SIMULATION-DRIVENFUELDESIGN

S.ManiSarathy

•  IntroducTon•  Background•  ResearchMoTvaTon

•  ResearchProgress•  Alcohol•  GasolineFuels•  PerfumedFuel•  CheapBiofuels•  MoreAlcohol

•  QuesTons

PresentaTonOutline/Timeline

0

20

40

60

80

100

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

1

2

34

56

7

1

12

34

56

7

1 2-methylheptane

1

24

56

7

1

O O

1

2

3

4

56

7

1

O O H

HH1

2

3

4

5

1

O O

-H

+ O2

6-member ring isomerization....

+ O2

1

2

3

4

56

7

1

O O H

O O

6-member ring isomerizationHH

1

2

3

4

5

6

7

1

O O H

O O

1

2

3

4

5

6

7

1

O O H

O O H

1

2

34

56

78

12

34

56

78

n-octane

1

24

56

78

O O

1

2

3

4

56

78

O O H

HH1

2

3

4

5O O

-H

+ O2

6-member ring isomerization....

+ O2

1

2

34

56

78

O O H

O O

6-member ring isomerization

HH

12

34

5

6

7O O H

O O

1

2

34

5

6

78

O O H

H O O

....

1

2

34

5

6

78

H O O

O

+ OH1

2

3

4

1

O O H

O 5

6

78

+

1

2

34

5

6

78

O

O

+ OH+1

2

3

4

1

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

5

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: Mani.Sarathy@kaust.edu.sa (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

1000

1500

2000

2500

3000

3500

0 0.005 0.01 0.015 0.02 0.025

Mol

e Fr

actio

n

Tem

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

1.E-03

1.E-01

500

1000

1500

2000

2500

3000

3500

0 0.005 0.01 0.015 0.02 0.025

Mol

e Fr

actio

n

Tem

pera

ture

(K)

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

10

15

20

25

30

10 20 30 40 50

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

شكرا

mani.sarathy@kaust.edu.sahqp://cpc.kaust.edu.sa

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Merci Grazie

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Danke

ευχαριστώ E~aristó