Seaweed Biorefinery in the Netherlands - TNO · Seaweed Biorefinery in the Netherlands J.W. van Hal...

Seaweed Biorefinery in the

Netherlands

J.W. van Hal

October 2012

ECN-L--12-051

www.ecn.nl

Seaweed Biorefinery in the

Netherlands

J.W. (Jaap) van Hal

Neeltje Jans

September 19, 2012

2012-09-19

Pre-

cultivation

on Land

Planting at

SeaCultivation Harvesting Transport

Primary

Bio-

Refinery

Secondary

Bio-refinery

Products

and Energy

SBIR EOS LT

2 Seagriculture ECN

The team:

Willem de Visser

Julia Wald

Willem Brandenburg

© ECOFYS | |

Ecofys module

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Aquatic Biomass

Seagriculture ECN

Mission: ECN develops market driven technology and know-how to enable a transition to sustainable energy

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Locations

Petten (head office)

Amsterdam

Eindhoven

Beijing

Wieringerwerf

Brussels


R&D fields

Energy

Efficiency &

CCS

Policy

Studies Energy

Engineering

Environment

Wind Energy

Solar Energy

Biomass


www.ecn.nl

Biomass & Energy Efficiency

Neeltje Jans

2012

Your energy. Our passion.

What we do

• Problem solving

Using our knowledge, technology, and facilities to solve our clients’ issues

• Technology development

Developing technology into prototypes and industrial application

• Studies & Policy support

Creating insights in energy technology and policy


Biomass – a diverse energy source

waste wood (agricultural) residues energy corps aquatic biomass

Biomass = all organic material of non-fossil origin

meant for energy or chemicals/materials

production


Biomass Pre-Treatment

Licensees, clients

• Torrefaction technology – Pilot plant under construction


http://www.shell.com/

http://www.ube-ind.co.jp/english/index.htm

Biomass Gasification:

Milena, Olga & Tara

http://www.dahlman.nl/index.php?l=0

Biorefinery and processing

• Organosolv: fractionation technology – Conversion of lignocellulosic biomass into cellulose and pure

lignin

– Cellulose conversion to bio-ethanol

– Lignin: base materials for bio-chemicals

• Seaweed (macroalgae) as a bio-feedstock – Conversions to chemical intermediates

– Source of protein: alleviates land-use issues

• Synthesis processes – Catalytic conversion

– Separation processes


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Parts of seaweed plant

Holdfast

Stipe

Blade

Seagriculture ECN

Does not compete with food

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No land use issues


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Bio-Offshore

• Seaweed cultivation area 5.000

km2 (<10 % of the NL area of the

North Sea @ 57.000 km2)

• Integration with off-shore wind

parks & (other) aquaculture

operations

• Energy potential up to 350 PJth (25

Mton dry biomass per year)

• ECN-C—05-008

Seagriculture ECN

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Potential Applications

• Furanics (carbohydrate conversion)

• Polyols for poly-urethanes (direct application)

• Butanol (fermentation)

• Bleach activators (derivatization)

• Phosphate recycling/fertilizers (Ash utilization)

• Fodder (protein fraction)

• …….

Seagriculture ECN

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Seaweed biorefinery process concept

Raw Seaweed

Processing Primary Biorefinery

Sugars

Proteins

Minerals

Fermentation

Chemical Conversion

Energy Carriers

Bulk Chemicals

Residues

Energy

Conversion

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21 2012-09-19

Process synthesis

• To determine the maximum allowable raw material cost • Compare different biorefinery options • Identify profit drivers • Methodology

– Determine market value of potential products – Determine mass balance – Estimate CAPEX and OPEX – Estimate gross revenue per product – Evaluate market size vs plant output

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Several Cases Estimated

• Full biorefinery

• Alginate only

• Simplified biorefinery

• Sugar refinery

• Etc.

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Refined economic model

23

-200

0

200

400

600

800

1000

1 2 3 4 5 6

€/T

on

d.w

.

Scenario

Maximum RM Price

POT 2 years

POT 5 years

POT 10 years

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Saccharina latissima Laminaria digitata

Ulva sp.

Laminaria hyperborea

Alaria esculenta Palmaria palmata

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Seaweed species native to the North Sea

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Palmaria (red seaweed)

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OO O

ROHO

OH

HOOH

OO

HO

OH

OR

Xylan (1,3 and 1,4 linkage)

O

HO OH

HO OH

OH

galactose

O

HO OH

HO OH

OH

glucose

Seagriculture ECN

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Total Carbohydrate compostion of Palmaria Palmata

0%

10%

20%

30%

40%

50%

60%

70%

Apr-98 May-98 Jun-98 Jul-98 Aug-98 Sep-98 Oct-98 Nov-98 Dec-98 Jan-99 Feb-99 Mar-99 Apr-99 May-99 Jun-99 Jul-99 Aug-99 Sep-99

Month

% S

ug

ar

Xylose Galactose Glucose total

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Differences between biomass

• Lignocellulosic biomass:

• Cellulose – Extremely recalcitrant

• Lignine – Heterogeneous polymer

– Species, source and time of harvesting dependent

• Hemicellulose – Easy to hydrolyse

• Ash – Low to high

• Overall composition reasonably stable

• Seaweed biomass • Carbohydrates

– Type dependent on species – Amount dependent on season and

location

• Proteins – Aminoacid composition dependent on

species – Amount dependent on season and

location

• Ash – Species dependent – Amount dependent on season an

location

• Extreme differences between seasons

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Rehydrated seaweed

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Fractionation

Water + Seaweed

Optional Catalyst

Liquid

Solid

T: 120-160 °C t: 1-4 h Liquid:Solid=1:10 Cat: 0-1 M H2SO4

• After reaction, separation by centrifugation (10 min, 4000 rpm) and separation of the phases.

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Simultaneous extraction and

hydrolysis of Palmaria

• Tests with freeze-dried Palmaria at 2.5 and 25 gr dw scale.

• Hydrolysis of Palmaria to xylose proven.

• Optimum conditions: 0.1M acetic acid, 100C, 2hrs.

• Xylose concentration is dependent on the [H]+ concentration not on acid

Scale up and with fresh seaweeds. 0

0.05

0.1

0.15

0.2

0.25

0.3

0

2

4

6

8

10

12

14

16

18

0 20 40 60 80 100 120 140

Glu

cose

(g

./L

)

Xy

lose

(g

/L

)Time (minutes)

Palmaria Hydrolysis with 0.1 M Acetic Acid, 100 °C)

g xylose/L ron g xylose/L arjan g glucose/liter


Palmaria hydrolysis


0.0

0.5

1.0

1.5

2.0

2.5

3.0

3.5

4.0

0 20 40 60 80 100 120 140

Co

nce

ntr

atio

n in

Liq

uid

(g

/L)

Time (minutes)

RT 50° 75° 100°C

Palmaria hydrolysis as

function of acid


0.0

2.0

4.0

6.0

8.0

10.0

12.0

14.0

16.0

0 20 40 60 80 100 120 140

con

cen

tra

tio

n g

/L

time (min)

geen 0,05M H2SO4 0,10M CH3COOH 0,10M CF3COOH

Fresh Palmaria tests (July

2012)

• Two tests in 20L autoclave (1 kg dw seaweed).

• >10 kg received, 5 kg wet per test.


Test 1

• 0.1M acetic acid, 100C, 2h, 9 L/kg dw seaweed.

• Red seaweed turned into green ‘soup’.

• After centrifugation, ~6L viscous liquid, ~ 4kg solid product.

• pH ND, solids recovery 51.6% dw.


Test 2

• 0.2M acetic acid, 100C, 2h, 9 L/kg dw seaweed. • Final pH 4.1! (pH 0.1M acetic acid 2.9)

– Acid neutralising capacity of seaweed

– Consumption of acetic acid?

– Acetic acid chosen because of integration possibilities with subsequent fermentation step. Another acid needed?

• Product looked similar.

• Solids recovery: 54.9% – Higher than test 1!

– Also observed for Laminaria! Reaction products of acetic acid? Less efficient extraction at lower pH?


Yields sugars

• Yields based on amount of extract.

• Max. achievable yield based on liquor starting amount.

• Yield xylose: ~45%.

• Optimization of separation extracted Palmaria / extract might increase yield to max ~65%.

• Future work: optimisation of process conditions.

0

20

40

60

80

100

120

Dry, 0.1M Hac Wet, 0.1M Hac Wet, 0.2M Hac

Galactose Yield

Galactose Yield (max)

Glucose Yield

Glucose Yield (max)

Xylose Yield

Xylose Yield (max)


After fractionation

• Convert chemically

• Convert biochemically

• Use the residues

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Digestion results

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0%

50%

100%

150%

200%

250%

300%

350%

400%

450%

Microalgae Seaweed low Seaweed high Cow manure Whole sugar beet

Normalized methane production

Normalized methane production

Seagriculture ECN

Applicable to all seaweeds?

Ulva (green seaweed)

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OO

OROHO

OH

OR

-O3SOOH

-OOC

OO

OROHO

OH

OR

-O3SOOH

OO

OROHO

-O3SO

OR

-O3SO OH

OO

-OOC

OR

OH

OH

OR

OH-O3SO

O

HO OH

HO OH

OH

glucose

HO

HO OH

HO OH

OH

mannitol

O

OHHO

OHHO

O

HO

glucuronic acid

O

HO OH

HO

OH

rhamnose

O

OH

HO

HO

OH

xylose

O

OH

HO

HO

OH

arabinose

Ulvans

Seagriculture ECN

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Ulva Lactuca carbohydrate seasonal composition changes

0%

5%

10%

15%

20%

25%

30%

Mannitol Glucuronic acid glucose arabinose xylose rhamnose

Carbohydrate

% c

arb

oh

yd

rate

(D

M %

ba

sis

)

Apr-71 Aug-71 Nov-71 Feb-72

Seagriculture ECN

Question?

Further information

Jaap W. van Hal

The Energy Research Center of the Netherlands (ECN)

Biomass, Bio-Refinery and Processing

P.O. Box 1, 1755 ZG Petten

+31-(0)224-564297

[email protected]

http://seaweed.biorefinery.nl

http://www.noordzeeboerderij.nl

http://www.atsea-project.eu

http://www.mermaidproject.eu


Seaweed Biorefinery in the Netherlands - TNO · Seaweed Biorefinery in the Netherlands J.W. van Hal...

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