Transcript 2005 OBP Bi-Annual Peer Review Project Presentation Template

2005 OBP Biennial Peer Review
Processing Integration
Dan Schell
Biochemical Platform
November 15, 2005
Project Goals and Objectives
• Investigate integrated processing to reduce
risk of industry-led efforts to commercialize
biomass refining technology
• Improve understanding of process chemistry and
integrated performance
• Identify problems and showstopper issues
• Develop integrated testing methods, tools, and
capabilities
Overview
Work Objective
• Barriers
• Process integration
• Pathways
• Agricultural Residues
• Energy Crops
Budget
Partners
• USDA/Universities
• Subcontracts
• Baylor University
• Hauser Laboratories
• Hazen Research
$2.5
$2.0
Funding $1.5
($M)
$1.0
$0.5
$0.0
FY04
FY05
FY06
(planned)
Platform Fit with Pathways
Feedstock
R&D
Sugars
R&D
Thermochemical
R&D
Products
R&D (from)
Integrated
Biorefineries
Program Outputs
Corn Wet Mill
Improvements
(Corn)
•Residual Starch Conversion
•Fiber Conversion
Corn Dry Mill
Improvements
(Corn, Grain)
•Residual Starch Conversion
•Fiber Conversion
•Milled Grain Fractionation
Systems-level
demonstration and
validation by 2009
Systems-level
demonstration and
validation by 2012
Agricultural
Residue Processing
(Corn Stover, Wheat
Straw, Rice Straw)
•Biomass Fractionation
•Sugars Production
Systems-level
demonstration and
validation by TBD
Energy Crops
(Perennial Grasses,
Woody Crops)
•Biomass Fractionation
•Sugars Production
Systems-level
demonstration and
validation by TBD
Pulp and Paper Mill
Improvements
(Mill Wastes, Wood)
Element
Strategic
Goals
Systems-level
demonstration and
validation by 2010
•New Fractionation Process
for hemiicellulose removal
Sustainably supply
biomass to
biorefineries
Low-cost sugars from
lignocellulosic
biomass
Chemical building
blocks from
lignocellulosic
biomass
Fuels, chemicals and
power from bio-based
sugars and chemical
building blocks
Biomass Program
Strategic Goal
Cost-competitive
biorefinery technologies
for the nation’s
transportation, chemical
and power industries
Approach
• Focus on integrated performance testing using a model
feedstock (corn stover) and a baseline process based on
thermochemical dilute acid pretreatment followed by
enzymatic cellulose hydrolysis
• Directly addresses process integration barrier
• Working to understand current performance and demonstrate
progress towards the sugar platform cost target, while
improving integrated testing capabilities and identifying
showstopper issues
• Measure performance relative to technical targets established
by economic analysis
Work Breakdown Structure
2.0
Biochemical Platform
2.1
Pretreatment and
Enzymatic Hydrolysis
2.1.1
Pretreatment and
Enzymatic Hydrolysis
2.1.1.1
CAFI 2 Support
2.1.1.2
Feedstock Qualification
2.1.1.2.1
Extended Fiber
Pretreatment
2.2
Feedstock-Biochemical
Interface
2.2.4
Preprocessing and
Storage Systems
Development/Qualification
2.2.5
Preprocessing Feedstock
Supply
2.3
Process Integration
2.3.1
Processing Integration
7.04.2.GO41221
Rheology and
CFD Modeling
2.4.1
Targeted Conversion
Research
2.4.1.1
Chemical Conversion
Fundamentals
2.3.2
Integrated Processing
2.4.2
Biological Processing
Fundamentals
2.3.3
Analytical Methods
2.4.3
Plant Cell Wall
Deconstruction
2.4.4
BSCL and Genomics
2.1.1.4
Enzymatic Hydrolysis
2.1.3
Integration of Leading
Biomass Pretreatment
Technologies (CAFI 2)
2.5
Biochemical Platform
Analysis
2.3.1
Feedstock Variability
2.1.1.3
Forest Biorefinery
2.1.1.5
Exploratory Pretreatment
2.4
Targeted Conversion
NREL
Academia
Industry
Earmark
2.4.4
Industrial Membrane
Filtration & Short Bed
Fractal Separation
Project Structure
Processing Integration
Integrated
Processing
Feedstock
Variability
Analytical Methods
 Test integrated performance
 High solids operation
 Assess advanced enzymes
 Develop and improve
methods
 Distribute methods
 Understand breath
and impacts of
feedstock variability
Barriers
Commercial Success Barriers
Price of Sugars from “Cellulosic” Biomass
Major General Barriers
Feedstock Cost
Sugars Composition
Sugars Yield
Conversion Rate
Sugars Quality
Capital Investment
R&D Technical Barriers
Feedstock-Sugars Interface
Biomass Pretreatment
Enzymatic Hydrolysis
Sugars Processing
Process Integration
Feedstock Variability
Stover Compositional Database
• Comparison of commercial (FY02)
and non-commercial (FY05) corn
hybrids
• The addition of non-commercial
hybrids in the sample set has
expanded the range of cellulose
and xylan compositions
Feedstock Variability
Stover Compositional Database
• Lignin content varies only
modestly between commercial
and non-commercial hybrids
• Further data mining is
necessary to answer questions
such as, “How does
carbohydrate content correlate
with lignin content and/or other
components?”
• We believe the corn stover
database now captures the
extent of feedstock
compositional variability
• No additional survey work is
planned for corn stover
Understanding Risks
Composition
used in 2002
Design Report
2,000 Tr ials
Fore cas t: MESP
Fr eque ncy Chart
8 Outlier s
.016
32
.012
24
.008
16
.004
8
.000
0
$0.9987
$1.0888
$1.1789
$1.2689
$1.3590
Analytical Methods
Identifying the Problems
Other Hemi.
Acetyl
Ash
Corn Stover
Cellulose
Xylan
Lignin
Extractives
Sucrose
Uronic
Acid
Protein
Pretreatment
Pretreated Corn Stover Solids
60.3%
1.9%
Liquor
Furfural
30.7%
6.6%
3.6%
2.4%
Glucose
Xylose
Other
Improving HPLC-Based Sugar Analysis
Implementing Solutions
Old
BioRad HPX-87P, RI Detector
New
BioRad HPX-87P, RI Detector
Shodex SP-0810, RI Detector
• Improved baseline
resolution produces
more accurate and
reproducible
compositional data
• Still need reliable
method to measure
fructose in
hydrolysates
Improving Lignin Analysis
• Current wet chemical methods for lignin determination
• Behavior-based definition: Lignin = Acid Insoluble Residue
• Valid assumption for wood
• Invalid for agricultural residues and herbaceous materials
• Interferences from protein, carbohydrate degradation products,
extractives, and silica
• Unacceptably high error, ± ~25%
• Application of method gives inaccurate mass closures
• Poor correlation with spectra limits ability to develop
reliable rapid analysis method
Strategies for Improving Lignin Analysis
• Investigate alternative analytical methods for measuring
lignin such as those now used in the food sciences
• Improve understanding of the fate of protein and
extractives and their effects on lignin measurements
• Develop functional group-based lignin determination
• Use this new information to develop more accurate
spectroscopic-based rapid analysis methods for lignin
Understanding Extractives
• Subcontract issued to Baylor University (work began in
May 2005)
• Goal
• Identify 90% or more of the extractives and develop analytical methods
for measuring the concentrations of extractive components
Progress
• Have identified several
major constituents that
comprise most of the
extractives
• Currently developing
analytical methods for
these materials
Protein
Ash
Sucrose
18
16
14
(%)
Weight
Dry
Percent
dry weight

Kramer Feedstock
Unknown
12
7.0
7.0
7.9
5.9
6.0
1.4
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1.6
1.7
6.5
6.7
6.7
6.8
6.8
0.05
0.10
2
4
6
5.9
10
8
6
4
3.5
1.3
1.4
1.0
1.0
5.6
2
4.1
0
0.00
0.04
Hours in water extraction
Hour in Water Extraction
Unknown
Protein
Ash
Sucrose
Improving Rapid Analysis Methods
• Real-time methods are needed to support commercial
biorefinery operation
• Process control and optimization
• Improved efficiency for in-house and CRADA research
projects
• Reduces cost
• Increases number of samples/experiments that can be run
On-line Testing and Validation
Direct light
spectrometer
installed in pilot plant
Controls
Spectrometer
Optics over conveyor weigh belt
Moving Toward Deployment
50
Glucan
Xylan
Lignin
Protein
NIR Model Predicted Values (%)
45
40
• Methods have been
transferred to
Vision® Software
2
R = 0.84
35
30
25
• Provides a more
flexible and robust
platform for using
these methods on
other instruments
R2 = 0.87
R2 = 0.87
20
15
10
5
R2 = 0.79
0
0
5
10
15
20
25
30
35
Wet Chemistry Values (%)
40
45
50
Drive Towards High Solids Operation
Pretreatment
• Significant reduction in
minimum ethanol selling
price (MESP) can be
realized through reduced
operating and capital costs
$1.30
$1.20
$1.10
$1.00
15
20
25
30
35
40
Reactor Solids Loading (wt.%)
• High solids operation
significantly increases
sugar concentrations
• Pretreatment is
possible at 30% solids
loading without
significant yield loss
• Still need to improve
hemicellulosic sugar
yields
180
Monomeric xylose
Sugar Concentration (g/L)
MESP ($/gal)
$1.40
160
Total xylose
140
Total sugars*
120
100
80
60
40
20
15
20
25
30
Solids Loading (wt.%)
35
40
Drive Towards High Solids Operation
Enzymatic Cellulose Hydrolysis
$1.12
MESP ($/gal)
$1.10
• Further cost reductions are
possible with high solids
enzymatic cellulose
saccharification
$1.08
$1.06
$1.04
$1.02
$1.00
$0.98
22%
24%
26%
28%
30%
Solids to Saccharification (wt. %)
• Inhibition by sugars and mass
transfer limitations become
important issues at high solid
concentrations
32%
Genencor Spezyme (40 mg/g)
100%
140
90%
120
80%
100
Total glucose
70%
80
60%
60
50%
40
Glucose generated by
enzymatic hydrolysis
40%
Washed Solids
20
Whole Slurry
30%
5%
10%
15%
20%
25%
Insoluble Solids (w/w)
30%
0
35%
Glucose Concentration (g/L)
20%
7-Day Cellulose Conversion
$0.96
18%
Understanding Process Relevant Performance
Recycle Water Studies
Hydrolysate liquor conditioned by overliming and
then fermented using xylose-utilizing Z. mobilis
100
90
Glucose Conversion
Xylose Conversion
Yield or Conversion (%)
80
Ethanol Yield
70
• Performance is
significantly affected
at modest solids
concentrations and
recycle water ratios
60
• Inhibitors besides
acetic acid are
responsible for poor
performance
50
40
30
20
10
0
15% Solids
1 Ratio
10% Recycle
15% Solids
2
25% Recycle
Ratio
20% Solids
3 Ratio
10% Recycle
20% Solids
4
25% Recycle
Ratio
Understanding Process Relevant Performance
Integrated Performance Testing
Water
70
Lime
Partially washed
solids
recombined with
liquor
conditioned by
overliming
Liquid
Lime Mixing
Solids
Acidification
S/L Separation
Cellulose hydrolysis with
Genencor Speyzme (40 mg/g,
45C, pH 4.8) and fermentation
with Z. mobilis (35C, pH 5.0)
Cells
Acid
Gypsum
Mixing
Water
Saccharification
Enzyme
Concentration (g/L)
S/L Separation
Cellobiose
Glucose
Xylose
Ethanol
60
50
40
30
20
10
0
0
1
2
3
Time (d)
Fermentation
Nutrients
Ethanol
 Ethanol yields are low due to
unutilized glucose (25% left as
mono- and oligo-glucose) and
incomplete xylose utilization
 Integrated processing illustrates
limitations of current ethanologens
100
Yield or Conversion (%)
Pretreated Corn
Stover
90
80
70
60
50
40
30
20
10
0
Cellulose
Conversion
Xylose Consumed
Ethanol Yield
4
Performance Summary
2012 Target
(FY06
Budget)
2020
Market
Target
$4.13
$1.73
$1.07
$53
$45
$30
2002
Latest Test
Estimate
Results
Minimum Ethanol Selling Price
Feedstock
Feedstock Cost ($/dry ton)
Pretreatment
Solids Loading (wt%)
Xylan to Xylose
Xylan to Degradation Products
Conditioning
Xylose Sugar Loss
Glucose Sugar Loss
Enzymes
Enzyme Contribution ($/gal EtOH)
Saccharification & Fermentation
Total Solids Loading (wt%)
Combined Saccharification & Fermentation Time (d)
Overall Cellulose to Ethanol
Xylose to Ethanol
Minor Sugars to Ethanol
19%
68%
16%
30%
70-75%
8%
30%
90%
5%
30%
90%
5%
13%
12%
13%
12%
13%
12%
0%
0%
$0.22
$0.10
20%
7
86%
85%
0%
20%
3
86%
85%
85%
$1.61
13%
10
86%
76%
0%
20%
7
~75-80%
~25-50%
0%
Interim Stage Gate Overview
• Processing Integration Task Interim Stage Gate Review
• Stage B project
• Meeting held September 15, 2004
• Reviewers:
• Rob Anex (Iowa State University)
• Susan Hennessey (Dupont)
• Dale Monceaux (Katzen International)
• Quang Nguyen (Abengoa Bioenergy)
• Amy Miranda (DOE OBP)
• Jim Spaeth (DOE GO)
• Stan Bower (NREL)
Review Meeting Feedback
• Feedback received in four categories
• Large view issues
• Feedstock variability
• Analytical methods
• Integrated processing
Large View Issues
• The answer to many questions raised at the meeting was
that the activity resides in a different part of the Biomass
Program. However, systems solutions are required and
fragmentation of the overall effort into manageable sized
projects should not be allowed to silo the Program.
• There is no capital cost reduction target. NREL has
capital cost modeled, but inclusion of depreciation in the
MESP is not an adequate reflection of the barrier of
raising large capital. Capital reduction should be targeted
and tracked.
Feedstock Variability
• Efforts to piggyback on work being performed by the USDA and others
are good and should continue. You not only obtain well-characterized
samples at very low cost, but add substantial value to the studies being
performed by the researchers that provide the samples.
• We have continued this effort and over 200 new samples were acquired this year.
• Need to extend the variability studies to determine the impact of corn
stover variability on pretreatability (sugar yields), enzymatic cellulose
hydrolysis, and fermentability. There is a theoretical impact based on
carbohydrate content; how does it play out in final yields?
• We acquired several new large lots of corn stover that enable this work to proceed.
• Need to expand interface to other areas to allow studies of impact of
storage on feedstock composition, pretreatability, enzymatic cellulose
hydrolysis and fermentability.
• This work should be accomplished in the Feedstock-Biochemical Interface Area with
NREL providing bioconversion processing and analytical support.
Analytical Methods
• Develop on-line monitoring capability, especially for monitoring the
enzymatic saccharification reactor. Enzymatic saccharification is the
least understood of all the unit operations. The second area for
application of on-line monitoring would be in the fermentation reactor.
• Moved forward last year with on-line feedstock monitoring
• Other on-line monitoring development activities planned in future years
• There is little point in trying to develop process control strategies
based on on-line monitoring. There is no clear target for what is being
controlled and the control parameters will be process specific.
• Will not be done
• Functional group based lignin determinations is an area that should be
pursued, as well as work to characterize chemical changes to lignin
during and after pretreatment.
• Work planned in future years, probably via subcontract
Integrated Processing
• Perform thin studies that indicate problems and generate representative
results, that is, determine the problem, skip the solution. In-depth
studies that provide solutions are not justified because they will not be
generally applicable across a range of processes.
• Integrated process testing this year identified problems with high recycle water use
and with achieving good C5 sugar conversion.
• Enzymatic saccharification time is too long and needs to be characterized with
unwashed materials, that is, with background components (non-sugars) present
during enzymatic saccharification. Determine components that are inhibitory to
the cellulases (e.g., Maillard reaction products). Perform spiking studies to
determine what chemicals inhibit cellulases.
• Initial performance results in the presence of background sugars were presented.
New work going forward in the Pretreatment & Enzymatic Hydrolysis Task.
• Move forward efforts to characterize waste streams; three years away is
too late for those studies to be useful. Also generate real data on thin
stillage evaporate. What is in it besides water? Are any of the streams or
residues appropriate for putting back on the fields?
• Initial effort began this year to understand effect of recycle water on process
performance.
Integrated Processing
• Examining the gypsum question is low priority and should not be
undertaken. The fact that gypsum is an issue was an important
recognition, but the solution will be unique to each process and
approaches for handling gypsum are well understood from existing
industries.
• Work in this area was eliminated
• Advance efforts to understand new feedstocks and new pretreatments.
• Work began this year in the Pretreatment & Enzymatic Hydrolysis Task
• Interface Question: What is the root cause of biomass recalcitrance?
Generate residue that can be characterized, both compositionally and
structurally.
• This work resides in Targeted Conversion Research Task
Future Work
Feedstock Variability
SWITCHGRASS
• Survey of corn stover composition finished
• Maintain collaborations with USDA and
academic institutions performing field
studies to advance understanding of the
effect of environmental and genetic factors
on stover composition, primarily through our
expertise with rapid biomass analysis
techniques
• Transition feedstock procurement activities
to Idaho National Laboratory (INL)
• Develop collaborations with INL and other
laboratories to explore variability issues for
other promising feedstocks (e.g.,
switchgrass)
Future Work
Analytical Methods
• Improve rapid analysis methods hand-in-hand with improved wet
chemical methods
• Direct Light spectrometer for feedstocks
• Demonstrate ability to measure stover composition on-line (FY06)
• Fourier Transform Infrared (FTIR) in-line probe for pretreated slurries
and solids (FY07)
• Near Infrared (NIR) opti-probe for fermentation broths (FY08)
• Improve wet chemical methods for agricultural and herbaceous
materials (FY07 and beyond)
• Lignin, extractives
• Automation
• Distribute and publish new methods as developed (ongoing)
• 2500 hits on EERE/Biomass web site accessing laboratory analytical
methods in last quarter of FY05
Future Work
Integrated Processing
• Determine effect of corn stover compositional and structural
variability on pretreatment hemicellulose hydrolysis yields and
enzymatic cellulose digestibility (FY06)
• Investigate integrated performance of new advanced enzyme
preparations from Genencor and Novozyme
• One new preparation will be tested this year (FY06)
• Other preparations will be tested in outyears (FY07 and beyond)
• In collaboration with the thermochemical platform, produce
representative lignin-rich process residues for thermochemical
conversion testing (FY06)
• In collaboration with the Feedstock-Biochemical Interface, determine
effect of wet storage on process performance (FY07 and beyond)
Future Work
Integrated Processing
• Improve hemicellulose conversion yields in dilute acid pretreatment
(FY07 and beyond)
• Collaborative effort across Biochemical Platform
• Continue to supply process materials to stakeholders, industry, and
universities (ongoing)
• In 2004 and 2005, we supplied over 100kg of raw stover and over 1500 kg
(wet) of pretreated stover to 5 industry stakeholders, 12 academic
institutions, and 2 government laboratories
End