Novel Quantitative Method for Biodiesel Analysis presentation_Mate...2009/08/25 · 5 International...

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

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

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

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

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

OutlineOutline

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

OutlineOutline

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.

OutlineOutline

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.

OutlineOutline

Biodiesel AnalysisBiodiesel Analysis3131PP--NMR chemical shiftNMR chemical shift librarylibrary

PhosphitylatingPhosphitylating agentagent3131PP--NMR chemical shiftNMR chemical shift librarylibrary

OutlineOutline

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

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

OHH2C1

C1 OHR

MMááttéé NagyNagy, et. al. , et. al. Fuel (2009), 88, 1793Fuel (2009), 88, 1793--1797.1797.

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.

Sample preparation Sample preparation Under 5 minUnder 5 min

Analysis time Analysis time 56 sec56 sec

Data analysis Data analysis ~30 minutes~30 minutes

OutlineOutline

Biodiesel AnalysisBiodiesel AnalysisProcess outline and samplingProcess outline and sampling

CATALYST

METHANOL

PARENT

TRANSESTERIFICATION

SETTLINGWASHING SEQUENCE

NEUTRALIZATION

DISTILLATION COLUMNS

FINAL BIODIESEL

FINAL GLYCEROL

RECOVERED METHANOL

C1 OHR

Biodiesel AnalysisBiodiesel AnalysisThe parent oilThe parent oil

147 146 145PPM 135 134

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)

CATALYST

METHANOL

PARENT

TRANSESTERIFICATION

NEUTRALIZATION

FINAL BIODIESEL

FINAL GLYCEROL

RECOVERED METHANOL

Biodiesel AnalysisBiodiesel AnalysisThe transesterification stepThe transesterification step

PPM147.6 147.2 146.8 146.4 146.0 145.6 145.2 144.8

PPM147.6 147.2 146.8 146.4 146.0 145.6 145.2 144.8147 146 145PPM 135 134

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

CATALYST

METHANOL

PARENT

TRANSESTERIFICATION

NEUTRALIZATION

FINAL BIODIESEL

FINAL GLYCEROL

RECOVERED METHANOL

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

CATALYST

METHANOL

PARENT

TRANSESTERIFICATION

NEUTRALIZATION

FINAL BIODIESEL

FINAL GLYCEROL

RECOVERED METHANOL

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)

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

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

CATALYST

METHANOL

PARENT

TRANSESTERIFICATION

NEUTRALIZATION

FINAL BIODIESEL

FINAL GLYCEROL

RECOVERED METHANOL

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)

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

CATALYST

METHANOL

PARENT

TRANSESTERIFICATION

NEUTRALIZATION

FINAL BIODIESEL

FINAL GLYCEROL

RECOVERED METHANOL

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

Thank You!Thank You!

Máté Nagy

E-mail: Mate.Nagy@ipst.gatech.edu Phone: (678)-549-6316

Novel Quantitative Method for Biodiesel Analysis presentation_Mate...2009/08/25 · 5 International...

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