Biomass conversion for

transportation fuel
DANISH BIOETHANOL CONCEPT

Concept developed at RISØ and DTU

Anne Belinda Thomsen (RISØ)

Birgitte K. Ahring (DTU)
 Biomass is a renewable
energy resource
DANISH BIOETHANOL CONCEPT

Plant production:
CO2 + H2O + sunlight (chlorophyll) (CH2O)n + O2

Combustion of plants (or plant derived products):

(CH2O) + O2 Energy + H2O + CO2

•Plants contain stored solar energy

•Plants capture and reduce CO2
 EU directive, March 12th 2003
DANISH BIOETHANOL CONCEPT

• 2% biofuel in year 2005

• 5.75% biofuel in year 2010

Objectives are CO2 reduction and sustainability

”Research and technological development in the field

of the sustainability of biofuels should be promoted.”
 Traffic in EU contributes with 20-30%
of the total CO2 emission
DANISH BIOETHANOL CONCEPT
 CO2-reduction by means of
bio-ethanol
DANISH BIOETHANOL CONCEPT

Transportation in Denmark and other EU

countries:

5.75 % bioethanol in diesel oil and gasoline

1.2 - 1.7% CO2 reduction

DANISH BIOETHANOL CONCEPT Bio-ethanol can replace MTBE and gasoline
 MTBE methyl-tertiær-butyl-ether
DANISH BIOETHANOL CONCEPT

Facts about MTBE

• functions as octan booster in gasoline

• is mobile and non-biodegradable
• is on the list of carcinogene
compounds
• is found in the ground water
• can be replaced by ethanol (5-10% i
gasoline)
 Global ethanol production forecast,
Bln. litres
DANISH BIOETHANOL CONCEPT

50

40

30 Fuel
Industrial
20 Beverage

10

0
1975 1980 1985 1990 1995 2002 2005 2010

F.O. Licht 2002

 World ethanol production in 2001
by continent
DANISH BIOETHANOL CONCEPT

Asia/Pacific
20%

Europe
13%

Americas
Africa
65%
2%

F.O. Licht, 2001

 World ethanol production (%) in 2001
by feedstock
60
DANISH BIOETHANOL CONCEPT

50

40

% 30

20

10

0
Synthetic Sugar crops (Brazil) Grains (US) Others

F.O. Licht, 2001

 Danish Bioethanol Concept
Wet Oxidation
In: Wheat Straw
DANISH BIOETHANOL CONCEPT

Water

SSF Fermentation
In: Enzyme, Yeast
Out: Ethanol

Xylose Fermentation
Out: Ethanol

Anaerobic Treatment
In: Manure
Out: Biogas
 Pre-treatment Step
Biomass is macerated
DANISH BIOETHANOL CONCEPT

The biomass is cut in small pieces

of 2-5 cm to ease handling

Wet oxidation in continuous

reactor
Temperature: 195°C (12 bar)
Additions: Oxygen & Na2CO3 or
NH3 (e.g. from manure)
Exothermic process
No heat required above 150oC
DANISH BIOETHANOL CONCEPT Lignocellulose and pre-treatment by wet oxidation

Cellulose

Hemicellulose

Lignin

Material Cellulose Hemicellulose Lignin NCWM Enz convertibility

(%) (%) (%) (%) (%)
Wheat straw 36 18 7 18 14
WO wheat straw 72 10 5 6 67
 Wet oxidation
1 kg wheat straw 0.5 kg solids
DANISH BIOETHANOL CONCEPT

Filter cake (solids): Liquid phase:

70-75% Cellulose • 35-45% Sugars
• 5-10 % Hemicellulose • 12-26 % Carboxylic acids
• 5-10 % Lignin
• 0.3-1 % Furans
• 0.3 % Ash • 0.5-1.8 % Phenols
• NH4,P, K, minerals

in % of total organic carbon

 SSF Fermentation
Hydrolysate cooled to 30°C
DANISH BIOETHANOL CONCEPT

No detoxification required

Enzymes added
Commercial enzyme mixture: ,
Cellulases & β-glycosidases

Mesophilic fermentation
Saccharomyces cerevisiae
 SSF of pre-treated wheat straw :
% cellulose converted to ethanol
80
DANISH BIOETHANOL CONCEPT

70
60
50
24 h
40
48 h
30 72 h
20
10
0
wet oxidation raw material

Conditions: 10% filter cake, enzyme loading 20 FPU/g DM

 Thermophilic Fermentation
High performance UASB reactor
DANISH BIOETHANOL CONCEPT

Immobilized cells
Fermentation at 70°C

Thermophilic fermentation
Thermoanaerobacter mathranii
A3M4 adapted to wheat straw
hydrolysate

Ethanol Destillation
Ethanol removed in-situ to avoid
ethanol inhibition
 T. mathranii A3M4 Data
DANISH BIOETHANOL CONCEPT

• Optimum at 70 ºC and pH 8.0

High resistance towards contamination

• High growth and ethanol productivity

Doubling time on xylose media: 70-80 minutes

• Substrates:
Hemicellulose, xylan, xylose, arabinose & mannose

• Products:
Ethanol, acetate, lactate, CO2 & H2
 Anaerobic Treatment
Co-Digestion
DANISH BIOETHANOL CONCEPT

Bioethanol effluent is converted

together with manure to biogas

Detoxification of process water

Inhibitors of the ethanol fermen-
tation are co-metabolically removed

Recirculation
Undigested fibers and lignin
compounds are recirculated back to
the wet oxidation step
 Anaerobic Treatment
COD - Reduction
DANISH BIOETHANOL CONCEPT

Residence Flow Rate Reduction

time (days) mL/d g- COD/l/d %
2.0 100 14 84
1.3 159 20 81
1.0 200 27 79
1.0 200 29 81
 Flow Sheet
150.000 t/y
Biomass Wet Oxidation
DANISH BIOETHANOL CONCEPT

“Wheat Straw”

SSF
Enzymes “ Enzyme treatment and
yeast fermentation”

Separation
35.000 t/y
Fermentation and Distillation
“Themophilic A3m4” Ethanol

150.000 t/y 20 mio m3/y

Manure Biogas Reactor Methane
“Purification step”

Separation Effluent Water

65% recirculation “Fertilizer”

150.000 t/y
 Mass Balance for Process
DANISH BIOETHANOL CONCEPT

INPUT OUTPUT
Wheat Straw 150,000 t/y
Manure* 150,000 t/y
Ethanol 35,000 t/y
6 3
Methane 20 10 m /y
Effluent Water** 150,000 t/y
* Estimated 7% TS (w/v) in manure
** At a recirculation rate of 65%
 Optimal Bioconversion
DANISH BIOETHANOL CONCEPT

Biomass converted
100% The extra step producing
Biogas produced
methane ensures optimal
utilization of the biomass.
What is not transformed
into ethanol can be
Ethanol produced converted into methane
0%
yield
 Straw Surplus in Denmark
DANISH BIOETHANOL CONCEPT

Unrecoverable (600)

Surplus (1,775)

Other (775)

Power Plants (75)

Thermal Power Plants (165)
District Heating (290)

Feed Stock (1,900) Private furnises (420)

Reference: Danish Energy Agency, 1998.

in mio tons
DANISH BIOETHANOL CONCEPT
1.8 mill tons straw surplus in Denmark

900.000 tons straw 200.000 tons ethanol

= one year consumption at 10% addition to

gasoline

3 - 6 plants in Denmark
 Advantages & Disadvantages
DANISH BIOETHANOL CONCEPT

ADVANTAGES DISADVANTAGES
• Re-circulation of process • New technology
water
• Large scale equipment
• High biomass
conversions not available
• No need for genetically
engineered • More research needed
microorganisms
• Minimal nutrient • Political goodwill required
requirements
 Future Research
DANISH BIOETHANOL CONCEPT

• Pilot scale testing of concept

• Continuous wet oxidation

• Thermofilic enzymes and

microorganisms

• Adoption to other types of

lignocellulosic wastes
 Ongoing projects at
Risø National Laboratory
DANISH BIOETHANOL CONCEPT

• ”Co-production Biofuels”
Partners: Elsam (DK), KVL/Risø (DK), EHN (Spain), Sicco
(DK), TMO-Biotech (UK)
-financed by EU with 8.600 KEuro (Risø)
total budget 13.000 KEuro

• ”TIME”
Partners: VTT (Fi), Lund Uni. (SE), Risø (DK), Royal Nedalco
B.V.(N), Royal Oy (Fi), Budapest Uni. (HU), ENEA (I)
-financed by EU with 2.619 Keuro (Risø)
total budget 4.342 kEuro

• ”Bioethanol production, part 2”

Partners: DTU/Risø (DK)
-financed by EFP with 2.5 mill Dkr.
DANISH BIOETHANOL CONCEPT

Thank you for your attention