INGAS “18 Months Meeting ”, “GDF-SUEZ Paris, France”, “20-21 May 2010” INGAS INtegrated...

INGAS “18 Months Meeting ”, “GDF-SUEZ Paris, France”, “20-21 May 2010”INGAS “18 Months Meeting ”, “GDF-SUEZ Paris, France”, “20-21 May 2010”

INGAS INtegrated GAS PowertrainINGAS INtegrated GAS Powertrain

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INGAS 18 months meeting

GDF-SUEZ, Paris - France

20 - 21 November 2010

InGas 18 months meeting: SPB2/Ecocat



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• Ecocat is taking part in: – WP2.1 (requirements/boundary conditions) – WP2.2 (advanced catalyst development)

– WP2.3 (exhaust heating/catalyst concepts)



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InGas 18 months meeting: SPB2/EcocatObjective and Innovative aspects

• WP2.1 (requirements/boundary conditions)

– The planned objectives in this WP are collection and definition of relevant information about fuels, exhaust, engine characteristics, ECU functions and testing conditions in order to ensure common working basis and guidelines for different partners.

– In the beginning Ecocat’s role is to deliver reference catalysts to the partners

– In task TB2.1.2 (Catalyst testing/ageing conditions) the reference catalysts have been prepared, which will be used as a reference matrix for the further catalyst (both substrate and washcoat) development

Ecocat´s role is to provide reference catalyst for Daimler´s, POLIMI, USTUTT and ISCS-PAS studies, commercial product.

• WP2.2 (advanced catalyst development)

The main work packet objectives during

the project are: – The development of new catalyst

formulations for methane oxidation with a light off temperature below 350°C

– A high thermal and sulphur stability, – Development of a modelling tool for

methane oxidation– Delivery of kinetic data, control

strategy for methane (lambda = 1, lambda >1) and NOx abatement (lambda>1)

– Development of coating methods for catalyst up scaling and canning

Ecocat´s role is to further develop existing formula based on new innovations from research parties within project (ICSC, POLIMI). Meanwhile, Ecocat does their own development, tasks depend on the engine test results by Daimler and the feed back from the other partners.

.

• WP2.3 (exhaust heating/catalyst concepts)

Planned objectives & starting points:– Definition of the EAT

concept with heat exchanger and catalyst /integrated or serial concept)

– Development of a modelling tool for the whole EAT system

– Simulation of the behaviour of the EAT depending on operating conditions

– Evaluation of the selected concept on a laboratory scale for methane and NOx removal

– Building of 2 prototypes for laboratory investigations and 2 prototypes for engine/vehicle testing

Ecocat´s role is to provide coated heat-exhangers to improve CH4 light-off based on the requests.



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Work performed in WP 2.1 (Requirements/boundary conditions)

• Reference samples– Washcoated with stoichiometric NG

coating– Washcoat thickness has been specified

to 50 g/m2

– Pd-Rh technology; 200 g/cft Pd:Rh 39:1– Sent to:

• Daimler (2 ceramic + 1 metallic)• Kracow (1 ceramic)• Politecnico Milano (1 ceramic)• Universität Stuttgart (1 metallic)

• Reference catalyst powder– Pd containing catalyst powder (6,3 wt-%

Pd) – Sent to:

• Krakow (20 g)• Politecnico Milano (20 g)

Ceramic I Ceramic II Metallic

Dimensions (mm) 118x70 118x50 118x50,8

Volume (dm3) 0,77 0,55 0,56

Wall thickness (Mills/µm)

6 3,5 50

Cell density (cpsi) 400 600 500

Total surface area, TSA (m2)

2,12 1,90 2,26



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InGas 18 months meeting: SPB2/EcocatWork performed in WP 2.2: Advanced catalyst development• Washcoat preparation for the CuMn2O4-oxide (+ Puralox SBa 150) powder achieved from ISC-PAS

CuMn2O4

+ Alumina+ Binder

CuMn2O4 + Alumina+ Binder+ Pd

ReferenceCatalyst + Pd

80 %

20 %

Reference

CuMn2O4

d50 = 3,39 µm

d50 = 4,46; 4,24 µm

Washcoat properties:

pH: 4,97 3,15 4,78Visco: 738 cP 2525 cP 2477 cp



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InGas 18 months meeting: SPB2/EcocatWork performed in WP 2.2:

CuMn2O4

+ Alumina+ Binder



80 %

20 %

Sample preparation for the CuMn2O4-oxide (+ Puralox SBa 150) powder

Pd-loading in ready samples 200 g/cft



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InGas 18 months meeting: SPB2/EcocatWork performed in WP 2.2

CuMn2O4

+ Alumina+ Binder



80 %

20 %

– Laboratory light off tests (25-600°C): as fresh and

LS-1030°C/20h aged

(LS = lean 10 min + stoichiometric 50 min;

CO, CO2, H2O, C3H6, O2, N2)

Ø 14 mm x L 75 mm

Stoich.

λ=1

Lean

λ=1,78

O2, % 0,8 10

NO, ppm 600 500

H2O, % 10 8

CO2, % 9 7,5

CO, ppm 8000 1200

H2, ppm 2800 -

CH4, ppm 1800 1500

C2H6, ppm 100 300

C3H8, ppm - 100

C2H4O, ppm - 150



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• Laboratory light off test results for fresh samples (λ=1)

CO Conversion in Light-off performance

0

10

20

30

40

50

60

70

80

90

100

50 100 150 200 250 300 350 400 450 500 550 600Temperature before catalyst, °C

Co

nv

ers

ion

, %

638 CuMn2O4

639 CuMn2O4 + Pd

640 REF (Pd)

NOx Conversion in Light-off performance

0

10

20

30

40

50

60

70

80

90

100


Co

nv

ers

ion

, %

638 CuMn2O4

639 CuMn2O4 + Pd

640 REF (Pd)

THC Conversion in Light-off performance

0

10

20

30

40

50

60

70

80

90

100


Co

nv

ers

ion

, %

638 CuMn2O4

639 CuMn2O4 + Pd

640 REF (Pd)



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• Laboratory light off test results for aged samples (λ=1)


0

10

20

30

40

50

60

70

80

90

100

100 150 200 250 300 350 400 450 500 550 600

Temperature before catalyst, °C

Co

nv

ers

ion

, %

638 CuMn2O4

639 CuMn2O4 + Pd

640 REF (Pd)

NOx Conversion in Light-off performance

0

10

20

30

40

50

60

70

80

90

100

100 150 200 250 300 350 400 450 500 550 600


Co

nv

ers

ion

, %

638 CuMn2O4

639 CuMn2O4 + Pd

640 REF (Pd)


0

10

20

30

40

50

60

70

80

90

100

50 100 150 200 250 300 350 400 450 500 550 600


Co

nv

ers

ion

, %

638 CuMn2O4

639 CuMn2O4 + Pd

640 REF (Pd)



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• Laboratory lambda window test results for fresh samples at 500°C

CO Conversion in Lambda performance at 500°C

0

10

20

30

40

50

60

70

80

90

100

0,97 0,98 0,99 1,00 1,01Lambda value

Co

nv

ers

ion

, %

638 CuMn2O4639 CuMn2O4 + Pd640 REF (Pd)

THC Conversion in Lambda performance at 500°C

0

10

20

30

40

50

60

70

80

90

100

0,97 0,98 0,99 1,00 1,01

Lambda value

Co

nv

ers

ion

, %

638 CuMn2O4

639 CuMn2O4 + Pd

640 REF (Pd)

NOx Conversion in Lambda performance at 500°C

0

10

20

30

40

50

60

70

80

90

100

0,97 0,98 0,99 1,00 1,01Lambda value

Co

nv

ers

ion

, %




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NOx Conversion in Lambda performance at 500°C

0

10

20

30

40

50

60

70

80

90

100

0,97 0,98 0,99 1,00 1,01

Lambda value

Co

nv

ers

ion

, %

638 CuMn2O4

639 CuMn2O4 + Pd

640 REF (Pd)

THC Conversion in Lambda performance at 500°C

0

10

20

30

40

50

60

70

80

90

100

0,97 0,98 0,99 1,00 1,01

Lambda value

Co

nv

ers

ion

, %

638 CuMn2O4

639 CuMn2O4 + Pd

640 REF (Pd)

CO Conversion in Lambda performance at 500°C

0

10

20

30

40

50

60

70

80

90

100

0,97 0,98 0,99 1,00 1,01Lambda value

Co

nv

ers

ion

, %



• Laboratory lambda window test results for aged samples at 500°C



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• Laboratory light off test results for fresh samples (Lean)


0

10

20

30

40

50

60

70

80

90

100


Co

nv

ers

ion

, %

638 CuMn2O4

639 CuMn2O4 + Pd

640 REF (Pd)


0

10

20

30

40

50

60

70

80

90

100

100 150 200 250 300 350 400 450 500 550 600Temperature before catalyst, °C

Co

nv

ers

ion

, %

638 CuMn2O4

639 CuMn2O4 + Pd

640 REF (Pd)



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• Laboratory light off test results for aged samples (Lean)


0

10

20

30

40

50

60

70

80

90

100


Co

nv

ers

ion

, %

638 CuMn2O4

639 CuMn2O4 + Pd

640 REF (Pd)


0

10

20

30

40

50

60

70

80

90

100

100 150 200 250 300 350 400 450 500 550 600Temperature before catalyst, °C

Co

nve

rsio

n, %

638 CuMn2O4

639 CuMn2O4 + Pd

640 REF (Pd)



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• Evaluation of tri-metallic catalyst (Pt-Pd-Rh) against Pd-Rh standard CNG washcoat (λ=1)

– 200 g/cft: Pd-Rh 39:1 vs. Pt-Pd-Rh 1:38:1 (based on the 2nd quarter 2010 PGM prices latter being about 5 % more expensive)

– Laboratory light off tests as fresh and LS-1030°C/20h aged (LS= lean 10 min + stoichiometric 50 min); with soithiometric test mixture (25-600°C)

– Engine tests in 1,2 litre bi-power E4 vehicle over the NEDC as fresh and 40 h RAH aged (catalyst size: 100x150 mm, 500 cpsi, 1.18 litre)


Work performed in WP 2.2:



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• Light off tests in laboratory


Light off in laboratory tests

348

135 122

340

132 123

395

167 154

388

176153

0

100

200

300

400

500

THC CO NOx

Lig

ht

off

T5

0 /

°C

Pd-Rh/Fresh Pt-Pd-Rh/Fresh Pd-Rh/Aged Pt-Pd-Rh/Aged




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• Engine test results for fresh and aged Pd-Rh vs. Pt-Pd-Rh samples– 1,2 liter E4 bi-power vehicle with CNG over NEDC (ageing 40 h RAH)


1 1 11,07

0,98 1,00

1,78

1,61

1,481,40

1,10

1,33

0

0,2

0,4

0,6

0,8

1

1,2

1,4

1,6

1,8

2

THC CO NOx

Rel

ativ

e em

issi

on

Pd-Rh/ Fresh Pt-Pd-Rh/ Fresh Pd-Rh/Aged Pt-Pd-Rh/Aged

Fresh Fresh Fresh

AgedAged Aged




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• Cumulative THC results in the engine after 40 h ageing





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Work performed in WP 2.2:• Cumulative THC results in the engine after 40 h ageing



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• Cumulative CO results in the engine after 40 h ageing





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Work performed in WP 2.2:• Cumulative NOx results in the engine after 40 h ageing



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• Conclusion

– Test with CuMn2O4 powder• Washcoat preparation was successfully progressed• Adhesion on the metal surface is comparable to the reference• Some activity found for CO and NOx; for THC the activity is poor

compared to the reference under stoichiometric conditions, in lean the HC activity is better, but not at the reference level

• Pd clearly improves the activity

– Tri metallic catalyst evaluated against standard Pd-Rh CNG catalyst:• In the laboratory tests minor improvements were found in the light off

(T50) temperatures• In engine tests fresh samples are performing equally but tri metallic

sample showed better durability against thermal ageing




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Samples for the test in Daimler/AVL:• Ceramic substrates (2 pieces)• 152,4 X 101,6 x 76,2 mm • V = 0,93 dm3, 600 cpsi, 3,5 mils• 170 g/cft 0:40:1, 50 g/m2 K5.7



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– Advanced coating

• High surface area – two layer washcoat

• Oxygen Storage

• Rear Earth Stabilizers

• Active metals – Pt/Pd/Rh




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– Laboratory scale heat exchanger prototype was prepared by Delphi and coated in Ecocat on March/2010

– Proto was coated with CNG washcoat developed for the stoichiometric use:

• 200 g/cft 0:39:1 Pt:Pd:Rh

• 50 g/m2 K5.7

Heat exchanger, Proto 2



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• Fins for the vehicle scale prototypewill be coated on weeks 21-22/2010

– Vehicle scale heat exchanger will be prepared by Delphi

– It consist of 4 similar units which will be coated in Ecocat

– Units will be coated with similar CNG washcoat as used in laboratory scale prototypes

– Coating is in progress and the units will be sent to the canning on week 22




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Problems encountered

• Less time than originally planned and budgeted was spent in activities due to the lack of resources due to the bad economical situation

• Characterization of the reference material was slightly delayed by the partners => further improvement was planned after the feed back

• Screening of the new materials is in progress in the partners => washcoating and upscailing activities (planned to start on month 9) will be done after new materials are available (during second and third year); The first material from ISCS-PAS was received and the first washcoating and testing in laboratory scale is in progress

• The further development on Ecocat is based on the feedback received from the partners; therefore the engine tests will be needed for further development



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• Main results

• WP 2.1:– Reference catalyst both full size catalysts in ceramic and metallic substrate as

well as powder catalyst was succesfully delivered for the partners• WP 2.2:

– To support new catalyst materials development on the partners reference material (powder and full size catalysts) were prepared and delivered

– Preliminary washcoat screening in own laboratory and engine tests to see the level of the reference catalyst for the project objectives

– Fuether development is dependant on the feed back from the engine and the laboratory results made by partners

– The first washcoating trials with a new catalytic material made in ISCS-PAS have been done and the tests are in progress at laboratory level

• WP 2.3:– Two laboratory scale heat exchange prototypes coated and sent to the partners– Vehicle scale prototype fins will be coated on week 21-22



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• Next– Continue the laboratory scale development for new catalyst materials

for an improved reference• Pd-based for methane • Promoters, stabilizers• Ageing examinations• Feed back from the partners needed

– Own engine tests: activity and durability

– Coating development and upscailing for the new materials in WPB2.2• DB2.7 (catalyst sample Gen1)

– The first vehicle scale heat exchanger unit coating is inprogress and will be sent for canning on week 22

INGAS “18 Months Meeting ”, “GDF-SUEZ Paris, France”, “20-21 May 2010” INGAS INtegrated...

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Transcript of INGAS “18 Months Meeting ”, “GDF-SUEZ Paris, France”, “20-21 May 2010” INGAS INtegrated...