Emission catalyst solutions

for Euro 5 and beyond

toni.kinnunen@ecocat.com

www.ecocat.com

ECT 2011, New Delhi

November 9-10, 2011

Dr Toni Kinnunen

CTO, Ecocat Group

Complete diesel aftertreatment system

Based on application, normally only some of above are needed

Ecocat has the whole range of catalysts in portfolio;

substrates and coatings

Ecocat has technology for both SCR and active DPF systems

UREA

INJECTION

Regeneration

Light-

off

DOC/

POC SCR DPF

AS

C H-cat

Portfolio of Products and Technology by Segments

Diesel Oxidation Catalyst (DOC)

Particle Oxidation Catalyst (POC) Diesel Particulate Filter (DPF)

Selective Catalytic Reduction (SCR) 3-way Catalyst and

Industrial and Off-road Catalyst

Tailor made interactions

PM

PM

PM PM

PM

PM

PM

PM

PM

Ready made

Powder or Slurry Ready made

Powder or Slurry

Pd, Rh, Pt, La, Al, Ce,

Zr, Pr, Sr, Nd, Y, Ba,

Si, Ti, W etc.

mainly as oxides

Chemistry in key role

Challenges in exhaust gas catalysis chemistry

Need for continuous development

- better cost efficiency (”better and cheaper”)

- improved durability (temperature, poisons)

Molecular scale modifications and analyses

Nanotechnology

Additional challenges

- impurities of poor biodiesels and batch-to-batch variations

- other alternative fuels require tailoring case by case

- regulations vs. dirty fuels (developing countries, off-road)

- city driving conditions in big cities

Chemistry in key role

Path Mechanism Reaction aE (eV) k (s-1

)

1/2 LH vacancy(g)COOCO 2

*

s

* 0.66 107

3 ER vacancy(g)COOCO(g) 2

*

s 0.70 10-3

4 LH O(g)COOCO *

2

*

2

* 0.57 108

(-3.20eV)

(-2.65eV)

Computational chemistry in daily use

Chemistry in key role

SCR technology

PM reduction technologies

Natural gas catalysis

SCR systems

Urea Hydrolyser

V-SCR catalyst (and ASC)

dosing units and control

Reactions in SCR systems

PreOxicat

Hydrolysis

NO + O2 NO2

CO(NH2)2CO + H2O 2 NH3 + CO2

SCR catalyst

4 NO + 4 NH3 + O2 4 N2 + 6 H2O

NO + 2 NH3 + NO2 4 N2 + 3 H2O

PostOxicat 4 NH3 + 3 O2 2 N2 + 6 H2O

4 NH3 + 3 NO2 3.5 N2 + 6 H2O

standard SCR

fast SCR

NO2-SCR

Metallic substrate for mixers and H-catalysts

EcoXcell®

• Welded, mixer-type structure for coated catalysts having efficient 3D

mass and heat transfer

• EcoXcell 20° for SCR applications

Hydrolysis catalyst coating

SCR catalyst coating

H cat only laboratory experiments

Product distribution with empty reactor

Nominal inlet: 1000 ppm NO, no NO2, 500 ppm Urea, 10 % O2, 8 % H2O, N2 balance

Standard flow rate

Urea hydrolysis products- empty reactor

0

200

400

600

800

1000

1200

450350300260230205180

Temperature before cat, °C

pp

m N N2O

NOx

HNCO

NH3

unreacted urea ~50 % of urea unreacted

H cat only laboratory experiments

Product distribution with HT700 KH1.1+KH2.2 (good adhesion/improved selectivity)

Nominal inlet: 1000 ppm NO, no NO2, 500 ppm Urea, 10 % O2, 8 % H2O, N2 balance

SV = 100 000 h-1

Urea hydrolysis products- KH1.1+KH2.2 (w8090-200 cpsi)

HT700 aged

0

200

400

600

800

1000

1200

450350300260230205180

Temperature before cat, °C

pp

m N

N2O

NOx

HNCO

NH3

unreacted urea

Almost only NH3!!

no by-products

Engine 6.9 L; Catalyst 12.8L, 500 cpsi Ecocat

NOx conversion curve

0

20

40

60

80

100

200 250 300 350 400 450 500 550

Temperature, °C

NO

x c

on

ve

rsio

n, %

(NH

3 <

20

pp

m)

16.500 h-1

1420 ppm NOx

51.000 h-1

930 ppm NOx

61.000 h-1

1170 ppm

NOx

57.000 h-1

990 ppm NOx

28.000 h-1

465 ppm NOx

Urea-SCR engine results- MAN 6.9L, 15 h aged

KSCR2, 500 cpsi, 12.7L

0

10

20

30

40

50

60

70

80

90

100

200 250 300 350 400 450 500 550

Temperature, °C

Cri

teri

a N

Ox c

on

vers

ion

, %

(20 p

pm

NH

3)

KSCR2, 20 ppm NH3

KSCR2, 10 ppm NH3

16.500 h-1

30.000 h-1

51.000 h-1 61.000 h-1 58.000 h-1

Effect of NH3 slip criteria limit

No significant changes in performance

without any additional NH3 slip catalyst

0

10

20

30

40

50

60

70

80

90

100

200 250 300 350 400 450 500 550

Temperature, °C

Cri

teri

a N

Ox c

on

vers

ion

, %

(20 p

pm

NH

3)

16.500 h-1

30.000 h-1

51.000 h-1 61.000 h-1 58.000 h-1

krit eeri2_14dec07

Extruded ref

Ecocat 500 cpsi

Ecocat 350 cpsiEcocat 220 cpsi

Effect of cell density (surface area)

Euro 6/US2010

Euro 5

Euro 4

Target conversions

Catalyst amounts:

Ecocat 500 cpsi 170 g/L

Extruded 300 cpsi ~ 500 g/L

Ecocat volume/engine volume = 1.86

- Good durability by burner ageing at 570°C/100 h expect a slight deacrease in mode 1 point

Compensation by the use of ASC

SCR Activity after burner ageings

66

9396 97 95

79

98 98 99

7777

9598 98

88

0

10

20

30

40

50

60

70

80

90

100

MODE 10 (230°C) MODE 9 (260°C) MODE3 (310°C) MODE2 (400°C) MODE1(480°C)

Cri

teri

a N

Ox

co

nv

ers

ion

, %

(2

0 p

pm

)

Pt-DOC+KSCR2-300 cpsi FRESH

Pt-DOC+KSCR2 300 cpsi - Burner aged 570°C/100h

Pt-DOC+KSCR2-300cpsi+4Pt/ASC- Burner aged 570°C/100h

230°C

20.000 h-1

260°C

19.000 h-1

310°C

43.000 h-1

400°C

48.000 h-1

480°C

51.000 h-1

Effect of ASC

Ecocat SCR: the first EPA and CARB approval for V-SCR (off-road)

Urea Dosing System

Injection nozzle

Electrical Air Pump

Aftertreatment Control Unit

Urea Tank

Motor:

• Iveco F1C E4 3l

• 4 cylinder

• 130kW

Turbolader

DOC

position

Horiba

Gas

Analyzer

NOx

Sensor

PM reduction technologies

coated DPF

POC-F (4th generation POC® )

active regeneration systems

KF1 20 g/L coated 150 cpsi SiC Uncoated 150 cpsi SiC

Very thin layer (< 2µm) on pore walls •Pores are kept open to keep filtration and p properties similar

to uncoated DPF

Sol-gel coating for DPF

Poresize distribution of 200 cpsi SiC

Pore diameter (µm)

0

0,05

0,1

0,15

0,2

0,25

10 100

Po

re v

olu

me [

ml/g

]

SiC 200 uncoated SiC 200 KF1 60 g/L

21,5

21,8

Sol-gel coating for DPF

Coating on pores by sol-gel coating and process:

• Surface area of coating >200 m2/g as fresh

• Very thin layer (< 2µm) on pore walls

• Can be coated on e.g. SiC, ceramic and sintered metal filters

• Pt (or Pd) is added as active material on coating

Higher surface area for active component

Higher activity and stability

Sol-gel coating for DPF

Soot load Ecocat CDPFs vs. serial CDPF

0

2

4

6

8

10

12

14

16

18

20

0 500 1.000 1.500 2.000 2.500

distance [km]

so

ot

ma

ss

[g

]

soot load serial DPF

soot load Ecocat DPF 7556.1 [30g/ft³]

35 g/cft Pt

30 g/cft Pt

Results Ecocat CDPF vs. Serial sample MVEG-B test

0,0

10,0

20,0

30,0

40,0

50,0

60,0

70,0

80,0

90,0

CO NOx HC + NOx PM

perc

en

tag

e E

UR

O IV

[%

]

Opel serial 2500km (measured with winter tires) Ecocat NP7556.1 2500km (measured with winter tires)

POC-F

applicable for diesel Euro4/5 and GDI Euro6

Cost competitive solution for particulate removal

• Proven efficiency and durability in both LDD and

HDD applications.

• Tailored coating recommended for particulate

collection efficiency and maintenance free

operation (regeneration).

• Cost efficient production technology.

POC® Particulate Oxidation Catalyst

Test engine:

Cummins, 4,5 Litre, Euro 4

Basics of POC sample:

D240, L300, 300cpsi,

10g/m2, Pt10g/ft3

ESC 11 – load 25%

ESC 3 – load 50%

ESC 12 – load 75%

ESC 10 – load 100%

POC® Particulate Oxidation Catalyst

SEM images of the coated POC- fibers from the inlet

Coating Fiber Carbon adhesive on holder

Other location One location

NO2 formation POC-F vs. Cordierite in E6 engine

POC-F

POC- F PM results

average of three tests

0,000

0,010

0,020

0,030

0,040

0,050

0,060

0,070

0,080

0,090

0,100

Constant speed

PM

g/k

m

0 %

10 %

20 %

30 %

40 %

50 %

60 %

70 %

80 %

90 %

100 %

Per

cen

tag

e ch

an

ges

RAW NP 9881 POC F partially closed by silica fiber %-changes

RAW 0,044 0,061 0,071

NP 9881 POC F partially closed by silica

fiber

0,012 0,015 0,015

%-changes 72,4 % 74,7 % 78,9 %

60 km/h 80 km/h 120 km/h

Steady point

POC and Gasoline (GDI)

Could POC be the solution for PM/ PN emission challenges in Euro6?

• Audi3 1.4 ltr (GDI, Euro4) vehicle

• in collaboration with Darmstadt Hochschule (GER)

• POC-L (143 x 152 mm) in addition to original TWC as first trial,

• followed by POC-F with identical dimensions

• Target to reduce both particle mass (PM) and number (PN) closer to the

Euro6 limit

•especially fuel-efficient GDI engines have a big challenge to meet the

limit

• partial filtering devices without any active regeneration would be

feasible

Note: more detailed information planned to be published in SAE World Congress 2012

Gidney J.T. et al., Environ. Sci. Technol. 2010, 44, 2562–2569

POC® and GDI

POC-L and Gasoline (GDI)

POC-F and Gasoline (GDI)

PN average

0,E+00

5,E+11

1,E+12

2,E+12

2,E+12

1Serial TWC

Serial TWC + POC (2nd sample)

PM average

0,0000

0,0005

0,0010

0,0015

0,0020

1Serial TWC

Serial TWC + POC (2nd sample)

On-road trial for POC-F

PM and PN efficiency after 14 400 km on-road/ GDI

Active regeneration systems

Alternative fuels

- case CNG and LPG -

Alternative fuels –need for catalyst tailoring

• New type of fuel, new type of emissions and conditions

– durability and selectivity requirements can vary

• Some molecules are difficult to convert

– methane from CNG

• poor selectivity can yield new type of pipe out emissions

– aldehydes, N2O, NH3 etc.

• Impurities of bio-based fuels might bring new challenges for chemistry itself and the whole afterteatment system

Alternative fuels –need for catalyst tailoring

• PGM loadings and ratios (Pt-Pd-Rh)

• Interaction with active sites and carrier

– Stabilizing, promoting

• Adsorption properties and selectivity tuning by varying the composition

• Different layers

• Zone coating

Advantages

• Lower CO2 emissions compared to gasoline and diesel

• No particulate emissions!

• Significantly lower NOx emissions

• Other benefits

Global natural gas sources

Lower noise level

Odourless exhaust gas

Disandvantages

• In heavy duty, need for engine development

• Methane emissions specific CNG catalysts is needed

Natural gas –potential solution

CH4 + 2O2 CO2 + 2H2O 809 kJ

High loadings

affect dispersion

negatively To avoid this effect

a promoter is needed

Promoter stabilizes

the surface

Enhancing activity

To tackle the high energy barrier is common to use high loaded catalysts

Slowing sintering

Extending durability

Methane oxidation major challenge

Effect of promoter on Activity/ CNG engine test

0,138

0,533

0,057

0,122

0,410

0,040

0,000

0,100

0,200

0,300

0,400

0,500

0,600

THC CO Nox

Em

issio

ns g

/km

K5.7 Without promoter K5.7 With promoter

Promoter Effect on Emissions: K5.7 for CNG only applications

Results Correspond to Aged Samples

engine optimisation with our K5.7, enhancing CH4 conversion

• Ideal operation point is correlated to temperature and lambda

• Sligthly rich operation under transient conditions improves CH4 conversion

Advantages

• Lower CO2 emissions compared to gasoline

• Significantly lower PM and NOx emissions than diesel

• Easy logistics, resources and distribution

• Safety issues vs. CNG

• Catalysts are typically low-loaded, optimized TWC catalysts

Disandvantages

• Low power output from powertrain

• Performance under cold conditions

LPG – growing fast

Summary

V-SCR technology is durable, robust and shown to be a feasible solution

also by EPA/ CARB

SCR catalysts combined with PreOxicat, PostOxicat, hydrolysis catalyst

or/and catalyzed particulate filters can be designed by the application

On DPF uniform coating through the wall provides good stability

Active regeneration needed when driving conditions do not ensure

passive systems (POC-F and DPF)

Alternative fuels and new engine technologies are coming, catalyst

tailoring is needed

Thank You for Your Attention!