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Novel Quantitative Method Novel Quantitative Method for Biodiesel Analysis for Biodiesel Analysis
Novel Quantitative Method Novel Quantitative Method for Biodiesel Analysisfor Biodiesel Analysis
Georgia Institute of TechnologyGeorgia Institute of Technology
North Avenue Trade School opened in 1888 with 84 students
Over 17,000 students are currently enrolled
Sits on 400 acre campus
Ranked # 8 among public universities in the nation
Ranked in the top 5 for most engineering disciplines
33
Fossil fuels vs. BiofuelsFossil fuels vs. Biofuels
Current biodiesel analytical methodsCurrent biodiesel analytical methods
Developing a new analytical toolDeveloping a new analytical tool
Chemical approachChemical approach
PhosphitylatingPhosphitylating agent agent 3131PP--NMR chemical shiftNMR chemical shift librarylibrary
Process sample analysisProcess sample analysis
Method optimizationMethod optimization
Rapid sample analysisRapid sample analysis
OutlineOutline
Broken cycleClosed cycle
FossilsBiomass
The CarbonThe Carbon--cyclecycle
55
International Energy OverviewInternational Energy Overview
460 quadrillion Btu in 2006.460 quadrillion Btu in 2006.
Fossil fuels accounted for 86 % of Fossil fuels accounted for 86 % of all energy produced worldwide.all energy produced worldwide.
World crude oil production World crude oil production totaled 74 million barrels totaled 74 million barrels
per day in 2008.per day in 2008.Need for Renewable Biofuels:Need for Renewable Biofuels:
Energy security (Local)Energy security (Local)Carbon neutral/climate changeCarbon neutral/climate changeSustainabilitySustainability
Energy Information Administration. Energy Information Administration. www.eis.doe.govwww.eis.doe.gov
66
HydrocarbonsHydrocarbons
NeedsNeeds
Potential Biofuel PrecursorsPotential Biofuel Precursors
460 quadrillion Btu460 quadrillion Btuannual consumptionannual consumption
74 million barrels per day74 million barrels per day
High energy contentHigh energy content CarbohydratesCarbohydratesStarchStarchCelluloseCelluloseHemicellulosesHemicelluloses
Fat (Fatty acids)Fat (Fatty acids)Oil (Triglycerides)Oil (Triglycerides)
High volumeHigh volume
Plant: Plant: (PVO, UVO)(PVO, UVO)
Animal:Animal: Animal fat Animal fat Yellow GreaseYellow Grease
Easily accessibleEasily accessibleLow costLow cost
Alkali fatty estersAlkali fatty esters(Biodiesel)(Biodiesel)
EthanolEthanol((BioethanolBioethanol))
Economically viableEconomically viable
BioBio--renewable resourcesrenewable resources
StarchStarchCelluloseCelluloseHemicellulosesHemicellulosesLignin Lignin
Produced biofuelsProduced biofuels
77
HydrocarbonsHydrocarbons
Potential Biofuel PrecursorsPotential Biofuel Precursors
CarbohydratesCarbohydratesStarchStarchCelluloseCelluloseHemicellulosesHemicelluloses
Fat (Fatty acids)Fat (Fatty acids)Oil (Triglycerides)Oil (Triglycerides)Plant: Plant: (PVO, UVO)(PVO, UVO)
Animal:Animal: Animal fat Animal fat Yellow GreaseYellow Grease
Alkali fatty estersAlkali fatty esters(Biodiesel)(Biodiesel)
EthanolEthanol((BioethanolBioethanol))
BioBio--renewable resourcesrenewable resources
StarchStarchCelluloseCelluloseHemicellulosesHemicellulosesLignin Lignin
Produced biofuelsProduced biofuels
88
Fossil fuels vs. BiofuelsFossil fuels vs. Biofuels
Current biodiesel analytical methodsCurrent biodiesel analytical methods
Developing a new analytical toolDeveloping a new analytical tool
Chemical approachChemical approach
PhosphitylatingPhosphitylating agent agent 3131PP--NMR chemical shiftNMR chemical shift librarylibrary
Process sample analysisProcess sample analysis
Method optimizationMethod optimization
Rapid sample analysisRapid sample analysis
OutlineOutline
99
Current Biodiesel Analytical MethodsCurrent Biodiesel Analytical Methods
ChomatographicChomatographicHPLCHPLC, GC, GC
Spectroscopic Spectroscopic MS, NIRMS, NIR
Time consuming Time consuming analysisanalysis
Glycerol, Glycerol, AcylglycerolsAcylglycerols
PhosphitylationPhosphitylation, , 3131PP--NMRNMR
Rapid technique Rapid technique with an easy data with an easy data
analysisanalysis
Acid Acid contentcontent
Wet chem. tech. Wet chem. tech. Pot. Pot. titrtitr, , IodomIodom. . titrtitr..
Residual Residual alcoholalcohol
ChomatographicChomatographicHPLC,GCHPLC,GC
Long sample Long sample preparationpreparation
Extended Extended analysis timeanalysis time
Complicated Complicated data analysisdata analysis
All aboveAll above
GerpenGerpen J.VJ.V, et. al. Biodiesel analytical methods, et. al. Biodiesel analytical methods, (2004) NREL/SR, (2004) NREL/SR--510510--3624036240
1010
Fossil fuels vs. BiofuelsFossil fuels vs. Biofuels
Current biodiesel analytical methodsCurrent biodiesel analytical methods
Developing a new analytical toolDeveloping a new analytical tool
Chemical approachChemical approach
PhosphitylatingPhosphitylating agent agent 3131PP--NMR chemical shiftNMR chemical shift librarylibrary
Process sample analysisProcess sample analysis
Method optimizationMethod optimization
Rapid sample analysisRapid sample analysis
OutlineOutline
1111
Chemical ApproachChemical Approach
Transesterification reaction for biodiesel production, Transesterification reaction for biodiesel production, RR11--33 are hydrocarbon groups are hydrocarbon groups
PhosphitylationPhosphitylation of partially substituted of partially substituted glycerolsglycerols with DOP or with TMDPwith DOP or with TMDPMMááttéé NagyNagy, et. al. , et. al. Journal of Biobased Material and Bioenergy, (2009), 3(1), 1Journal of Biobased Material and Bioenergy, (2009), 3(1), 1--4.4.
1212
Fossil fuels vs. BiofuelsFossil fuels vs. Biofuels
Current biodiesel analytical methodsCurrent biodiesel analytical methods
Developing a new analytical toolDeveloping a new analytical tool
Chemical approachChemical approach
PhosphitylatingPhosphitylating agent agent 3131PP--NMR chemical shiftNMR chemical shift librarylibrary
Process sample analysisProcess sample analysis
Method optimizationMethod optimization
Rapid sample analysisRapid sample analysis
OutlineOutline
1313
GlycerolGlycerol
TMDPTMDP
~85% 1,3~85% 1,3--Dioleoylglycerol and ~15% 1,2Dioleoylglycerol and ~15% 1,2--Dioleoylglycerol mixtureDioleoylglycerol mixture
DOPDOP
TMDP provides greater spectral resolution of the individual hydrTMDP provides greater spectral resolution of the individual hydroxyl groups of oxyl groups of glycerolglycerol--derivatives derivatives reagent of interest for additional studies. reagent of interest for additional studies.
PhosphitylatingPhosphitylating AgentAgentDOP vs. TMDPDOP vs. TMDP
MMááttéé NagyNagy, et. al. , et. al. Journal of Biobased Material and Bioenergy, (2009), 3(1), 1Journal of Biobased Material and Bioenergy, (2009), 3(1), 1--4.4.
1414
Fossil fuels vs. BiofuelsFossil fuels vs. Biofuels
Current biodiesel analytical methodsCurrent biodiesel analytical methods
Developing a new analytical toolDeveloping a new analytical tool
Chemical approachChemical approach
PhosphitylatingPhosphitylating agent agent 3131PP--NMR chemical shiftNMR chemical shift librarylibrary
Process sample analysisProcess sample analysis
Method optimizationMethod optimization
Rapid sample analysisRapid sample analysis
OutlineOutline
1515
Biodiesel AnalysisBiodiesel Analysis3131PP--NMR chemical shiftNMR chemical shift librarylibrary
H2C1
HC2
H2C3
OH
OH
OH
H2C1
HC2
H2C3
Oa
Ob
Oc
R OH
1616
Fossil fuels vs. BiofuelsFossil fuels vs. Biofuels
Current biodiesel analytical methodsCurrent biodiesel analytical methods
Developing a new analytical toolDeveloping a new analytical tool
Chemical approachChemical approach
PhosphitylatingPhosphitylating agentagent3131PP--NMR chemical shiftNMR chemical shift librarylibrary
Process sample analysisProcess sample analysis
Method optimizationMethod optimization
Rapid sample analysisRapid sample analysis
OutlineOutline
1717
The process sample and the reagent mixture has to be in solutionThe process sample and the reagent mixture has to be in solution
Phosphitylation of 1,2-diacylglycerol with 2-chloro-4,4,5,5-tetramethyl-1,3,2-dioxaphospholane at c-position. RR11--22 are hydrocarbon groups are hydrocarbon groups
TMDP/TMDP/3131PP--NMR Method OptimizationNMR Method OptimizationSolvent system for biodiesel constituentsSolvent system for biodiesel constituents
MMááttéé NagyNagy, et. al. , et. al. Journal of Biobased Material and Bioenergy, (2009), 3(1), 1Journal of Biobased Material and Bioenergy, (2009), 3(1), 1--4.4.
Solvent mixture
1818
TMDP/TMDP/3131PP--NMR Method OptimizationNMR Method OptimizationSpinSpin--lattice relaxation time of biodiesel precursorslattice relaxation time of biodiesel precursors
Rapid analytical method Rapid analytical method Reduce analysis time to a minimumReduce analysis time to a minimum
Anhydrous pyridine/CDCL3/DMF in 1:1.2:1 ratio
Chromium acetylacetonate (Cr(acac)3) as a relaxation agent (~3.60 mg/mL )
31P spin-lattice relaxation time measurement
400 MHz, 25 °C, magnetic field of 9.4 T, standard inversion recovery pulse sequence (recycle delay-180°-τ-90°-acquistion)8 μs (90° pulse), 16 μs (180° pulse), 20 s recycle delay, 8 scans.
MMááttéé NagyNagy, et. al. J. Phys. Chem. A, (2009), , et. al. J. Phys. Chem. A, (2009), doidoi: 10.1021/jp906543g: 10.1021/jp906543g
O P
O
O
OHH2C1
HC2
H2C3
Oa
Ob
Oc
R OH
H2C1
HC2
H2C3
OH
OH
OH OH
C1 OHR
O
R P
O
O
O P
O
O
H
Cl P
O
O
H2O
MMááttéé NagyNagy, et. al. , et. al. Fuel (2009), 88, 1793Fuel (2009), 88, 1793--1797.1797.
1919
TMDP/TMDP/3131PP--NMR Method OptimizationNMR Method OptimizationOptimized TMDP/Optimized TMDP/3131PP--NMR analysis protocolNMR analysis protocol
Solvent mixtureSolvent mixtureAnhydrous pyridine/CDCL3/DMF in 1:1.2:1 ratio~3.60 mg/mL of Cr(acac)3 (relaxation agent)~4.00 mg/mL of cyclohexanol (internal standard)
PhosphitylationPhosphitylationBiodiesel process sample (150 μL) or Glycerol process sample (10 μL) Solvent mixture 500 μL MixTMDP (100 μL) Mix NMR
Optimized NMR pulse programOptimized NMR pulse program ((400 MHz, at 25 °C)
5 sec pulse delay, inverse-gated decoupling (Waltz-16), 90° pulse angle, a time domain of 32 K with one degree of zero filling, 4.0 Hz line broadening, and 16 acquisition transients.
MMááttéé NagyNagy, et. al. J. Phys. Chem. A, (2009), , et. al. J. Phys. Chem. A, (2009), doidoi: 10.1021/jp906543g: 10.1021/jp906543g
Sample preparation Sample preparation Under 5 minUnder 5 min
Analysis time Analysis time 56 sec56 sec
Data analysis Data analysis ~30 minutes~30 minutes
2020
Fossil fuels vs. BiofuelsFossil fuels vs. Biofuels
Current biodiesel analytical methodsCurrent biodiesel analytical methods
Developing a new analytical toolDeveloping a new analytical tool
Chemical approachChemical approach
PhosphitylatingPhosphitylating agent agent 3131PP--NMR chemical shiftNMR chemical shift librarylibrary
Process sample analysisProcess sample analysis
Method optimizationMethod optimization
Rapid sample analysisRapid sample analysis
OutlineOutline
2121
Biodiesel AnalysisBiodiesel AnalysisProcess outline and samplingProcess outline and sampling
CATALYST
METHANOL
PARENT
OIL
TRANSESTERIFICATION
SETTLINGWASHING SEQUENCE
NEUTRALIZATION
DISTILLATION COLUMNS
FINAL BIODIESEL
FINAL GLYCEROL
RECOVERED METHANOL
PO
H2C1
HC2
H2C3
Oa
Ob
Oc
C1 OHR
O
R OH
MMááttéé NagyNagy, et. al. J. Phys. Chem. A, (2009), , et. al. J. Phys. Chem. A, (2009), doidoi: 10.1021/jp906543g: 10.1021/jp906543g
2222
Biodiesel AnalysisBiodiesel AnalysisThe parent oilThe parent oil
147 146 145PPM 135 134
b)
a)
Methanol
Mono - C Glycerol – B
Di – B
Mono – B
Glycerol – A/C
Cyclohexanol
Fatty acids
Quantitative Quantitative 3131PP--NMR spectra of parent oil samples of NMR spectra of parent oil samples of waste vegetable oil (a) and soybean oil (b)waste vegetable oil (a) and soybean oil (b)
MMááttéé NagyNagy, et. al. J. Phys. Chem. A, (2009), , et. al. J. Phys. Chem. A, (2009), doidoi: 10.1021/jp906543g: 10.1021/jp906543g
2323
CATALYST
METHANOL
PARENT
OIL
TRANSESTERIFICATION
SETTLINGWASHING SEQUENCE
NEUTRALIZATION
DISTILLATION COLUMNS
FINAL BIODIESEL
FINAL GLYCEROL
RECOVERED METHANOL
PO
AT
Biodiesel AnalysisBiodiesel AnalysisProcess outline and samplingProcess outline and sampling
MMááttéé NagyNagy, et. al. J. Phys. Chem. A, (2009), , et. al. J. Phys. Chem. A, (2009), doidoi: 10.1021/jp906543g: 10.1021/jp906543g
2424
Biodiesel AnalysisBiodiesel AnalysisThe transesterification stepThe transesterification step
1
PPM147.6 147.2 146.8 146.4 146.0 145.6 145.2 144.8
1
PPM147.6 147.2 146.8 146.4 146.0 145.6 145.2 144.8147 146 145PPM 135 134
b)
a)
Methanol
Mono - C Glycerol – B
Di – B
Mono – B
Glycerol – A/CCyclohexanol
Fatty acids
Quantitative 31PQuantitative 31P--NMR spectra of samples taken after the transesterification step NMR spectra of samples taken after the transesterification step utilizing different process conditions using soybean oil as feedutilizing different process conditions using soybean oil as feedstockstock
MMááttéé NagyNagy, et. al. J. Phys. Chem. A, (2009), , et. al. J. Phys. Chem. A, (2009), doidoi: 10.1021/jp906543g: 10.1021/jp906543g
2525
CATALYST
METHANOL
PARENT
OIL
TRANSESTERIFICATION
SETTLINGWASHING SEQUENCE
NEUTRALIZATION
DISTILLATION COLUMNS
FINAL BIODIESEL
FINAL GLYCEROL
RECOVERED METHANOL
PO
BW
A1W
AT
Biodiesel AnalysisBiodiesel AnalysisProcess outline and samplingProcess outline and sampling
MMááttéé NagyNagy, et. al. J. Phys. Chem. A, (2009), , et. al. J. Phys. Chem. A, (2009), doidoi: 10.1021/jp906543g: 10.1021/jp906543g
2626
Biodiesel AnalysisBiodiesel AnalysisThe washing phaseThe washing phase
Quantitative 31PQuantitative 31P--NMR spectra showing the washing efficiency of NMR spectra showing the washing efficiency of a soybean oil based commercial process on samples taken a soybean oil based commercial process on samples taken
before wash (a) and after the first washing cycle (b)before wash (a) and after the first washing cycle (b)MMááttéé NagyNagy, et. al. J. Phys. Chem. A, (2009), , et. al. J. Phys. Chem. A, (2009), doidoi: 10.1021/jp906543g: 10.1021/jp906543g
2727
CATALYST
METHANOL
PARENT
OIL
TRANSESTERIFICATION
SETTLINGWASHING SEQUENCE
NEUTRALIZATION
DISTILLATION COLUMNS
FINAL BIODIESEL
FINAL GLYCEROL
RECOVERED METHANOL
PO
BW
A1W
FB
AT
Biodiesel AnalysisBiodiesel AnalysisProcess outline and samplingProcess outline and sampling
MMááttéé NagyNagy, et. al. J. Phys. Chem. A, (2009), , et. al. J. Phys. Chem. A, (2009), doidoi: 10.1021/jp906543g: 10.1021/jp906543g
2828
Biodiesel AnalysisBiodiesel AnalysisThe final biodieselThe final biodiesel
Quantitative 31PQuantitative 31P--NMR spectra of final biodiesel samples of NMR spectra of final biodiesel samples of soybean oil (a) and waste vegetable oil (b)soybean oil (a) and waste vegetable oil (b)
MMááttéé NagyNagy, et. al. J. Phys. Chem. A, (2009), , et. al. J. Phys. Chem. A, (2009), doidoi: 10.1021/jp906543g: 10.1021/jp906543g
2929
Biodiesel AnalysisBiodiesel AnalysisQuantitative analysis on final biodiesel sampleQuantitative analysis on final biodiesel sample
Quantitative Quantitative 3131PP--NMR spectra of biodiesel samples from commercialNMR spectra of biodiesel samples from commercialbiodiesel operations based on soy oilbiodiesel operations based on soy oil
C1 OHR
O
H2C1
HC2
H2C3
OH
OH
OH
H2C1
HC2
H2C3
Oa
Ob
Oc
R OH
3030
Biodiesel AnalysisBiodiesel AnalysisMonitoring the biodiesel process streamMonitoring the biodiesel process stream
MMááttéé NagyNagy, et. al. , et. al. Fuel (2009), 88, 1793Fuel (2009), 88, 1793--17971797
TRANSESTERIFICATION
SETTLING
FINAL BIODIESEL
WASHING SEQUENCE
DISTILLATION COLUMNS
BW
A1W
FB
MMááttéé NagyNagy, et. al. J. Phys. Chem. A, (2009), , et. al. J. Phys. Chem. A, (2009), doidoi: 10.1021/jp906543g: 10.1021/jp906543g
3131
CATALYST
METHANOL
PARENT
OIL
TRANSESTERIFICATION
SETTLINGWASHING SEQUENCE
NEUTRALIZATION
DISTILLATION COLUMNS
FINAL BIODIESEL
FINAL GLYCEROL
RECOVERED METHANOL
PO
BW
A1W
SG
DGFB
AT
Biodiesel AnalysisBiodiesel AnalysisProcess outline and samplingProcess outline and sampling
3232
Biodiesel AnalysisBiodiesel AnalysisThe glycerol process streamThe glycerol process stream
MMááttéé NagyNagy, et. al. , et. al. Fuel (2009), doi:10.1016/j.fuel.2009.01.020Fuel (2009), doi:10.1016/j.fuel.2009.01.020
Quantitative 31PQuantitative 31P--NMR spectra on glycerol samples from soybean oil based NMR spectra on glycerol samples from soybean oil based commercial process of the separated glycerol before neutralizaticommercial process of the separated glycerol before neutralization (a) on (a)
and of the final and of the final demethylateddemethylated glycerol (b)glycerol (b)
3333
Biodiesel AnalysisBiodiesel AnalysisQuantitative analysis on final glycerol samplesQuantitative analysis on final glycerol samples
Quantitative Quantitative 3131PP--NMR spectra of glycerol samples from commercialNMR spectra of glycerol samples from commercialbiodiesel operations based on soy oil, poultry fat & tallowbiodiesel operations based on soy oil, poultry fat & tallow
C1 OHR
O
H2C1
HC2
H2C3
OH
OH
OH
H2C1
HC2
H2C3
Oa
Ob
Oc
R OH
3434
CATALYST
METHANOL
PARENT
OIL
TRANSESTERIFICATION
SETTLINGWASHING SEQUENCE
NEUTRALIZATION
DISTILLATION COLUMNS
FINAL BIODIESEL
FINAL GLYCEROL
RECOVERED METHANOL
PO
BW
A1W
SG
DGFB
AT
Biodiesel AnalysisBiodiesel AnalysisProcess outline and samplingProcess outline and sampling
MMááttéé NagyNagy, et. al. J. Phys. Chem. A, (2009), , et. al. J. Phys. Chem. A, (2009), doidoi: 10.1021/jp906543g: 10.1021/jp906543g
3535
ConclusionsConclusions
Current methods vs. TMDP/Current methods vs. TMDP/3131PP--NMR methodNMR method–– Fast sample preparation (under 5 min)Fast sample preparation (under 5 min)–– Rapid analysis and data acquisition (56 sec)Rapid analysis and data acquisition (56 sec)–– Accurate quantitative method (Accuracy: +95%)Accurate quantitative method (Accuracy: +95%)–– Easy data analysis (Good separation, spectroscopic information Easy data analysis (Good separation, spectroscopic information
related to the structure)related to the structure)–– Sensitive novel research tool (1.9 Sensitive novel research tool (1.9 µµmol/mol/mLmL LOD, LOD, ±±1.1% error 1.1% error
margin)margin)Additional benefitsAdditional benefits
–– Independent from feedstock Independent from feedstock –– Direct measurement for theDirect measurement for the intermediate products through the intermediate products through the
whole production line whole production line Process step optimizationProcess step optimization–– Direct measurements for contamination in the final products Direct measurements for contamination in the final products
Quality controlQuality control
AcknowledgmentsAcknowledgments
IPST@GT Student FellowshipIPST@GT Student Fellowship
Rachel BurtonRachel BurtonPiedmont BiofuelsPiedmont Biofuels
