SIMULATION-DRIVEN FUEL DESIGN - Clean Combustion Research ... · and biodiesel) in internal...
Transcript of SIMULATION-DRIVEN FUEL DESIGN - Clean Combustion Research ... · and biodiesel) in internal...
SIMULATION-DRIVENFUELDESIGN
S.ManiSarathy
• IntroducTon• Background• ResearchMoTvaTon
• ResearchProgress• Alcohol• GasolineFuels• PerfumedFuel• CheapBiofuels• MoreAlcohol
• QuesTons
PresentaTonOutline/Timeline
0
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40
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0 5 10 15 20InterestLevel(%
)Time(min)
NTC-regime (nap time comfort)
SimulatedACenTonSpanP=1atm,T=298K,τ=1800s
Molecular-level Fuel Design WhataretheeffectsoffuelmolecularstructureoncombusTonandemissions?
PetroleumFuels SyntheTcFuelsandBioFuels
hCp://images.google.ca(biodiesel)
OH3C
O
hCp://images.google.ca(GTLfuel)hCp://images.google.ca(crudeoil)
OH
HO
4
n-alkanes branched alkanes cycloalkanes aromatics
tetralin
1-methylnaphthalene
1,2,4-trimethylbenzene
decalin
n-dodecylcyclohexane
n-hexadecane
n-dodecane
2-methylpentadecane
3-methyldodecane
2,9-dimethyldecane
1.MolecularLevelFuelCharacteriza7on
2.SurrogateFuelFormula7on• ReproducestargetproperTesofrealfuel• H/CraTo,funcTonalgroups,molecularweight,igniTon
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1 2-methylheptane
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24
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O O
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O O H
HH1
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-H
+ O2
6-member ring isomerization....
+ O2
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O O H
O O
6-member ring isomerizationHH
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n-octane
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O O
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HH1
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-H
+ O2
6-member ring isomerization....
+ O2
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O O
6-member ring isomerization
HH
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7O O H
O O
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O O H
H O O
....
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H O O
O
+ OH1
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O 5
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O
O
+ OH+1
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O O
+ + OH
+ OH
3 3
3.ChemicalKine7cModeling
4.ExperimentalTes7ng
5.PredictCombus7onCoupledkine7c/fluidmodels
6.Fuel/EngineDesign
Fuels
Light Gases Diesels Solid fuels
Naphthas Lubricants Synthetic fuels
Gasolines Heavy fuel oils Oxygenates
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Review
Alcohol combustion chemistry
S. Mani Sarathy a,*, Patrick Oßwald b, Nils Hansen c, Katharina Kohse-Höinghaus d
aClean Combustion Research Center, King Abdullah University of Science and Technology, Thuwal 23955-6900, Saudi Arabiab Institute of Combustion Technology, German Aerospace Center (DLR), Pfaffenwaldring 38-40, D-70569 Stuttgart, GermanycCombustion Research Facility, Sandia National Laboratories, Livermore, CA 94551, USAdChemistry Department, Bielefeld University, Universitätsstraße 25, Bielefeld D-33615 Germany
a r t i c l e i n f o
Article history:Received 22 December 2013Accepted 14 April 2014Available online xxx
Keywords:BiofuelCombustion chemistryAlcoholsKinetic modelingPollutant emissionsInternal combustion enginesFlame speedIgnition delay
a b s t r a c t
Alternative transportation fuels, preferably from renewable sources, include alcohols with up to five oreven more carbon atoms. They are considered promising because they can be derived from biologicalmatter via established and new processes. In addition, many of their physical-chemical properties arecompatible with the requirements of modern engines, which make them attractive either as re-placements for fossil fuels or as fuel additives. Indeed, alcohol fuels have been used since the early yearsof automobile production, particularly in Brazil, where ethanol has a long history of use as an automobilefuel. Recently, increasing attention has been paid to the use of non-petroleum-based fuels made frombiological sources, including alcohols (predominantly ethanol), as important liquid biofuels. Today, theethanol fuel that is offered in the market is mainly made from sugar cane or corn. Its production as afirst-generation biofuel, especially in North America, has been associated with publicly discusseddrawbacks, such as reduction in the food supply, need for fertilization, extensive water usage, and otherecological concerns. More environmentally friendly processes are being considered to produce alcoholsfrom inedible plants or plant parts on wasteland. While biofuel production and its use (especially ethanoland biodiesel) in internal combustion engines have been the focus of several recent reviews, a dedicatedoverview and summary of research on alcohol combustion chemistry is still lacking. Besides ethanol,many linear and branched members of the alcohol family, from methanol to hexanols, have been studied,with a particular emphasis on butanols. These fuels and their combustion properties, including theirignition, flame propagation, and extinction characteristics, their pyrolysis and oxidation reactions, andtheir potential to produce pollutant emissions have been intensively investigated in dedicated experi-ments on the laboratory and the engine scale, also emphasizing advanced engine concepts. Researchresults addressing combustion reaction mechanisms have been reported based on results from pyrolysisand oxidation reactors, shock tubes, rapid compression machines, and research engines. This work iscomplemented by the development of detailed combustion models with the support of chemical kineticsand quantum chemistry. This paper seeks to provide an introduction to and overview of recent results onalcohol combustion by highlighting pertinent aspects of this rich and rapidly increasing body of infor-mation. As such, this paper provides an initial source of references and guidance regarding the presentstatus of combustion experiments on alcohols and models of alcohol combustion.
! 2014 Elsevier Ltd. All rights reserved.
Contents
1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 002. Alcohol fuels e origins, sustainability, properties, and present use . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
2.1. Origins and sustainability . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 002.2. Alcohol fuel properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 002.3. Present use of alcohol fuels . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
* Corresponding author. Tel.: þ966 2 808 4626 (work), þ966 (0) 544 700 142(mobile).
E-mail address: [email protected] (S.M. Sarathy).
Contents lists available at ScienceDirect
Progress in Energy and Combustion Science
journal homepage: www.elsevier .com/locate/pecs
http://dx.doi.org/10.1016/j.pecs.2014.04.0030360-1285/! 2014 Elsevier Ltd. All rights reserved.
Progress in Energy and Combustion Science xxx (2014) 1e63
Please cite this article in press as: Sarathy SM, et al., Alcohol combustion chemistry, Progress in Energy and Combustion Science (2014), http://dx.doi.org/10.1016/j.pecs.2014.04.003
AcomprehensivesynthesisoffundamentalexperimentalandtheoreTcalstudiesonalcoholcombusTonchemistry.
ASyrianmercenarydrinkingbeerinthecompanyofhisEgypTanwifeandchild,c.1350BC.Photograph:BeCmann/Corbis
Alcohol fuel origins
Alcohol fuel origins
8
• FirstwriCenaccountofboilingwineandobservingflammablevaporsisfoundinthewriTngsofJabiribnHayyan(c.721-815CE).
• Al-Kindi(c.801-873CE)later
describedthedisTllaTonofwineinhisKitabal-Taraffuqfial-‘itr(TheBookoftheChemistryofPerfumeandDisTllaTons).
Alcohol fuel origins
9
• Methanol(i.e.,woodalcohol),andethanolwerelampfuelspriorto1800.Alcoholssavedthewhales!
• FirstICengines,includingthosebySamuel
Morey,NikolausOCo,andGeorgeBrayton,uTlizedethanolasthefuel.
• HenryFordandCharlesKeCeringwerestrongproponentsofethanolasafuelforinternalcombusTonenginesintheUSA.
• SirHarryR.Ricardostudiedalcoholfuelsin
engines.1923:“Itisperfectlywellknownthatalcoholisanexcellentfuel…”
THE INTERNAL-COMBUSTION ENGINE
found in the author's fuel research engine when using petrol and ethyl alcohol under precisely similar conditions as to temperature, &c., and at a compression ratio of 5 : 1 . In both cases a careful series of measurements was made at mixture strengths ranging from 20 per cent weak to 25 per cent over-rich.
In the case of fuels whose volatility is very low, such as kerosene, butyl alcohol, &c., advantage cannot be taken of the latent heat of evaporation, because it then becomes necessary to add an excessive amount of heat before entry to the cylinder, in order to prevent condensation in the induction system. For this reason alone the power output obtainable from kerosene is actually some 15 per cent
Fig. 2.—Observed Volumetric Efficiency on Petrol and Alcohol at different Mixture Strengths
lower than from petrol or other volatile hydrocarbons at the same compression ratio.
Volatility.—The mean volatility of a fuel is of importance since this determines the amount of pre-heating required to give reason-ably uniform distribution. The amount of pre-heating governs, in its turn, the use which may be made of the latent heat of the liquid fuel.
In single-cylinder engines volatility is, between wide limits, of comparatively little consequence since the exposed surface of the induction pipe is relatively small, but as the number of cylinders is
16
CCRC’s Alternative Fuels Project
• Develop fuel blends with better combustion performance compared to traditional fuels.
• Study physical, chemical, and combustion property targets to design fuel.
• Characterize engine combustion of pure fuels and blends.
• Develop kinetic models validated against experimental data.
• Reduce and optimize kinetic models using UQ tools.
• Perform simulations of advanced engine technologies to formulate fuels. 10
!
1.0E-05
1.0E-04
1.0E-03
1.0E-02
1.0E-01
1.0E+00
0.7 0.9 1.1 1.3 1.5 1.7
Igni
tion
Del
ay (s
ec)
1000/T (1/K)
iso-pentanol in air, 40 atm
phi=1
const vol
phi=2
const vol
Objec7ves Tools
Smokept. Mol.Wt.apparatus
Singlecylinderengineexp.&sim.
ComputaTonalchemistryKineTcmod.&exp.
Ign.Qual.Tester(IQT)
Surrogates for gasoline and naphtha
11
Comprehensive Chemical Kinetics
• Cyclopentane (w/ Sandia & LLNL) • 2-methylhexane, 2,5-dimethylhexane • 2,7-dimethyloctane (w/ LLNL & Stanford) • iso-Octane (w/ LLNL & NUIG) • 1,2,4-trimethybenzene (w/ LLNL)
• n-hexane and n-heptane (w/ NUIG) • C5-C12 n-alkanes (w/ RWTH) • C1-C5 alcohols + PRFs and TPRFs • Ethyl levulinate (Dooley @ Limerick) • 2-phenylethanol • 2-butanone (w/ RWTH & Bielefeld) • multi-component surrogates (w/ LLNL & NUIG)
LowToxidaTonandhighTpyrolysismechanisms PotenTalenergysurfaceandmastereqn.ratecalcs.
Fuel Design Tool
• A new approach to surrogate fuel formulation
• Regression modeling is combined with physical and chemical kinetics simulations
• Various physical and kinetic target properties • H/C ratio, PIONA, carbon types, distillation
curve, RON, MON, TSI, density, avg. mol. Wt. • Surrogates made for various gasoline and
naphtha fuels • Engine experiments are used to compare
surrogates with gasoline fuels 0 10 20 30 40 50 60 70 80 90
330
340
350
360
370
380
390
400
Tem
pera
ture
(K)
% vol recovered as distillate
FACE F FGF-KAUST TFACE F-TFGF-KAUST
FGF-LLNL TFACE F-TFGF-LLNL
-10
-5
0
5
10
15
20
25
T fuel-T
surr(
K)
12Ahmedetal.,FUEL,2015
The purpose of models is not to fit the data but to sharpen the questions.
13
Samuel Karlin
Target Property for Fuel Design • Kalghatgi has shown
• OI = RON – K*S
• K is negative for most modern engines due to down-sizing, turbo-charging, down-speeding, intercooling, and EGR
• Fuel with greater sensitivity has a
higher OI and can allow engines to operate more efficiently.
• Low load GCI operation is better for
fuels with a higher OI. Vuilleumier,Dibble,Sarathy,Berkeley/KAUST,2015
14
Fuels for Advanced Combustion Engines FACE Gasolines
Collabora7veresearchprogramledbyKAUSTwithLLNL,UConn,RPI,UCBerkeley,CNRS...-Acquisi7onof6FACEfuels(A,C,F,G,I,J)-Composi7onalAnalysis-Tes7nginST,RCM,andJSRatdifferentfacili7es-Formula7onofsuitablesurrogates,modelingandvalida7on-Kine7canalysis
Onlysoldin55galbarrels
15
RON70to97Sensi7vity0to11Aroma7cs0to35%
16
Fuel design from chemical kinetics • HighersensiTvityfueldisplayslessNTCbehavior;
lessreacTveatRON-likeandmorereacTveatMON-like.
• AtRON-likecondiTons,fuelcomponentsthatcontrolOHradicalpoolareratecontrolling
• AtMON-likecondiTons,fuelcomponentsthatdriveOHandHO2radicalcouplingareimportant
1.E-03
1.E-02
1.E-01
1 1.1 1.2 1.3 1.4 1.5
Igni
tion
Del
ay T
ime
(s)
1000/T (1/K)
const. vol. simulations 20 atm, stoichiometric fuel/air mixtures
RON=94, S=5.6
RON=97, S=11
700KRON-like825K
MON-like
1.E-15
1.E-13
1.E-11
1.E-09
1.E-07
1.E-05
1.E-03
1.E-01
500
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0 0.005 0.01 0.015 0.02 0.025
Mol
e Fr
actio
n
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pera
ture
(K)
Time (s)
20 atm, 700 K, phi=1
FGG-Temp FGF-Temp FGG-OH FGF-OH FGG-HO2/1000
1.E-15
1.E-13
1.E-11
1.E-09
1.E-07
1.E-05
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Mol
e Fr
actio
n
Tem
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ture
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Time (s)
20 atm, 825 K, phi=1
FGG-Temp FGF-Temp FGG-OH FGF-OH FGG-HO2/1000 FGF-HO2/1000
• ModelingraTonalizesnon-linearblendingeffects(source/sinkinteracTons)
• AromaTc/alcoholandaromaTc/naphtheniccouplings
Sarathyetal,CombustFlame,submiCed2016
17
RON, MON, and S correlations
CPC group
4
MC90.5(2.5) TRF89.1(3.5) MC90.9(8.2) TRF89.3(11.1)20.2 16.007 11.74 5.1191
12.84 10.156 7.89 3.74858.97 7.1356 5.81 2.96576.68 5.3565 4.54 2.4595.2 4.2129 3.7 2.10414.19 3.4302 3.1 1.84173.47 2.8686 2.66 1.6398
2.9376 2.4504 3.6188 1.4796MC90.5(2.5) TRF89.1(3.5) MC90.9(8.2) TRF89.3(11.1)
1572.9 1090.3 453.61 82.03431.606 31.561 31.352 31.029
0.99998 0.99992 0.99989 0.99967
0
5
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Igni
tion
dela
y tim
e (m
s)
Pressure (bar)
MC90.9(-0.2) MC90.5(2.5) TRF89.1(3.5) MC90.9(8.2) TRF89.3(11.1)
TRF92.3(11.6)TRF,93.7,(3.4)
TRF97.7(11.5)TRF95.2(4.7)
TRF86.6(2.4)TRF85.7(1.1)
TRF98(10.6)
TRF65.9(8.2)TRF76.2(5.3)TRF75.6(8.7)TRF85.2(10.4)TRF89.3(11.1)TRF93.4(11.9)TRF96.9(11.7)TRF99.8(11.1)
0
0.2
0.4
0.6
0.8
1
1.2
1.4
1.6
1.8
2
0 1 2 3 4 5 6 7 8 9 10 11 12
Pres
sure
Exp
onen
t (N
)
Fuel Sensitivity (S)
850 K, 50 bar in Air Phi 1.0 IDT = a * P ^ -N
Sarathy,Badra,Khalifa,MehlinpreparaTon,2016
• EngineeringcorrelaTonscanbemadeusingsimulatedigniTondelayTmes(79fuelsintrainingset)
• ReacTonpathanalysisshowstheeffectsoffuelcomposiTon(PIONA)onradicalsource/sink
• PressuredependenceofaigniTondelayiscorrelatedtosensiTvitysuchthatquanTtaTvepredicTonscanbemade
RON(S)
18
ETHANOL FFFECTS ON GCI LOW LOAD PERFORMANCE David Vuilleumier, F. Schwerdt, D. Bestel, M. Mehl, A. Frank, R. Dibble, S.M. Sarathy UCBerkeley,LLNL,KAUST
Seven Fuels Tested 3 AKI Levels – (RON+MON)/2 85AKI:
• 0%ethanol(FACECGasoline,Neat)
• 23%ethanol(FACEJGasoline,Blended)
88AKI:• 7%ethanol(FACECGasoline,Blended)
• 10%ethanol(HaltermannCARBLEVIIICert.Fuel)
91AKI:• 0%ethanol(FACEGGasoline,Neat)
• 14%ethanol(FACECGasoline,Blended)
• 36%ethanol(FACEJGasoline,Blended,AKI90,5)
19
The Big Picture: Minimum Load for All Tested Fuels
91AKI
85AKI
88AKI
20
LTHR Onset Intake Pressure in HCCI Engine Correlated to GCI Performance
21
Octane Index Provides Best Correlation with Lowest-Load Performance
Correlation w/GCI Lowest - Load 1.4 Bar
Correlation w/GCI Lowest - Load 1.23 Bar
Correlation w/GCI Lowest - Load 1.05 Bar
RON R2 = 0.89 R2 = 0.93 R2 = 0.84
MON R2 = 0.09 R2 = 0.18 R2 = 0.53
AKI R2 = 0.63 R2 = 0.67 R2 = 0.56
OI R2 = 0.94 R2 = 0.98 R2 = 0.97
LTHR R2 = 0.95 R2 = 0.97 R2 = 0.98
22
Ignition Delays Reflect HCCI Experiments
Low-TemperatureChemistrySuppression
IncreasingSensi7vity
IncreasingLTHR
25bar,φ=1.0
• Ethanol and Toluene Inhibit Low-Temperature Heat Release o Seen in both HCCI
engine and ignition delay curves
o Also well described by Octane Index
• LTHR Enables Low-Loads in GCI Engines
24
2-PHENYLETHANOL – CHEMICAL KINETICS OF A LIGNOCELLULOSIC OCTANE BOOSTER Vijai S. B. Shankar, M. Al-Abbad, M.El-Rachidi, S.Y. Mohamed, Z. Wang, A. Farooq, S.M. Sarathy KAUST SubmiCedtoProcCombustInst2016
Lignin – So Many Possibilities
Representa)veStructureofLignin
OxygenatesfromUpgradingBio-Oil[1]
FastPyrolysis
Upgrading
2-Phenylethanol*
[1]McCormickRL,RatcliffMa.,etal.Energy&Fuels2015;29:2453–61
[2]ZhouL,BootMD,deGoeyLPH.SAETechnicalPaper,2012
*BDEcalculatedusingCBS-QB3leveloftheory,valuesinkcal/mol
* Calculated from Derived Cetane Number (DCN)
Toluene 2-PE EtOH
Molecularformula C7H8 C8H10O C2H6O
RON 120 110[2]* 108
S 12 21[2]* 9
Densityat300K[kg/l] 0.866 1.017 0.784
Boilingpoint[K] 373 493 371
Molarmass[kg/mol] 0.092 0.122 0.046
LHV[MJ/kg] 40.6 36.7 26.7
HeatofVaporiza7on[KJ/mol]
37.3 69 42.3
25
Anti-Knock Quality of 2-PE and Kinetic Modeling
KLSAatIntakeTemperatureof302K(RON-like)
KLSAatIntakeTemperatureof378K(MON-like)
Igni)onDelayTimemeasuredinIQT(ASTMD6890)
26
BasefuelFACEIRON=70S=0.7
Results, Discussions and Impressions
Expandsimigndelay)mesof2-PE,Phi1,10and20Bar
27Simigndelay)mesof2-PEandotheroctaneboostersatPhi1inAirat20Bar
Reac)onPathwaysat20%fuelconsump)on,1100K,phi=1,20bar
• 2-PEhassimilargas-phasereacTvityasethylbenzene.
• RaTonalizedbyanalysisofreacTonkineTcs.
• TheOHgrouphasliClekineTceffectandmoreofachargecoolingeffectonincreaseoctanequality.
• Whocares?
• Itsmellslikeroses!
28
ENGINE PERFORMANCE OF LOW COST FUTURE FUELS Raman Vallinayagam, S. Vedharaj, Eshan Singh, William L. Roberts, Robert W. Dibble, S. Mani Sarathy KAUST
PRODUCTION OF PINENE & TERPINEOL
29
High Energy Density Fuels – Pinene & Terpineol
PINENE
TERPINEOL
30
Terpineol – a Novel Octane Booster for Gasoline
FACE F (RON = 94.4)
Euro V (RON = 97)
Terpineol (RON = 104)
SI engine
Terpineol blended FACE F
Spark timing advancement
Improved Combustion
Reduced Knock intensity
Raman,Vedharajetal.,inpreparaTon2016
Raman,Vedharajetal.,Fuel,2016
31
Pinene – a Gasoline-like Fuel for SI Engines
SI Engine characteristics of Pinene
PineneislessreacTveatlow
temperatureandmorereacTve
athightemperaturecompared
toiso-octane.HighsensiTvity.
IDT vs temperature in IQT Pinene can also be produced from inexpensive sugars [1] by
using bacteria to attain self sufficiency
[1] Sarria S, Wong B, Martín HG, Keasling JD, Peralta-Yahya P. Microbial synthesis of pinene. ACS synthetic biology. 2014;3:466-75. Raman,Vedharajetal.,inpreparaTon2016
32
LIFECYCLE OPTIMIZED ETHANOL-GASOLINE BLENDS FOR TURBOCHARGED SI ENGINES Bo Zhang, S. Mani Sarathy KAUST
• Controversial literature on the impact of ethanol on CO2 emissions.
• Ethanol can improve fuel quality and engine efficiency, besides biogenic carbon offset.
• No previous lifecycle emission studies have accounted for these engine benefits.
• Quantified lifecycle CO2 emission of ethanol blended gasoline from well-to-wheel.
– RON, sensitivity, EtOH%, ethanol source, and engine operating conditions considered.
• Identified optimal blend for turbocharged engines.
Introduction and Motivation
33
USGulfCoastRefineryModel
• The CO2 emissions from fuel production, transportation and combustion are considered.
• Fuel composition is optimized in PIMS for various fuel standards (RON, MON, etc.).
• Emission is assessed on a component-dependent basis in GREET. • Additional emission benefit from ethanol blending is quantified
through improved engine efficiency.
LCA methods
FuelExtracTonProducTonOpTmizaTon
(PIMS)
EngineEnhancement
&FuelCombusTon
GREET Empirical
Process:
CO2 34
Leoneetal.,EnvSciTech,2016
Results
35
Atoms-to-Engine & Wells-to-Wheels
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