Lars J. Pettersson Chemical Engineering and Technology
Abatement of emissions from ships –
A Baltic perspective
Pohjoisen Itämeren alueen kestävä kemia ja prosessiteknologia (POKE), Vaasa, 22-23 October, 2013
Vaasa
Emissions of SO2 1990-2030 (kton)
Emissions of NOx 1990-2030 (kton)
Land and sea-based emissions
Emissions from trucks on long hauls with different EU standards and from cargo vessels of various sizes
Heavy duty truck with trailer
CO2 PM SO2 NOx VOC (HC)
Before 1990 50 0.058 0.0093 1.00 0,120 Euro 0 (1990) 50 0.019 0.0093 0.85 0.040 Euro 1 (1993) 50 0.010 0.0093 0.52 0.035 Euro 2 (1996) 50 0.007 0.0093 0.44 0.025 Euro 3 (2000) 50 0.005 0.0093 0.31 0.025 Euro 4 (2005) 50 0.001 0.0093 0.22 0.017 Cargo vessel Large (>8000 dwt) 15 0.02 0.26 0.43 0.017 Medium size (2000-8000 dwt)
21 0.02 0.36 0.54 0.015
Small (<2000 dwt) 30 0.02 0.51 0.72 0.016 RoRo (2-30 dwt) 24 0.03 0.42 0.66 0.029
g/ton-km
Map over SECA and Europe
SECA – Sulphur Emission Control Area
Marpol – International Convention for the Prevention of Pollution from Ships
SOx Emission Control Areas (SECA) approved by IMO (Annex VI)
International Emission Control Areas according to MARPOL Convention
Area SOx NOx Adopted Demanded
Baltic Sea x 1997 2005
North Sea x 2005 2006
North American
ECA
x x 2010 2012
US Caribbean ECA x x 2011 2014
NOx limits for ships
Tier
#
Year NOx Limit, g/kWh
n < 130 130 ≤ n < 2000 n ≥ 2000
I 2000 17.0 45 · n-0.2 9.8
II 2011 14.4 44 · n-0.23 7.7
III 2016† 3.4 9 · n-0.2 1.96 † In NOx Emission Control Areas
(Tier II standards apply outside ECAs).
n - engine max rpm
Maritime fuels
Fuel HFO MDO MGO
Density (kg/m3) 930-996 850-900 820-860
Viscosity @ 50oC (mm2/s) 204 19.3 3.1
Eff. Heating value (MJ/kg) 40.96 42.19 42.65
Carbon (wt%) 86.61 86.68 86.74
Sulphur (wt%) 3.0-5.0 0.5-1.5 0.5-1.0
Oxygen (wt%) <0.1 <0.1 <0.1
Hydrogen (wt%) 11.34 12.62 13.23
Nitrogen (wt%) 0.33 <0.1 <0.1
Ash content (wt%) 0.05-0.1 0-0.01 0-0.01
HFO - Heavy Fuel Oil Light marine distillates: MDO - Marine Diesel Oil, MGO - Marine Gas Oil
The curve of allowed MARPOL NOx
emissions (IMO TIER I)
MARPOL Annex VI NOx Emission Limits
Sulphur content in land and marine fuel
www.imo.org
Sulphur content in various fuels
The influence of fuel sulphur on particulate emissions
Why?
Particulate emission composition with 0.1 wt% sulphur in the fuel
SOX and metallic
oxides (10%) (H2O 5%)
HC (40%)
Soot (45%)
Particulate emission composition with 3.0 wt% sulphur in the fuel
H2O (5%)
HC (10%)
Soot (25%)SOX and metallic
oxides (60%)
MARPOL Annex VI and EU regulation on fuel sulphur limits
Date Ship type Area % Act by
2000 all Baltic ECA(SOX) 1.5 Marpol&EU
Worldwide 4.5 Marpol
2006 passenger ships All EU 1.5 EU
2007 all North Sea & English
Channel ECA(SOX)
1.5 Marpol&EU
2010 all ECA(SOx) 1 Marpol
all EU ports 0.1 EU
inland waterway vessels inland waterways
2012 all Worldwide 3.5 Marpol
2015 all ECA (SOx) 0.1 Marpol
2020a all Worldwide 0.5 Marpol
aAlternative date 2025
EU sulphur limits in marine exhaust gas
Transportation emissions
7 k
m l
ong p
ipel
ine
Refining of crude oil The main part of the crude oil
comes from the North Sea
6 mountain storage facilities, Totally 480 000 m3
3 tanks each 35 000 m3
13
00
0 m
3 /
day
37
5°
C
GAS CLEAN.
SULFUR
RECOVERY
CRUDE OIL
DISTILLATION
SULFUR to paper industry
DESULFURIZ.
GASOLINE
ISOMERIZATION
CATALYTIC
REFORMING
LPG
GASOLINE
KEROSENE WASH KEROSENE
DESULFURIZATION
DEAROMATIZATION
DIESEL CITY DIESEL
DESULFURIZ.
LIGHT GAS OIL
25 %
FUEL OIL
DESULFURIZ.
HEAVY GAS OIL SHELL WRD
THERMAL
CRACKER
480°C
HEAVY
FUEL OILS
H2
SULFUR-FREE REFINERY GAS
GÖTEBORGS
ENERGI AB WASTEWATER
TREATMENT GÖTAÄLV
Ca 3 ships/month each 120 000 m3 MOUNTAIN STORAGE
HJÄRTHOLMEN
TANK CRUDE OIL
1%
25%
19 %
30 %
Waste heat 93 MW (22% of the heating i nGöteborg)
TG 42 MW
HVC Boiler 2 x 21 MW
50°C
90°C
Oil refinery
Structural characteristics of
petroleum fractions
Gas Light
gasoline
Gas oil Vacuum
distillate
Vacuum
residue Heavy
gasoline Kerosene
Paraffins
Naphthenes
Overview of an SCR system
Main components of an SCR system
• Reducing agent storage tanks (typically 5-50 m³)
• Reducing agent pump or pump station
• Reducing agent dosing unit
• Mixing unit with injection nozzle
• Catalyst housing (reactor) including SCR catalysts
• Control unit
SCR Catalyst for stationary applications
• V2O5-WO3/TiO2 Monolithic Catalyst
• Dimensions
- catalyst channels 4 to 8 mm
- modules of 1*2*1.5 m
- 10 to 500 modules per installation
• Temperature 250 to 425 C
• Typical performance levels
- 90 % NOx removal
- 2 ppm Ammonia slip
Reducing agents
•Maritime Grade Urea solution (40 wt%, freezing point: 0 C)
•NH3 (g)
•NH3 (aq)
Urea SCR system for ships
inches
Costs for SCR systems
• Investment cost: Siemens SINOx SCR with a V2O5 catalyst ~ 40-70 USD/kW1 (15-70 €/kW2)
• Operational cost: ~ 3-4 USD/MWh 1using a 40 % urea solution ~ €5-€7/MWh2
• normal cruising ship on the Baltic Sea, e.g. Viking Line Cinderella with 28,800 kW 1.5 million USD.
1Pounder et al.
2IACCSEA - The International Association for Catalytic Control of Ship Emissions to Air
Siemens SINOX system for ships
Catalyst element from Haldor Topsøe
Temperature – Catalyst Activity
Operating Temperature
NO
x C
on
vers
ion
Temperature
Limited -
Inadequate
Activity
Preferred Temperature Window
290°C – 425°C V/ W / TiO2
Catalyst
Sintering
and
Ammonia
Oxidation
SCR Catalyst deactivation Fuel influence
KTH Royal Institute of Technology • www.kth.se
0
0.2
0.4
0.6
0.8
1
1.2
0 10000 20000 30000 40000 50000 60000
Operation hours [h]
Re
lati
ve
ac
tiv
ity
k/k
0
Wood (CFB-boiler)
Bituminous
Heavy fuel oil
Light fuel oil
Straw
Typical Tail-end
bio fuel
Chart from Haldor Topsøe
SCR Catalyst Deactivation
Na K As P Ca Fe Ni Cr Pb V
Coal Bituminous x x x x
Bio-fuel Wood x x
Straw x x
Recycle wood x x x
Fuel oil x x x x x
Fuel oil/diesel (engines) x x x x
Syn-gas x x
FCC off gas
Ethylene cracking furnace x
Sewage sludge x x x x
Bone meal x x x x
Bone fat x x x x
Coal Co-combustion With
Straw x x x
Most Important Poisons from different types of fuel
Ammonium Sulphate Formation
• 2 NH3 + SO3 + H2O (NH4)2SO4
• 2 NH3 + H2SO4 (NH4)2SO4
• Equilibrium between H2SO4 and SO3:
- SO3 + H2O H2SO4
SCR on ships
Catalysts used for SCR
•V2O5 /WO3 on TiO2
•V2O5 on TiO2 or on SiO2 or on Al2O3
•WO3 on TiO2
•Pt on Al2O3 or SiO2
•Fe2O3 on TiO2 or on Cr2O3/Al2O3
•CuO on TiO2 or on Al2O3
•Cu(II) zeolites, Pt-, Fe-, Ni- Y-zeolites
Information required for catalyst sizing
• Exhaust Gas Flow Rate
• Exhaust Gas Composition (O2, CO2, H2O, Ar)
• Exhaust Gas Temperature
• Exhaust Gas Pressure
• NOx Content
• SO2 and SO3 Content
• Ash or Particulate Quantity
• Fuel Type, Firing Rate, Ash Composition
• NOx Removal Requirement (x)
• Ammonia Slip Limit
• Pressure Loss Limit
• Service Lifetime
• Reactor Dimensions and Layers
Harbour electrification
An overview of the Humid Air Motor (HAM) system
Scrubber technology
LNG transportation ships
Why use Liquefied Natural Gas (LNG) as ship fuel?
• Reduction of NOx emissions for both pure gas engines and four-stroke dual-fuel engines
• Reduce SOx emissions by 90-95%
• 20% - 25% reduction in CO2 emissions is possible
• LNG could be offered at a price comparable to heavy fuel oil (HFO)
• Commercially attractive compared with the low-sulphur marine gas oil (MGO) which will be required to be used within the ECAs
Conclusions
•The Baltic Sea is a SECA area
•Sulphur levels in maritime fuels are rapidly changing
•Refinery capacity for low sulphur fuel can be a problem
•Large investments on SCR technology necessary to meet future emission standards
•LNG seems to increase as ship fuel in the Baltic
Photo: Johnér bildbyrå
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