INGAS 18 months meeting, Paris, 20./21.5.2010 DAIMLER AG INGAS INtegrated GAS Powertrain InGas 18 months meeting May, 20th/21st 2010 Paris, France SPB2

INGAS 18 months meeting, Paris, INGAS 18 months meeting, Paris, 20./21.5.201020./21.5.2010

DAIMLER AG

INGAS INtegrated GAS PowertrainINGAS INtegrated GAS Powertrain

InGas 18 months meetingMay, 20th/21st 2010

Paris, France

SPB2



2

References and Targets of SPB2

INGAS: references and targets of the project

CH4 conversion efficiency (*)HC conversion efficiency

stoichiometric conditions (**)CH4 light off temperature (**) NOx conversion efficiency (**) NOx conversion efficiency (**)

[%] [%] [°C] [%] [%]

Reference SoA CNG (DoW) <80 on 100.000 km 90 gasoline starting 400 not developped not developped

Target INGAS SPB2 >90 on 160.000 km 90 CNG starting 330 >50 >90

NICE final status

Where we are (month 12) currently no value in NEDC currently no value in NEDCcurrently between 330°C and 400°C

depending on test and ageing conditions (laboratory scale)

no value in NEDC - regenerability of NSC as well as H2 production during

rich spike demonstrated

Where we are going (month 36) 90% 90%350°C after long term ageing + exhaust heat management for

faster lightoff>50% (based on modelling)

Key advantages SP B2 - 50 °C vs SoA DoWNSC to apply on technology way 2

(SP A2)SCR to apply on technology way 3 (SP A3)

(*) page 9 of DoW(**) page 38 of DoW

SP B2

not applicable



Comment 1 - SPB2: In the document Annex 1 - DoW pg. 38 it was clearly stated that "For small and mid size engines (<2 liter swept volume) ..." while in the 12 month Periodic Report pg. 24 it has been stated that " The required NOx-conversion can be done in only one way by means of a large volume (4 litres) SCR ….".

These two conflicting statements need to be explained and deviation from the DoW justified.

Answer: - In general there are only two technologies able to reduce NOx under lean conditions with the appropriate efficiency for fullfiling future emissions standards. Each EOM has his own strategy for considering either the NOx- storage system or the urea SCR-technology. The choice is driven by a compromise between required NOx-performance, temperature profile in the considered driving cycles, cost of the system, durability and packaging considerations.

- As written in the DoW, our philosophy is to consider the NOx storage technology rather for small engine applications, especially in cases where the required NOx conversion is not too high (in the Dow, objective is >50%). But it is also clear that in the particular case of the CNG engine it has to be proven that it is possible to regenerate the NOx storage catalyst

under rich conditions particular to the CNG engine. - One approach consists in the development of engine measures for producing more CO and H2 during the rich spike, which is possible with a flexible DI-system.

- It has already been demonstrated (DA2.11) that with changing the injection timing, more CO can be produced with unbalanced cylinder adjustment at lambda=1.

- A second aspect to consider is that the NOx storage catalyst is coated on the heat exchanger and takes benefit from its thermal characteristics.

- A third possibility is to add a reforming catalyst (not part of DoW) in front of the NOx storage catalyst in order to generate more H2 through steam reforming of methane and WGS.

SPB2: Comment 1



Answer: - Concerning the statement in the 12-month report, it corresponds to a choice made by SPA3, which is not conflicting with the work performed in SPB2, and which has been done in agreement with SPB2 in order to cover both NOx technologies in the IP.

- Furthermore, the objective for NOx reduction in SPA3 is around 90%, and in that case the performance of the urea SCR technology is more suitable than a NOx storage catalyst, especially when considering sulfur poisoning and thermal durability aspects.

- Additionally, from a technical point of view, the use of urea SCR in combination with the heat exchanger seems not to be appropriate because of restricted available mixing length in front of the catalyst and plugging risks of the heat exchanger.

- However, implementation of the urea SCR system is also very challenging for a CNG application.

- Finally, as mentioned in the DoW, the objective in SPB2 for NOx reduction under lean conditions is limited to an assessment of the potential of the NOx storage technology without an implementation on an engine.

- All those aspects demonstrate that it makes sense to develop both technologies in parallel in order to assess the potential of both technologies for a CNG application.

- There are no deviations from the DoW.

SPB2: Comment 1



Comment 2 – SPB2: The success of InGas to a large extend is dependent on the development of an efficient catalyst for stoichiometric or lean burn operation to fulfil future EURO6 regulations. The currently proposed solution of a Pd-based catalyst material does not seem to perform better than an available reference case catalyst. Please comment what are today within InGAS the main achievements in methane catalysts development when compared to the state-of-the-art at project start and what convincing ideas should help to find a solution up to the end of the project.

Answer:

- Developing a new CH4-catalyst with a better lightoff temperature than a high loaded Pd-based catalyst is a huge challenge. Therefore it can not be expected that after 1 year of work the objective can be achieved. However a lot of work has been done at POLIMI and ICSC-PAS in order to find new catalyst formulations able to compete with the reference material or to improve it in terms of activity and cost. Contrary to the comments of the reviewers, some interesting aspects and materials have been identified.

- Additionally, the success of InGas is not dependent on the development of a new catalyst but on the development of an integrated heat exchanger. The key innovation is the combination of an improved material with a better temperature management of the catalytic system through integration in a heat exchanger.

SPB2: WPB2.2 – Comment 2



Answer:

Pd-based:- The results from POLIMI showed that Pd-only catalysts supported on CeO2-Al2O3 exhibit the same activity than the TWC reference catalyst with a significantly lower Pd-loading (2% vs. 6%). Due to different preparation routes, the characteristics of the surface, the particle size and the metal-support interactions promote the activity performance.

- Furthermore, addition of small amount of Pt at constant Pd loading slightly promotes the activity performance.

- Results will be used by Ecocat in order to improve the performance of the reference catalyst.

Mixed Oxide:- Concerning the development of catalysts based on mixed oxides, the most active catalysts can be found among hydrotalcite-derived mixed oxide catalysts (MnAl and CuMnAl systems). Deposition of mixed CuMn oxide on a Puralox carrier stabilizes dispersion of spinel phases, and prevents rapid degradation of the catalyst, thus limiting the loss of activity upon ageing.

- The developed catalysts perform better than references in the literature but, of course, are not competitive compared to Pd-based materials.

- But with regard to cost, it is conceivable that an increased amount of such a catalyst could be used , resulting in lower SV and, consequently, to a better activity in combination with the heat exchanger.

SPB2: WPB2.2 – Comment 2



Outlook WPB2.2:

- For future development, combining mixed oxides and especially perovskite-type materials with Pd will represent one interesting route. As reported by Cataler Corporation and Daihatsu Motor Co., the incorporation of Pd in a perovskite structure can stabilize the Pd-particles and consequently improve the reactivity of the system through the design of an intelligent catalyst.

- Another approach will consider the incorporation of Au in Pd-based catalysts. It is well known that Au in well dispersed form exhibits a high activity for CO oxidation even at very low temperatures but suffers from thermal ageing. In the last years a lot of progress has been made in the stabilisation of Au nano-particles in combination with Pd as oxidation catalyst (Nanostellar). Through the early oxidation of CO, coupled with engine measures as described in DA2.11, the exhaust system can be heated more rapidly, leading to a faster CH4 lightoff.

- In conclusion, developing completely new formulations with low lightoff temperature, especially for methane oxidation, can not be achieved easily within one year of development. However interesting aspects have been identified and will be used by Ecocat in order to improve the reference catalyst. New ideas, as described previously, will be investigated in the next months.

SPB2: WPB2.2 – Comment 2 Outlook



SPB2: WPB2.3 – Comment 3 Integrated heat exchanger

Comment 3 – SPB2: For the burner concept a critical point is seen in the available catalytically coated heat exchanger area for methane conversion. This is for example far less than in a porous medium. Furthermore, to assess

validity of this approach, more details on the computer model used for concept development are required. Please supply additional information.

Answer:

- Separate presentation from M. Rink/ F. Ayad (USTUTT, Delphi)



InGas: Overall Assessment



In reviewing the individual partner contributions it became evident to the reviewers that the contribution of ECOCAT due to delayed start of work currently is behind schedule. However, the issue of a low temperature methane oxidation catalyst is still an open question. Up to now all investigated catalyst materials show less activity than the reference catalyst of ECOCAT.

SPB2: This deals with the development of an after treatment system for natural gas vehicles having special demands to methane conversion efficiency and NOx abatement under lean combustion conditions.

WPB2.2: The development of a new CH4 catalyst with a better light-off temperature than a high-loaded Pd-based catalyst turns out to be a huge challenge. So far all catalyst materials investigated have not shown better performance than the reference catalyst of ECOCAT. To remedy the situation it was suggested by the Consortium members thatfuture work should concentrate on Pd/Zk/Al formulations with a support based on Cerium-Oxide. Also Pd/Au materials will be investigated.

WPB2.3: The exhaust gas after treatment system of this technology pathway is based on a heat exchanger containing a PROMEOS burner for catalyst heating. The complete hardware is manufactured by DELPHI. A laboratory prototype is already finished and tests at USTUTT have just started. Some problems are seen concerning thermal stresses within the proposed system and the counteraction of the burner gases with the exhaust gas stream. Also fooling of catalyst surfaces due to burner start-up operations might be critical.

InGas: Overall Assessment



Status Delayed at month???Deliverable Name TaskDelivery

dateDisseminatio

n level

MB2.1 Aftertreatment Concept assessment

B2.3 11 Preliminary assessment respect to Table B2.1

Delivered

MB2.2 Potential heat exchanger concept/new catalyst formulation demonstrated

B2.4 18 Theoretical and experimental assessment of results respect to table B2.1

Missing

Expected for Month 25

(10/2010) together with DB2.11

MB2.3 Principle feasibility demonstrated B2.5 31 Final results validation respect to Table B2.1

1 B2.1 Delivered & approved P1





6 B2.6 Missing Month 21 (06/2010) DELPHI HW + Report

7 B2.7 Missing Month 21 (06/2010) ECOCAT HW + Report

8 B2.8 Missing Month 21 (06/2010) DAIMLER Report

9 B2.9 Missing Month 22 (07/2010) USTUTT Report

10 B2.10 tbd at the 18-Month meeting DELPHI HW + Report

11 B2.11 expected for Month 25 (10/2010) AVL Report

12 B2.12 expected for month 27 (12/2010) ECOCAT HW + Report

13 B2.13 no delay expected

14 B2.14 no delay expected

DB2.1 Fuel requirements to B0 B2.1.1

DB2.2 Reference catalyst B2.1.2

B2.1.2

CO 3

CO 3

CO 4

DB2.5 2 laboratory prototypes

DB2.3 Boundary/testing conditions

DB2.4 CH4-kinetics/model B2.2.2

CO 13

B2.3.1/B2.3.4 CO 10

CO 10

CO 16

Bench prototype 1

DB2.7 Catalyst samples Gen.1/new formulations B2.2.1/B2.2.4

B2.3.4

B2.2.3/B2.4.1

DB2.9 EAT operation strategy 1 B2.3.2/B2.3.3

DB2.8 CH4/NOx operation strategy

B2.3.2/B2.4.1/B2.4.2

DB2.10 Bench/vehicle prototype 2 B2.3.4

DB2.11 EAT operation strategy 2

CO 31

B2.2.1/B2.2.4

B2.5.1/B2.5.2

CO 21

CO 22

DB2.12 Catalyst samples Gen.2/new formulations

DB2.14 Results summary/assessment

DB2.13 Vehicle/EAT/strategy to SPA2

B2.5.2

CO 18

CO 18

CO/PU 33

CO 24

SPB2

DB2.6

Deliverables are considered as important as periodic reports, reflecting the work progress

SPB2: Deliverables - Milestones



Deliverables – Milestones until E2010

Engine test bench at AVL

No delay expected for:DB2.13 „Vehicle/EAT/strategy to SPA2“DB2.14 „Results summary/assessment“

MB2.2 (Potential heat exchanger concept demonstrated)

# #

WP 2.3 (Task: System Coating/Procurement/Engineering)

DB2.5-1 (1st lab-Hex TWC coating) Jul 09

DB2.5-2 (2nd lab-Hex TWC + NSC coating) Jul 09

DB2.6 (first TWC-bench-prototype w/o burner) Okt 09

DB2.10 (2nd TWC-bench-prototype with burner, with improvements) Jun 10 Date will be fixed at mid-term meeting in Paris X

WP 2.2 (Task: Coating Methods / Upscaling)

DB2.7 (Catalyst sample Gen1) Jan 10 HW R

DB2.12 (Catalyst sample Gen2) Sep 10

WP 2.2 (Task: Strategy for CH4 / NOx Abatement)

DB2.8 (CH4/NOx operation strategy) Mar 10

WP 2.3 (Task: Components / EAT System Laboratory)

DB2.9 (EAT operation strategy1) Mar 10

WP 2.4 (Task: EAT / CH4 Catalyst Evaluation)

DB2.11 (EAT operation strategy2) Jul 10

Sept. Octob. Nov. Dec.June July Aug.Febr. Mar. Apr. MayTask

Due Date

Jan.July Dec.Aug. Sept. Octob. Nov.2009 2010



SPB2: Road Map Catalyst Development

2010 2011June July Aug Sept Oct Nov Dec Jan Febr March April May June July Aug Sept

Catalyst Development

Reference catalyst (Ecocat) Ref. catalyst 1 (full monolith) Eng. Bench Further development of Ref. Catalyst (Pd-based, increase of Pd content, 300 g/cft) Pd/Rh = 39/1 Engine tests and durability Substrate: Ceramic, metallic

New Ref. Catalyst (full monolith) Eng. Bench further development of new Ref. Catalyst (Pd-based + Pt, promoters, stabilizers, ageing, increased amount of Pd) Tri-metallic Pt/Pd/Rh = 1/38/1 Engine tests and durability Substrate: Ceramic

Upscaling New formulations (Ecocat) CuMn2O4/Al2O3 (Lab monolith) Lab. CuMn2O4 + Pd (Lab monolith) Lab.

New identified formulations Coating process, lab. tests, durability Lab.: Activity depends on performance of new formulations (next step: 2% or 6% Pd/CeO2/Al2O3)

if successful.: upscaling on full monolithDevelopment new formulations Pd-based formulations (Polimi) Pd on different supports (CeO2,…) Lab. Increase of Pd content up to 6% with CeO2/Al2O3 Pd/Pt bi-metallic Lab.

Pd/Au bi-metallic Main focus (Lab.)

Mixed oxides (ICSC-PAS) Differents structures and prep. routes Lab. Max. of surface area, synthesis mod.

Incorporation of Pd Main focus (Lab.): Increase of Pd content, new synthesis route

Engine testing (AVL) Ref. catalyst 1 (Pd/Rh) DB2.7: Evaluation on engine test bench (AVL)

Pd/Rh = 170 g New ref. catalyst (Pt/Pd/Rh) (AVL)

Pd/Rh = 200 g Best formulation Pd/Rh = 300 g DB2.12: Evaluation on engine test bench (AVL)

Pt/Pd/Rh = 200 g Polimi material optional



2010 2011May June July Aug Sept Oct Nov Dec Jan Febr March April May June July Aug Sept

HEX Development

Laboratory HEX (USTUTT, DELPHI) First prototype (TWC coating) Engineering, manufacturing, canning DB2.5-1 in March

Simulation DB2.9: EAT operation strategy 1

Testing

Second prototype (TWC coating) Engineering, manufacturing, canning DB2.5-2

Testing Does it make sense w/o NSC or rather simulation with NSC

Bench HEX (USTUTT, DELPHI) Cat. Cat. Cat. Cat. First prototype (TWC coating) Engineering, manufacturing, canning DB2.6: First bench prototype w/o burner

Simulation

Testing on test Bench (AVL) DB2.11: EAT operation strategy 2 Testing on test bench with serial NSC

Second prototype with burner (TWC coating) Engineering, manufacturing, canning Freeze Configuration DB2.10: 2d bench prototype w burner

Simulation

Testing on test bench (AVL) Demonstrator DB2.13 DB2.14: Validator demonstrated

SPB2: Road Map HEX



Open issues:WP B2.2:Reference material: Ref 1: K5.7 200g/cft washcoat, Pt/Pd/Rh = 0/39/1

Ref 2: Pt/Pd/Rh = 1/38/1Coating of new materials: CuMn2O4/Al2O3

Pd/Al2O3-CeO2WP B2.3:Canning of monoliths (Katcon)2d lab HEX with TWC/NSC coating (when?, NSC feasible?, does it make sense on lab scale?)2d bench HEX with TWC or TWC/NSC? (when?, with burner or heating device or flaps?)

WP B2.4:Test program monolithsTest program HEXEngine? Rich spike, lean? Injection timing for CO/H2 production?Availability dynamic test bench -- demonstrator

WP B2.5: shift from Vehicle to engine test bench (AVL)?

SPB2: Open issues

Documents

INGAS 18 months meeting, Paris, 20./21.5.2010 DAIMLER AG INGAS INtegrated GAS Powertrain InGas 18 months meeting May, 20th/21st 2010 Paris, France SPB2