Post on 21-Jul-2020
transcript
FEEDSTOCK
DEVELOPMENT
Integrated Biomass Cropping Systems for Optimal Fuel Production and Ecosystem
Services. E. Trybula, P. Woodson, I. Chaubey, J. Volenec, R. Turco, R. Dierking, S. Brouder, Purdue Univ.
KNOWLEDGE GAP
To protect US food security, cellulosic bioenergy production has been
targeted to “marginal” lands. To date, “marginal” land productivity
potential and environmental consequences of cellulosic bioenergy
production remain largely unknown.
TECHNOLOGICAL INNOVATION
Ex. 1: Optimize nutrient cycling at watershed scales to deliver
maximum energy production with minimal air / water quality impacts.
Ex. 2: Optimize yield of bioenergy species under low soil test K
conditions in an effort to minimize K accumulation in biomass.
ADVANTAGES OVER EXISTING TECHNOLOGY
Ex. 1: Corn stover derived cellulosic biomass has long been
associated with significant environmental N loss. Theoretically NUE
Miscanthus g. and switchgrass may have reduced
environmental impacts and a better net energy balance.
Ex. 2: Plants can “luxury consume” soil K but high tissue K contents
reduce energy yield from pyrolytic conversion. Bioenergy
production of native perennials on marginal soils may increase
bio-oil yields without reducing crop biomass.
SIGNIFICANCE AND IMPACT
Ex. 1: Confirms that marginal lands that typically have low fertility
levels may be well-suited for production of cellulosic bioenergy
Ex. 2: Integration of biomass production / management with
conversion processes identifies management strategies that
positively impact system profitability.
•
M. g. yr 1 Ex. 1: N loss to H2O w/ perennials decreases following stand establishment
Ex. 2: Biomass drives ethanol yield; tissue K depresses bio-oil yield
High and low-throughput cell wall compositional analyses Nicholas Carpita, Dept. Botany & Plant Pathology, Purdue University, West Lafayette, IN 47907
KNOWLEDGE GAP
The structural complexity of plant cell walls, the
principal component of lignocellulosic biomass, requires
constant improvement in methods for carbohydrate and
lignin analyses
TECHNOLOGICAL INNOVATION
My lab has over thirty years experience in analysis of
cell wall polymer composition, dynamics, and
biosynthesis. We are expert in derivatization and
determination of polysaccharide fine structure, and the
use of enzyme and antibody analysis, HPLC, HPAEC,
GC-MS, MALDI-TOF MS, ESI MS-MS, and FTIR
spectroscopy.
ADVANTAGES OVER EXISTING
TECHNOLOGY
• Combinatorial methods are approaching sequencing
capability
• High throughput analysis has been optimized to
screen large populations of genetic variants to identify
novel genes that impact biomass structure
SIGNIFICANCE AND IMPACT
• Cell wall analyses performed as collaboration or
service
• Workshop and training opportunities are available
Gene discovery depends critically on the
trait followed – saccharification screens
reveal different QTL than pyrolysis-based
screens
Lignin modification for improvement of biomass crops Clint Chapple, Department of Biochemistry, Purdue University
KNOWLEDGE GAP
How is lignin made and how can we gain control over the
process to improve bioenergy crops?
TECHNOLOGICAL INNOVATION
Nucleic acid and protein synthesis: template-dependent
Polysaccharide synthesis: enzyme specificity-directed
Lignin synthesis: dependent only on precursor supply
ADVANTAGES OVER EXISTING TECHNOLOGY
Cell wall modification technologies that are currently
available
Enhanced potential for replacement of petroleum-derived
specialty chemicals
SIGNIFICANCE AND IMPACT
Alteration in lignin cross-linking and architecture leads to
enhanced saccharification efficiency
Yield penalties can be mitigated
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Optimizing plant carbon partitioning for more efficient biofuel feedstocks Cliff Weil, Department of Agronomy, Whistler Center for Carbohydrate Research, Purdue University
KNOWLEDGE GAP Something that can fill the immediate need for an additional
biofuel feedstock that is not corn grain while cellulosic
technologies are being developed
TECHNOLOGICAL INNOVATION • Tropical, sugar-accumulating maize and sweet sorghum,
sensors to monitor optimal sugar levels for harvest
• Corn (for the share of feedstock that is corn) that is a
more effective starting material
ADVANTAGES OVER EXISTING TECHNOLOGY • Exceptional growth (15-18 ft.) in temperate climates,
delayed flowering, increased biomass, reduced seed
formation so requires little fertilizer, high levels of sugar in
the stalk
• Grows like typical maize in tropics (for seed)
• Biomass and sugar here, grow for seed in the tropics
SIGNIFICANCE AND IMPACT • More effective production now of biofuel from existing
feedstock
Sucrose FRET sensors attached to optrode fibers monitor sugar levels for harvest. (W. Frommer, Stanford, J. Rickus, BioMed Engineering)
QTL Analysis of Brix° for CML69
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typical corn
95% high
95% low
Genetic variation for how easily corn starch can be converted to glucose for fermentation
Groth et al (2008) BioEnergy Research
BIOMASS
CONVERSION
Green Tech America, Inc. The engine for cellulosic ethanol and green chemicals Professor Nancy W. Y. Ho, Purdue School of Chemical Engineering, Lab of Renewable Resources Engineering (LORRE)
TECHNOLOGICAL INNOVATION
• Green Tech America, Inc. (GTA) is a unique technology based
company, focused on commercialization of an innovative, yeast-
based cellulosic ethanol technology pioneered by Dr. Nancy Ho at
Purdue University.
• Fermentation of hydrolysates with our current Ho-Purdue
424A(LNH-ST) Saccharomyces yeast strain is showing in the
graph
ADVANTAGES OVER EXISTING TECHNOLOGY
• Our further improved yeast is ready for industry for producing
ethanol
• It is twice as efficient and can produce more than 10% ethanol in
less than 36 hrs.
SIGNIFICANCE AND IMPACT
• GTA will license its current Ho-Purdue yeast, 424A(LNH-ST), and
its further improved derivatives to any company that wishes to
produce cellulosic ethanol and provide technical assistance on
how to use the yeast.
www.greentechamerica.com
The glycerol is not produced by fermentation of the sugars but from the enzymes used for preparing the hydrolysates
Enzyme Mimics for Biomass Fractionation Nathan S. Mosier, Ag and Bio Engineering, Lab of Renewable Resources Engineering (LORRE), C3Bio
KNOWLEDGE GAP
Development of catalysts to interact with solid biomass
requires understanding of the mechanism and kinetics of
polysaccharide hydrolysis in situ. Catalyst systems must
be compatible with existing and likely future processes for
producing advanced biofuels
TECHNOLOGICAL INNOVATION
A proprietary pair of Lewis and Brösted acid catalysts is
able to rapidly hydrolyze and dehydrate cellulosic
polysaccharides to platform chemicals (furfural and HMF)
at high yields.
ADVANTAGES OVER EXISTING
TECHNOLOGY
• Unlike enzymes, catalysts are compatible with
processing conditions (temperatures, pressures) for
thermochemical processing.
• Superior catalyst selectivity compared to sulfuric acid
enables higher yields
SIGNIFICANCE AND IMPACT
• May enable use of celllulosic biomass as feedstock for
advanced biofuel production through thermochemical
processing
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CONVERSION
KNOWLEDGE GAP
• Conversion of entire biomass to liquid fuel
• Impact of process parameters on product distribution
• Primary vs. Secondary products
• Removal of oxygen → Upgrading energy content
• Thermochemical biomass reactor design
TECHNOLOGICAL INNOVATION
• Unique reactors
•Provide insight about primary and secondary products
•High pressures
• Development of hydrodeoxygenation catalysts for molecular
tailoring
• Integration with various hydrogen sources – Solutions from
now to future
ADVANTAGES OVER EXISTING TECHNOLOGY
SIGNIFICANCE AND IMPACT
• High carbon recoveries due to conversion of entire biomass
into liquid fuel
• Direct production of stable and high energy density fuels
• Flexible processing plant – All types of biomass
• High throughput due to low residence time
• Dispatchable, compact processing plants
High Yield Thermochemical Processes for Biomass to Liquid Fuel Prof. Rakesh Agrawal, Prof. Fabio Ribeiro, Prof. Nicholas Delgass, Department of Chemical Engineering, Purdue
Graduate Students
Fast-hydropyrolysis provides high energy efficiency
Hydrodeoxygenation (HDO) upgrades bio-oils to blend with petroleum products
Fuel grade oil (oxygen content <5wt.%)
Don’t just burn it…lignin as a valuable feedstock for high value chemicals Joseph J. Bozell, Center for Renewable Carbon, C3Bio, University of Tennessee
KNOWLEDGE GAP
Lignin is up to 25% of renewable carbon available in the
biorefinery but it still primarily burned as a co-firing fuel.
If we could get $1.00/lb, why are we settling for $0.05/lb?
TECHNOLOGICAL INNOVATION
Develop efficient catalytic transformations targeting structural
features common to all lignins and overcoming the large
number of structural features of lignin that frustrate attempts
to convert it to higher value materials
ADVANTAGES OVER EXISTING TECHNOLOGY
• Will ultimately employ minimal amounts of catalyst
• Uses environmentally benign O2 as the oxidant
• Can be modified to take place in water
• Exploits the structural features of lignin provided in the
biorefinery
SIGNIFICANCE AND IMPACT
• We are able to convert both primary types of aromatic
units in lignin
• The processes integrate well with lignin anticipated to be
available from actual biorefinery (organosolv and
extracted kraft)
• C3Bio collaborative work with Purdue has identified new
products resulting from lignin oxidation
• Our results have identified processes that position lignin
as a chemical feedstock instead of a low-value fuel,
opening new opportunities in biobased chemical
production
Navigating lignin’s structural minefield…
…affords access to low molecular weight aromatics:
b-O-4
pinoresinol (b-b)
phenylcoumaran (b-5)
4-O-5
coumarate
ferulate
guaiacyl
syringyl
Cleavage and Hydrodeoxygenation (HDO) of Lignin using Pd/Zn Synergistic Catalysis Mahdi M. Abu-Omar, Department of Chemistry, Purdue University
KNOWLEDGE GAP
Lignin makes up 25% of the plant’s mass but accounts for 40% of the energy content of biomass. It is recalcitrant.
TECHNOLOGICAL INNOVATION
A selective catalytic process that disassembles lignin and removes oxygen atoms under reasonably mild conditions.
ADVANTAGES OVER EXISTING TECHNOLOGY
• C-O bonds are deoxygenated while the aromatic C=C bonds are left unscathed.
• Mild conditions: 150C and 20 atm of H2.
• Catalyst is completely recyclable.
SIGNIFICANCE AND IMPACT
• Lignin can be utilized for its high energy aromatic fuel value.
• The synergy in catalysis between Zn and Pd is novel and can be exploited in other bio-conversion venues.
ANALYSIS
High Throughput Biomass Recalcitrance Analysis for Biofuels Melvin Tucker, National Renewable Energy Laboratory
KNOWLEDGE GAP
Biomass recalcitrance affects deconstruction of
biomass for biofuels and chemicals production.
Screen for thousands of samples needed.
High-throughput methods are critical for
comparing new developments in feedstocks.
TECHNOLOGICAL INNOVATION
Robotic systems allow for rapid screening of
hundreds of samples.
• Natural variants, and GMO biomass
feedstocks
ADVANTAGES OVER EXISTING
TECHNOLOGY
• Rapid screening: ~1500 samples/week
• Conventional screening ~dozen(s)/week
• Small sample size (~50 mg)
• Results in 1 week
• HTP Solids Compositional Analysis helps
explain recalcitrance
SIGNIFICANCE AND IMPACT
• Compare variants, environmental factors,
GMO’s
• Guide research to decrease biofuels costs
• Ultimately correlate plant cell wall changes
to biofuels conversion costs
Stack
Plates
Pretreat
Load
Plates
Add
Catalyst
and Seal
Disassemble,
add buffer,
enzymes, Seal,
Incubate
Enzyme
Mediated
Sugar
Detection
Robotic Systems
Enable High Throughput
Mass Spectrometric Characterization of Unknown Lignin Degradation Products Hilkka Kenttämaa Department of Chemistry, Purdue University
KNOWLEDGE GAP Conversion of lignin to useful chemicals requires the ability to identify
previously unknown lignin degradation products in complex mixtures.
TECHNOLOGICAL INNOVATION Reversed-phase HPLC coupled with NaOH doped electrospray
ionization (ESI) and multiple-stage high-resolution tandem mass
spectrometry provides MWs and a variety of fragmentation data for
unknown lignin degradation products directly in mixtures.
The interpretation of the data requires a thorough understanding of
the fragmentation pathways of deprotonated lignin degradation
products. We have examined the fragmentation patterns of almost
50 model anions and are in the process of developing a
fragmentation library to facilitate these analyses.
ADVANTAGES OVER EXISTING TECHNOLOGY • No HPLC methods existed for separation of lignin related molecules
that are compatible with NaOH doped ESI, the best ionization
method
• The fragmentation patterns of anions derived from molecules
related to lignin are poorly understood
SIGNIFICANCE AND IMPACT Unknown lignin degradation products can be identified directly in
mixtures.
Reversed-phase HPLC of
Organosolv Oak Lignin
Time
Ammonium formate buffer
Zorbax SB-Phenyl column
Reversed-phase HPLC of A Known Mixture
One of the
identified
molecules
Time
UTILIZATION
Biodiesel Refining via Molecular Clathration Bernard Tao, Department of Agricultural and Biological Engineering, Purdue University
KNOWLEDGE GAP Developing consistent quality, differentiated fuel products requires an efficient refining process. Due to the wide variety of source material compositions in biodiesel production (animal fats, numerous plant oils), fuel production suffers from inconsistent quality. This is particularly problematic at low temperatures when biodiesel fuels can crystallize/gel, resulting in storage, pumping, and fuel line blockages. Most biodiesel fuels start to crystallize/gel at around 32oF.
TECHNOLOGICAL INNOVATION This work describes a novel, simple refining process for biodiesel-based fuels using molecular clathration to produce biodiesel fuels with cloud point down to - 55 oF.
ADVANTAGES OVER EXISTING TECHNOLOGY Production of biodiesel fuels with cloud points from +40oF to
-55oF
Can refine blend mixtures from a variety of sources
Operates at room temperature
Can be integrated into existing biodiesel plants
SIGNIFICANCE AND IMPACT Overcomes cold weather limitation of biodiesel fuels
Provides opportunities to produce differentiated products for fuel and chemical applications
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Thermodynamic modeling of
cloud point of ternary FAME
mixtures , data (points) vs.
model (colored surface)
ln ln lnR i
i ki k k
k
-
' 'ln 1 ln 5 1 lnC i ii i i i
i i
V VV V q
F F
- - -
ln ln ln lnC R
i i i ix
Technology has been shown
to be effective by
demonstration under
extreme cold conditions
(north of arctic circle)
Experimental
Curve Bi2O
3
Experimental
Curve
Fitted Curve
Pt
PtO2
KNOWLEDGE GAP
High cost to purify crude glycerol to
refined grade (99.5%) using
traditional distillation
Impurities in crude glycerol affect
selective oxidation catalyst
TECHNOLOGICAL INNOVATION
Convert crude glycerol to purified
grade (95%) in an economic way
and use it directly in selective
oxidation
ADVANTAGES OVER EXISTING
TECHNOLOGY
Catalyst: 3% Pt-0.6% Bi /C Metal particle size (TEM): 4.5 nm
Surface concentration (XPS):
7.7% Pt, 3.6% Bi
Conversion: 80%, Yield: 48% Conditions: 80°C, 30 psig, pH: 2,
1M glycerol in water
Kinetics model shows good fit SIGNIFICANCE AND IMPACT
Utilization of byproduct glycerol
enhances the economic viability of
biodiesel production
Purification
HO OH
OH
HO
OH
HO OH
O
HO
OH
OH
HO
OH
O
OH
OH
O
OH
O
O
OH
OH
O
OO
O OO
Glycerol
(GLY)
Dihydroxyacetone(DHA)
Glyceraldehyde
(GLA)
Hydroxypyruvic Acid(HPA)
Glyceric Acid(GCA)
Tartronic Acid
(TTA)
Glyoxalic Acid(GOX)
Oxalic Acid
(OXA)
O C
Carbon Dioxide
(CO2)
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O
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107 9
OH
W. Hu, D. Knight, B. Lowry and A. Varma, I&EC Res, 49 (2010), 10876-10882 W. Hu, B. Lowry and A. Varma, Appl Catal B, 106 (2011), 123-132 R. Banavali, R. Hanlon and A. Schultz, Patent No. US 20090048472A1
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Biodiesel Production Glycerol Price Trend
+Sulfuric acid
Methyl esters
Salt
Acidification
Purified Glycerol
Glycerol
Phase separation
Neutralization & distillation
TEM
Bi
Pt
XP
S
Kin
etic
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Glycerol Oxidation Network
New Utilization: ~$20/lb Dihydroxyacetone (DHA)
Crude glycerol
Catalytic Upgrading of Bioproducts: Selective Oxidation of Glycerol Arvind Varma, School of Chemical Engineering, Purdue University
Model-Based Closed-Loop Control to Enable Fuel-Flexibility in IC Engines Greg Shaver, Associate Professor of Mechanical Engineering, Purdue University
KNOWLEDGE GAP
Alternative fuels can provide significant benefit,
however variation in feedstock or blend ratio will
cause non-optimal changes to the stock engine
behavior – example: up to a ~35% increase in NOx
emissions, and up to 20% increase in fuel
consumption, with biodiesel in diesel engines.
TECHNOLOGICAL INNOVATION
Closed-loop control to estimate and accommodate
variations in biodiesel feedstock and blend ratio.
ADVANTAGES OVER EXISTING
TECHNOLOGY
• Model-based and generalizable, so strategy can
work in any diesel engine
• Does not require additional engine calibration for
different blend ratios and feedstocks
• Utilizes stock engine sensors
SIGNIFICANCE AND IMPACT
• Allows the clean and efficient use of biodiesel
• Empowers end user to make decision about what
fuel to use
Air Transport Institute for Environmental Sustainability – AirTIES Denver Lopp, Department of Aviation Technology, Purdue University
KNOWLEDGE GAP
The coordinating structure necessary to bring new fuels from the
field and the laboratory to sustainable implementation is missing.
The means by which to quickly feedback information from end
users and policy makers to basic fuel researchers is also absent.
TECHNOLOGICAL INNOVATION
AirTIES provides the overarching infrastructure and organization
that enables basic researchers to collaborate toward the goal of
true implementation.
ADVANTAGES OVER EXISTING TECHNOLOGY
• AirTIES creates the coordinating link to academic researchers,
industry partners, end users, and the regulating bodies.
• AirTIES provides in-depth knowledge of fuel operational
requirements, FAA regulations, and endpoint testing of fuels for
drop-in quality.
SIGNIFICANCE AND IMPACT
• Through AirTIES, your organization gains the leverage necessary
to collaborate on large scale field-to-fly projects..
• With the practical focus of AirTIES, real time feedback of new fuel
performance is accelerated.
AirTIES Co-directors Denver Lopp & David L. Stanley
Through the AirTIES Research Center, the capabilities required to develop aviation drop-in fuels at Purdue University exist….
…AirTIES can address
the practical issues for implementation
National Test Facility for Fuels and Propulsion - NaTeF David L. Stanley, Aviation Technology, Purdue University
KNOWLEDGE GAP The operational and fit-for-purpose knowledge and research
capabilities for new fuels is not currently available in one
academic setting.
TECHNOLOGICAL INNOVATION NaTeF has the capabilities to conduct turbine and piston
engine testing, including exhaust emissions, and is equipped
to study the effects of new fuels on materials and
components.
ADVANTAGES OVER EXISTING TECHNOLOGY
• Provides fit-for-purpose and operational capabilities under
one roof.
• Specific test work may be contracted to analyze and
characterize fuel under development
• In consideration of both the available quantities and cost of
test fuels, NaTeF engines available for test operations are
relatively small while being representative of current day
technology.
SIGNIFICANCE AND IMPACT • The principals of NaTeF are deeply engaged in the overall
effort to develop new aviation fuels. This positions the
NaTeF organization advantageously to provide relevant
feedback of research and test findings to those developing
the new fuel processes and the feedstock technology.
From component and materials testing …
…through engine operation and emissions analysis to…
..flight and full implementation
NaTeF capabilities to serve your needs
Principals: D. L. Stanley, J.M. Thom, D. Lopp
Cellulose Nanomaterials: A Sustainable Building Block for Advanced Composites Robert Moon: USDA-Forest Service-Forest Products Laboratory, & Purdue University
KNOWLEDGE GAP
There is a Need for improved composite processing methodologies
of cellulose nanomaterials (CN) that exploit their unique properties
(thermal, mechanical, barrier, self-assembly) for use in industrially
relevant configurations: films, fibers, foams, network structures, etc.
TECHNOLOGICAL INNOVATION
Development program on fundamental to applied research on CNs:
• Characterization
• Surface modification (nanoparticles for new functionality)
• Predictive modeling for composite design
• Composite processing: fibers, films and spheres
• Hierarchical designed composite structures
ADVANTAGES OVER EXISTING TECHNOLOGY
• Sustainable Nanoparticle, low EHS impact
• High mechanical properties & Self-assembly (unique composites)
• Surface modification for new functionality
SIGNIFICANCE AND IMPACT
• CN are a potential product stream from biofuels
• Used in high value products
Nanocrystals Functionalization
Continuous Fibers Spheres
Films: Filter/Barrier
PURDUE
BIOENERGY
Tap into the expertise of 80 faculty working on the biomass-to-biofuels pipeline Maureen McCann, Purdue University
KNOWLEDGE GAP
Academic and industrial research often operate on
different timescales with differently-configured teams
and with different types of deliverables.
Communication on the focus, development and
application of discoveries needs to occur in both
directions
TECHNOLOGICAL INNOVATION
80 faculty form a cross-disciplinary “Brain Trust” for
bioenergy with over 1000 years of combined
experience at the cutting-edge of research
ADVANTAGES OVER EXISTING
TECHNOLOGY
User-friendly!
SIGNIFICANCE AND IMPACT
Committed to help build the new bioeconomy
together
Contact: mmccann@purdue.edu
“Purdue’s land-grant mission puts our scientists in a
position to use their knowledge for the public’s benefit”
Purdue Acting President, Timothy Sands