Biofuels and Chemical Products from Woody Biomass

M.Sc. Sari Hyvärinen1

Prof. D. Yu. Murzin1 Prof. Jyri-Pekka Mikkola1,2, 1Lab. of Industrial Chemistry and Reaction Engineering

Process Chemistry Centre, Åbo Akademi University2Technical Chemistry, Chemical-Biological Center,

Dep. of Chemistry, Umeå University

Contents of the presentation:

• Biomass & lignocellulosics: focus on wood

� Use of wood:

Biofuels & chemical products

• My work and other projects at Åbo Akademi University in Finland

and collaborators in Chile etc.

• Conclusions

Part of lignin structure

Wood

Total forest energy potential per land area

•Pulpwood is probably the most important source for biorefining.•Competition on woody biomass increases (� EU’s ambitious targets for bio-energy and –material•Need to combine raw material sources

Source: METLA

OUR BEST AND MOST IMPORTANT RESOURCE – FOREST

How should we utilize this resource?

And how is our wood utilized today?

Source:

Conversion Conversion –– Upgrading of Upgrading of

BioBio--raw material:raw material:•• FFermentation ermentation -- BioBio--catalysis, enzymescatalysis, enzymes

•• EExtraction, Fractionationxtraction, Fractionation(structure(structure--holding)holding)

•• ThThermal FFPT processesermal FFPT processes-- Burning, Gasification, Pyrolysis, Burning, Gasification, Pyrolysis, torrefactiontorrefaction))

•• CCATALYSISATALYSIS–– A tool for refining/processing and modifying A tool for refining/processing and modifying

of molecules so that they can be used as fuels, chemicalsof molecules so that they can be used as fuels, chemicalsfood and drugs/medicinesfood and drugs/medicines

•• IIonic Liquidsonic Liquids-- Organic salts which are liquids at low temperatures,Organic salts which are liquids at low temperatures,

do not evaporate (no VOC’s), high thermal stability,do not evaporate (no VOC’s), high thermal stability,green solvents and much more!green solvents and much more!

Key technologies:Key technologies:

Catalysis

– Father: Jöns Jacob Berzelius

Catalyst on a bed

Catalysis and Process conditions control product assortment/selection!

Different (metal) catalysts

• Ionic liquids, micro-organisms and metallic catalysts together (’one-pot’)

• Even dissolving and chemical modification of bio-macromolecules, e.g. cellulose or even wood chips

Metal catalyst and ionic liquids together with hydrolysis & fermentation for next generation’s

Bio-products:

F

P -F

F

F

FF

NN(CH2)n

SO -

+BASIONICSTM

OPTIMAL TREATMENT PROCESSES OF LIGNOCELLULOSES FOR BIOETHANOL,

OPTBIO

Academy Research Fellow Jyri-Pekka MikkolaLab. of Industrial Chemistry and Reaction Engineering

Åbo Akademi UniversityProf. Kai Peiponen Department of Physics University of Joensuu

Assoc. Prof. Maria Elena Lienqueo ContrerasCentre for Biochemical Engineering and Biotechnology University of Chile

Chilean co-operation

- Researchers visiting in Turku:•Dr. Alejandro García 2008•Master’s thesis workers RicardoPezoa and Victoria Cortinez 2009

- My visit to Santiago:•Tomás Niklitschek & Ricardo Pezoashowing local methods

- Visits and meetings of professors

My work in Finland

My work in Finland

…My work in Finland

…My work in Finland

…My work in Finland

…My work in Finland

…My work in Finland

HPLC results• retention times near each other

Other projects at the Laboratory of Industrial Chemistry and Reaction

Engineering, at Åbo Akademi University

Bio-Butanol & -Pentanol etc.• Academy of Finland Sustainable Energy Program: SUSFUFLEX

(collaboration with University of Oulu and KTH)• NEW, INNOVATIVE SUSTAINABLE TRANSPORTATION FUELS FOR MOBILE

APPLICATIONS: FROM BIOCOMPONENTS TO FLEXIBLE LIQUID FUELS• can be used in gasoline motors• Can be mixed/blended with E95 or with EtOH • even potential for other chemicals

EtOHEtOH to to BuOHBuOHvia via

catalysis !catalysis !

Sugars – catalyst for various products

• Carbohydrates (sugars) from lignocellulose (wood, grass, agricultural waste) and from processes related to foodstuff production

sugar (1)aldehyde or ketone

sugar (2)aldehyde or ketone

sugar acids

sugar alcohols

dimers (trimers)e.g. potential biodiesel components

sugar acid esterse.g. surfactants and emulsifiers

hydrolyzed sugarsCatalytic reactions:1. Isomerization2. Hydrogenation3. Oxidation4. Hydrolysis5. Dimerization6. EsterificationSubstitution, additionand eliminationreactions

2.

2.2.

1.3.

3.

3.

4. 4.

5. 6.

Chem. Commun., 2006, 2696–2698

APR

Cellulose,Hemicellulose

Aldoses

Sugar alcohols

Aqueous reforming

Hydrogenation

Fuels

Lubricants

EsterificationChemicals

Hydrolysis Oxidation

Sugar acids

Oligomers

Hydrolysis

Platform chemicals: cellulose

10-30 wt.% water solutionFeed rate 0.1 ml/min

V’(N2)= 30 ml/min

+ N2

+intermediates+ By-products

HO

HO OH

HO OH

HO

Sorbitol

6CO + 7H2

217-225 oC24-29.3 bar

5%Pt/Al2O3

m = 1g

6CO2 + 13H2

WGS

+ 6H2O

Aqueous phase reforming of sorbitol

A. Tokarev

On-line

Off-line3rd version

35

Analysis of products

A. Tokarev

•Hydrogen yield is 2-6%

1% He

H2

N2

butane

isopentane

pentane

cyclopentanehexane

methyl-cyclopentane

Gas-phase

A. Tokarev

Chem.pulping

Paper&

BoardMech.pulping

Chem.pulp(Cellulose)

Hemicelluloses(ex.arabinogalactans)

Mech.pulp

Chips

Many opportunitiesHemicellulose

• Catalysis: Zn/Cr, Cu/Zn for MeOH; Fe, Co for Fischer-Tropsch; solid acids (zeolites) and metals for bio-oils; custom-made ionic liquids etc.

Thermal 2nd Generation’s SynFuel: Gasifying, Pyrolysis, torrefaction, Aqueous-Phase Reforming (APR)...

Bio-to-liquid: BTLGas-to-liquid: GTL

Biogas platform

Alternative to direct burning – higher revenues:• Upgrading to vehicle fuel (pure CH4) with new IL

purification• Upgrading to chemicals via catalysis• Option: capturing & utilization of CO2 from wastewater

digestion

• Two projects, funded by:• Academy of Finland and TEKES

DOI: 10.1039/b809533g

’Switchable solvent’: an organic base + alcohol + CO2 ����carbonate IL

Gasification

Biomass

Pyrolysis

without O2

400-600°C

Char

Gases Condensation

Bio Oil

Gases

Pyrolysis of biomass

A. Aho

Fast pyrolysis

• Moderate temperature

– 400-500°C

• High heating rate

• Short residence time– 1-2s

• Rapid cooling

• Fluidized bed reactor

[http://media3.washingtonpost.com/wp-srv/photo/gallery/090418/GAL-09Apr18-1902/media/PHO-09Apr18-158607.jpg]

Gas

Char

Char

Water

Bio-Oil

Gas

Bio- oil

NExBTL-Process

Conversionof fatty acids

toparafins and isoparafins

Stabilization

Feed tank

PretreatmentImpuritiesremoval

Fuel gas

Sour water

Sludge AcidCausticWater

Hydrogen

Bio Oil

Biodieseltank

Dieseltank

Diesel +BiodieselBlends

NExBTL component sales

Mineral oil diesel

Bio Oil - Rape seed oilPalm OilSoya Oil Animal fat

Tall oil

Porvoo, 170 kt/a

Biomass to Fuel: NexBTL

Superior quality all Synthetic Diesel –NOT a fatty acid

Methyl/ethyl ester

Fatty acids & ExtractivesCatalytic processes

’classic’ biodieselNexBtl biodiesel

NextGen SynFuel (Fischer-Tropsch, etc.)

Fatty acids & ExtractivesCatalytic processes

• FUTURE: Diesel, hydrocarbons for chemical industry, pre-cursors for medicine industry, health effective nourishment addition, fine chemicals as well as other products with high added value...Multi-product factory

Carbohydrate & tall oil based (fine) chemicals

’URAKAMU’ –project funded by the Finnish Funding Agency for Technology and Innovation (TEKES), Danisco A/S and Forchem Oyj

Tekes ’BioRefine’ technology program

Chem.pulping

Paper&

BoardMech.pulping

Chem.pulp(Cellulose)

Turpentine

LigninHemicell. degr.

Mech.pulp

Chips

pinene

Turpentine oils

Chem.pulping

Paper&

BoardMech.pulping

Chem.pulp(Cellulose)

Tall Oil

Lignin

Mech.pulp

Chips

Feedstocks: wood based oil

Resinous yellow-black oily liquid composed mainly of a mixture of rosin acids, fatty acids and sterols; obtained as a byproduct in the treatment of pine pulp.

Tall oil

Rauma, Finland

� tall oil contains much linoleic acid� CLA has physiological effects

From Wood to Food

Linoleic acid Conjugated linoleic acids (CLA)

Ru & Au Au: O. Simakova

Bernas et al, Appl. Catal. A. Gen., 2004, 267, 121 , Org. Proc. Res.&Devel., 2004, 8, 341; Appl. Catal. A. Gen., 2003, 245, 257; Ind. Eng. Chem. Research, 2003, 42, 718

Triglyceride

Fatty acid ester

Fatty acid

CH2──O ── C ── R′

CH──O── C── R′′

CH2──O ── C ── R′′′

O

O

O

CnH2n+1──O ── C ── R′

O

H──O ── C ── R′

O

het. cat.

het. cat.

het. cat.

3CO2 + R′-H + R′′-H + R′′′-H + light CXHY

CO2 + CnH2n + R′-H

CO2 + R′-H

Biodiesel

R′, R′′, R′′′ = Fatty acid alkyl chain, (saturated and unsaturated, C5-C23)

Renewable source

CnH2n+1 = Ester alkyl group (C1-C4)

Animal fats & vegetable oils

Wood

XVIII International Conference on Chemical Reactors CHEMREACTOR-18 September 29 - October 3, 2008, Malta

Deoxygenation

Chem.pulping

Paper&

BoardMech.pulping

Chem.pulp(Cellulose)

Tall Oil

Mech.pulp

Chips

Sitosterol

Functional Food

Sitosterol

Stigmasterol

Campesterol

Brassicasterol

Sitostanol

Campestanol

SterolH2 esterification

Stanol Stanol ester

β-sitosterol 82%, β-sitostanol 9%,campesterol 7%, campestanol 1% Components

Chem.pulping

Paper&

BoardMech.pulping

Knots LignansFlavonoidsStilbenes

Functional foodPharmaceuticalsNatural antioxidants & biocides

Chem.pulp(Cellulose)

Mech.pulp

Chips

Functional Food

In cooperation with prof. Santti´s group and Hormos Nutraceutical

Knot – the branch base inside the stem

Knots: nature´s richest source of antioxidants

Forgotten knots

0.0 %0.1 %0.1 - 5 % 6 - 24%

Hydroxymatairesinol (HMR)

Lignans in spruce trees

70-85% of the lignans

O

O

MeO

OH

OH

OMe

OH150-200 tons/a in one pulp mill

Specialty chemicals from Forest Biorefinery

• Substances are complex, chemistry can be simple

• Often feedstocks/products are mixtures, can contain impurities

• Analytics is a challenge

• Wood chemists are not too easy to find

General Challenges

Final conclusions

Biomass: platforms for chemicals and fuels

A lot of room for catalysis

www.abo.fiwww.umu.se

Laboratory of Industrial Chemistry and Reaction Engineering