Next generation SCR system for fuel-efficient NOx reduction Conference Selective Catalytic Reduction 2011 26 - 28 September, 2011, Dorint Pallas Wiesbaden, Germany Dr. Tue Johannessen Amminex A/S [email protected]

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The environmental paradox: Low CO2 - but at the expense of NOX? • • •

NO2 is already today a major problem in many European cities Focus on low CO2 ⇒ efficient engines. Efficient diesel engines ⇒ low exhaust temperature –

(often below 200°C

⇒ Significant challenge for future legislative targets and off-cycle NOx control with AdBlue® Annual mean NO2 concentration (ug/m3) in London

Limit for 2010

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US study on off-cycle performance with urea-SCR Pick-up truck

Avg. urban engine-out (No DEF) Urban driving – with DEF in the tank

Average urban tailpipe 0.2 g/bhp-hr

DEF = Diesel Exhaust Fluid = North America generic name for Aqueous Urea Solution

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Ammonia-SCR: High NOx reduction potential in cold exhaust

•

NOx conversion data with NH3 provided by Haldor Topsøe A/S

1.0

Test conditions:

0.8

– – – – –

•

250 ppm NOx Conversion measured with 20 ppm NH3 slip Space velocity: 63000 hr-1. Catalyst: Fe-zeolite; aged for 50hr at 750C NO2 content: NO2/NOx= 0.3

Curve for AdBlue is based on the assumption that: –

–

AdBlue gives as high conversion as pure ammonia gas as long as injection is possible (urea hydrolysis complete) Steady-state AdBlue injection requires an exhaust temperature of 190-200°C (e.g. Dr. Rusch: “Urea SCR – Interaction of spray generation and exhaust system”, CTI Forum: SCR systems, Stuttgart, Oct. 08)

NOX conversion relative to 200 ° C

•

Urban NOx control with ammonia gas

0.6 NH3-dosing: Normalized conversion (NO2/NOx=0.3)

0.4

AdBlue (inj. at Tscr >190 °C)

0.2

Illustration of urban NOx control potential with liquid injection (AdBlue)

0.0 150

160

170

180

190

200

SCR catalyst temperature (°°C) IQPC - SCR 2011

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AdAmmineTM: Safe storage enables ammonia for mobile applications Ammonia is very useful in many applications – incl. mobile and portable •

Storage of ammonia as pressurized liquid is inherently dangerous :

•

AdAmmineTM: Safe storage in compacted solid provides the safety essentially without loss of volumetric capacity:

AdAmmine: Usable capacity: ∼ 450g NH3 per liter AdAmmine Ammonia release: Controlled thermal desorption Sr(NH3)XCl2 ↔ Sr(NH3)X-1Cl2 + NH3 IQPC - SCR 2011

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How safe is it? •

Ammonia stored in an AdAmmine cartridge is about four orders of magnitude less ‘accessible’ than pressurized anhydrous ammonia.

•

Even with a broken automotive cartridge/connector, passive release is very slow

•

–

About 300 days before 1.65kg has diffused out of the broken cartridge at ambient conditions

–

3.6 liter cartridge for LD/automotive:

Fire test shows no risk of cartridge bursting. –

Plastic connector melts and causes controlled venting of ammonia. Vented ammonia is oxidized in the flames.

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Amminex ASDS technology: Ammonia Storage and Delivery Systems •

Amminex is working jointly with OEMs primarily on two system variants

•

ASDS-1: Electrical system for small/medium cars – – –

•

Two smaller main cartridges pr. system 3.5-4.5 liter cartridges Control strategy for low fuel economy impact

ASDS-2: Engine coolant system for MD/HD – –

Main cartridge(s) is approx. 11 liters Modular system concept (1-3 cartridges)

Key features: • Start-up unit: Rapid dosing after cold start • Main unit(s): System capacity • AFM: Dosing manifold • SW: Control of NH3-release on-demand IQPC - SCR 2011

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ASDS-2: Example of system for MD/HD •

Two-tank system – –

•

∼ 11 liter cartridge (∼24 liter AdBlue) 4.5kg NH3 per main unit

Start-up unit –

1.2 liter; 550W heater

• • • •

AFM (ammonia Flow Manifold) Heating/Mounting bracket Stand-alone ‘Box’ for easy installation ASDS-controller + Amminex SW

•

Production parts:

Ammonia dosing performance: –

Dosing turn-down ratio is at least 1/100 • •

–

Example: Min/Max: 1/100 mg NH3/s (or zero flow). Can be varied by control SW.

Accuracy is at least ±5% on actual measured value in the entire range (not ‘just’ ± 5% of max. flow).

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Off-cycle NOx control during urban driving: Improved SCR performance without additional fuel penalty

NOx conversion / Catalyst temperature (°C) / Flow [mg/s], Temperature [°C], Speed [kmph] Speed (km/hr) / Ammonia dosing

250 SCR_avg_T [°C] NOx_conversion [%] Vehicle_speed [kmph] Ammonia_dosed [mg/s]

Required catalyst temperature for operating AdBlue: > 200-225°C 200

SCR Catalyst temperature

150

High NOx conversion possible with continuous “cold” exhaust gas using Amminex solid storage technology.

100

50

0 0

500

1000

1500

2000

2500

3000

3500

4000

4500

Time [s]

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ASDS-1: Electrically heated system for passenger cars

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Example of components for automotive system • • • • •

Start-up unit Main cartridge(s) Compact Ammonia Flow Manifold (AFM) Heating/mounting structure for main cartridges DCU with software

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Key performance parameters •

Dosing of pure ammonia gas – – –

•

Time-to-dose from cold start: – –

•

Generally in the 60-180s range Depends on cold soak temperature, size and heating power

Power consumption: – –

•

Example of applied dosing ranges: [0-30], [0-50] mg NH3/s Turn-down is at least 1:100 High dosing accuracy (e.g. ± 5% on measured value)

Peak power: 250W Average power consumption: 30-70W

Main unit storage capacity: 450 g NH3 (available NH3) per liter AdAmmineTM

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CO2-friendly control SW strategy for ASDS-1 • • •

From a vehicle integration standpoint, electrical current is simpler than coolant ‘current’ Target: Keep power low by using the STU ‘all the time’. Only use electrical power for heat main unit to transfer ammonia back into the STU (regeneration).

STU fill level

Main unit fill level

Regeneration of STU by “activation of main unit Time (Weeks) IQPC - SCR 2011

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Automotive AFM design High accuracy and robustness Attractive component cost structure Parts from automotive suppliers Dosing specs: – –

•

Dynamic turn-down ratio: 1:100 (e.g. 0.3 to 30 mg NH3/s) Accuracy: ±5% on measured value in entire dosing range

Operating pressure: – –

Pressure: 2 bar(a) < PCartridge < 6 bar(a) Exhaust back-pressure: Accuracy is not sensitive to dynamic changes in exhaust back-pressure caused by engine load.

On-going endurance test: 75 million valve cycles reached ! 90 kg ammonia dosed Accuracy remains at of ±5% on actual value.

Error on actual dosed mass (%)

• • • •

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5.0% 2.5% 0 mill

0.0% 0

10

20

43 mill

30

75 mill

-2.5% -5.0%

Dosing demand [mg NH3/s]

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Example from automotive testing of NH3-SCR

M. Fischer. Honda R&D Europe, Emission Control Concepts, November 2010 15 IQPC - SCR 2011

High conversion – even for under-floor SCR position Source: M. Fischer. Honda R&D Europe

•

NEDC test result with 200°C SOI temperature for Urea and 120°C for Ammonia

Vehicle Speed NOx Engine Out NOx post SCR Urea NOx post SCR NH3

59% less NOx

AdBlue

80

97

NH3

60 49

40

42

20 10

300

Temperature [C]

NOx conversion [%]

100

Temperature upstream SCR Temperature downstream SCR SCR catalyst Temperature

250 200

SOI time difference between Urea and NH3 gas Start of injection Urea SCR Start of injection NH3 SCR

150 100 50

0

0

Phase 1

Phase 2

0

200

400

600

800

1000

1200

Time [s]

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High uniformity, no risk of deposits, low pressure drop • • •

Exhaust interface is a steel tube – not an injector. No droplets – high flexibility. High uniformity index at different exhaust flow conditions is demonstrated (the actual interface designed by Honda not disclosed) Source: M. Fischer. Honda R&D Europe

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Benefits for exhaust system design •

High uniformity with direct ammonia gas dosing

•

Flexibility in SCR configuration – – –

•

Close coupled Under-floor SCR-coated filter

Flexibility in exhaust configuration – – –

No risk of deposits Low pressure drop possible at ammonia inlet zone Significantly reduced corrosion risk (no acids intermediate of urea hydrolysis)

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AdAmmineTM industrialization

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Amminex manufacturing for MD/HD • • • •

Approx. 11 liter unit. Material: Aluminum 4.5kg ammonia available for onboard usage. Quick-connector –

• • • • •

Rapid exchange possible

Approx. 500W heater (12V) Approx. 1.2 liter Quick-connector (gas) Electrical connector Other designs can be developed according to application requests. IQPC - SCR 2011

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The first AdAmmine plant: Nyborg, Denmark

Land : 45.800m2. Building: 6.424 m2 (up to 20.000 m2 allowed) Administration, lab, cantina : 850 m2 Production: 5.600 m2

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The first 10 ton of NH3 at Nyborg

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Applicable standards for AdAmmineTM cartridges •

AdAmmineTM is not classified as hazardous goods for on-road, sea or air transportation

•

European REACH: No outstanding issues

•

AdAmmineTM cartridges do not have to fulfill requirements of the European Pressure Directive

•

Amminex has environmental approval for the Danish AdAmmineTM plant: – –

45 ton on-site ammonia storage Warehouse: • •

•

10,000 HD cartridges 10,000 Start-up units

Amminex HQ is ISO 9001 certified. –

Production facility will be ISO and TS certified

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AFTERMARKET CARTRIDGE SERVICING & REFILLING

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Servicing strategy and aftermarket •

Standard production method: First-fit cartridges on new vehicles

•

Cartridge replacement: Depleted cartridge is exchanged with a full unit (e.g. at OEM service station or fleet). Rapid exchange via quick-connecting (hot-swapping possible)

•

Depleted cartridges can be: – –

•

Resaturated at a decentralized facility (however not directly at OEM dealer or Fleet) Once “exhausted”, a cartridge can be recycled completely with full utilization of raw materials.

The AdAmmineTM “aerosol can” –

For certain limited applications, the cartridge strategy may be complete recycle because the value of the “housing” is low compared to the additional efforts of quality assuring a cartridge in a resaturation scenario.

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Aftermarket: AdAmmineTM cartridges – similarities with propane distribution Propane canister (one-time use) 0.5-1kg propane

Propane transported in bottles: hazardous goods (logistics “risk fee”) Solid AdAmmineTM cartridges: not hazardous goods

Price in retail: $2.5-3 EUR (Including VAT)

Propane bottle (refill) 11kg propane Price in retail: 11-13 EUR

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Refilling (resaturation) •

US strategy: –

•

Done by industrial partner on a license basis

Europe –

Initially, refill can be done at Amminex facility • •

–

•

Amminex plant is an existing ammonia ‘hub’ Ex. Works with 3rd party logistics company

Refill

By industrial partner

Other regions –

To be done on a license basis.

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Examples of AdBlue price levels Cans

AdAmmineTM logistics

No of Cans Price (£/litre) 10 x 10L = 1.60/litre 100 litres 40 x 10L = 0.85/litre 400 litres 400 x 10L = 0.77/litre 4000 litres

Delivery Total Price (£ net)

IBCs

Price (EUR/liter)

Free

£

160

100

Free

£

340

400

Free

£

3080

4000

Drums No of Drums 2 x 210L = 420 litres 12 x 210L = 2540 litres 24 x 210L = 5040 litres

Liter

Cans ∼ Cartridges Drums ∼ Pallets 1244.6 IBCs ∼ £Containers

Price Delivery Total Price (£ net) (£/litre) 0.575/litre Free £ 241.5 0.49/litre

Free

0.46/litre

Free

£

Liter

2318.4

1.92

€

1.02

€

0.92

Price (EUR/liter) 420 2540 5040

Cost level for end-users Delivery Total Price (£ net) Liter depends on usage pattern

No of IBC's Price (£/litre) 1 x IBC = 0.400/litre Free 1000 litres 5 x IBC = 0.379/litre Free 5000 litres 10 x IBC = 0.365/litre Free 10000 litres

€

€

0.69

€

0.59

€

0.55

Price (EUR/liter)

£

400 + deposit

1000

£

1895 + deposit

5000

£

3650 + deposit

10000

€

0.48

€

0.45

€

0.44

Source: http://www.adblueonline.co.uk/home.php IQPC - SCR 2011

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Bulk ammonia: Yara’s ammonia plants in Europe. •

There is a dialogue with Yara to use the synergy between existing NH3 plants and the establishment of cartridge recharge facilities to support development of infrastructure and for AdAmmineTM aftermarket.

Porsgrunn

Sluiskil Brunsbüttel Le Havre

Tertre

Ferrara

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Summary: A few key-numbers •

2.4: Volume saving factor relative to liquid urea tank with same ammonia quantity

•

27: Number of pending patent families

•

9: Solid benefits: – – – – – – – – –

AdAmmine™: Safe solid-state ammonia storage. Direct, on-demand ammonia dosing to the SCR catalyst. High storage capacity. High dosing accuracy. No liquid injection and no risk of deposits in the exhaust line. High NOx conversion – also during urban driving. Mechanically simple – no problems with freezing. Customer-friendly: No refilling – fast cartridge replacement. Stable NOx reductant: Very long cartridge shelf life

•

70: Current number of employees in Amminex.

•

50: Number of millions of Euro invested in Amminex A/S –

•

20 Million Euro invested by Faurecia in January 2011.

2011: Year of first AdAmmineTM plant PPAP IQPC - SCR 2011

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