PROCESS CHEMISTRY CENTRE
ÅA
Department of Chemistry
ÅBO AKADEMI UNI VERSI TY
Green Chemistry and Biofuels:
... Everybody knows about ClimateGate - How about Bio-Gate ? Prof. Jyri-Pekka Mikkola Technical Chemistry, Dep. of Chemistry, Chemical-Biological Center Umeå University Industrial Chemistry & Reaction Engineering Process Chemistry Centre, Åbo Akademi University
co2isgreen.org
Atmospheric CO2 concentrations measured at Mauna Loa Observatory.
ignoranceisfutile.wordpress.com
’Window of Opportunity’
Energy consumption - sources Oil
Gas
Coal
Nuclear
Hydro
Primary energy total
2%
13%
2%
12000
37%
43%
10000
3%
1987
8000 Mtoe
1967
20%
3%
6000
29%
3%
4%
4000
41%
2000
AP
0 1960
NA
26%
34%
1965
1970
1975
1980
1985 Year
2007
1990
1995
2000
2005
2010
5% 3%
5%
Nearly 3-fold increase in energy consumption in the last 40 years Main growth in Asia (500 Mtoe 3500 Mtoe)
BP statistical review of world energy 2008
27%
E+EA
Greenhouse gases emissions Trends in USA
12
World: 22.5 28.2
Asia & Oceania
based on global warming potential
8
North America
6
Europe
China
Billion Metric Tons CO2 Equivalent
8 7 6
CO2
5 4 3
CH4+N2O+freons
2 1 0 1978
1983
1988
1993
1998
2003
4
Eurasia
2 0 1995 1996 1997 1998 1999 2000 2001 2002 2003 2004 2005 2006 Year
based on sector
2.5
2
industrial
transportation
1.5 1
residential
0.5 0 1978
commercial 1983
1988
1993
1998
2003
Year
2008
Year
Billion Metric Tons CO2
Billion Metric Tons CO2
10
>80% of global warming potential is caused by CO2 ? GHG emissions grow fastest in transportation and in developing countries
EIA, Annual energy review 2007
2008
Targets – EU’s vision Biofuel proportion from the total sales in EU (traffic fuels; gasoline and diesel ):
Target : 2.00 % during 5.75 % 20 %
2005 2010 2020
Current energy resources Nuclear 3%
Biofuels 0.3% Power generation 0.8% Hot water/heating 1.3% Large hydropower 3%
Fossil fuels 79%
Renewables 18% Traditional biomass 13%
traditional biomass – mainly in developing countries for cooking etc.
EU goal 20 – 20 – 20 REN21: Renewables, Global status report, 2006
Role of renewables 2000 2000 140
Potential: 100-300
2050
29-50
Renewable 14%
2100 250-600
1500-50000
500-5000
Nuclear 2%
120 100
Fossil 84%
458 EJ 6 Gt C
EJ
80 60
2100
40 Renewable 40%
20
Fossil 57%
0 Traditional biomass
Modern biomass
Hydropower
R.A. van Santen in Catalysis for Renewables, 2007
Wind
Solar
Geothermal
Nuclear 3%
1200 EJ 1-2 Gt C
Biofuels – net energy ratios Critical issues Ethanol
Biodiesel
3.5
Net energy ratio
3 2.5 2 1.5 1 0.5 0 Pimentel 2005
Grabovski 2002
Pimentel 2005
Morris 1995
D. Morris, Institute for Local Self-Reliance, 2005
Sheehan 1998
crop yield per acre, ethanol yields per bushel energy input in fertilizers energy use in production energy value of coproducts other energy inputs (machinery, workers) use of land (new vs. existing)
Production million m3/year
Current growth trends in liquid transportation fuels + other biofuels (gas, solid fuels) ...even products Biotaxi in India
Data by F.O.Licht, 2006, www.earthpolicy.org
Biofuels – pros & cons Current biofuels ethanol from corn, sugar cane, … biodiesel from rapeseed, soy bean, palm oils …
PROS
renewable sustainable? CO2 neutral compatible with current engine technologies
Future biofuels
ethanol from cellulose biodiesel from algae FT diesel, bio-DME HC from sugars, oils, lignin
CONS expensive competition with food? not efficient use of biomass?
S L ? E U E F BL O A I B IN E A R T A S U S NON-FOOD BIO
BEST
WORST
FOOD BIO
FOSSILE
’Carbon neutral 2050 -vision’? ...in a country that has significant interest groups within the automotive industry
So, the Government builds road-infrastructure... ...the towns designate more shoppping malls and residential areas at outskirts...
... prognosis 25% increased car-traffic in 20 years ...’miljöminister’ believes that new technology will solve the problems since people must move around for the growth in economy ...resulting in maximally 1 promille reduction in traffic emissions (the best case) due to new technology by experts
...DRASTIC changes in the society structures and life-style the only way the goals could be reached by the leading analysts ... but the ’miljöminister’ goes to Copenhagen having fate on new technology...
Societal Structures !
Consume less Drive less Buy less Fly less Eat less Be less ... in numbers ? A shift from Global-to-Local thinking is needed !
Anyhow, we are in transition ...
’The end of the age of oil’
BIO vs. FOSSIL RESOURCES
Carbohydrates Cn(H2O)n
Hydrocarbons CnHn+2
BIOMASS CARBON ’ C’
+
OXYGEN ’ O’
HYDROGENHYDROGEN
’ H’ n pieces
FOSSIL ’MASS’ CARBON ’ C’
+
HYDROGENHYDROGEN
’ H’
’ H’
’ H’
n pieces
n pieces
n+2 pieces
Different structure – what technology ?
Why Biorefineries ? Oil price constantly increasing Insecure supply (political instability) Ever increasing consumption of energy and liquid fuels peak oil ? Abonadon all-synthetic products instead, natural bio-based solutions www.oil-price.net/ Driving force and focus country-dependent
Most Abundant Bio Feedstocks – depending on geographical location and local politics
Trees Forest residues Grasses Agricultural crops Animal waste Municipal waste Algae Food & Feed ...
Fast Wood Forestry ? www.cifor.cgiar.org/publications/ pdf_files/Books/ForestPerspective.pdf
Fennoscandia – the richest in forest resources in Europe and in the whole world...
E.g. Chile ?
Ca. 3-4
Nordic forest industry in trouble - Investment in Eucalyptus
Iltalehti 2008-09-10 Forest giants let thousands to go UPM:1600 (FI) Stora Enso 1700 (550 i Finland) ’Factory was my second home’
Fray Bentos Uruguay
008-09-10 2 r e t e h y N Dagens
UPM Tervasaari, Valkeakoski
...but we should be worried ore m x 0 1 r ea y d n a r cta e h r e p w th o r g s u t Eucalyp Birch: 1 Mt/a Growth: 5.5 m3/hectar & annum
Eucalyptus: growth 50 m3/hectar & annum
Source: The required area for hardwood plantations In Brazil and the Nordic countries
So, how much the forest actually does Warm summer day: capture CO2 ? Sunny winter day
Maximum (’rainy, cold summer’):
www.hiilipuu.fi
Ex-Soviet bioindustry – today in ruins but Russia wants to 1990: revigorate it ! 18 EtOH fabriker 16 fabriker för djurfoder 15 furfural & xylitol fabriker
Source: Mikhail L. Rabinovich
FOREST BIOREFINERY
Optimum use of biomass raw material in an integrated process: Chemicals to process industry Chemicals to pharmaceutical industry Liquid and solid fuels Pulp and paper Heat and power (electricity)
LIGNOCELLULOSICS FOR FUTURE Early visioners: E. Glesinger, The Coming Age of Wood (Simo Schuster, New York, 1949) Kyösti V. Sarkanen (Chem Eng News 53: 24, 1975)
Conversion – Upgrading Biofeedstock: Technology Challenge !
Extraction, purification (structure preserving) Combustion Gasification Pyrolysis Fermentation (enzymes)
CATALYSIS – still in its infancy when dealing with biorefinery feedstocks in contrary to the well-established petroleum-based refinery technology (almost 100 years of development, fine-tuning and research for perfection)
What does the modern society need ?
Maintain employment and markets in Nordic
Countries
Examples: COMMERCIAL
(and semi- commercial)
EFFORTS IN NORDIC COUNTRIES REED CANARY GRASS
Xynergo BTL/Torrefiering Norske Skog Follum – Statoil (2010-2015) Uniol FAME unit, Fredrikstad,Norway Chrisgas - gasification, Växjö-Värnamo Biorefinery of the Future (Processum) in Örnsköldsvik ChemRec & SunPine, ETC, fuels, Piteå BioEndev & BTC mm. (torrefaction) BTL/FT UPM Kymmene – Andritz EPV Energy – VAPO (Neova), FischerTropsch diesel – 2010 start-up Succinic acid etc. Luleå (C.Berglund) Higher alcohols (BuOH mm.), other alcohols, organic carbonates etc.,... Research e.g. at ÅA, UmU, LTU, ... You name it
Pelletsindustrin och andra energigrödor
...samt resten av Norden och i baltikum
... More ...
NSE Biofuels (50-50 joint venture - NesteOil och StoraEnso Oyj) biomas gasification, Varkaus for NextGen Biodiesel NexBTL NesteOil (2x170.000 ton/a in Finland; 800.000 ton/a in Singapore & 400.000 ton/a in Rotterdam) St1 Etanolix,Bionolix, Cellunolix, Fiberix processer in Finland ... later also in Sweden and ... Many BioGas units & bio-powerplants in Nordic countries
ChemPolis (Oulu) Formico™Fib – fiber mass Formico™Bio – bioethanol Formico™Chem – chemicals Formico™Frac – fractionation Etc.
LignoBoost Innventia (STFI-Packforsk) in Sweden Side-fuel for coal-powered Powerplants (e.g. Fortum Stockholm)
Asphalt emulsions for reduced carbon dioxide emissions Akzo Nobel
TallDiesel SunPine in Piteå harbour, Sweden
Black liquor gasification Piteå, Sweden: Methanol and/or Dimethylether
Fischer-Tropsch fuels StoraEnso (Finland)
www.storaenso.com
SYNFUEL UPM KYMMENE (Finland)
From any Oils/fats NesteOil NexBtl, (Finland) Bio Oil
Acid Caustic Water
Feed tank Pretreatment Impurities removal
Sludge
Bio Oil - Rape seed oil Palm Oil Soya Oil Animal fat
NExBTL-Process Hydrogen
Conversion of fatty acids to parafins and isoparafins Stabilation
Biodiesel tank
Porvoo, 170 kt/a
Fuel gas Sour water
Mineral oil diesel
Diesel tank
Diesel + Biodiesel Blends
NExBTL component sales
Biodiesel
Integrated Biorefinery Örnsköldsvik Biorefinery cluster (Sweden)
New Research - Many solutions, some more difficult than other ...
Wood tar – a classical important product from 16th to 19th century Complex concistency
Many BioFuels on the market Diesel FAME - Fatty Acid Methyl Ester RME - Rapeseed Methyl Ester NExBTL - Next generation biomass to liquid GTL-products (various technologies) Gasoline : Bioethanol: E85, ReFuel (St1) ETBE, TAEE Biogas
OPTIMAL TREATMENT PROCESSES OF Upgrading biogas for LIGNOCELLULOSES FOR vehicle fuel - BIOGASUP BIOETHANOL – OPTBIO Certain ionic liquids are capable for reversible capture of CO2
Jyri-Pekka Mikkola Lab. of Ind. Chem. and Reaction Eng., Åbo Akademi Univ.
Prof. Kai Peiponen Department of Physics, University of Joensuu
Assoc. Prof. Maria Elena Lienqueo Contreras Centre for Biochemical Engineering and Biotechnology
University of Chile
Prof. Jukka Rintala
Department of Biology and Environmental Science,, University of Jyväskylä
Jyri-Pekka Mikkola
Lab. of Ind. Chem. and Reaction Eng., Åbo Akademi Univ.
Dr. Romel Jiménez
Unidad de Desarrollo Tecnológico (UDT), Universidad de Concepción
EVEN INTEGRATED BIOREFINERIES PRODUCE A LOT OF CARBON DIOXIDE - WHAT TO DO WITH IT ? CO2UTIL & SUSE – Utilization of CO2 for chemicals (incl. fuels)
Carbon dioxide to organic carbonates
Abundant C1 feedstock Non toxic, non-inflammable Affordable Easy to handle, store, transport Oxygen carrier Solvent (scCO2: solvent and reagent) + enhances rate and selectivity (Green house gas)
E.g. Direct synthesis of dimethylcarbonate – catalytic route
CO2 + 2CH3OH
DMC + H2O
M.Sc. Valerie Eta & M.Sc. Ewelina Leino
CO2: FROM WASTE TO RESOURCE !
Available Non-toxic, non-flammable Cheap; easy to storage, transport Solvent (scCO2: liquid) Chemical raw material (Green house gas ?)
s y l ta a k a vi DMC, DEC
“Climate Religion: Don’t build your businesses on the claim that carbon dioxide is dangerous", says Per-Olof Eriksson. (Dagens Industri 2009-01-16)
Bio4Energy From seed to advanced fuels and chemicals.
A Strategic Research Area, appointed by the Swedish government. Granted 20 Million euros for five years.
The tree of life !
For green products For fuels For food For health For YOU !
Chemicals Electricity Heating Medicins Transportation F Fermentation E Extraction-Fractionation T Thermal upgrading C Catalysis I Ionic Liquids
TO THINK GREEN !
Use of CO2 as a chemical building-block www.flickr.com/photos/23882161@N03/2713741990/
Prof. Jyri-Pekka Mikkola
