Introduction

Catalyst Technology for Emission
Reductions in Mobile and
Stationary Applications
Toni Kinnunen, CTO
Ecocat Oy
[email protected]
If the Globe was size of a football...
... the thickness of atmosphere (with all the emission
impurities) would be about 1 mm
So it really matters what kind of air quality we have
and how we develope it for future!
2
Sunny day in New Delhi
3
Contents
• Introduction
• Ecocat in brief
• Exhaust gas catalysis technology
– Diesel aftretreatment
– Natural gas and other alternative fuels
• Chemistry in key role
• How to develope further?
4
Introduction
•
Clean Air is nice to inhale, also in future!
•
Typical harmful emissions from mobile and stationary sources burning
fossil fuels
•
•
•
•
•
•
•
•
Nitrogen oxides NOx
Particulate matters PM
Hydrocarbons HC
Carbon monoxide CO
Volatile organic compounds VOC
Carbon dioxide CO2
Sulphates SOx
Others (N2O, NH3, CH2O...)
5
Introduction
World primary energy demand by scenario
Source: World energy outlook 2010
Introduction
Shares of energy sources in world primary demand by scenario
Source: World energy outlook 2010
7
Introduction
•
Health Impact of NOx:
– Causes respiratory problems such as asthma, emphysema and
bronchitis
– Aggravates existing heart disease
– Premature death
•
Environmental Impact of NOx:
– Component in ground-level ozone and smog
– Contributes to acid rain
– Combines with particles to reduce visibility
– Is a greenhouse gas that contributes to global warming and
climate change
8
Introduction
•
Health Impact of (Diesel) Particulate Matter:
– Inflammation of lung tissue
– Asthma attacks
– Bronchitis
– Premature births
– Stroke
– High blood pressure
– Heart attack
– Premature Death
•
Environmental Impact of (Diesel) Particulate Matter:
– Contributes to smog
– Reduces visibility
– Absorbs sunlight causing global climate forcing (weather
changes)
– May affect local climate changes
– Contributes to global warming
9
Introduction
•
Health Impact of Hydrocarbons:
– Acute respiratory symptoms
– Headaches
– Dizziness
– Vomiting
– Reduced cardiovascular function
– Arrhythmia
– Brain Damage
– Coma
– Premature death
•
Environmental Impact of Hydrocarbons:
– Precursor to ground-level ozone
– Major component of smog
10
Introduction
•
Are the laws, rules, technical solutions and public & political
motivations fullfilling our requirements?
– Only limited amount of retrofit projects
– Stationary sources still without proper requirements of emission control
– Off-road almost totally without catalysts so far
•
CO2 topic is heavily dominating discussions and decision making, while fast
actions are needed in other aspects as well
–
Is CO2 the major concern?
11
Introduction
2005 Annual average PM2.5 (dia < 2.5 µm) concentrations relative to WHO guidelines
Source: Brauer et al., Env.Sci.Tech, 2012
12
Introduction
Emissions of air pollutants Index 1990=100
13
Introduction
Indexed trend in annual mean urban air quality over the period 1997-2008
14
What can be done to reduce
harmful emissions?
-Emission regulation trends-
Introduction
European Union Emission Limits for Light Duty Diesel Vehicles:
3
CO
HC+Nox
2014
1
HC
2009
2005
2000
1,5
1996
2
1992
Emissions (g/Km)
2,5
Nox
PM
0,5
0
Euro 1
Euro 2
Euro 3
Euro 4
Euro 5
Euro 6
Regulation Tier
16
Introduction
Global trend for emission limits in heavy duty vehicles
Source: Daimler
17
Introduction
Emission limit development in developing countries
2000 2001 2002 2003 2004 2005 2006 2007 2008 2009 2010 2011 2012 2013 2014 2015
China
P&LCV (Beijing)
Euro I
Euro II
Euro III
Euro IV
Euro V
P&LCV (Nationwide)
Euro I
Euro II
Euro III
Euro IV
HCV
Euro I
Euro II
Euro III
Euro IV
Non-road
Standard I
Standard II
India
P&LCV (big cities)
Euro I
Euro II
Euro III
Euro IV
Euro III
P&LCV (Nationwide)
Euro I
Euro II
Euro III/ Euro IV (earlier
Light-Duty Vehicles
Euro I
Euro II
implementation
in big cities)
HCV
Euro I
Euro II
Non-road (Diesel)
Stage II (=EU stage)
Stage III (= US Tier II/III)
Iran
P&LCV
HCV
Euro I
Euro II
Euro III
Euro IV
Non-road
Russia
P&LCV
Euro I
Euro II
Euro III
Euro IV
Euro V
HCV
Euro I
Euro II
Euro III
Euro IV
Euro V
Non-road
Stage I
Uzbekistan
P&LCV
Euro II
Euro III
Euro IV
Current EU standard adaption globally would lead to
HCV < 85 kw
120 000 - 280 000 avoided premature deaths in 2030
HCV > 85 kw
(Shindell et al., 2011 Nature Climate Change)
Non-road
18
Introduction
On-road vs Off-road, emission limits
0,25
Non-regulated
PM [g/kWh]
0,20
Stage III A (2006)
Stage II (2002)
0,15
US 04 (2004)
0,10
US 10 (2010)
Euro 3 (2000)
Euro 6 (2014)
Stage IV
(2014)
0,05
Stage III B
(2011) = Euro 5
(2009)
Euro 4 (2006)
0,00
0
1
2
3
4
NOx [g/kWh]
5
6
7
Source: Agco
19
Introduction
Emission limits tightening in marine sector
Source: Dieselnet
20
Introduction
600 mg/Nm3 is equivalent to 1,6 g/kWh
Source: Dieselnet
21
Introduction
Comparison of NOx emission limit levels
22
Introduction
To achieve the tightening emission limits,
all the related technologies need to be improved
Engine
development
Fuel
improvements
Catalyst
development
Lower emissions
Cleaner Air
23
Introduction
In addition to the tightening limits, new emission types likely to be regulated
•
•
•
•
•
NO2 and N2O
NH3
Ethanol
Specific organic compounds (aldehydes etc.)
Nanoparticles
Not in laboratory only, more and more concern in real-world emissions
• OBD and not to exceed
• Type approvals also by on-road measurements
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Ecocat and catalyst technology
Ecocat global presence
Finland - Vihtavuori (Headquarters)
Finland - Oulu (R&D Centre)
Russia - Nizhniy Novgorod
China - Nanjing
Italy - Genoa
Iran - Tehran
India - Faridabad
•
•
Approximately 300 employees in five countries
Sales agents close to key customers
26
Integrated know-how for fulfilling customers´ requirements
Catalytic converter
• Fast and highly effective response to
meet application requirements
• Easy integration into exhaust system
Coating process
Metallic substrate
• Low back pressure
• Size benefit
• Flexibility in shape
• Durability
• Immediate catalytic performance
Outsourced substrates
Chemical know-how
• Formulas for several applications
• Silicon carbide and cordierite substrates
- Gasoline
- Diesel
- CNG/LPG
- Gasoline
- Diesel
- Natural Gas
- VOC
27
Ecocat
Ecocat's Products are Organized Around Four Business Areas
Passenger and Light
Commercial Vehicles
Industry
Heavy Commercial
Vehicles
Off-Road
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Ecocat
HD oxicat
LD oxicat & TWC
HD and off-road
V-SCR
HD CNG
LD oxicat & TWC
HD H-MIXER
LD & HD partial DPF
LD & HD DPF
Power Generation
oxicat
HD SCR
Off-Road H-MIXER
Locomotive
oxicat
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Ecocat
30
Ecocat
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Ecocat
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Structure of a Catalyst for Exhaust Aftertreatment
Components and Their Main Functions:
Catalytic converter
Catalyst monolith (substrate)
Washcoat
(support + promotors)
Wall of substrate
* Packaging
* Shock and vibration
resistance
* Surface area
* Flow turbulence
* Thermal conductivity
* Heat Capacity
* Pressure drop
* Porosity
* Active metal dispersion/SA
* Thermal resistance
* Poison tolerant
33
What does a Catalyst do on a car?
Oxidation of carbon monoxide (CO)
CO + ½ O 2 ⇔ CO2
CO
HC
NOX
Oxidation of hydrocarbons (HC)
C3H8 + 5 O2 ⇒ 3 CO2 + 4 H2O
CO2
H2
N2
Reduction of oxides of nitrogen (NOx)
NO ⇒ ½ N 2 + ½ O 2
34
Diesel emission aftretreatment
Complete diesel aftertreatment system
DOC
CO
CO2
Hydrocarbons CO2 and H2O
NO
NO2
H-cat
SCR
Urea NH3
NOx N2
UREA
INJECTION
ASC
Lightoff
DPF
NH3 NRegeneration
Particle mass CO2
2
Based on application, normally only some of above are needed
DPF can be located in upstream of SCR, too
Ecocat has the whole range of catalysts in portfolio;
substrates and coatings
Together with partners, the complete systems
tailored to fulfill customers requirements
36
Diesel Oxidation Catalyst (DOC):
Main Reactions:
1.Oxidation of carbon monoxide (CO)
CO + ½ O 2 ⇔ CO2
2. Oxidation of hydrocarbons (HC)
C3H8 + 5 O2 ⇒ 3 CO2 + 4 H2O
3. NO2 formation for SCR and particle regenerations
2NO + O2 ⇒ 2 NO2
37
Particle Oxidation Catalyst (POC):
Takes care of particulate matter; soot and volatile organic fractions.
It traps the particles and oxidize them by catalytic reactions.
*Pt-only
*Useful for
• Passenger Cars
• Trucks/ Buses
• Working machines
• Off-road
• Stationary
38
Diesel Particulate Filter (DPF)
*Takes care of PM.It traps and oxidizes soot
*Pt-only
*Typically coated with catalysts
*Useful for:
•Passenger cars
•Trucks/ Buses
Selective Catalytic Reduction (SCR)
*Takes care of NOx
*Vanadia base
*Vanadia-free
*Useful for:
•Trucks/ Buses
•Tractors
•Stationary engines
•Marine engines
39
Reactions in SCR systems
PreOxicat
NO + O2 ⇔ NO2
Hydrolysis
CO(NH2)2CO + H2O ⇒ 2 NH3 + CO2
SCR catalyst
standard SCR
4 NO + 4 NH3 + O2 ⇒ 4 N2 + 6 H2O
fast SCR
NO + 2 NH3 + NO2 ⇒ 4 N2 + 3 H2O
NO2-SCR
4 NH3 + 3 NO2 ⇒ 3.5 N2 + 6 H2O
PostOxicat
X
X
4 NH3 + 3 O2 ⇒ 2 N2 + 6 H2O
Optimization of DOC together with H-kat and SCR needed:
NO2 formation, backpressure, temperatures and costs
40
Concept of SCR System
Schematics
Urea level
Urea
temperature
Air pressure
Engine
ECU
Urea pressure
CAN
Urea temperature
Engine
Coolant
Dosing System
AdBlue Tank
Electronics (ACU)
Actuators
Engine
Coolant
Urea
Air
Air
Sensors
Urea
Engine Coolant
SCR Muffler with Injection Nozzle
Air Supply (vehicle
air or electrical air
pump)
Temp. Sensor
Nozzle
NOx
sensor
Temp.
Sensor
Exhaust
stream
41
Alternative fuels
- case CNG and LPG -
43
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
44
Natural gas –potential solution
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
Lean-burn CNG
City buses, airport buses
light commercial vehicles
powerplants
marine
Stoichiometric CNG
passenger cars
Dual-fuel and bi-fuel technologies as compromises
Disandvantages
•
In heavy duty, need for engine development
•
Methane emissions specific CNG catalysts is needed
45
LPG – growing fast in passenger cars
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
46
Chemistry in key role
Chemical
Engineering
Surface
Science
REACTOR DESIGN
PROCESS ECONOMICS
PILOT PRODUCTION
Analytical
Chemistry
CHARACTERIZATIONS
EMISSION
ANALYSIS
ADSORPTION
SURFACE ANALYSIS
METAL DISPERSION
Exhaust
Gas
Catalysis
PGM-SUPPORT
INTERACTION
SOLVENT
METAL COMPLEXES SELECTION
Coordination
Chemistry
CATALYST
WASHCOATS
STABILIZERS
PROMOTERS
Inorganic
Chemistry
SELECTIVITY
REACTION
MECHANISM
Reaction
Kinetics
48
Tailor made interactions
Ready made
Powder or Slurry
PM
PM
PM
PM
PM
PM
PM
Ready made
Powder or Slurry
PM
PM
Pd, Rh, Pt, La, Al, Ce, Zr, Pr, Sr,
Nd, Y, Ba, Si, Ti, W etc.
mainly as oxides
49
Active sites in optimum usage
Pt/Pd/Rh
nanoparticles
tailored interactions
Ce-Zr
Ce-Zr
Ce-Zr
Alumina
Constant need for enhanced activity without significant increase in cost
Optimised usage of precious metals needs improvements in catalytic chemistry
50
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
51
Chemistry in key role
Computational chemistry in daily use
Mechanism
Reaction
E a (eV)
k (s-1 )
1/2
LH
CO * + O *s → CO 2 (g) + vacancy
0.66
107
3
ER
CO(g) + O *s → CO 2 (g) + vacancy
0.70
10-3
4
LH
CO * + O *2 → CO 2 (g) + O * + ∗
0.57
108
Path
(-3.20eV)
(-2.65eV)
52
Chemistry in key role
CATALYST CHARACTERISATIONS
PARTICLE SIZE ANALYSIS
METAL CONTENTS (XRF, AAS)
COMPOSITION AND CRYSTALLINITY (XRF, POWDER-XRD)
BET SURFACE AREA (SORPTOMATIC)
METAL DISPERSION (SORPTOMATIC)
TPR/TPO ANALYSES (QUADRUPOLE MS)
OSC MEASUREMENTS (QUADRUPOLE MS)
TEM, SEM, XPS, AFM, ETC. IN COLLABORATIONS WITH PARTNERS
53
Collaborative Research/ strategy
•
All of our collaborative projects are linked to our own development needs
•
Most important outputs are additional know-how and results for
development and marketing needs
•
Due to collaborative projects, relatively wide contact network exists
– Universities and research centers
– Test institutes and centers
– R&D contacts at customers´ base
•
Public funding utilised
•
Networking and subcontracting for both chemical and mechanical
development
How to develope further?
Highlights from recent R&D achievements
From research to customers´needs
Application engineering
customer projects
troubleshooting
on-going development
Product development
Roadmap
projects
new technology
main task
Research & pre-development
linked to roadmap
future projects
networking
12 mo
12 mo
12 mo
56
Improvements in methane oxidation
• The use of natural gas in increasing market is growing
• The emission limits are tightening methane oxidation need to be improved
• The importance of sulphur resitance and regeneration properties
Lean-burn oxidation
Laboratory light off tests as HT-700°C/20h
Aged samples
THC Conversion in Light-off performance
100
Operation area
98 vs. 88 %
Conversion, %
80
60
Light off area
∆T = 25°C
40
20
856 New Pt:Pd 1:4 250g/cft
857 KLN3 Pt:Pd 1:4 250g/cft
0
100
150
200
250
300
350
400
450
500
550
600
Temperature before catalyst, °C
57
Improvements in methane oxidation
Stoichiometric oxidation
Driving simulations (NEDC)
Aged samples
0,665
CNG engine test
0,7
38% less emissions
0,410
56% less emissions
0,4
0,040
0,1
0,039
0,113
0,122
0,2
64% less emissions
0,152
0,3
0,279
emissions g/km
0,5
0,440
0,6
0
THC
CO
Previous generation product
gasoline chemistry
Nox
New K5.7
58
SCR for high temperature applications
• The regeneration of DPF causes temperatures more than conventional SCR
coatings can withstand
• In off-road, engines driving mainly in full-load, continuously at high temperatures
•
New chemistry needed
NOx conversion, %
• At the same time, also low temperature performance need to be improved (coldstart emission limit Euro VI)
Vanadia catalyst preferred
100
90
80
70
60
50
40
30
20
10
0
-10
-20
150
HT700/20h
Inlet: NO 600 ppm, NO2 400 ppm,
NH3 1000 ppm,
O2 10 %, H2O 8 %, N2 bal.
Thermally stable V-SCR-w1241
Std V-SCR-w1249 REF
200
250
300 350 400 450
Temperature, °C
500
550
600
59
Summary
• The energy consumption based on fossil fuels is still increasing causing
additional need for environment-friendly technical solutions
• Global regulation with tightening and new limits is a key driver for cleaner
future
• Catalyst technology for exhaust aftertreatment is the continuously
developing solution in combination of fuel and engine improvements
• Close collaboration between industry and universities and other research
specialists in northern countries has proven to be a competitive way to
solve challenges
60
TO BE OPTIMISTIC; FUTURE SCENARIO?
Light duty vehicle type scenario in California
Source: California Air Resources Board, Green car report
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Thank you for your attention!
[email protected]
www.ecocat.com