FEEDSTOCK - Purdue University · High Throughput Biomass Recalcitrance Analysis for Biofuels Melvin Tucker, National Renewable Energy Laboratory KNOWLEDGE GAP Biomass recalcitrance

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


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


• 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?


Nucleic acid and protein synthesis: template-dependent

Polysaccharide synthesis: enzyme specificity-directed

Lignin synthesis: dependent only on precursor supply


Cell wall modification technologies that are currently

available

Enhanced potential for replacement of petroleum-derived

specialty chemicals


Alteration in lignin cross-linking and architecture leads to

enhanced saccharification efficiency

Yield penalties can be mitigated

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glu

cose

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ease

(%

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time (hrs)

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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1.2

1.4

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min

A5

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uc

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su

ga

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HI YIELD

NORMALSIBStypical corn

95% high

95% low

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RAPIDMUTANT

NORMALSIBS

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)


• 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


• 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.


• 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


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.


TECHNOLOGY

• Unlike enzymes, catalysts are compatible with

processing conditions (temperatures, pressures) for

thermochemical processing.

• Superior catalyst selectivity compared to sulfuric acid

enables higher yields


• May enable use of celllulosic biomass as feedstock for

advanced biofuel production through thermochemical

processing

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HMF

Ff

DIRECT

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


• 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



• 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?


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


• 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


• 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.


A selective catalytic process that disassembles lignin and removes oxygen atoms under reasonably mild conditions.


• 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.


• 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.


Robotic systems allow for rapid screening of

hundreds of samples.

• Natural variants, and GMO biomass

feedstocks


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


• 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


Convert crude glycerol to purified

grade (95%) in an economic way

and use it directly in selective

oxidation


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)

1

2

3

5

6

4

O

8

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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Vegetable

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Oi

ll l

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

s

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.


Closed-loop control to estimate and accommodate

variations in biodiesel feedstock and blend ratio.


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


• 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.


AirTIES provides the overarching infrastructure and organization

that enables basic researchers to collaborate toward the goal of

true implementation.


• 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.


• 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

http://upload.wikimedia.org/wikipedia/commons/2/29/PanicumVirgatum.jpg

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.


• 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.


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


• Sustainable Nanoparticle, low EHS impact

• High mechanical properties & Self-assembly (unique composites)

• Surface modification for new functionality


• 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


80 faculty form a cross-disciplinary “Brain Trust” for

bioenergy with over 1000 years of combined

experience at the cutting-edge of research


TECHNOLOGY

User-friendly!


Committed to help build the new bioeconomy

together

Contact: [email protected]

“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

Documents

FEEDSTOCK - Purdue University · High Throughput Biomass Recalcitrance Analysis for Biofuels Melvin Tucker, National Renewable Energy Laboratory KNOWLEDGE GAP Biomass recalcitrance