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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