IncorporationIncorporation ofof CatalyticCatalytic CompoundsCompounds inin thethePorosityPorosity ofof SiCSiC WallWall FlowFlow FiltersFilters ––
44 WayWay CatalystCatalyst andand DeNOxDeNOx ApplicationApplication examplesexamples
DEER MEETING
August 15TH-2007 - Detroit (MI)
Jean-Pierre JOULIN CTI Bruno CARTOIXA CTI Didier TOURNIGANT CTI
Arnold LAMBERT IFP Jean-Christophe RUIZ CEA Anne JULBE IEM
CERAMIQUES TECHNIQUES ET INDUSTRIELLES S.A.La Resclause - Route de Saint Privat F 30340 SALINDRES - FRANCE
E-mail: [email protected] Site internet: www.ctisa.frPhone: +33 466 858 870 Fax: +33 466 857 009
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AGENDA
• Short CTI presentation
• Introduction – Why to concentrate in one or two components all the exhaust gas
containing HC, CO, NOx and PM
• Exploration of 3 different methods of catalyst impregnationinside the pore of a SiC DPF – Supercritical CO2 method – Sol Gel impregnation – Incorporation of catalyst with the slurry forcing method
• Zeolith impregnation of SiC DPF for DeNOx function usingSCR method
• Conclusions CTI - CONFIDENTIAL
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SHORT CTI PRESENTATION
CTI is specialized in perfecting the design of a wide range of technical ceramics often porous, whose applications are mainly in environment, filtration, catalysis fields and SOFC.
These include :
• Liquids filtration : membranes supports in ultra and micro filtration. • Gas and particles filtration : tubular, flat, honeycomb, foam filtration
carriers, diesel particulate filter. • Catalysts supports : pellets with high specific area, honeycombs,
smooth and grooved porous rings. • Liquid metals filtration : honeycombs and foams refractories. • Special refractories : withstanding temperatures higher than 1 600°C. • Special ceramic washcoast for COx, DeNOx, VOC treatment and
SOFC applications.
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Factory area : 6 000 m2
Laboratory and pilot area : 1 000 m2
Industrial and laboratory equipment :
mixers (1 to 1200Kg), extrusion press (1 to 400L), high frequency and microwave dryers, gas and electric kilns (0.4 to 10m3 until 1700°C), laboratory equipment, ...
•Scientific manager : JP. JOULIN • Adm. & Financial Manager : N. DELBIANCO •Dr in Catalysis & membranes : E. LOURADOUR
D. TOURNIGANT •4 Ceramic engineers : L. ESPIN
B. CARTOIXA F. PEY G. GAUDRY
• Quality insurance : S. ENJOLRAS •10 Technicians & laboratory people
Created : 8th of march 1990
Independent SME . French Institute Of Petrol as Share holder Capital : 220 000 €
Numbers of employees: 75
Membrane materials and design forHigh temperature applications ( > 500°C)
Inert porous supports (mainly for filtration):Al2O3, SiO2, TiO2, SiC, ZrO2, Y2O3….
Geometry design Active materials (for catalysis)CeO2/ZrO2
granules, foams, tablets,
Honeycomb, flat, tubular, CeO2/Al2O3/Pt, CeO2/Gd zeolithes,
washcoat, membrane ZnO, V2O5
Perovskites (LSM), ….. 5
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HC, CO, NOx, PM
INTRODUCTION
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Diesel emissions reduction legislation trends in Europe
Euro4 UFEuro4 UF DPFDPF systemsystem
VehicleVehicle’’s environmental progresss environmental progress
Fiat courtesy
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CURRENTLY DPF SYSTEM + DeNOx TRAP
CURRENTLY DPF SYSTEM + DeNOx TRAP
SYSTEMS PROCESS
Catalysed DPF Cordierite Catox + SiC DPF - Soot Oxydations with NO2 with or without catalysis
SCRT System (JM)
Cordierite Catox + SiC/cordierite DPF+SCR-NOx
-Soot Oxydations with NO2
NO2+PM CO 2+N2
-Catalytic reduction of NOX
DPNR System (Toyota)
Cordierite Catox + DPF+N0x trap 4 WAY CATALYSIS
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4-WAY CATALYSIS : eliminate HC, CO, NOx and PM with a single treatment
Catalytic phase impregnation + NOX deeptrapping within the pores of the filtering
support
¾ Favor the NOx trapping and the oxidative catalysis in terms of volume (high SBET) together with the important function of absolute particles filtering (no thick covering of the surface that would desactivate the catalyst and blocks the NOx trapping).
¾ Favor the synergy effect between NOX trapping and particles oxidation
Interest of nanophased materials :
¾ Homogeneous materials, finely divised with
high SBET
¾ specific properties (surface activity highly increased)
device
Particles trapped and oxidized when passing through the pores
Catalyst + NOx trap deposited onto the
ceramic walls
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CTI has developed a new composite SiC DPF able to be easily catalysed. The catalyst is impregnated inside the porosity of wall flow :
• Porosity of the CTI SiC DPF is around 46% and pore size around 17/19 µ.
• The great advantage of CTI’SiC composite product is to be already treated against all the oxidation attacks and so to preserve the catalyst performance during ageing. 11
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Since 2003 CTI has explored 3 different ways of catalysis impregnation :
• CO2 supercritical impregnation with CEA(Pierrelatte, Atomic Energy Center)
• Sol gel impregnation with IEM Montpellier (European Institute of membrane)
• Forced slurry method with IFP (French Petroleum Institute) (patented)
EXPLORATION OF 3 DIFFERENT METHODS OF CATALYST IMPREGNATION
INSIDE THE PORE OF A SiC DPF
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SEM PHOTO OF A CTI’S DIESEL PARTICULATE FILTER (DPF)
Wall flow filter
Soots
Soot Deposit configuration before regeneration
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SUPERCRITICAL CO2 METHOD
with collaboration of CEA Pierrelatte - 2004
Pressure
Supercritical CO2
7,4 MPa LiquidSolid Critical
point
Triple Gaz point
Temperature 304,1 K
Phase diagram of supercritical CO2
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MATERIALS
Particularity : The synthesis and macroporous support impregnation was carried out in a single step, in a 1 litre high-pressure vessel. After introducing a specific amount of selected catalyst formulation in the autoclave containing the monolith, the liquid CO2 was pumped into the vessel up to the operating pressure of 30 MPa. The reaction temperature was regulated at 573 K using an external electric heater. The contact time of the reactants in SC CO2 was 1 hour
Vent TP
Pumps Cooler
Heater
High pressure vessel
T
PPPP
Solution of Precursors + Monolith
Liquid CO2 Tank
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SiC grain
Catalyst layer
Catalyst layer
SiC grainSiC grain
Catalyst layer
SiC grain
Cordierite
Catalystlayer
layer
eriteCatalystlayer
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RESULTS – SEM – SiC and Cordierite analysis
SiC grain
Catalyst layer
Catalyst layer
SiC grain 550
400 - 700
150
Thickness (nm)
3.2SiC 76mm**
1.7Cordierite 15mm
1.5SiC 15mm
Mass deposited (%wt)
Samples material / length
Sol composition : Alumina – Zirconia – Ceria – Baryum oxyde
CordiCordierite
Catalyst layer Cordierite
Catalyst layer
**thickness of the active layer after 2 impregnations
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SOL GEL IMPREGNATION
with collaboration of IEM Montpellier
CERAMICS GRIT IMPREGNATED WITH NANOPHASE
CATALYST (350 nm layer) ON HONEYCOMB FILTER 1/2
19Sol gel composition Alumina, Ceria, Zirconia, Baryum oxide CTI - CONFIDENTIAL
2 3 4
ise
de p
oids
cum
ulée
(%)
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0 1 5 0,0
0,5
1,0
1,5
2,0
2,5
3,0
3,5
4,0
4,5
5,0
Pr
Nombre d'imprégnations
CERAMICS GRIT IMPREGNATED WITH NANOPHASE
CATALYST (350 nm layer) ON HONEYCOMB FILTER 2/2
Number of coatings
Wei
ght
incr
ease
(%)
SiC3092 SiC1891
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ONFIDENTIAL
MULTI IMPREGNATION RESULTS
4M18SiC3092-3 (coupe)
4M18SiC3092-9 (cloison)
4M18SiC3092-2 (coupe-surface)
* Layer thickness is around 2µ after depositio * Cracks can appear up to 4 layers
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INCORPORATION OF CATALYST
WITH THE SLURRY FORCING METHOD
with collaboration of IFP (French Petroleum Institute)
Incorporation of a NOx-trap type catalytic formulation inside the porosity of a SiC wall flow filter
(WFF) has been performed, forcing a slurry of the catalyst
through the substrate.
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SLURRY PREPARATION
NOx trap formulation :
Precious metal Pt, Pd, Rh
Catalyst oxide :BaO - CeO2 - ZrO2 - Al2O3
Adjust the viscosity and particle size distribution
• fluid enough
• Dv90/Dpores < 0.25
Dv90 : measured by laser diffraction
Dpores : mean pore size of the WFF, measured by Hg porosimetry
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IMPREGNATION
SiC cores characteristics:
1" diameter, 3" length, 180 cpsi,
20 µm mean pore diameter,
55% porosity
impregnation unit
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CHARACTERISATION / TESTING
SEM pictures of a core loaded with 159 g/l catalyst
• Washcoat inside the porosity
• Whole SiC surface coated
•Thickness 1 to 8 µm
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SCALE UP
5"66 diameter, 6" length, 180cpsi, 19 µm mean pore
diameter, 50% porosity
washcoat loading : 190 g/l
washcoat-induced pressure drop : 15 mbar (50000 h-1)
Scale up succeeded
• high loading
• low pressure drop
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0
5
10
15
20
25
108 103 159 185
Washcoat loading (g/l)
P r es
su r e
d r o
p in
d u ce
d b y
w as
h co a
tde
po s i
t io n
( m b
a r ),
at 6
3 00 0
h -1
Pressure drop as a function of washcoat loading
0
10
20
30
40
50
60
70
80
90
100
100 150 200 250 300 350 400 450 500
temperature (°C)
NO
x co
nver
sion
(%)
110 g/l
208 g/l
Synthetic gas bench testing of deNOx activity
• Low pressure drop at high loading
• DeNOx activity comparable to that of flow through monoliths
CONCLUSIONS OF IFP/CTI METHOD
• Versatile method to deposit any type of catalytic formulation inside the porosity of wall flow filters • Method has been scaled up to real size filter • Key point resides in adapting the slurry's particle size distribution to the mean pore size of the substrate.
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0
10
20
30
40
50
60
70
80
100 150 200 250 300 350 400 450 500
Temperature ( °C)
Con
vers
ion
NO
x(%
)
Reference ceramic contactorsol gel route 60g/LSupercritical CO 2 route 48 g/L
Reference ceramic contactorsol gel route 60g/LSupercritical CO 2 route 48 g/L
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FIRST QUALITATIVE CATALYSIS RESULT FOR NOx CONVERSION COMPARISON OF THE DIFFERENT METHODS
0
10
20
30
40
50
60
70
80
100 150 200 250 300 350 400 450 500
Temperature ( °C)
Con
vers
ion
NO
x(%
)
180 g/L sol gel route 60g/L Supercritical CO 2 route 48 g/L
OTHERS ‘ IMPREGNATION TRIALS WITH THE SAME TECHNOLOGY
Zeolith impregnation of CTI SiC DPF for DeNOx function using SCR method.
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IMPREGNATIONN° Filter CTI CTI 039/06 CTI 031/06 CTI 033/06
N° Filter IFP EC89 EC90
Mass before impregnation (g) 1817 1877 1811
Mass after impre + Calcination IFP (g) 2156,4 2059,5 non calcined
Impregnated
Non
Mass after impre + Calcination CTI 500°C/2h00 (g) 2048,2
Masse addes cata in g 339,4 171,2
Volume of the filter in liter 2,47 2,50 2,47
Content cata in g/liter 137,41 68,48 0
Sight face
Sight cells ∆P - mb
Stream of air co-current to the direction of impregnation
Flow 100 m3/h 7 5 3
Flow 200 m3/h 16 12 9
Flow 300 m3/h 27 21 16
Stream of air against the current of the direction
of impregnation
Flow 100 m3/h 6 5 3
Flow 200 m3/h 15 13 9
Flow 300 m3/h 26 22 16
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PHOTO OF THE CTI’S DPF AFTER IMPREGNATION
IMPREGNATIONMEB PHOTO
Total zeolith deposition is inside the pore. There is no layer at the surface. Porous cavity of the support are sometimes plugged by the zeolith depending
on the concentration.
68g/l 279g/l
3420/12/2006 B. Cartoixa CTI - CONFIDENTIAL
IMPREGNATIONMEB PHOTO
68g/l 279g/l
Excellent catalyst penetration with partial plugging of some pores, depending of the slurry concentration
20/12/2006 B. Cartoixa CTI - CONFIDENTIAL
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200
300
600
ΔP
(mm
H2O
)
Débit air à 100 m3/h
Débit air à 200 m3/h
Débit air à 300 m3/h
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IMPREGNATION BACK PRESSURE MEASUREMENT
20/12/2006 B. Cartoixa
ΔP = f (wt% cata avec flux d'air à contre-courant de l'imprégnation)
0
100
400
500
0 50 100 150 200 250 300
wt% cata (g/l)
∆P
(mb)
10
20
30
40
50
60
Air flow 100m3/h
Air flow 200 m3/h
Air flow 300m3/h
100
200
300
400
500
600
Débit air en m3/h
ΔP
(mm
H2O
)
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IMPREGNATION CHARACTERISATION DP
20/12/2006 B. Cartoixa
ΔP = f (débit d'air à contre-courant de l'imprégnation)
0 0 50 100 150 200 250 300 350
EC 88 257g/l
EC 89 137g/l
EC 90 68g/l
ref 0g/l
20
10
30
40
50
60
∆P
(mb)
Air flow in m3/h
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190-230° C 250 - 300° C
• MOTOR BENCH TEST FOR ZEOLITH DeNOx DPF Content 137 g/l
Exhaust sytem schema
temps
NOx EMISSION
BEFORE AND AFTER DPF
sans injection
injection d'air injection air + injection d'Urée
sans in jection d'air
injection d'air
1000
900
800
700
600
500
400
300
200
0 0 600 1200 1800 2400 3000 3600 4200 4800 5400 6000 6600 7200
émissions amont FAP
dilution
émissions aval FAP
rétention rétention
di+
lution
Time (s)
NO
x (p
pm)
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100
EFFICACITE FAP ((NOx amont - NOx aval)/NOx amont)
temps
Effic
acité
FA
P (%
)
efficaciefficact
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0
10
20
30
40
50
60
70
80
90
100
0 600 1200 1800 2400 3000 3600 4200 4800 5400 6000 6600 7200
té réelle é relative
efficacité due à la dilution efficacité due à
la rétention
REAL AND RELATIVE EFFICIENCY
DPF NOx efficiency ((NOx amont – NOx aval))/NOx amont)
Efficien
cy F
AP
(%)
Real efficiency
Relative efficiency
Time (s)
EVOLUTION DE LA PERTE DE CHARGE DU FAP
temps
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DELTA P EVOLUTION OF THE DPF
0
20
40
60
80
100
120
140
160
180
200
0 600 1200 1800 2400 3000 3600 4200 4800 5400 6000
(mba
r)
VVH 30000 VVH 66000
retour
∆P
Time (s)
CTI rev3.0 CTI rev3.242
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PM / MVEG Cycle
0
0,001
0,002
0,003
0,004
0,005
0,006
CTI rev3.1
PM g/K
m PM EFFICIENCY OF THE PARTICULATE FILTER
(test made by IFP)
The CTI product when it is virgin (worst condition) is 3 to 4 time below the upper limit requested for Euro V in 2009 (SMPS test done by IFP).
EURO 5
CTI 20µ CTI 15µ CTI asymetric shape
CONCLUSIONS
• The 3 different impregnation methods shows a real industrial potential for 4 way catalysistechnology or separatively CatOx + DPF DeNOxfunction.
• Today the most easy and cheapest method seems to be the slurry forcing technology (Patent IFP – CTI)
• CTI’s composite SiC product could be easilyimpregnated with catalyst with very low increaseof back pressure.
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This work has been done with the financial support of the : French Research Ministry Predit VP008
convention 04K133 From june 2004 until june 2007 (Cti - Peugeot -Irma –Faurecia- Le moteur moderne Eft )
FSH (Fonds de soutien hydrocarbure) from 2001 until 2004 (A50004/01 – A59009/01)
(IFP –CTI)
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CERAMIQUES TECHNIQUES ET INDUSTRIELLES S.A.
THANK YOU FOR YOUR ATTENTION
CERAMICS MANUFACTURER AS ENVIRONMENTALLY FRIENDLY
MATERIALS
C.T.I. S.A.La Resclause - Route de Saint Privat F 30340 SALINDRES - FRANCE E-mail: [email protected] Site internet: www.ctisa.fr
�: +33 (0) 4 66 85 88 70 Fax: +33 (0) 4 66 85 70 09 45
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