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Graeme Walker
BiofuelsBiofuels Production & Environmental Impacts: Production & Environmental Impacts: A European perspectiveA European perspective
www.abertay.ac.uk
Federation of Latin American Chemical Societies Meeting July, 2008
Outline
• European Biofuels: overview
• Bioethanol: pros & cons, environmental impact
• Bioethanol: current processes, future challenges & opportunities
• Bioethanol from lignocellulose
• Conclusions & future prospects
Environment
Agriculture
Fuel Security
Why biofuels?
• Biogas (Anaerobic Bacteria)
• Biodiesel (Brassica napus, Animal/veg oils)
• Bioethanol (Yeast)
• Biohydrogen (Cyanobacteria, Clostridia, PNS bacteria)
• Bio-oil (Botryococcus braunii, other microalgae)
• Biobutanol (C.butylicum, C.acetobutylicum)
European BiofuelsThe 20:20 goal = 20% renewables by 2020
Current production
Research & Development
Biodiesel in Europe
• Biodiesel accounts for 76% of total biofuelconsumed in the EU
• EU biodiesel production set to increase by 55% in 2008 to 16Mt (European Biodiesel Board)
• But, in 6 EU countries, biodiesel production has fallen since 2006 (due to higher feedstock prices and subsidised imports from USA)
Projected Fuel Ethanol Consumption. Source: IEA
0
20000
40000
60000
80000
100000
120000
140000
1975 1980 1985 1990 1995 2000 2005 2010 2015 2020
Year
Mill
ion
Litre
s
Brazil US & Canada EU World
Bioethanol: Global Consumption[Note: All Biofuels expected to account for 8.5% of global energy use by 2030
– US Energy Information Administration]
European bioethanol?
Substrates:- Sugarbeet
- Wheat
0
50
100
150
200
250
300
350
400
Country
SpainGermanyFrancePolandItalySwedenHungaryLithuaniaCzech RHolandLatvia
millionL2006
Biofuels in the UK(HGCA Newsletter 2/4/08)
• So far, UK biofuel production is much less than the amount required to fulfil the RTFO target (5% by 2010) • Currently biofuels only account for a small percentage of the UK fuel market, a mere 0.70%.• There is presently only one ethanol plant in operation (British Sugar, production capacity of 55,000t).• This would suggest that total UK biofuel production for 2007 was around a quarter of a million tonnes.
British bioethanol (1936)
Why Bioethanol?
Pros ConsCO2 neutral Food-to-fuelReduced dependence on oil Lower oil priceAgricultural diversification SustainabilityClean burning, low toxicity Energy balanceLess GHG emissions (~65% less) Residues, emissionsHigher flash points (better fire safety) Inefficient microbesBetter biodegradability Hydroscopic Co-generation of electricity Less mpg
[Climate saviour or climate pariah?]
Bioethanol:current substrates?
Brazilian ethanol programme (Proalcool*)
SUGAR CANE
Bagasse Ethanol Sugar CO2 Fusel oil Vinasse Yeast
Animal feed, Fuel Food Chemicals Biogas Animal feedelectricity
*~380 Distilleries in Brazil>24bn litres ethanol/yr
[40% of transport fuel]
>700,000 jobs created>$2bn savings pa.
USA Bioethanol processes (Gasahol)
CORN (maize)
Crude starch
Syrup conversion
Fermentation
Distillation
GASAHOL
Microbial amylases
Yeast
By the end of 2007, U.S. will have processed 3 bn bushels of corn for
ethanol = 30.28 billion liters
Bioethanol
Scientific & technological challenges(especially from lignocellulosic feedstocks)
NOTE: lignocellulosic ethanol production/consumptionestimated to result in 75-80% Green-House-Gas emissions reduction compared with gasoline
Second-generation bioethanol:some potential cellulosic (non-food) feedstocks
• Wood chips/sawdust/forestry residues/SRC
• Waste paper
• Corn fibre/cobs/stover
• Municipal Solid Waste, MSW
• Straw, bagasse
• Cereal hulls/spent grains
• “Energy crops”(Switchgrass, Miscanthus, Ryegrass, etc.)
• Cyanobacterial cellulose
Some cellulose-to-ethanol plants (USA)
• New York & Michigan (wood chips – Mascoma)
• Tennessee (switchgrass – Mascoma)
• Maine (wood chips – RSE Pulp & Chemical)
• Kentucky (corncobs – Ecofin/Alltech Inc)
• Louisiana (bagasse – Celunol)
• Ohio (corn fibre – Genahol)
Selected international others:Iogen (straw –Canada); Abengoa (straw –Spain, US); Etek (softwood –Sweden); Elsam (straw –Denmark); TMO (straw/wastepaper–UK); NEDO (rice straw –Japan); Tavda (wood –Russia); Mossi & Chistophi (sorghum fibre –Italy)
Lignocellulosic bioethanol– key areas for improvement
• Cellulose hydrolysis– Steam explosion, acids, enzymes (cellulases, arabinozylanases, ligninases)– New pre-treatments: ozonolysis+ultrasound?– SSF (e.g. Thermoanaerobacterium saccharolyticum)
• Fermentation– Xylose fermenting yeasts or bacteria– Very high gravity wort (>20%v/v ethanol)– Thermotolerant/alcohol tolerant/inhibitor tolerant yeasts– Optimised nutrition (esp. metal ions like Mg, Zn)
• Distillation– Anhydrous ethanol (molecular sieves, azeotropes, membrane pervaproation)– Energy balances!
SecondSecond--generation generation bioethanolbioethanol: research challenges: research challenges
Lignocellulosicmaterial
Pre-hydrolysis [physico-chemical]
Hydrolysis [biological]
Fermentation (hexose)
Distillation
BIOETHANOL
Pretreatment
3
2
1
4
EnergyFermentation (pentose)
Ethanologenic yeasts
Feedstock Fermentable substrate Yeasts*-Wheat, Maize, Barley Starch hydrolysate (maltose, glucose) Saccharomyces-Sugarcane/Beet Sucrose Saccharomyces
-Potato, Rice Starch hydrolysate (maltose, glucose) Saccharomyces-Agave/Artichoke Inulin hydrolysate (fructose) Kluyveromyces-Cheese whey Lactose Kluyveromyces-Raw starch Starch Schwanniomyces-Seaweed Laminarin (glucose) Pichia angophorae-Paper, sawdust, straw, Xylose, arabinose, glucose, Pichia, Candida, wood, spent grains, cellobiose Pachysolen,cornsteep liquor, paper, Kluyveromycesrapeseed residues, MSW, GMS.cerevisiaebagasse, corn fibre
*Other microbes? Zymomonas, E. coli (GM), Klebsiella (GM),Bacillus (GM), Thermoanaerobacterium saccharolyticum
Saccharomyces cerevisiae strains cannot ferment pentose sugars as D-xylose and L-
arabinose. Too bad, because…
•Grass (16% xylan, 5% arabinan)
•Corn stover (19% xylan, 3% arabinan)
•Wheat bran (19% xylan, 15% arabinan)
•Barley husks (20% xylan, 9% arabinan)
Xylose fermentation pathway
Xylose
Xylitol
Xylulose
ETHANOL
XR
XDH
Xylose isomeraseBacteria, Piromyces
S. cerevisiae
• Brettanomyces naardenensis
• Candida intermedia var intermedia
• Candida lyxosophila
• Candida shehatae var. lignosa
• Candida tenuis
• Cryptococcus albidus
• Kluyveromyces marxianus
• Pachysolen tannophilus
• Pichia stipitis
• Yeasts are extremely diverse physiologically(but yeast biodiversity virtually untapped)
• S.cerevisiae is a rather exceptional yeast and may not be the best for bioethanol (xylose non-fermenter)
• We need more knowledge of yeast cell physiology (Especially in non-Saccharomyces yeasts)
• Yeast stress is a dilemma (e.g. ethanol tolerance)
• Bacteria are competitive
The yeast message
BioethanolBioethanol from from spent grains?spent grains?
???
Whisky Production (x106 L p.a.)
Yield alcohol (L/t)
Residues
(1000 t dry matter)
Grain
(wheat or maize)
273 490 209
Malt (barley)
170 531 135
Spent grains are cereal residues from breweries
and distilleries
Lager brewery Grain distillery Ale brewery Malt distillery
100% malt85% malt 15% wheat
86% maize 14% malt
96% malt4% roasted
malt
Scottish grain and malt distilleries
2006 figures
Bioethanol from spent grain: Current Research
Pre-hydrolysis
Enzyme Hydrolysis
Distillation
BIOETHANOL
Pretreatment
Fermentation (Glucose, xylose, arabinose)
1. Temp? Acids?
2. Novel pre-treatments?
3. Enzymes
4. Characterisation of sugars, inhibitors
−Ale (malt)
− Lager (malt + wheat)
−Whisky (malt)
−Spirit (maize + malt)
• C6 & C5 sugars
• P. stipitis,
K. marxianusetc.
“Potential” bioethanol from UK spent grains
British Breweries (2007)
• 210,974 tonnes SG
• Would yield:
21M litres bioethanol
Scottish Distilleries (2007)
• 297,000 tonnes SG
• Would yield
20.5M litres bioethanol
NOTE: Existing (lab-based) process is inefficient(hydrolysis and Pichia or Kluyveromyces fermentation ~20%CE)
- estimated potential >100M litres/year
Novel lignocellulose pre-treatment technology?
• Ultrasound (20 kHz-1 MHz)
+• Ozonolysis (O3)
O3 O2 + O .O + H2O 2HO
2HO H2O2
. ..
oxygen atom
hydroxyl radical
hydrogen peroxide
O
OO
OH
OH
O
CH2OHOOH
OH
CH2OH
O
OO
OH
OH
O
CH2OHOOH
CH2OH
O
O
OO
OHO
CH2OHOOH
OH
CH2OH
O
OO
OO
CH2OHOOH
OH
CH2OH
HO.
(1)
(1)
(2)
(2) hydroxyl radical
Conclusions & future prospects
• Global biofuels increasing rapidly
• Europe is lagging behind (esp. bioethanol in UK)
• Yeast biodiversity is untapped for fermentation
• New lignocellulosic pre-treatments required
• Plentiful biowaste available (eg. spent grains, straw, wood, corn residues, paper etc.)
• 2nd-generation bioethanol is the way forward!
Acknowledgements
• Abertay University Yeast Group
(Raffaele De Nicola, Jane White, Biju Yohannan, Stelios Logothetis, Irma
Ochigava, Paola Bruno, Jason McColm, Jason Bennett, David Bremner, Rashmi
Chand)
• Royal Society of Chemistry, FLAQS organisers
Thank you!
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