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SHORT-LIVED CLIMATE POLLUTANTS:
OXIDATION AND BEYOND
Copyright Impact Global emission Solutions Ltd 2015. All Rights reserved.
What are SLCPs?SLCPs - MAIN TRANSPORT POLLUTANTS IN CITIES:• Precursors to CO2 – not yet fully oxidised to CO2• Not exposed to full oxidation temperatures• BLACK CARBON – PM10+ 2.5 and smaller, global warming
potential up to 3200 times of CO2• METHANE –CH4, 28 times global warming potential of CO2• NO & NO2 – Precursors to TROPOSPHERIC OZONE• adverse climate and health impactsOTHER TRANSPORT POLLUTANTS IN CITIES: • BENZENE - Carcinogenic• FORMALDEHYDE - Carcinogenic• ACETALDEHYDE - Carcinogenic
Copyright Impact Global emission Solutions Ltd 2015. All Rights reserved.
SLCPs Effect on Global Climate Change
CO2 55%
SLCPs 45%
Copyright Impact Global emission Solutions Ltd. 2015 All Rights reserved
• SLCPs account for nearly half of all global climate-forcing emissions
Source: IGSD, 2013: 10
Combustion Process and Thermal Reaction
Boil Water 1000C
Combustion Commences
2250C
SLCPs, Benzene, Formaldehyde, Acetaldehyde 100-2000C
Completed Combustion
Oxidation to Co2?
380-6000C
DPF & DOC Incomplete Oxidation of Unburned Pollutants ?
250-3750C
Increased NOX due to DPF, DOC &
Oxygen 150-4000C
Copyright Impact Global emission Solutions Ltd 2015. All Rights reserved.
Combustion Process and Thermal Reaction
CombustionDe
g C
=+
Acetaldehyde
NO2
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Formaldehyde
Combustion Commences 225O C
Benzene
Real World Operating temperatures of DPF ?
• Highway = 380 Degrees C
• Urban = 250-280 Degrees C
• During Regen Only ( if they have regen ) = 500-550 Degrees C ………………………….at Core
• Regen is required to at Best Oxidise to CO2
Copyright Impact Global emission Solutions Ltd 2015. All Rights reserved.
Short to Long-Lived Climate Pollutants – CO2
Engine Exhaust Gas = 580 O C
Boil Water
100 O C
DPF/DOC Exhaust into DPF/ DOC 250-375 O C
Let’s make NOx and SLCP
150-400 O C
Oxidation to CO2 380- 600 O C
= LTCP
Copyright Impact Global emission Solutions Ltd 2015. All Rights reserved.
What Diesel particulate Filter ( DPF) and Diesel Oxidation Catalyst (DOC) Do
1) PM10+ all species come from engine
2) Catalyses PM10 to
smaller more harmful Micro -PM: PM2.5 and
smaller
3) Creates more harmful
pollutant species and
NOx
4)4) Do not fully Oxidise all PM & black carbon
to CO2 !
Copyright Impact Global emission Solutions Ltd 2015. All Rights reserved.
Copyright Impact Global emission Solutions Ltd 2015. All Rights reserved.
Carbon Mass =1 in = 1 outTherefore:
CO2= OxidisedOR Unoxidised =
Co + C6H6 + CH2O + C2H4O or Variants PAH + VOC
CARBON MASS is still the same !
Copyright Impact Global emission Solutions Ltd 2015. All Rights reserved.
Diesel particulate matter is emitted in three usually distinct but overlapping size modes:
the nucleation mode, typically 3-30 nm diameter, containing most of the particle number;
the accumulation mode, roughly 30-500 nm, containing most of the particle mass;
and the coarse mode consisting of larger particles and usually comprising less than 10% of the mass . Lubricating oil is a dominant component of the nucleation mode particles produced without after treatment
And co2 is 0.33nm … ! … What Can you actually measure?
Copyright Impact Global emission Solutions Ltd 2015. All Rights reserved.
NO + NO2 ( NOX )
Cause or Effect ?
Cause = Increased temperature at DPF & DOC + Exposure to Oxygen and Nitrates in fuel
Effect = Increase of up to 200% ( Euro 3 to Euro 5 )
Increase up to 1400% ( Euro 3 to Euro VI )
Therefore PM is the source of the problem !
Thermal Decomposition of Water –Boiling a Kettle
1) Put the kettle on 2) Boil to 100 O C 3) Liquid becomes gas
4) Steam Evaporates
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Thermal decomposition of SLCP TO CO2 and Beyond – CO2 Decomposition
1) CO2 and black carbon + incomplete
oxidation
e.g. benzene
2) Subject to higher temperature and
pressure
3) Decompose to C + O 4) Reform by adding H2 to CO2 + CO + C = CH4
( Sabatier process )
Oxidation Temp
=+ Heat & Pressure
=
Decomp. Point
500-3000 O C
+=
CO2 + 4 H2→CH4 +
2 H2O + energy+
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If Covalent bonds are created by reaction to heat + pressure,what can they be reformed to with heat and pressure ?
Therefore; CO2 + 4 H2 →CH4 + 2H2O + energy (Sabatier Reaction)
Combustion
Oxidation
Decomposition
Reform to CH4
FUEL CH4
OXIDISE DECOMPOSE REFORM
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THEREFORE: Normal Oxidation – IPCC 2006 ( Diesel )
SFC x NCV x mass 44/12 x oxidation factor 99/100 (assume 100% ) = CO2
ADVANCED COMBUSTION : Beyond Oxidation
SFC x NCV x mass 44/12 x oxidation factor 99/100 x decomp factor x/y = C+O
Where X will be % CO2 reduced by decomposition or reformation Y= CO2
Where: SFC = Specific Fuel Consumption;
NCV = Net Calorific Value
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Cup of tea ?
Copyright Impact Global emission Solutions Ltd 2015. All Rights reserved.
www.impactglobalemissionsolutions.com
Eric Keogh [email protected]
Ref: EJ Grootendorst, Y Verbeek, V Ponec 1995
FS USA http://www.fs.fed.us/t-d/pubs/pdf/08511816.pdf
Winati, W. S., Purwanto, W. W., Bismol, S. (2014) Decomposition of Carbon Dioxide in the Three-Pass Flow Dielectric Barrier Discharge Plasma Reactor, International Journal of
Technology, 1, 1-11.
Srivastava, M.P., Kobyashi, A. 2010 Carbon dioxide decomposition by plasma methods and application of high energy and high density plasmas in material processing and nano
structures, Transactions of JWRI, 39(1), 11-25.
Miller, J.E. 2009 Why not split harmful carbon dioxide into harmless carbon and oxygen? Scientific American, 7.9.2009, available at: http://www.scientificamerican.com/article/splitting-
carbon-dioxide/, accessed: 3.5.2015
Lunde, P.J, Kester, F.L. (1974) Carbon dioxide methanation o a ruthenium catalyst, Industrial Engineering Chemical Process Des Dev, 13(1), 27-33.
Transport & Environment (2015) Six Facts About Diesel the Car Industry Would Rather not Tell you, Transport & Environment, Brussels.
Johnson Mathey 2012, Paul Sabatier, https://www.dieselnet.com/tech/dpf_regen.php
http://www.researchgate.net/profile/Hiromu_Sakurai/publication/6795746_Chemical_and_physical_properties_of_ultrafine_diesel_exhaust_particles_sampled_downstream_of_a_catalytic_tr
ap/links/02e7e52478115d51ac000000.pdf
https://dspace.lboro.ac.uk/dspace-jspui/bitstream/2134/4835/1/samuel2.pdf
* Depending on Fuel and Engine configuration – pressure and temperatureCopyright Impact Global emission
Solutions Ltd 2015. All Rights reserved.
References