progress in astm standards for biofuels · – composition difficult to control in feedstock ......
TRANSCRIPT
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Progress in ASTM Standards for Progress in ASTM Standards for BiofuelsBiofuels
Foster A AgblevorBiological Systems Engineering
Virginia Polytechnic Institute and State University, Blacksburg, VA 24061
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Outline of PresentationOutline of Presentation
l Introductionl Biomass conversion standardsl Analytical methodslManufacturing proceduresl Terminology
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E48.05 Biomass ConversionE48.05 Biomass Conversion
l Scope of work of subcommitteel The promotion of knowledge and the
development of standards (classifications, guides, practices, specifications, terminology, and test methods) for biomass conversion.
l Analytical standardsl Standard Reference Materials
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Why biomass standards?Why biomass standards?
l There are large compositional variations in biomass materials
l Biomass composition is affected by species, geography, season, harvesting and post harvest treatment
l Biomass components change easily during isolation, processing, and analysis
l Variation in analytical methods
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Why Biomass standards? Why Biomass standards?
lManufacturing processesl Standard operating proceduresl Safety, health, and environmental
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Feedstock ComparisonFeedstock Comparison
Portfolio of methods needed for each feedstock type
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POPLAR PINE CORN STOVER SUGAR CANEBAGASSE
CORN FIBER
Per
cen
t Dry
Wei
gh
t
starchfatcutinproteinashextractivesligninuronic acidsacetylarabinangalactanmannanxylanglucan
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Importance of Analysis in Importance of Analysis in Biomass UtilizationBiomass Utilization
Natural heterogeneity of biomass– Inherent property of biomass – Complex polymer matrix– Composition difficult to control in feedstock– Presents significant risk in process environment
Challenge for emerging industries– Understanding biomass properties is key to economic
viability – Complexity of biomass underestimated– Information needed to evaluate new processes
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Areas that need standardsAreas that need standardsl Chemical Characterization of Biomass Feedstocksl Chemical Characterization of Biomass-derived
Materialsl Sample preparationl Measurement of Chemical Constituents
– Moisture, Ash, Extractives, Sucrose, Structural Carbohydrates, Lignin, Protein
l Summative Mass Closure Analysis– Hardwoods– Softwoods– Agricultural Residues– Energy Crops– Pretreated biomass– Saccharification liquors– Fermentation systems
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Analytical StandardsAnalytical Standards
l Traditional standard analytical methods
l Rapid analytical methods
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Current standard methodsCurrent standard methods
lAll current methods are based on traditional analytical methodslDeveloped through round robin
process in the 1990sl17 Active Standards l10 Work Items
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Biomass standard methodsBiomass standard methods
l E1690-01 Standard Test Method for Determination of Ethanol Extractives in Biomass
l E1721-01 Standard Test Method for Determination of Acid-Insoluble Residue in Biomass
l E1755-01 Standard Test Method for Ash in Biomass
l E1756-01 Standard Test Method for Determination of Total Solids in Biomass
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Biomass standard methodsBiomass standard methods
l E1757-01 Standard Practice for Preparation of Biomass for Compositional Analysis
l E1758-01 Standard Test Method for Determination of Carbohydrates in Biomass by High Performance Liquid Chromatography
l E1821-01 Standard Test Method for Determination of Carbohydrates in Biomass by Gas Chromatography
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Current biomass standard Current biomass standard methods and guidesmethods and guides
l E1117-97(2006) Standard Practice for Design of Fuel-Alcohol Manufacturing Facilities
lE1344-90(2006) Standard Guide for Evaluation of Fuel Ethanol Manufacturing Facilities
l E1535-93(2006) Standard Test Method for Performance Evaluation of Anaerobic Digestion Systems
l E1358-97(2006) Standard Test Method for Determination of Moisture Content of Particulate Wood Fuels Using a Microwave Oven
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Current methodsCurrent methods
• E1534-93(2006) Standard Test Method for Determination of Ash Content of Particulate Wood Fuels
• E870-82(2006) Standard Test Methods for Analysis of Wood Fuels
l E871-82(2006) Standard Test Method for Moisture Analysis of Particulate Wood Fuels
l E872-82(2006) Standard Test Method for Volatile Matter in the Analysis of Particulate Wood Fuels
l E873-82(2006) Standard Test Method for Bulk Density of Densified Particulate Biomass Fuels
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New analytical methodsNew analytical methods
l NREL LAP methodsl Analysis of sugars (HPLC)l Ligninl Proteinsl Ashl Total solidsl Biomass preparationl Pretreatment liquors and solid residues
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Rapid analytical methodsRapid analytical methods
l Pyrolysis molecular beam methodsl Thermogravimetric methodsl Near Infrared (NIR) methodsl Pyrolysis GC/MS
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Advantages of Advantages of Rapid Biomass AnalysisRapid Biomass Analysisl Faster
– Minutes instead of days– Minimal sample preparation
l Cheaper– About $10 per sample – Compared to $800-$1,000 for wet
analysisl Better
– Calibrated using best methods– Less operator dependent
l Industrial Applications
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Rapid Analysis EssentialsRapid Analysis Essentialsl Calibration Samples
– 100 samples for robust model
l Chemical Characterization– Determines precision and accuracy of new method
l Rapid Technique– Determines speed and cost of new method
l Multivariate Analysis– Translates spectroscopic data into compositional
data
l QA/QC– Calibration checks– Sample screening
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Pyrolysis Molecular Beam mass Pyrolysis Molecular Beam mass spectrometryspectrometry
l High temperature processl Small sample size (<10 mg)l Reaction time <5 minl Coupled with multivariate statistical
analysisl Needs reference materials and traditional
wet chemical methods for calibration
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Molecular beam mass spectrometer
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Pyrolysis Molecular beam mass spectra of biomass
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Thermogravimetric method of Thermogravimetric method of analysisanalysis
l Small sample sizel Provides kinetic datal Provides partial compositional data
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Near Infrared (NIR) methodNear Infrared (NIR) method
l Near Infrared spectra of biomasslMultivatriate statistical analysisl Calibrate with traditional ASTM
standard methodsl Needs Standard Reference Materials
for calibration
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NIR Rapid Analysis of NIR Rapid Analysis of biomass Feedstock biomass Feedstock
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Percent dry weight by wet chemistry
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cen
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NIR
/PL
S
SucroseGlucanxylanLigninProteinSt_inorg
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Applications for Rapid Biomass Analysis
EthanolOther ProductsHeating ValueEthanol Production Capacity
HarvestManagement Purchase Blend
Milled Feed
Feedstock Process Product
Process Monitoring
On-lineFeed CharacterizationField
Characterization
Standing BiomassCharacterization
PretreatmentIntermediates
ResiduesStorage
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Rapid Analysis Field Rapid Analysis Field MethodsMethods
•Live plants•Non-destructive•Non-invasive•Seedlings to flowering plants•Genetic screening•Mobile NIR spectrometer•Fixed optics probe http://www.asdi.com
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Where do we go from here?Where do we go from here?
l Standardize the new wet chemical methodsl Standardize the new rapid analytical methodsl Conduct round robin tests on selected methods to
evaluate efficacy of the methodsl Convert some of the NREL LAP standards into
ASTM standardsl Form new working subcommittees to format new
standards for ballotingl
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Standard reference materials for Standard reference materials for pyrolysis oilspyrolysis oils
l There is a need to define terminologies for biomass pyrolysis oils (bio-oil, biocrude oil, pyrolysis oil, pyrodiesel)
l Define a standard characteristics of biomass pyrolysis oils ((density, viscosity, moisture, BTU (HHV), ash, sulfur, nitrogen, flash point etc))
l Develop standard analytical methods
AcknowledgementAcknowledgement
l Dr Bonnie Hames for the NIR material
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Thanks you!Thanks you!
lQuestions?
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Improving Research Improving Research More Samples More Samples -- More DataMore DataUS/DOE Corn Stover Feedstock
Assessment– Requires analysis of hundreds of samples
l Not possible using traditional methods – Too expensive by wet chemical methods
• $2,000/ sample x 500 samples = $1,000,000 – NIR/PLS
• $20/ sample x 500 samples = $10,000– Too slow by wet chemical methods
• Year to process 500 samples– NIR/PLS
• 3 days to process 500 samples
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Pretreatment MonitoringPretreatment MonitoringHybrid Poplar Model
(NREL Hardint8.eqa)– 45 Samples– 4 Factors– Glucan
l 42%-75% l SEV 1.4
– Lignin l 23%-51% l SEV 2.1
– Xylan l 0-7%l SEV 1.4
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Wt %
sample
sample
Hardwood Intermediates
xylanLigninglucan
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Saccharification MonitoringSaccharification Monitoringl Softwood Method
– Douglas Fir – White Fir– Ponderosa Pine
l 71 Samplesl Whole Trees
– Forest Thinnings– Bark, needles, branches
l 6 Principle Components
Softwood IntermediatesPredicted vs Measured
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1 2 3 4 5 6 7 8
sample
lignin (measured) lignin NIR glucan (measured) glucan NIR
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Cellulase Production Cellulase Production Monitoring Monitoring
Solkacel.eqa, 3 factors, 118 samplesSECV 7.1 cellmass, 21.0 spore count
Fermenter 1 Expt 50
-20.0
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0 24 48 72 97.5 121 144 168
time
spores*10^6 per mL
cellmass (wt %)
Solka-floc (wt%)
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Rapid Analysis Field Rapid Analysis Field MethodsMethods
•Live plants•Non-destructive•Non-invasive•Seedlings to flowering plants•Genetic screening•Mobile NIR spectrometer•Fixed optics probe http://www.asdi.com
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Biological Screening Biological Screening
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% xylan
normal inbreds 3160 3164A B
Possible cell wall mutations
Normal population
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Thank You. Questions?Thank You. Questions?For additional information…
Bonnie Hames, Ph.D.Manager of Chemistry
Acknowledgements:Ceres, IncThousand Oaks, CAwww.ceres-inc.com
U.S. Department of EnergyOffice of Biomass Programs
National Renewable Energy LabNational Bioenergy Center
www.nrel.gov
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ASTM InternationalASTM International
ASTM International 100 Barr Harbor DriveW. Conshohocken, PAwww.astm.org
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Histogram of MESPs for 735 Stover Compositions
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$1.00
$1.02
$1.04
$1.06
$1.08
$1.10
$1.12
$1.14
$1.16
$1.18
$1.20
$1.22
$1.24
$1.26
$1.28
$1.30
$1.32
MESP ($/gal)
Num
ber
of O
ccur
renc
es
MESP for stover composition used by Aden, et al, 2002.
Mean = $1.14Stdev = $0.06Range = $0.30
Impact of Rapid Biomass AnalysisOn Projected Economics
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Biomass CharacterizationBiomass Characterization
Standard Methods - ASTMStandard Materials - NISTValidation - IEA
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About ASTM InternationalAbout ASTM Internationall Organized in 1898l Independent, private sector, not-for-profit
organizationl Provides a management system and the
administrative framework for the development of voluntary, consensus standards and promotion of related knowledge
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Principles of ASTM Standards Principles of ASTM Standards DevelopmentDevelopment
l Openness and Balance– All who are interested or affected may join– One vote per voting interest; no one interest dominates
l Relevance– Stakeholders set standards development priorities and content– Each standard must be reviewed every five years; revision may
occur more frequently if needed
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Technical Committee Technical Committee OrganizationOrganization
l Technical Committees form to address specific industry subjects.
l Subcommittees are established to address subsets of specialized subject matter.
l Subcommittees organize their expertise into Task Groups to write standards.
Main Committee
Subcommittee.01
Subcommittee.02
Subcommittee.03
Task Group 1
Task Group 2
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Technical Committee OfficersTechnical Committee Officers
l Chairmanl Vice Chairmanl SecretarylMembership Secretaryl Subcommittee Chairmenl Task Group Chairmen
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E48 Scope of WorkE48 Scope of Work
The promotion of knowledge and the development of standards (classifications, guides, practices, specifications, terminology, and test methods) for biotechnology. The work of this Committeewill be coordinated with other ASTM Committees and other organizations having mutual interests
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ASTMASTM’’s Balloting Process s Balloting Process
TGTG
SOCIETYSOCIETY
MAINMAIN
SubcommitteeSubcommittee
Main CommitteeMain Committee60% return; 90% affirmative60% return; 90% affirmative
SubcommitteeSubcommittee60% return; 2/3 affirmative60% return; 2/3 affirmative
TG TG –– draft development;draft development;no formal ballotingno formal balloting
COSCOS Ensures due process is afforded to Ensures due process is afforded to all participantsall participants
Final level of approvalFinal level of approval
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Balance Balance and and
Voting vs. Non Voting Voting vs. Non Voting StatusStatus
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Producer
User&
General InterestASTM
Technical Committees are balanced. Technical Committees are balanced. No excess influence by any interest group.No excess influence by any interest group.
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Balance of InterestBalance of Interest
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Voting Rights Voting Rights -- Voting vs. Voting vs. NonNon--VotingVoting
l 1 official vote per interest (company)l All are welcome to participate in
technical discussionsl All members receive a ballot and are
eligible to vote on technical issuesl All negatives are considered the same
way
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Subcommittee BallotSubcommittee Ballot
lSubcommittee Ballot– New Standards– Major Revisions
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Six Resolutions of a Six Resolutions of a Negative VoteNegative Vote
l PersuasivelWithdrawn OutrightlWithdrawn with Editorial Change(s)l Not Relatedl Not Persuasivel Previously Considered
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Handling Voting ResultsHandling Voting Results
l A single negative vote halts the ballot process until resolution is reached
l Technical changes require re-balloting
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The Main Committee BallotThe Main Committee Ballot
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Electronic Tools for ParticipationElectronic Tools for Participation
l Members-only features on committee pages– Electronic balloting • Broadcast email– Minutes • Meeting information– Rosters
l Standards tracker (Email notification at no charge)– Search of new drafts or approved standards in sectors
you select– Automatic notification – Provides current status
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How do I get involved?How do I get involved?
l Technical Committee membership is open to all.l Membership is inexpensive,($75) and provides access
to committee rosters and proposed standards actions for review and voting.
l Balloting of standards is done on-line at your convenience.
l Go to www.astm.org for more information on membership to Committee E48 or Brynn Iwanowski Manager at 610-832-9640
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Committee E48Committee E48
Overview of ASTM Committee E48on Biotechnology
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E48 BiotechnologyE48 Biotechnology
l Organized in 1972l 86 Membersl 3 Technincal Subcommitteesl 42 Standardsl International membership
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E48 on Biotechnology
SubcommitteeE48.02
SubcommitteeE48.03
Subcommittee E48.05
Task Groups Task Groups
Technical Main Committees formed to address specific industry subjects.
Subcommittees address specialized subject matters under the Main Committee.
Task Groups handle individual document development.
Technical Committee Organization
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E48.02 Characterization and Identification E48.02 Characterization and Identification of Biological Systemsof Biological Systems
l Practices and guides for detection and identification of viruses, bacteria and mycoplasma. Includes determination of purity and contamination in biological drug products. Also standardizes preservation methods for biological materials and determination of isoaspartic acid in proteins. Includes PCR guides for detection of nucleic acids
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E48.02E48.02
16 Active Standardsl Preservation, Storage, and Handling
– Bacteria– Fungi– Protista– Viruses– Genetic Elements– Animal Tissues– Plant Tissues
l Determination of Purity, Impurities, and Contaminates in Biological Drug Products
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E48.02E48.02
l Identification and Characterization– Bacteriophage Lambda– Herpes simplex– Bacteriophage M13– Mycoplasma– Mycobacteriun Tuberculosis Complex– HIV-1
l Polymerase Chain Reaction (PCR)– Traditional techniques– Real-time PCR
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E48.03 on Unit Processes and Their E48.03 on Unit Processes and Their ValidationValidation
l test methods, guides, practices for aseptic sampling, fermentor/bioreactor design, membrane ultrafilter characterization, protein size determination, biosensors and bio-specific equipment.
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Current standard methodsCurrent standard methods
l E1705-95..Biomass terminologyl E1755-95 Preparation of biomass for
analysisl E1690-05 Extractives in biomassl E1756-95 Total solids in biomassl E1755-95 Ash in biomassl E1721-95 Acid Insoluble residue in biomass
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Current standard methodsCurrent standard methods
l E1758-01 Carbohydrates by high performance liquid chromatography (HPLC)
l E1821-96 Carbohydrates by gas chromatographyl Design and Evaluation of Fuel Ethanol Mfg.
Facilitiesl Characterization of Wood Fuelsl Anaerobic Digestion Systems
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E48.03E48.03
8 Active Standardsl Aseptic Samplingl Membrane Characterizationl Protein Characterization l Particle Size Distribution of Chromatography Medial Biobleachingl Bioreactor Designl Safety of Biotechnology Productsl Architectural Design of Biopharmaceutical Facilities
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For More InformationFor More Information
l ASTM web site – www.astm.org
l Brynn Iwanowski [email protected]
(610) 832 - 9640