Air Pollution and Climate Change

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


SLCP

LTCP

GLOBAL WARMING

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


Combustion Process and Thermal Reaction

CombustionDe

g C

=+

Acetaldehyde

NO2


Formaldehyde

Combustion Commences 225O C

Benzene

Oxidation Temperatures?


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


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


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 !


Causes and effects

PM 10

PM 2.5 and smaller


Carbon Mass =1 in = 1 outTherefore:

CO2= OxidisedOR Unoxidised =

Co + C6H6 + CH2O + C2H4O or Variants PAH + VOC

CARBON MASS is still the same !


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?


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


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+


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


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


Cup of tea ?


www.impactglobalemissionsolutions.com

Eric Keogh [email protected]

http://www.impactglobalemissionsolutions.com/

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

http://www.fs.fed.us/t-d/pubs/pdf/08511816.pdf

http://www.scientificamerican.com/article/splitting-carbon-dioxide/

http://www.researchgate.net/profile/Hiromu_Sakurai/publication/6795746_Chemical_and_physical_properties_of_ultrafine_diesel_exhaust_particles_sampled_downstream_of_a_catalytic_trap/links/02e7e52478115d51ac000000.pdf