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Institut für Agrartechnologieund Biosystemtechnik
Institut für Agrartechnologieund Biosystemtechnik
Butanol from Biomass
Klaus-Dieter Vorlop, Thomas WillkeJohann Heinrich von Thünen-Institut
Institute of Agricultural Technology and Biosystems Engineergingklaus.vorlop@vti.bund.de
vTI Vorlop page 1
Institut für Agrartechnologieund Biosystemtechnik
Institut für Agrartechnologieund Biosystemtechnik
Butanolmarket and properties
Market• Production (fossil), worldwide
� about 3 Mio. t/a (BASF 2009)� about 5 Mio. t/a (DuPont 2007)
• Price: about 2 €/kg• Application currently almost completely for the chemical industry
Properties (as fuel)• Vapor pressure lower than that of ethanol• Flash point higher than that of ethanol• Mixable with diesel at all temperatures• Better cold start properties as ethanol• Water solubility is lower than of ethanol
vTI Vorlop page 2
Institut für Agrartechnologieund Biosystemtechnik
Institut für Agrartechnologieund Biosystemtechnik
n-Butanolproperties and production
• Properties and applications� Solvent for laquers� Solvent for TLC� Base chemical (ethers, esters,
cleaning agents, fuels)• Production
� Historical: fermentation(molasses, potatoe, grain)
� currently: from crude oil• Market volume:
estimated 1,5 …. 5 Mio t/a (DuPont2007)
• Demand: 3.5 Mio. t (BASF2008)• Price: 2,0 €/kg (CCM 2009)
96Research Octane number (RON)
~ 29 MJ/LVolumetric energy density
77 g/LiterSolubilitiy in water (20°C)
35 – 37 °CFlash point
5,6 hPaVapor pressure (20°C)
117,7 °C-89,5 °C
Boiling pointMelting Point
0,81 g/cm³Density (20°C)
74,12 g/molMolecular mass
C4H10OFormula
1-Butanol(butane-1-ol; n-butanol; butyl alcohol)
vTI Vorlop page 3
Institut für Agrartechnologieund Biosystemtechnik
Institut für Agrartechnologieund Biosystemtechnik
iso -Butanolproperties and production
• Properties and applications� Solvent for laquers� Base chemical (Ethers, Esters,
cleaning agents, fuels)• Production
� from crude oilIn future?� Fermentation (from syngas or
residues)� Enzymatic (from keto-acids,
Genetic engineering)
• Market volume: ??? • Price: ???
> n-ButanolResearch Octane number (RON)
~ 29 MJ/LVolumetric energy density
85 g/LiterSolubitiy in water (20°C)
35 – 37 °CFlash point
5,6 hPaVapor pressure (20°C)
108 °C-108 °C
Boiling pointMelting point
0,80 g/cm³Density (20°C)
74,12 g/molMolecular mass
C4H10OFormula
iso-Butanol(2-methylpropane-1-ol, isobutyl alcohol)
vTI Vorlop page 4
Institut für Agrartechnologieund Biosystemtechnik
Institut für Agrartechnologieund Biosystemtechnik
>96
22
?
0,81
74
Isobutanol
96
87
22
7
0.81
74
Butanol
129
92
35
53
0,79
46
Ethanol
125-131
100-109
53
81
1,07
90
DMC
n.n.15225095Vapor pressureat 25°C [mm Hg]
> 120
0
0,88
78
Benzol
11810288Mol.-weight
[g/mol]
0,980,740,74Density
[kg/L]
110-112
95-103
118
102
116
101
Octane number*RON
MON
411618Oxygen content[weight-%]
DECETBEMTBE
•*for comparison: RON/MON: Benzin 91/82.5 - Super 95/85 - Superplus 98/88 various sources, combined
Butanol as Fuelproperties
vTI Vorlop page 5
Institut für Agrartechnologieund Biosystemtechnik
Institut für Agrartechnologieund Biosystemtechnik
Methanol
Pyrolysis oil
Whole crops, residiues
Sugar, starch,residues, biomass
H2
EthanolSyngas
Routes to Butanol – from Biomasscurrently and in the future
Fermentation
FermentationGasification
Pyrolysis
Catalysis
Gas separation
Butanol
Catalysis
Catalysis CatalysisFermentation
vTI Vorlop page 6
Institut für Agrartechnologieund Biosystemtechnik
Institut für Agrartechnologieund Biosystemtechnik
Butanol-Synthesisby catalytic reaction: past and at present
Route 1: Hydrogenation of crotonaldehyde (up to 1950)
EthanolEthylene
Butanol
Route 2: Alcohol synthesis (Reppe 1942)Mild conditions (100°C, 10-15 bar) but expensive
vTI Vorlop page 7
Institut für Agrartechnologieund Biosystemtechnik
Institut für Agrartechnologieund Biosystemtechnik
Butanol-Synthesisby catalytic reaction: at present and prospective
Route 4: (Lassi 2009) Catalyst: Ni/Al2O3,250°C, non optimizedConversion: max 30%Selectivitity: 70%
Route 3 : Oxo-synthesis (main process)
Propylene Butyraldehyde Butanol
vTI Vorlop page 8
Institut für Agrartechnologieund Biosystemtechnik
Institut für Agrartechnologieund Biosystemtechnik
ButanolButanol --SynthesisSynthesisABE-fermentation (acetone, butanol, ethanol)
Starch(grain, corn)
Cellulose, Hemicellulose(wood, straw, etc.)
ABEFuel additiveResidues
FermentationClostridium spp.
15-20% Acetone
70-80% Butanol
5-10% Ethanol
vTI Vorlop page 9
Institut für Agrartechnologieund Biosystemtechnik
Institut für Agrartechnologieund Biosystemtechnik
Butanol-SynthesisABE-fermentation - fundamentals
• Microorganisms� C. acetobutylicum� C. beijerinckii� C. saccharobutylicum� C. saccharoperbutylacetonicum
• Metabolism� Biphasic fermentation
• Acidogenesis (acid production)• Solventogenesis
(solvent production and sporulation)
� Products and yield• ABE: 18-22 g/L (3:16:1) • Butanol: 13-16 g/L• Best results:
ABE 33 g/L; Butanol 21 g/L(Qureshi & Blaschek 2001)
Acidogenesis Solventogenesis
Butanol
vTI Vorlop page 10
Institut für Agrartechnologieund Biosystemtechnik
Institut für Agrartechnologieund Biosystemtechnik
Butanol-SynthesisABE-fermentation - problems
• High feedstock costs• Low product concentration
13-16 g/L (best: 21 g/L)• Product toxicity
� Butanol is more toxic than Ethanol
� Inhibition of growth (> 200 mM product)
� Liquefaction of membranes� Brakedown of transport systems
• Unwanted byproducts� Acetone 15 %� Ethanol 5 %
� (Butanol 80 %)
vTI Vorlop page 11
Institut für Agrartechnologieund Biosystemtechnik
Institut für Agrartechnologieund Biosystemtechnik
Butanol (ABE) – Fermentationperformance and problems
Recently
• Matured technology, extensive experience exist
• Potential use of residual biomass (also lignocellulosic, whey)
• High value byproducts (acetone, ethanol, H2) usable
• Actual (batch) about 13/10 g/L butanol, max. 17 g/L, improvable
• Continuously: max. 10 g/L Butanol, productivity 6 g/L·h, yield: 0,3 g/g
• Process optimization (feedstock, yield, productivity, down stream processing)
currently in pilot scale
Problems
• Low product concentration (due to inhibition)
• Low yield (byproducts)
• Process instability (cell degeneration, infection by phages)
• Complex and energy intensive down stream processing
vTI Vorlop page 12
Institut für Agrartechnologieund Biosystemtechnik
Institut für Agrartechnologieund Biosystemtechnik
Butanol-Productionconventional process (since 1920)
• Batch-process:200.000 - 800.000 L
• Ferm. time: 40 – 60 h• Feedstock: corn mash,
molasses• Product concentration (total
solvents):� 12 – 20 g/L (corn)� 18 – 20 g/L (molasses)
• Product separation: distillation• Yield (total solvents)
� By theory: 38 % (w/w)� realized: 25-26 % (corn),
29-33% (molasses)
• Productivity: 0,2 - 0,6 (g/L·h)
200.000 L Fermentation, © Commercial Solvents Corp.
Source: Bahl 2008
vTI Vorlop page 13
Institut für Agrartechnologieund Biosystemtechnik
Institut für Agrartechnologieund Biosystemtechnik
Butanol (ABE) – Fermentation prospects
Cost reduction• Screening, mutation, genetic engineering
� Increase of product concentration� Increase of butanol yield
� Utilization of low cost feedstock (residues, whole crops)
• Optimization of fermentation process� Application of immobilized cells� Continuously processes
• Application of integrated product separation (Butanol, Ethanol, Acetone, H2)� Extraction, membrane technologies
vTI Vorlop page 14
Institut für Agrartechnologieund Biosystemtechnik
Institut für Agrartechnologieund Biosystemtechnik
Butanol-Synthesis – ExampleImmobilisates, continuously, 2-step-pilot plant, 150 L
1. Acidification (butyrate)Clostridium thyrobutylicum
2. Alcohol productionClostridium acetobutylicum
Down stream
DOE Final Report (Ramey, Yang 2004)
adsorption&
desorption
distillation
decanter
10 L inoculum1. step
10 L inoculum2. step
fermenter150 L
fermenter40 L
ValveValveValvevalve
Gas
Gas
water
Gas
condensor
sterilemedium recycle
Butanol
Butyl Fuel LCC
vTI Vorlop page 15
Institut für Agrartechnologieund Biosystemtechnik
Institut für Agrartechnologieund Biosystemtechnik
Butanol-Fermentation (ABE)batch vs. continuous processes using immobilized cells
Huang et al., 2005
0,9108,60,43„fibrous bed“ FBB
Qureshi et al., 2000
27,9160,38clay particle
Park et al., 1989
0,27164,20,34thrickle-bed (foam)
Immobilized cells
Qureshi & Blaschek, 2001
0,2~ 20
A/B/E: 6/12/2~1,50,28-0,33batch
LiteratureDillution-rate
[1/h]Products, total
[g/L]Productivity
[g/L·h]Yield*[g/g]
Process
* Butanol from Glucose (1mol/mol): 0,41 g/g (theoretical yield assuming 100%)
vTI Vorlop page 16
Institut für Agrartechnologieund Biosystemtechnik
Institut für Agrartechnologieund Biosystemtechnik
Butanol - Synthesisprocess integrated product separation
Lee et. al. Biotech Bioeng 2008
stripping liquid-liquidextraction
pervaporation
vTI Vorlop page 17
Institut für Agrartechnologieund Biosystemtechnik
Institut für Agrartechnologieund Biosystemtechnik
Butanol-Production in Russiabiorefinery-concept (realized market routes)
Zverlov et al., 2006
90.000 t/a
45.000 t/astarch equivalent
4.100 t/a 8.550 t/a 2.300 t/a
8,7 Mio m3/a13,1 Mio m3/a11 Mio m3/a ?
?
vTI Vorlop page 18
Institut für Agrartechnologieund Biosystemtechnik
Institut für Agrartechnologieund Biosystemtechnik
Butanol Production in ChinaABE-produktion plants (fermentation)
vTI Vorlop page 19
Institut für Agrartechnologieund Biosystemtechnik
Institut für Agrartechnologieund Biosystemtechnik
Butanol-Industrial Projectsconventional process incl. genetic engineering 1
• BP-Dupont (UK)� „Butamax“-demonstration plant 2010, commercial from 2013
• Cathey Industrial Biotech (China)� 30,000 t plant in Jilin, in operation since 3/2008,
upgrading to 200,000 t/a projected
• Cobalt Biofuels (USA)� Continuously
� Patented „vapor compression destillation separation“
� Pilot plant since 1/2010
• Butyl Fuel LCC (USA)� Patented 2-step process via butyrate (thermophilic)
vTI Vorlop page 20
Institut für Agrartechnologieund Biosystemtechnik
Institut für Agrartechnologieund Biosystemtechnik
Butanol-Industrial Projectsconventional process incl. genetic engineering 2
• Tetra Vitae Bioscience (USA)� Conventional technology
� New substrates
� Integrated down stream processing (new technologies)
• Arbor Fuel Inc (USA)� Genetical modified yeasts
� Lignocellulosis feedstock
• Butalco (Switzerland)� Genetical modified yeasts
� Butanol/Isobutanol from lignocellulose
• Metabolic Explorer (France)� Genetic engineering, fermentation techniques
� Butanol fermentation from starch, sugar, lignocellulose
vTI Vorlop page 21
Institut für Agrartechnologieund Biosystemtechnik
Institut für Agrartechnologieund Biosystemtechnik
Butanol-Industrial Projects thermochemical via syngas
• Green Biologics (UK)
� Thermophilic pretreatment
� Product-tolerant strain (up to 4% Butanol-concentration)
� Utilisation of C5-sugar
• Syntec Biofuel (Canada):
� Isobutanol
� Thermochemical
� Versatile biomass spectrum
• Syngas Biofuels Energy (USA):
� Virtuelle Internet company (syngas portal)
� Thermochemical routes
� Syngas-biotechnology
vTI Vorlop page 22
Institut für Agrartechnologieund Biosystemtechnik
Institut für Agrartechnologieund Biosystemtechnik
Butanol-Industrial Projectsbutanol/isobutanol enzymatic from keto acids
• Gevo (USA)
� Isobutanol with E.coli (genetically modified) from keto acids
� Demonstration plant
vTI Vorlop page 23
Institut für Agrartechnologieund Biosystemtechnik
Institut für Agrartechnologieund Biosystemtechnik
--
80…120
880…920
12…18ca. 4
ca. 1
970…980
Product concentration [g/L]
- Butanol (TB: 118°C)- Acetone (TB: 56°C)
- Ethanol (TB : 78°C)
- Water (TB : 100°C)
19,629,2Energy density [MJ/L]
1…5
0,510,45
glucosesucrose
Ethanol
0,2…1,2
0,380,33
biomass, residues
Butanol
Substrates
Mass yield, by theorie [g/kg GEQ*]realized [g/kg GEQ*]
Productivity [g/(L·h)]
* GEQ: Glucose-Equivalent
Various sources, combined
Butanol vs. Ethanolfermentation and separation
vTI Vorlop page 24
Institut für Agrartechnologieund Biosystemtechnik
Institut für Agrartechnologieund Biosystemtechnik
Conclusion
• Currently production costs are too high for using butanol as biofuel
• Using biobutanol as feedstock for chemicals is the preferredoption
• Significant technological improvements are necessary beforebutanol can be used as biofuel
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