Transcript DOE Biomass RDD Review Template

Production of higher alcohols
liquid biofuel via acidogenic
digestion and chemical upgrading
of industrial biomass streams.
DE-FG36-08GO18165
April 7, 2011
Algae Platform Peer Review
G. Peter van Walsum
Clayton Wheeler
University of Maine
This presentation does not contain any proprietary, confidential, or otherwise restricted information
Goal Statement
• Determine feasibility of converting pulp mill and
sea weed processing streams to advanced fuels
via carboxylate platform processing.
Relevance to the Biomass Program:
 Low cost enzymatic hydrolysis
 Complete carbohydrate fermentation
 Integrated biochemical and thermochemical
processing
 Improving economics of biomass processing
industry: Kraft pulping, carrageenan extraction.
2
Quad Chart Overview
Timeline
•
•
•
Barriers addressed
Project start date: 10/’08 (03/’09)
Project end date: 09/’11 (12/’11)
Percent complete: 73%
– Bt-F, G Enzyme cost + loading
• Autohydrolytic cultures
– Bt-J Organism development
• Evolving microbial ecosystem
– Bt-K Biological Process Integration
• Consolidated bioprocessing
– Bt-L Biochemical/Thermo-chemical
Integration
• Acidogenesis + TC upgrading
Budget
•
Total project funding
•
•
•
– DOE share: $713k
– Contractor share: $181k
Funding received in FY09: $118k
Funding for FY10:$203k
ARRA Funding: none
•
•
Partners
Old Town Fuel + Fiber (OTFF)
FMC Biopolymer
Stage
•
A,B Exploratory
Project Overview
Existing
biomass
processing
industries:
Hardwood pulp
Algal
carrageenan
Alkali / neutral pH
treated
carbohydrates
•Separation and
conversion :
•L/L extraction
•Thermal
conversion
•Esterification
I: Ferment to
carboxylic
acids
Acidogenic
digestion
Carboxylate
salts
Ketones
Esters
III:Process
modeling
H2
II:Upgrade to
alcohols
H2 treatment
Alcohols
Ketones, Esters, Organic acids
Overview, cont’d
feed
Distilled water
stm
fermentation
Carboxylate
brine
Dewater
Ca lcium
Carboxylates
CKA configuration
Thermal
conversion
H2
Hydrogenation
Ketones
Alcohols
CaCO3
Distilled water
stm
feed
fermentation
Carboxylate brine
CO2
Dewater
Ammonium
Carboxylates
fermentation
Distilled water
Ca or NH4
carboxylates
Dewater
CO2
NH4HCO3 or CaCO3
Esters
NH3
stm
Carboxylate
brine
Esterification
H2
Hydrogenolysis
Alcohols
Distillation
H2O
NH4HCO3
feed
CEA configuration
NH3 or CaCO3
Acid
springing
Long chain alcohols
CHEA configuration
Carboxylic
acids
Esterification
Esters
H2
Hydrogenolysis
Long chain alcohols
Alcohols
Distillation
1-Approach
•Existing industries:
Alkali / neutral pH
Existing biomass
treated
processing
•Infrastructure, adding value
carbohydrates
industries:
Acidogeni
Hardwood pulp
c digestion
•Alkali / neutral pH treated streams:
Algal
carrageenan
Carboxylate
•Good digestibility
salts
H2
•Low inhibition likely
•Separation and
Ketones
•Evolving mixed culture:
conversion :
Alcohols
Esters
•L/L extraction
H
treatment
•Thermal
•Low cost
conversion
•Esterification
•Autohydrolytic
Ketones, Esters, Organic acids
•Complete sugar utilization
•Optimized through evolution
•Conventional thermochemical conv.:
•Low technical risk
•Demonstrated, scaled technologies
•Still opportunities for innovation + optimization: integrations
•Higher value products
•Chemicals
•Higher alcohols preferable to ethanol as fuel
2
Project objectives:
 I) Convert pre-pulping hemicellulose extract and seaweed sludge
(AlgefiberTM)from carrageenan production into carboxylate salts via
mixed culture evolving fermentation.
 II) Upgrade the carboxylate salts into chemicals and alcohols via one
of three possible routes:
 CKA:
 CEA:
 CHEA
carboxylates-ketones-alcohols,
carboxylates-esters-alcohols
carboxylates-acids-esters-alcohols .
 III) Develop process models to evaluate the M + E balances and
costs of three configurations. Assess process synergies with existing
facilities.
7
1 –Project pathway
• Milestones:
–
–
–
–
–
Produce carboxylic acids at bench scale from both feedstocks.
Assemble and run larger ( 50 gal) fermentation.
Produce ketones, esters and alcohols from stock chemicals.
Produce ketones or esters, and alcohols from biomass.
Generate economic numbers with techno economic model.
• Go / no-Go decision points:
– Task A.GN: Identify fermentation cond’s: Temperature, buffer type.
– Tasks D. F. G. GN: Decide on continuation of CKA, CEA or CHEA
past pure feedstock.
– Tasks H. J. K.GN: Decide on continuation of CKA, CEA or CHEA
to alcohol products.
8
2 - Technical Accomplishments/
Progress/Results
• Objective I: Fermentation to carboxylic acids.
– Several feedstock samples characterized for
carbohydrate, solids.
– Fermentations completed on several samples of
AlgefiberTM and wood extracts at two temperatures,
using calcium or ammonium buffers.
– Carboxylic acids produced at up to 25 g/L in batch
culture.
– Verified autohydrolysis of oligomers.
– 50 gal fermentors built and in use.
9
Fermentation work:
Algefiber® + chicken Manure
Kelp results
Autohydrolysis in fermentor
Xylan
2 - Technical Accomplishments/Progress/Results (cont’d)
• Objective II: Upgrade acids to mixed alcohols
– Characterized ketonization of different cation
carboxylates (Na+, Ca++, Mg++, NH4+).
– Converted stock carboxylate salts to ketones.
– Converted fermentation salts to ketones.
– Extracted acids from model systems and wood extracts.
– Esterified carboxylic acids with ethanol and octanol.
– Esterified ammonium acetate to octyl acetate.
– Hydrogenated ketones to alcohols.
– Developed kinetic model for hydrogenation.
– Selected CKA (Ketone) upgrading pathway
13
Compounds investigated
•
CaPr
– Dehydration: < 200 °C
– Ketonization: 380 – 480 °C
– Calcining: > 600 °C
NaAc
•
Mg(Ac)2
Ca(Ac)2, Ca(Pr)2:
Ca(Ac)2
Mg(Ac)2(H2O)4:
– Dehydration: < 200 °C
– Ketonization + calcination 270 –
420 °C
NH4Ac
•
NaAc
– Dehydration: < 200 °C
– Ketonization: 425 - 535 °C
•
NH4Ac:
– Decomposition to Acetamide < 200
°C
Ketonization of
Fermentation (AlgefiberTM) salts
Hydrogenation kinetics:
Arrhenius plots
5
2.5
No water
with water
EA= 17.4 ± 80 kJ/mol
EA= 27 ± 59 kJ/mol
3
5.3
ln(Rate)
ln(Rate)
3.5
5.6
4
6
1
337
1
325
1
314
1
T(K)
1
305
1
337
1
325
1
314
1
T(K)
1
305
Acid extractions: pH vs chain length
2 - Technical Accomplishments/Progress/Results (cont’d)
• Objective III: Techno economic modeling
– Developed ASPEN-Plus model of CKA, CEA, CHEA
upgrading pathways
– Compared yields, costs and energy balances of three
pathways
– Different strengths and weaknesses associated with
each pathway.
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Production volumes
Annual production amount in gallons of alcohol produced for
each pathway: 1000 tpd pulp mill.
CKA
CEA
CHEA
Ethanol
--
10,208,068
10,111,793
Propanol
--
976,292
969,151
2-Propanol
7,051,684
--
--
3-Pentanol
Total
(gallons)
731,446
--
--
7,783,130
11,184,360
11,080,944
Net energy production
And the winner is...
Upgrading
Scenario
Capital
Cost
CKA
Yearly Total
Alcohol
Production
(gallons)
Cap. $/
annual gal
$/Gal to
achieve
break-even
point
Cap.
$/MJ
$31.4 MM 7,783,130
4.03
3.38
0.049
CEA
$39.5 MM 11,184,360
3.53
3.40
0.070
CHEA
$32.8 MM 11,080,944
2.96
3.29
0.058
2 - Technical Accomplishments/Progress/Results (cont’d)
Most important technical accomplishments:
– Demonstrated autohydrolysis and fermentation in
inhibitory wood extracts.
– Demonstrated ketone production from biomassderived carboxylates—including several longer Cchain molecules.
– Identified catalytic action of water in ketone
hydrogenation to 2-alcohols.
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2 - Technical Accomplishments/Progress/Results (cont’d)
Key Milestones and Status, Barriers addressed
– Produce acids at bench scale from both feedstocks.
– Assembled and running larger ( 50 gal) fermentation.
– Narrowed conditions from 8 to 2. Working on increasing titer.
– Barriers addressed: Bt-F,G (enzymes); Bt-J (organisms); Bt-K
(consolidated bioprocessing)
– Produce ketones, esters, alcohols from stock chemicals.
• Ketones and alcohols work well. Esters have had low yields
– Produce ketones or esters, and alcohols from biomass.
• Ketones produced from AlgefiberTM. Alcohols to come.
– Barrier: Bt-L Biochemical/Thermo-chemical Integration
– Economic numbers from techno economic model.
• Have estimates for 3 pathways. Mill integration to come.
23
2 - Technical Accomplishments/Progress/Results (cont’d)
Ties to applications
– Mixed culture CBP of undetoxified feedstocks:
•
•
•
•
Process simplification: no hydrolysis step
Operating cost savings: no acid, base, enzymes needed
Robust operation: fewer shutdowns
Cap cost savings: Plastic/concrete instead of SS
– Demonstrated ketone production from biomassderived carboxylates.
• Process works, easy separation of ketones from residues
• Lignin, other residues do not hinder ketonization
– Identified catalytic action of water in ketone
hydrogenation to alcohols.
• High yields, fast rates, good catalyst durability.
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3 - Relevance
Mission of the Biomass Program MYPP
•
•
•
•
•
Renewable biomass resources: Wood hemicellulose + macro algae
Cost-competitive: $3.30 – 3.40/gal (wood extracts, ~10 MMgal/yr)
High-performance biofuels: Mixed alcohols. HCs possible
Bioproducts and biopower: Chemical intermediates
• Program Goals:
•
•
•
Reduce dependence on oil: blendable mixed alcohols
36 bgy by 2022 : High carbon retention in liquid products
Applicable to bio wastes and energy crops.
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3 – Relevance, Cont’d
•
•
•
•
•
Contribution to goals of the Program
Enable the production of biofuels nationwide
Technology suitable to forested and coastal areas of the US.
Reduce dependence on oil
Producing higher alcohols--higher blend ratios than ethanol.
•
•
•
•
•
•
Addressing critical issues
Low enzyme cost:
CBP has no enzyme costs.
Improve catalyst performance:
Ketonization catalyst (Ca++) works with biomass residues
Hydrogenation works on relatively clean ketone condensate
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3 – Relevance, Cont’d
•
•
•
Technology development timeline
2012: $0.86/gal processing cost ethanol
2017: $1.56/gal gasoline, diesel blendstocks
•
•
•
•
•
Cost estimates for processing wood extracts are:
For a scale of a 1000 tpd pulp mill (Typical in North America)
Mixed Alcohol production: 7.8 - 11 MM gallons/year
Capcost: $3 - $4/annual gallon mixed alcohols
Processing cost: ~$1.60/gal mixed alcohols
•
•
•
Downstream processing costs for AlgefiberTM similar
Feedstock for AlgefiberTM lower cost.
Fermentation and solids handling for AlgefiberTM may be higher.
27
3 – Relevance, cont’d
• Applications of the expected outputs
•
Working with OTFF on 50+ gal wood exact fermentation.
•
•
Results on AlgefiberTM too low in titer ( so far)
Looking at raw kelp as feedstock (different project).
•
Technology development transferable to other feedstocks
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4 - Critical Success Factors
• Technical
•
•
•
•
•
Acid concentrations in fermentation, fermentation rates.
Being improved through:
continuous culture (adaptation)
percolation processing (higher solids/liquid ratio)
counter-current solids processing (reducing inhibition)
•
•
Yield from ketonization reaction, products from other components.
Yield is being assessed. Operating procedures improving
(mixing, heating rates, condensation temperatures)
•
•
Durability of catalyst in hydrogenation.
So far so good, but not yet tested with biomass derived ketones.
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4 - Critical Success Factors, Cont’d
• Business
•
•
Feedstock supply
Industrial partners currently source their biomass.
•
•
•
Capital costs, technology risk
Project partners may enable co-location to diminish cost and risk
Partners have expertise in biomass processing
•
•
•
Partner motivations:
FMC Biopolymer can achieve some avoided disposal costs.
Oceans Approved (Separate project) interested in expanding
market for kelp, using waste from processing.
OTFF has $30M DOE biorefinery grant.
Terrabon (IP holder) desires business-relevant research.
•
•
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4 - Critical Success Factors, Cont’d
• Market
•
•
•
•
•
•
•
No fuel market for mixed 2-alcohols
Others have interest in mixed alcohols: FT or C-4 alcohol
fermentators—this should come eventually.
Distill alcohols for fuel (ethanol, butanol) and chemical markets
Conversion of mixed alcohols to gasoline range alkanes has
been demonstrated by Terrabon (70 gal/ton biomass).
Accessing chemical market
FMC or Patriarch Partners (OTFF) may be able to use or
market chemical products (Acids, Ketones, Esters)
Distilled chemical products may be marketed as bio-derived
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4 - Critical Success Factors, Cont’d
• Regulatory
•
•
•
•
Permitting
Co-location could diminish permitting barriers
FMC Biopolymer may benefit from waste reduction.
No GMOs being used
• Legal
•
•
Most IP on carboxylate platform held by Terrabon
UMaine and Tarrabon negotiating a research license agreement.
32
4 - Critical Success Factors, Cont’d
Top 2-3 potential challenges
• Fermentation: Low titers, slow rates.
•
Evolve cultures, counter current and sequenced processing
• Poor yield through ketonization (?)
•
Optimize conditions, utilize all products
• Economies of scale too small.
•
•
Demonstrate technology, apply at larger scale
Target chemical markets
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4 - Critical Success Factors, Cont’d
Advancing the state of technology and positively
impacting the commercial viability
– Cross-Cutting Analysis: Aspen modeling of processes.
– Feedstock Supply R&D: Technology applicable to many
feedstocks, mixed feedstocks.
– Downstream Refining R&D: Demonstrating integrated process.
– Environmental sustainability:
–
No GMOs.
–
Reducing wastes from existing industries.
–
May be viable at smaller scale than other technologies.
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Future Work
• Increase acid titer from algaefiber through countercurrent percolation processing.
• Continue 50-gal scale fermentations of wood extract
to generate kg quantities of carboxylate salts.
Operate in sequencing batch.
• Integrated production: Upgrade fermentationderived salts to ketones and then to alcohols.
• Continue to refine ASPEN model and costing.
Integrate pulp and carageenan mill interface into
model.
• Decision points: Final economics will determine
continued development.
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Summary
– Relevance: Demonstrating low hydrolysis and fermentation cost,
integrated bio and thermochemical platform.
– Approach: No breakthroughs needed. Focus on robust technology,
cheap feedstock, existing industries.
– Technical accomplishments: Demonstrated fermentation and
downstream unit ops—need to demonstrate integrated process.
– Success factors and challenges: Higher fermentation concentrations
needed.
– Technology transfer and future work: Working closely with OTFF.
FMC option looks less promising (low titer). Terrabon relationship
developing.
Since 2009 review: 2009 we had just started project (1-2 months in).
Have attained most milestones.
Have down-selected to final demonstration pathway.
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Additional Slides
37
Abbreviations used
•Ac: Acetate
•CBP: Consolidated bioprocessing
•CKA: carboxylates-ketones-alcohols
•CEA: carboxylates-esters-alcohols
•CHEA: carboxylates-acids-esters-alcohols
•FT: Fischer Tropsch synthesis
•GMO: Genetically modified organism
•MYPP: DOE Multi year program plan
•OTFF: Old Town Fuel and Fiber—Kraft pulp mill
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Responses to
Previous Reviewers’ Comments
• Process complexity
– The hydrolysis and fermentation are very simple compared to
sterile cellulose fermentations
– Downstream processing is complex, but unit operations are
familiar and commercial (ex. hydrogenation)
– Our down selection chose the simplest pathway (ketones2alcohols)
• Feedstock and culture variability
– Feedstock is likely to be variable. Mixed culture is better than
pure cultures for adapting to different inputs.
– Operation in acidogenic phase is more stable than
methanogenic stage, so should be more stable than regular
AD.
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Publications and Presentations
Patent disclosure filed:
Removal of lignin and other contaminants from recycled liquid-liquid extraction solvent by means of contacting with
alkaline pulping liquors.
Publications:
Rakhi Baddam, M. Clayton Wheeler, G. Peter van Walsum. Anaerobic Fermentation of Hemicellulose Present in PrePulping Extracts of Northern Hardwoods to Carboxylic Acids. Proceedings of the AIChE annual meeting, Nashville TN,
November 2009.
Aymn Abdulrahman, Adriaan van Heiningen, M. Clayton Wheeler, G. Peter van Walsum. Acetic Acid Removal from
Pre-Pulping Wood Extract. Proceedings of the AIChE annual meeting, Nashville TN, November 2009.
Mohit, Keith Hurley, G. Peter van Walsum, M. Clayton Wheeler. Thermal conversion of carboxylate salts derived from
biomass fermentation to ketones. Proceedings of the AIChE annual meeting, Nashville TN, November 2009.
Abigail Engelberth, M. Clayton Wheeler, G. Peter van Walsum. Exploring Three Pathways to Convert a Hemi-Cellulose
Rich Pre-Pulping Extract Into Long-Chain Alcohols Via the MixAlco™ Process. Proceedings of the AIChE annual
Meeting, Salt Lake City, UT, November 2010..
Sampath Karunarathne, Clayton Wheeler, G. Peter van Walsum. Production of Carboxylic Acids From Acidogenic
Fermentation of Algefiber™ (Sea Weed Sludge) Using a Mixed Culture of Marine Microorganisms. Proceedings of the
AIChE annual Meeting, Salt Lake City, UT, November 2010.
40
Publications and Presentations cont’d
Presentations:
Rakhi Baddam, M. Clayton Wheeler, G. Peter van Walsum. Anaerobic Fermentation of Hemicellulose Present in Pre-Pulping
Extracts of Northern Hardwoods to Carboxylic Acids. AIChE annual meeting, Nashville TN, November 2009.
Aymn Abdulrahman, Adriaan van Heiningen, M. Clayton Wheeler, G. Peter van Walsum. Acetic Acid Removal from PrePulping Wood Extract. AIChE annual meeting, Nashville TN, November 2009.
Mohit, Keith Hurley, G. Peter van Walsum, M. Clayton Wheeler. Thermal conversion of carboxylate salts derived from
biomass fermentation to ketones. AIChE annual meeting, Nashville TN, November 2009.
Abigail Engelberth, M. Clayton Wheeler, G. Peter van Walsum. Alcohol Production from Pre Pulping Extracts: A modeling
Assessment. 32nd Annual Symposium on Biotechnology for Fuels and Chemicals, April 2010. Invited presentation.
Sampath Karunarathne, Clayton Wheeler and Peter Van Walsum. Production of Carboxylic Salts via Mixed Culture
Acidogenic Fermentation of Algefiber™ (Sea Weed Sludge) for Chemical Upgrading to Higher Alcohols Liquid Biofuel. 32 nd
Annual Symposium on Biotechnology for Fuels and Chemicals, April 2010.
Abigail. Engelberth, M. Clayton Wheeler, G. Peter van Walsum. Comparative economics and yields for mixed alcohols from
pre-pulping hemicellulose extracts via three MixAlcoTM pathways. 32nd Annual Symposium on Biotechnology for Fuels and
Chemicals, April 2010.
Abigail Engelberth, M. Clayton Wheeler, G. Peter van Walsum. Exploring Three Pathways to Convert a Hemi-Cellulose Rich
Pre-Pulping Extract Into Long-Chain Alcohols Via the MixAlco™ Process. AIChE annual Meeting, Salt Lake City, UT,
November 2010.
Sampath Karunarathne, Clayton Wheeler, G. Peter van Walsum. Production of Carboxylic Acids From Acidogenic
Fermentation of Algefiber™ (Sea Weed Sludge) Using a Mixed Culture of Marine Microorganisms. AIChE annual Meeting,
Salt Lake City, UT, November 2010.
Mohit Bhatia, Adriaan van Heiningen,G. Peter van Walsum, Clayton Wheeler. Kinetics and Mechanism for Acetone
Hydrogenation by Ru/Carbon. AIChE annual Meeting, Salt Lake City, UT, November 2010.
41