xylose

Lignin

Lignocellulose Products

Pretreatment

?Products

Products

Biogas

?

ResiduesWastewater

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 at the FAL

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BiorefineriesManifold interactions

BiorefineryProducts

Heat, powerFuels

MaterialsFeed & Food?

ManNeeds

Population developmentSocial aspects

BiomassYield, Quality, Price

Seasonal Availability

TechnologyMethods

ProcessesTransport

EconomyEnergySituation

Prices, GlobalisationForeign Trade

Feedstocks

PolicyDirections, Rules

Subsidies, Tax Benefits

LocalityClimate, Soil, Water

Infrastructure, LogisticIndustry

AuxilariesEnergy, Seed, Fertilizer

Pest Management

MarketConsumer, Products

Heat & Power

Thank you for your attention!