Butanol from Biomass - FNRveranstaltungen.fnr.de/fileadmin/allgemein/images/veranstaltungen/Neue... · Institut für Agrartechnologie und Biosystemtechnik Butanol from Biomass Klaus-Dieter

Institut für Agrartechnologieund Biosystemtechnik


Butanol from Biomass

Klaus-Dieter Vorlop, Thomas WillkeJohann Heinrich von Thünen-Institut

Institute of Agricultural Technology and Biosystems [email protected]

vTI Vorlop page 1



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



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



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



>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



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



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



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



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



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



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



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



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



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



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



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



Butanol - Synthesisprocess integrated product separation

Lee et. al. Biotech Bioeng 2008

stripping liquid-liquidextraction

pervaporation

vTI Vorlop page 17



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



Butanol Production in ChinaABE-produktion plants (fermentation)

vTI Vorlop page 19



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



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



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



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



--

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



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



Thank youfor your attention

Documents

Butanol from Biomass - FNRveranstaltungen.fnr.de/fileadmin/allgemein/images/veranstaltungen/Neue... · Institut für Agrartechnologie und Biosystemtechnik Butanol from Biomass Klaus-Dieter