Experimental Studies of the Pyrolysis and Oxidation of Diesel Type Fuels

Experimental Studies of the

Pyrolysis and Oxidation of Diesel Type Fuels

N. Chaumeix

1 Naples, 23-02_2012

ICARE – CNRS

Institut de Combustion, Aérothermique Réactivité et Environnement

1c, avenue de la Recherche Scientifique 45071 Orléans – Cedex 2 – France

Orléans Paris

ICARE is in Orléans, 125 km from Paris

Total staff : 110 35 Researchers

30 Engineers and technicians 30 PhD students and post-docs 15 Various trainees

Where is ICARE ?

Research domains of ICARE

Energy & Environment Propulsion & Space

• Combustion

• Chemical kinetics • Plasmas physics

• Fluid mechanics, turbulence • Two phase flows

• Supersonic, hypersonic flows • Ionized, rarefied flows

Application domains

• Aerospace propulsion

• Electric propulsion

• Liquid and solid propulsion

• Atmospheric reentry

• Atmospheric chemistry

• Energy production

• Alternative fuels, biofuels, hydrogen

• Pollutant emissions reductions

• Industrial risk prevention

Main cooperations

International co-operations: All EU countries, Russia, USA, Canada, China, Japon, Ukraine, Turkey, Argentine, etc

Research Activities of the S. W. Group

 Combustion Chemistry

 Elementary Reaction Rates involving O and H atoms

 Pollutant Formation from Gasoline Components

 Reduced Mechanism of soot precursors from kerosene fuel

 Soot Formation from fuels

• Diesel, Gasoline, kerosenes

 Soot Oxidation

• In engine conditions behind shock waves

• Particles Filter

Research Activities of the S. W. Group

 Flame and Explosions Dynamics

 Laminar Flame properties and their instabilities

 DDT using hot jet ignition

 Flame acceleration in obstructed areas

 Detonation criteria and industrial safety

 Hypergolic limits of propellant agents

 Propellants for PDE

 Solid Explosives and their thermal aging

Main Objectives

SLOW

DEFLAGRATIONS

HIGHLY ACCELERATED DEFLAGRATIONS

DETONATIONS stable & unstable COMBUSTION CHEMISTRY

Chemical Explosion

Premixed Flames Laminar or turbulent

Methodology and Techniques

Several High Pressure Shock-Tubes

Laminar Flames

 Spherical Bomb 8 l

 P_max = 75 bar

 T_max = 353 K

 Spherical Bomb 56 l

 P_max = 75 bar

 T_max = 520 K

ENACCEF

Accelerated Flame Facility

Simi l-GV

 Volume = 850 l

 P_max = 45 bar

 T_max = ambiant

Different obstacles

12

Experimental Studies of the

Pyrolysis and Oxidation of Diesel Type Fuels

N. Chaumeix

Naples, 23-02_2012

Motivations

 To improve the knowledge of the chemistry

 Need for fundamental data

 Acquired in well-defined conditions

 At conditions relevant to diesel engines

 For pure fuels and surrogates

 Identification of the main families

 Identification of surrogates

Methodology applied

 Soot tendency

 Using a shock tube

 Auto-ignition delay times

 Using a shock tube

 Laminer Flame Speeds

 Using a spherical bomb

EXPERIMENTAL FACILITIES

Experimental setup

16

52 mm I.D.

LOW PRESSURE 5.15 m

HIGH PRESSURE 2 m

Stainless Steel Reservoir (30 liters)

He

Vacuum Pump Pressure Gauge

0 - 50 bars

Vacuum Pump Pressure Transducers

CP4 CP3 CP2 CP1

Pressure Gauge 0-10 torrs

Magnetic Stirring ^Ar

0-10² torrs

Pressure Gauges

Vacuum Pump

114 mm

Toluene

0-10³ torrs0-10⁴

torrs Gas syringe

Setup (shock tube, pipes, tank) @ 405±2K

► Laser Extinction

Diagnostics Coupled to the Shock Tube

CH1 CH2

Transmitted Light

Narrow-band PM Filter He - Ne

Laser

Pressure Transducer

Oscillocope Numérique

Quartz Window

0 0.4 0.8 1.2 1.6 2

Temps (ms)

Lumière transmise

Pression

Diagnostics Coupled to the Shock Tube

Shock Tube End

Removable plate

5 nm 5 nm

Outer shell

 0,35 nm

0,14 nm

Inner core

Sonic Waves

► TEM at low and High Resolution

Diagnostics Coupled to the Shock Tube

Shock Tube End

Removable plate

0 100 200 300 400 500 600

0 100000 200000 300000 400000 500000

23 39 47 69 178 202 228 252 276 300 326 350 374 398 424 472 498

a.i.

m/z

0 100 200 300 400 500 600

0 100000 200000 300000 400000 500000

23 39 47 69 178 202 228 252 276 300 326 350 374 398 424 472 498

a.i.

m/z

0 100 200 300 400 500 600

0 100000 200000 300000 400000 500000

23 39 47 69 178 202 228 252 276 300 326 350 374 398 424 472 498

a.i.

m/z178 - 572 amu

LDIToFMS Sampling Holder

Soot on the plate

Mechanical chopper at 40KHz

m = mirror

d.m.= dichroic mirror f = interferential filter pol=polarizator

M=monochromator PMT = photomultiplier L = lens

PHD = photodiode

488 nm Ar ion laser

IR laser

chopper

periscope

m d.m

PHD+f

488+632.8 nm 90°

L pol PMT

PMT pol

PHD L

L

fv  I/I₀  Extinction diode laser l = 800 nm

Scattering Ar⁺ laser l = 488 nm  I_scat & I/I₀ d_p

Diagnostics Coupled to the Shock Tube

► Laser Scattering / Extinction

Gas inlet

Gas Sampling Behind the RSW

Sampling Bulb

Electromagnet

PM

Filter at 307 nm Photomultiplier C₄

F₁ F₂

OH* spontaneous emission

PM

Photomultiplier

CH* spontaneous emission

Filter at 432 nm

15

Auto_ignition Delay times

SW speed and Auto-ignition

0 4E-005 8E-005 0.00012

Time (s)

-0.05 0 0.05 0.1 0.15 0.2 0.25

PressureSignal

-2 -1.6 -1.2 -0.8 -0.4 0

EmissionSignal (V)

_ind

(a.u.)

0 4E-005 8E-005 0.00012

Time (s)

-0.05 0 0.05 0.1 0.15 0.2 0.25

PressureSignal

-2 -1.6 -1.2 -0.8 -0.4 0

EmissionSignal (V)

_ind

(a.u.)

-0.0004 -0.0003 -0.0002 -0.0001 0

Time (s)

-0.1 0 0.1 0.2 0.3 0.4 0.5

PressureSignal

n-propylcyclohexane

  

C2 : -3.869E-004 C3: -1.968E-004 C4 : -2.500E-007

-0.0004 -0.0003 -0.0002 -0.0001 0

Time (s)

-0.1 0 0.1 0.2 0.3 0.4 0.5

PressureSignal

n-propylcyclohexane

  

C2 : -3.869E-004 C3: -1.968E-004 C4 : -2.500E-007

(a.u.)

Volume : 56 L

P_max = 50 Bars

T_{max =} 470 K

Central Ignition

4 Silica Windows

diameter=550 mm

Schlieren System

High Speed Numerical Camera

VHT

Spark Electrodes

Oscilloscope HT

High Voltage Source

Spherical Bomb

Current Probe

To the Camera

I High voltage probe /1000

Experimental Setup: Laminar study

24

Spatial flame speed determination

Electrodes

Burned gases

Fresh gases

Flame front

25

Outward Spherical Flame Front Propagation

26

 

 



 



 



 

 

 



 

 

 



 

 

 u

b b

u u

b b

b S b

L P

P T

T M

M dt

dP P

3 V r

S

Eschenbach & Agnew (1958) expression

• M : relative molar mass

• P, T : pressure and temperature

• r : flame radius

•  : gas expansion ratio

  ^s

L V

In the early stages of the flame propagation

S

• t : time

• u : relative to unburned gas

• b : relative to burned gas



o Spherical flame

o Curvature and thickness negligible

o Adiabatic process and isentropic compression

o Chemical equilibrium behind the flame front

o No dissociation or reactions in the fresh gas

o Local deposit of the energy

Spatial flame speed determination

0 0.004 0.008 0.012 0.016

Time (s) 0

10 20 30 40 50

Radius (mm)

E.R. =1.05 E.R.=1.2 E.R.=0.85

^s

L

S V

Pressure remains constant

0 0.2 0.4 0.6

Time (s) -2

0 2 4 6

Overpressure(bar)

G222 + Air - MANIP 187 Equivalence ratio = 1.05 and

P_ini = 1 bar T= 363 K

-0.02 0 0.02 0.04

Time (s)

0 2 4

Overpressure (bar)

G222 + Air - MANIP 187 Equivalence ratio = 1.05 and

P_ini = 1 bar T= 363 K Pressure

Observation Window

t= 0.00033s t= 0.0025 s t= 0.0035 s

t= 0.00616s t= 0.009 s t= 0.01183s

V_burned

= 0.8 %V_total

27

Unstretched velocity

f S

r 2V

 







  V L

V _{s s} S _L ^  S _L  L  



Finite flame thickness



A uniform & well-defined stretch



Visualisation of the flame propagation

o Laminar flame velocity versus stretch

o Derive the laminar flame velocity at zero-stretch

28

EXEMPLE OF STUDIES

Real Fuels

Conventional Diesel Fuel

C7

C15 C8

C10 C9

C14

C11

C12

C15

C13 C13

C12 C11

C7 C8

C9 C10

C14 C15 C7 C8

C10 C9

C14

C11

C12

C15

C13 C13

C12 C11

C7 C8

C9 C10

C14 C8

C10 C9

C14

C11

C12

C15

C13 C13

C12 C11

C7 C8

C9 C10

C14 n-paraffins:

57.22 %_mass iso-paraffins:

42.78 %_mass

Fisher-Tropsch Cut at 403 K Fuel

Conventional Gazoline Fuel

Data source: TOTAL

Studied Fuels

 Hydrocarbons representing major component of the real fuel

 Diesel : n-hexadecane, butyl-benzene, n-heptyl benzene, decaline, a-methylnaphtalene, propyl-cyclohexane, butyl- benzene, 2,2,4,4,6,8,8 heptamethylnonane

 Gazoline : iso-octane, toluene, 1-hexene, 2M2B

 Kerosenes : n-decane, trimethyl-benzene, cyclohexane, n- propylbenzene

 Fischer-Tropsch : propyl-cyclohexane, 2,2,4,4,6,8,8 heptamethylnonane

 Additives

 ETBE , Thiophene, 3-methyl-thiophene

8

Diesel Fuel

 Pure Fuels

 n-decane, n-propylcyclohexane, n-butylbenzène

 Mixtures 60/40 (v/v)

 n-decane/n-propylcyclohexane

 n-decane/n-butylbenzene

 Mixtures 40/30/30 (v/v/v)

 n-decane/n-propylcyclohexane/n-butylbenzene

 EGR mixture (according to PSA) :

 77,6 % N2 + 11,5 % O2 + 6,8 % CO2 + 0,2 % CO + 3,9 % H2O

Studied Fuels

 Diesel Surrogate

 47 % Propyl-cyclohexane + 22 % Heptamethylnonane + 31

% Butyl-benzene

 Gazoline Surrogate

 50 % Iso-Octane + 35%Toluene + 15%1-Hexene

 Kerosene Surrogate

 80% n-decane + 20% n-propylbenzene

 Real Fuel : Fischer-Tropsch

 Cut at 403 K

What is soot ?

 Soot is:

 Solid phase with condensed molecules

 Mainly carbon and H with a ratio 8/1

 The density is roughly 1.85 g/cm³

 The primary particle is spherical

 Soot is constituted of

 Soluble fraction that depends strongly on the combustion conditions (fuel, engine load, injection system

 Dry fraction which is characterised by a turbostratic structure

34

SOOT TENDENCY OF FUELS

Soot Organization

 From the texture point of view

o soot is a particle of about a micrometer size

o If one looks closer, they are in fact agglomerate of primary spheres with an average size about 10 &

40 nm

o Their number can be as high as 100s

 The size is the main factor in the toxicity of soot particles

36 100 nm

Toluene pyrolysis @ 2000 K &14 bars

50 nm

Microtexture and structure

37

5 nm

TEM @ low resolution x 50 000

TEM @ high resolution x 310 000

Objectives of the Study

 How long does it take to form soot?

 How much soot can be formed?

 What is exactly formed?

 How do soot look like ?

 What kind of species are adsorbed on the surface ?

 How can these data be useful to the soot modeling?

Soot Properties

 Soot Optical Properties will depend on

 Type of agregates

 Mean diameter of the primary spheres

 Micro-Structure

 Soot Reactivity will depend on

 Micro-Structure

 Adsorbed phase

Refractive Index

Soot Oxidation Rate

Reaction Time

First Ring Formation

Inception and Growth of PAHs Soot Nucleation

Soot Growth due to surface growth and coagulation

Bockhorn, 1994

Main Soot Formation Mechanism

Soot Volume Fraction Measurement

BEER-LAMBERT Law & Graham’s model (1975)

I

I

I I m

E

f_v L ln ^o

) ( 6  

 

l

0 0.0004 0.0008 0.0012

Time (s)

0 4E-007 8E-007 1.2E-006

Soot volume fraction (cm3/cm3)

0 0.4 0.8 1.2

Pressure (a.u.)

_ind

f_vmax

t f k

f

ln f _f

v v

v 

 



     I

ln I C

l ) m ( E 72

N C

C ₀

total av

total suies



 l





 Growth Constant

 Soot Yield

 Induction Delay

    



 





 







 R T

exp E Diluant

HC

A ^{a b ind}

ind

Studied Parameters

 Morphology and structure of the soot (T.E.M.)

CRMD

 Low Resolution: Aggregates, diameter distribution

 High Resolution: Arrangement of the carbon layers

 Adsorbed Phase on soot

Experimental Conditions

FT

(C_11.23H_24.46) T₅(K) P₅(MPa) [Carbon]₅

(atoms.cm-3)

Eq. ratio ()

O₂% (mol.) in Ar 0.4% mol.

1675-2540 1.24-1.71 (1,83-2,76).10⁺¹⁸  0%

1630-2325 1.51-1.65 (2.11-2,50).10⁺¹⁸ 18 0.42%

1525-1920 1.05-1.48 (2,17-2,49).10⁺¹⁸ 5 1.33%

0.2% mol. 1500-2225 1.15-1.65 (1,15-1.38).10⁺¹⁸  0%

Argon Dilution usually > 99 %

Induction Delay Times

4.0E-004 5.0E-004 6.0E-004 7.0E-004

1/T5 (K-1)

1 10 100 1000

Induction delay time (µs)

Mathieu et al. (31^st Symp):

: [C₅] = 1.0±0.1x10¹⁸ at.cm^-3 1100 < P₅ (kPa) < 1650

Douce et al. (28^th Symp):

1245 < P₅ (kPa) < 1805

: [C₅] = 2.0±0.4x10¹⁸ at.cm^-3

: [C₅] = 4.9±0.8x10¹⁸ at.cm^-3

 



 



 





 ^{ }

) ( 21690 exp

] [

046 .

0 ^{0.50 0.93}

K P T

x

µs _toluene

ind

4 4.5 5 5.5 6 6.5 10000/T₅ (K^-1)

1 10 100 1000 10000

ind(µs)

0.75 < [C]10^-18 (at.cm^-3) < 1.42 1.56 < [C]10^-18 (at.cm^-3) < 2.39 3.63 < [C]10^-18 (at.cm^-3) < 5.71

LP

HP

HP

TOLUENE PYROLYSIS

LP : 200 < P5 (kPa) < 460 HP : 1250 < P5 (kPa) < 1800

Douce et al. (28^th Symp):

Induction Delay Times

4.0E-004 4.5E-004 5.0E-004 5.5E-004 6.0E-004

1/T₅ (K^-1)

10 100 1000

Induction delay (µs)

Fischer-Tropsch n-decane [1]

Iso-octane [2]

cetane [3]

Iso-cetane [4]

Diesel surrogate [4]

Pyrolysis

1.400.4 MPa 2.00.5 C at. cm^-3

Pyrolysis (2.00.5)x10¹⁸at.cm^-3 1.4 MPa 0.4

 

 





K T n

µs n

H C

ind 8,314

165000 exp

10 4 , 1

04 , 3

 3 ^{R2 = 0,9355}

4x10^-4 5x10^-4 6x10^-4 7x10^-4

1/T₅ (K^-1)

10⁰ 10¹ 10² 10³ 10⁴

Induction Delay (µs)

n-hexadecane

decahydronaphtalene

n-heptylbenzene Toluene

1-methylnaphtalene

Summary

46

C₄ Route : C₂H₃+C₂H₂C₄H₅

C₂H+C₂H₂C₄H₃ puis,

C₄H₅+C₂H₂ +H C₄H₃+C₂H₂C₆H₅ Slow

Route Aromatic

Aliphatic

Fast Route

C₃ Route:

C₃H₃+C₃H₃C₆H₅+H C₃H₃+C₃H₄ +H

2 nm

20 nm

+H

HACA Mechanism

HAP

+ H  + H₂

+C₂H₂ -H

+C₂H₂ -H

+H -H₂

+C₂H₂

Soot Yield - Toluene

1600 2000 2400 2800

T5 (K)

0 4 8 12 16 20

Soot Yield (%)

Douce et al. (PCI, 2000):

: [C₅] = 2.0±0.4x10¹⁸ at.cm^-3 Mathieu et al. (PCI, 2007) :

: [C₅] = 1.0±0.1x10¹⁸ at.cm^-3















 



 







2

max exp

T T A T

Y

Y ^opt

 



 _v

initial av

initial

soot f

C N C

Y C



 12

] [

] [

• Soot Yield’s definition:

• Soot Yield’s representation:

Soot Yield

1200 1600 2000 2400 2800

T₅ (K)

0 20 40 60

Soot Yield (%)

1-methylnaphtalene Toluene

decahydronaphtalene n-heptylbenzene n-hexadecane

Douce et al. (PCI, 2000)

Mathieu et al. (Combst. Flame, 2009)

1600 2000 2400

T5 (K)

0 2 4 6 8

Soot yield (%)

Pyrolysis

 ISO [10]

 7MN (this work)

 HDC [9]

1600 2000 2400

T5 (K)

0 2 4 6 8

Soot yield (%)

Pyrolysis

 ISO [10]

 7MN (this work)

 HDC [9]

Effect of Oxygen

4.0x10^-4 5.0x10^-4 6.0x10^-4 7.0x10^-4

1/T₅ (K^-1)

10¹ 10² 10³ 10⁴

Induction delay (µs)

Decahydronaphtalene Pyrolysis

Equiv. Ratio = 18 Equiv. Ratio = 5

r = 0,994 r = 0,987 r = 0,994

1200 1600 2000 2400

T5 (K)

0 4 8 12

Soot Yield (%)

Decahydronaphtalene Pyrolysis

Equiv. Ratio = 18 Equiv. Ratio = 5

Douce et al. (PCI, 2000)

TEM - Toluene / Ar

50 T₅ = 1700 K ; P₅ = 1714kPa

T₅ = 2000 K P₅ = 1433kPa

446 measurements Average d_m = 26.2 nm Standard deviation = 3.78

8 12 16 20 24 28 32 36 40 44 0

20 40 60

Number of particles

Particle diameter (nm)

297 measurements Average d_m = 17.9 nm Standard deviation = 1.71

8 12 16 20 24 28 32 36 40 44 0

20 40 60 80

Number of particles

Particle diameter (nm)

TEM – Size distribution

Toluene Pyrolysis (T₅=1700 K ; P₅= 1714 kPa)

Nb of data points used : 446 Average d_m = 26.19 nm Standard deviation = 3.78

Toluene Oxidation (=5) (T₅= 1685 K ; P₅= 1266 kPa)

Nb of data points used : 81 Average d_m = 17.95 nm Standard deviation = 2.33 Toluene Oxidation (=18)

(T₅=1685 K ; P₅= 1802 kPa)

Nb of data points used : 150 Average d_m = 26.44 nm Standard deviation = 2.43

Number of particles

8 12 16 20 24 28 32 36 40 44 0

20 40 60

Particle diameter (nm)

8 12 16 20 24 28 32 36 40 44 0

4 8 12 16 20

Number of particles

Particle diameter (nm)

8 12 16 20 24 28 32 36 40 44 0

10 20 30

Number of particles

Particle diameter (nm)

MET

52

1400 1600 1800 2000 2200

T5 (K)

10 20 30 40

Primary particles diameter (nm)

Microtexture and structure

53

Raw Image Coherent

Domain

% single layer L : layer diameter

d₀₀₂ : interlayer spacing L_a : BSU diameter

L_c : BSU height

a : desorientation degree

Layer Extension

54

1% toluene + 99% Argon T₅ = 1718 K, P₅ = 1720 kPa

0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5 5.5 6 L_a (nm)

0 0.2 0.4 0.6 0.8

Fréquence relative Toluene/Argon

1700 K, 1714 kPa Thickness: 0.247 nm

La moy = 0.58 nm

Toluene/Argon

T5 = 1700 K ; P5 = 1714kPa

Toluene/Argon

T5 = 2000 K ; P5 = 1433kPa

Mean diameter : 26 nm Interlayer spacing : - inner core : 0.43 nm - outer shell : 0.39 nm Carbon layer : 0.58 nm

Texture : spherical, homogeneous

Mean diameter : 18 nm Interlayer spacing : - inner core : 0.39 nm - outer shell : 0.39 nm Carbon layer : 0.58 nm

Texture : spherical, homogeneous

5. Soot micro-structure

(a) 1475 K

10 nm (a) 1475 K

10 nm (a) 1475 K

10 nm

(b) 1765 K

10 nm (b) 1765 K

10 nm (b) 1765 K

10 nm (c) 2135 K

10 nm (c) 2135 K

10 nm (c) 2135 K

10 nm 10 nm

(d) 2135 K

10 nm (d) 2135 K

10 nm (d) 2135 K (a) 1475 K

10 nm (a) 1475 K

10 nm (a) 1475 K

10 nm

(b) 1765 K

10 nm (b) 1765 K

10 nm (b) 1765 K

10 nm (c) 2135 K

10 nm (c) 2135 K

10 nm (c) 2135 K

10 nm 10 nm

(d) 2135 K

10 nm (d) 2135 K

10 nm (d) 2135 K

x 310 000

La = Lateral extension of the poly-aromatics layer.

Interlayer spacing  as the temperature of

formation  (Douce et al., Proc. 4^th Int. Conf. on Internal Comb. Engine)

At 1475 K:

- Short La and low

degree of organization - Short La = important density of edge site

carbon atoms  reactive surface (Vander Wal and

Tomasek, Comb. and Flame 134, 2003)

Effect of Temperature on micr- structure

56

Optical Properties of Soot

57

Authors Spectral Domain Real Parti Imaginary Part

Erickson et coll. visible 1,4 1

Chippet et Gray Visible 1,9-2,0 0,35-0,50

Bockhorn et coll. Visible 1,1 0,37

Lee et Tien Visible 1,8-2,0 0,45-0,65

Dalzel et Sarofim Visible 1,57 0,56

Stagg et 633 nm 1,531±0,004 0,372±0,007 Charalampopoulos

Mullins et Williams 633 nm 1,91±0,02 0,425±0,035 Chang et Visible 1,94 0,6

Charalampopoulos

Habib et Vervisch 600-650 nm 1,47 0,24±0,01 Vaglieco et coll. 637 nm 2,515 0,836 Felske et coll. 2-10 µ m 2,46±0, 15 0,8±0,14

Effect of soot refractive index on Fv

58

P₅ = 1299 kPa T₅ = 1865 K

0,4% de n-décane 99,6% d ’argon

[C]_total = 2,01.10¹⁸ at.C/cm³

0 0.001 0.002 0.003 0.004

Temps (s) -5E-007

0 5E-007 1E-006 1.5E-006 2E-006

Fraction Volumique (cm3 de suies.cm-3)

Felske et coll.

Chippet et coll.

Lee et coll.

Bockhorn et coll.

Dalzell et coll.

Erickson et coll.

Fractions Volumiques

P₅ = 1299 kPa ; T₅ = 1865 K



 







 

 m 2

1 Im m

) m (

E ₂

2

Species adsorbed on Soot

O. Mathieu et al, PCI, 2009

Mass increment sequences

of 24 amu between major peaks interrupted by increment

of 26 amu

Major Peaks are Benzenoïd

LDIToFMS Study

0 100 200 300 400 500 600

0 100000 200000 300000 400000 500000

23 39 47 69 178 202 228 252 276 300 326 350 374 398 424 472 498

a.i.

m/z

0 100 200 300 400 500 600

0 100000 200000 300000 400000 500000

23 39 47 69 178 202 228 252 276 300 326 350 374 398 424 472 498

a.i.

m/z

1670 K

Rendement = 7 %

Major Peaks:

• Benzenoïd HAP : 202, 228, 252, 276…

• Non Benzenoïd HAP: 165, 190, 216, 240, 266, 290 & 314

1475 K Y_suies = 1 %

O. Mathieu et al, PCI, 2009

AUTO_IGNITION DELAY TIMES

Fuel T (K) P (bar) X_fuel (ppmv) X_O2 % Ar 

(PCH) C₉H₁₈ 1 250 – 1 800 10 - 20 75 – 1 000 4 500 – 68 000 93,1 – 99,75 0,2 – 1,5 (BBZ) C₁₀H₁₄ 1 225 – 1 800 10 - 20 75 – 1 000 4 500 – 67 500 93,2 – 99,5 0,2 – 1,5 (DEC) C₁₀H₂₂ 1 225 – 1 825 10 130 - 875 9 000 – 10 000 99 0,2 – 1,5

Mélange T (K) P (bar) X_mélange (ppmv) X_O2 % Ar 

C₁₀H₂₂ - C₉H₁₈ 1 250 – 1 750 10 135 – 930 9 000 – 10 000 99 0,2 – 1,5 C₁₀H₂₂ -

C₁₀H₁₄

1 225 – 1 750 10 135 – 930 9 000 – 10 000 99 0,2 – 1,5

T (K) P (bar) X_mélange (ppmv) X_O2 % Ar % EGR 

1 275 – 1 850 10 90 - 600 5 800 – 10 000 99 0 et 40 0,2 – 1,5

17

Experimental Conditions

Pure Fuels

Binary Mixtures

Ternary Mixtures + EGR