Unregulated Engine Emissions and Their Control Using g DOC, , PFF and CRT

Tarun Gupta

Introduction

The increasing use of diesel engines due to their fuel economy, durability and power advantages has contributed to the sum total of exhaust emissions. Need of clearly understanding these emissions. Emission can be classified into two broad categories Regulated R l d emissions i i Unregulated emissions Most of the emission regulations in the world are mainly concerned about regulated emissions. Need to reduce the unregulated emissions. Unregulated g emissions are more challenging g g to compare p among g investigators for several reasons. Vast number of unique compounds that exist in combustion exhaust s p products. d c s. Requires expensive analysis techniques [Mullen et al1].

Major Unregulated Emission Compounds

Major unregulated emissions: PAHs Carbonyl compounds BTEX etc. PAH known PAHs k f their for h i carcinogenic i i properties. i No strict regulations for PAHs emission. PAHs toxicity is very structurally dependent. A carbonyl group is a functional group composed of a carbon atom double-bonded to an oxygen atom. BTEX is an acronym that stands for benzene, benzene toluene, toluene ethylbenzene, and xylenes. Have harmful effects on the central nervous system.

Major Unregulated Emission Compounds

Fig 2 Carbonyl Group, Aldehyde and Ketone

Fig 1 Priority listed PAHs. *Not included in priority list, D (not listed as to human carcinogenicity), B2 (probable human carcinogen). [Ravindra et al7]

Measurement Techniques for Unregulated Emission from CI Engines

Karavalakis et al, have performed experiments for determining the regulated and unregulated emissions Constant volume sampling (CVS) technique in a dilution tunnel. tunnel For determining the carbonyl compounds, they have collected the samples in a 3L Tedlar bags. Diluted exhaust pumped through the cartridges at a flow rate of 150 mL/min. mL/min Cartridges contains 2, 4-dinitrophenylhydazine on silica substrate. By using ultra-violet visible detector, carbonyl-DNPH derivatives were analyzed. C18 column l was used d for f the h separation i of f carbonyl b l compounds. d For determining the PAH and nitro-PAH, samples were collected on glass fiber filter. Fi Finally ll a gas chromatograph h h (GC) (Agilent (A il 6890) with i h a mass spectrometric i (MS) detector (Agilent 5975B) was used for the PAH and nitro-PAH analysis.

Tan et al, have used five different diesel fuel with different sulfur content For F the h measurement, they h have h used d an AVL PEUS multi-component li gas analyzer. l capable of measuring over 25 gaseous components including the measurement of Paper # unregulated emissions (HCHO, MECHO and SO2) also.

Measurement Techniques for Unregulated Emission from Engines

Karavalakis et al8, have performed experiments for determining the regulated and unregulated emissions by a passenger vehicle using diesel/biodiesel blends under ADC (Athens driving cycle) and NEDC (New european driving cycle). Diluted Dil d with i h air i in i dilution dil i tunnel. l For determining the carbonyl compounds, C18 column was used. For determining the PAH and nitro-PAH- glass fiber filter, Gas chromatograph(GC) with a mass spectrometric(MS) detector were used. For the measurement, AVL PEUS multi-component gas analyzer used. used Capable of measuring over 25 gaseous components including the measurement of unregulated emissions (HCHO, MECHO and SO2) also. also

Measurement Techniques for Unregulated Emission from CI Engines

Cheung g et al10 have p performed experiments p on a four cylinder y direct injection diesel engine for regulated and unregulated emission with ULSD and its blends with ethanol as fuels. (benzene toluene, toluene Measured the unregulated emission (benzene, formaldehyde, ethanol etc) by using the Air-sense multicomponent gas analyzer. Ethanol E h l was calibrated lib d by b an indirect i di way. Kept the engine running for some time till the exhaust gas temperature, cooling water temperature, lubricating oil temperature and CO2 gas concentration in the exhaust stabilizes.

Effect of Engine Operating Condition and Fuel Composition Co pos o on o Unregulated U egu ed Emission ss o
Effect of diesel/biodiesel blends under ADC and NEDC. [Karavalakis et al8] Main focus was to investigate the impact of regulated and unregulated emissions with the use of diesel/biodiesel blends under ADC and NEDC. NEDC Carbonyl compounds (CBCs), Polyaromatic hydrocarbons (PAHs) and Nitro-PAHs have been measured. Four F diff different f l diesel fuels, di l and d three h bl d with blends i h 5, 5 10, 10 15% biodiesel from soybean oil were used for the experiment. Formaldehyde was the major compound in both the cases which was followed f ll d by b acetaldehyde. ld h d Determined 11 PAHs and 5 nitro-PAHs. Major PAHs emission were of low molecular weight which are followed by higher molecular weight PAHs.

Effect of Engine Operating Condition and Fuel Composition Co pos o on o Unregulated U egu ed Emission ss o
Table 1: Emissions of carbonyls (mg km-1) from diesel fuel and biodiesel blends when the vehicle operated over NEDC and ADC. [Karavalakis et al8]
Carbonyls(mg km-1) Formaldehyde Acetaldehyde Acrolein/acetone Propionaldehyde Crotonaldehyde Methacrolein 2-Butanone Butyraldehyde Benzaldehyde Valeraldehyde p-Tolualdehyde Hexanaldehyde Diesel 6.84 2.86 0.73 2 1.72 3.81 3.58 5.94 1.34 NEDC B5 B10 5.46 4.61 2.24 1.9 0.75 1.56 0.96 1.75 1.89 3.51 14.3 0.82 0.85 4.3 2.46 3.76 4.17 5.47 2.56 1.87 3.15 0.63 0.47 ADC B20 3.64 0.49 1.02 1.42 1.52 0.56 Diesel 11.1 3.82 2.31 3.49 7.75 3.62 12.8 2.28 B5 7.74 4.05 2.2 2.89 3.37 2.24 1.38 7.87 3.98 9 2.82 7.86 B10 6.55 2.1 0.67 3.99 3.3 2.04 6.23 6.75 11.1 6.88 5.66 B20 4.35 1.58 0.71 5.47 1.29 6.35

Higher concentration of CBCs in ADC while lower in NEDC. NEDC Lower saturated aromatic hydrocarbons in biodiesel blends responsible for lower HCHO emission for higher blends.

Effect of Engine Operating Condition and Fuel Composition on Unregulated Emission

Table 2: SOF, PAH and nitro-PAH emissions from the diesel vehicle over the European and the Athens driving cycles. [Karavalakis et al8]
Pollutants PAH emissions, mg Phenanthrene Anthracene Fluoranthene Pyrene Chrysene [ ] Benzo[a]anthracene Benzo[b]fluoranthene Benzo[k]fluoranthene Benzo[a]pyrene Indeno[1,2,3-c,d]pyrene Benzo[g,h,i]perylene Nitro-PAH, mg km-1 2-Nitro-anthracene 3-Nitro-fluoranthene 1 Nit p 1-Nitro-pyrene 7-Nitro-benzoathracene 6-Nitro-benzopyrene km-1 0.01 0 009 0.009 0.008 0.011 0.003 0.002 0.004 0.0001 0 0003 0.0003 0.0003 0.008 0 008 0.008 0.007 0.009 0.002 0.005 0.0001 0 0001 0.0001 0.0002 0.007 0 005 0.005 0.006 0.009 0.002 0.0002 0.009 0 008 0.008 0.008 0.01 0.002 0.002 0.003 0.015 0 014 0.014 0.01 0.009 0.002 0.003 0.006 0.0001 0 0004 0.0004 0.0003 0.013 0 012 0.012 0.01 0.005 0.002 0.005 0.0002 0 0002 0.0002 0.0005 0.01 0 009 0.009 0.008 0.004 0.002 0.002 0.0001 0 0002 0.0002 0.0003 0.012 0 011 0.011 0.01 0.008 0.003 0.003 0.004 0.0001 0.0002 NEDC Diesel B5 B10 B20 ADC Diesel B5 B10 B20

Effect of Engine Operating Condition and Fuel Composition p on Unregulated g Emission

Effect of different sulfur content. [Tan et al9] p on a light g duty y diesel engine g with different Performed experiment sulfur content fuels (S50, S350, S500, S800 and S1500). The investigations have been done on three unregulated emission, , formaldehyde, y , acetaldehyde y ( (MECHO, , as mentioned) ) and SO2. Formaldehyde emission was non-detectable. The tests were carried out in a sequence of S50, S50 S350, S350 S500, S500 S800 and S1500 at two different speeds at 1900 rpm for maximum torque and 4000 rpm at maximum power with increasing g load in each case ( (0%, %, 25%, %, 50%, %, 75% % and 100% % loads).

Effect of Engine Operating Condition and Fuel Composition Co pos o on o Unregulated U egu ed Emission ss o

Fig 5: MECHO emission (n=1900 rpm)

Fig 6: MECHO emission (n=4000 rpm)

Acetaldehyde emission decreases with increasing load and decreases with fuel sulfur content. Trends of curves are same for different sulfur content fuels and it decreases with decreasing sulfur content in fuel.

Effect of Engine Operating Condition and Fuel Composition Co pos o on o Unregulated U egu ed Emission ss o

Fig 7: SO2 emission (n=1900 rpm)

Fig 8: SO2 emission (n=4000 rpm)

SO2 emission increases with increasing sulfur content As the fuel injection quantity increases, the emission of SO2 will i r increase.

Effect of Engine Operating Condition and Fuel Composition on Unregulated Emission

Fig 9: SO2 reduction and fuel sulfur content (n=4000 rpm), [Tan et al9]

Calculated the average reduction extent of SO2 emission for five fuels with different sulfur content keeping S1500 as base fuel. Engine SO2 emission is directly related to the sulfur quality in the fuel.

Effect of Engine Operating Condition and Fuel Composition on Unregulated Emission

Effect of ULSD and its different ethanol blends. [Cheung et al10] Conducted an experiment on a four cylinder direct ignition engine with ULSD and its different ethanol blends. They have taken ULSD as base fuel and four blends with ethanol (bl d 1 blend-2, (blend-1, bl d 2 blend-3 bl d 3 and d blend-4). bl d 4) (performed ( f d at 1800 rpm) )

Fig 10: Effect of ethanol and engine load on unburned ethanol emission

Effect of Engine Operating Condition and Fuel Composition p on Unregulated g Emission

Fig 11: Effect of ethanol and engine load on formaldehyde emission

Fig 12: Effect of ethanol and engine load on acetaldehyde emission

Formaldehyde emission increases with the increase in engine load and it decreases with the increase in alcohol content in ULSD. The possible reason is increased H/C ratio. Decrease in acetaldehyde emission at high load because of high combustion temperature.

Effect of Engine Operating Condition and Fuel Composition on Unregulated Emission

Table 3: Ethene, ethyne y and 1,3-butadiene emissions at various engine g loads. 1800(revmin1) C2H4 ULSD Blend1 Blend2 Blend3 Blend4 35.8 44.7 23.7 33.6 41 0.20MPa C2H2 106 109 49.6 62.5 73 8 73.8 C4H6 46.2 49 29.5 41.1 50 7 50.7 C2H4 35 30.1 22 28.1 30 1 30.1 0.38MPa C2H2 97.2 82.8 43.5 47.5 53 1 53.1 C4H6 45.2 44.4 28.1 35.8 37 3 37.3 C2H4 22.4 19.2 14.4 16.8 16 3 16.3 .55MPa C2H2 54.3 45.7 26.4 28.1 27 7 27.7 C4H6 31.1 24.3 21 21.8 23 6 23.6

(ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm)

Ethene and ethyne are the products of pyrolysis between diesel and ethanol. C2H2 and C2H4 emission decreases with the increase of engine load.

Effect of Engine Operating Condition and Fuel Composition on Unregulated g Emission

Table 4: Benzene, toluene and xylene emissions at various engine loads. mg KWh-1 C6H6 ULSD Blend-1 Blend-2 Blend-3 Blend-4 79.2 95.9 97.2 112.6 153 0.20 MPa C7H8 C8H10 17.1 8.7 9.1 9.4 13.8 69.7 58.3 38 55.3 66.8 0.38 MPa C7H8 C8H10 8.3 4.3 4.3 4.1 5.8 33.2 28.9 18.2 24.5 25.3 .55 MPa C7H8 C8H10 3.3 2.6 2.5 1.9 3.2 18.7 17 10.6 12.5 13.4

C6H6 57 54 53 48.9 63.4

C6H6 28.1 23.6 20.8 26 30.3

Benzene oxidizes easily at high combustion temperature (high load). Toluene and xylene also have the same trend as benzene. At low engine load (low exhaust temperature) with high blend may lead the BTX emission. emission

Conclusions

It has been observed that addition of biodiesel with diesel reduced the content of aldehyde emission in the exhaust and the emission in hot start condition NEDC test cycle is less than the cold start ADC test cycle. Formaldehyde was by far most abundant carbonyl in the exhaust. The concentration of MECHO emission of the engine decrease with the fuel sulfur content. The SO2 concentration increases with the engine load. SO2 emission decreases linearly with descending fuel sulfur content. With ethanol blended fuel, fuel it can be concluded that unburned ethanol emission reduces with increasing engine load. There is a sharp decrease in the unburned ethanol emission with decreasing sulfur content. For ethanol blended fuel, fuel formaldehyde emission is higher at higher engine load and decreases with the addition of ethanol in diesel with ultra low sulfur content. For BTX emission, emission temperature is a crucial factor. factor At low engine load, load the low combustion temperature leads higher BTX emission.

Diesel Oxidation Catalyst

Diesel Oxidation Catalysts (DOC)

Oxidizes CO and HC to CO2 and H2O ( (desired) ) Oxidizes toxics such as aldehydes O idi Oxidizes SO2 to SO3 (undesired) ( d i d) Oxidizes Soluble organic fraction (SOF, HCs) adsorbed ads rbed on n Particulates Partic lates to t reduce red ce PM CO, HC reduction up to 90%. PM reduction up to 50% depending on SOF yp y 25% on new engines g content of PM; Typically
Ceramic Catalyst

DOC in a muffler

S Sulphur problem

Particulate Matter Oxidation

Catalyst

Carbon Soot

Carbon Soot

Note: Soluble Organic Fraction, Sulfates and Water are in Vapor form.

S tO Soot Oxidation: id ti NOx NO vs Oxygen O

C + 2NO2 2NO + CO2 C + O2 CO2

Soot Oxidation Mechanism viz a viz Design of Catalytic Materials

L-H;

E-R;

MVK Mechanisms

Diesel

Catalytic Converter (Diesel Oxidation Catalyst)

Oxidizes SOF fraction of PM Lower cell density and low back pressure with no regeneration constrains Thermal & Chemical stability of catalyst is a challenge May M b be useful f l under d Indian I di scenario, if fuel quality is improved

Limitations

Lower particulate control efficiency Formation F ti of f sulfuric lf i acid, id sulfate lf t

Noble Metals vs Non Non-Noble Metals

Pt, , Pd, , Rh (cost ( !!) ) Mixed oxides, oxides Perovskites

Catalysis / Adsorption: Environmental Applications

Multicomponent p systems y Poor control on catalytic processes Complex interface Interference and selectivity Chemical & thermal stability Cost, techno-economic feasibility Disposal , LCA (catalyst or adsorbent volume?) Phase transfer not feasible

Non-Noble Metal Based Catalysts

Very wide range of catalysts: metals; metal complexes; oxides; composites mixed oxides; perovskites; etc Many industrial applications- From Fe based catalyst for Habers process to Ti-silicalite, Ceria to SnO2

Oxides, Mixed Oxides & Perovskites in Environmental Catalysis

- V2O5 : - Some mixed oxides: (including perovskites) - Ceria based catalysts:

- De-NOx applications - Indoor heating - Automobiles ?? - VOCs ?? - Promoter - Oxygen storage - catalyst

-Co, Ni and other transition -metal based : A few applications

Mixed Oxides and Perovskites

Advantages: - Low L cost: - Sometimes cost is not a big b issue ! - Disposable type catalysts ? VOCs Environmental issues ?? - Tailoring possibilities - New designs (still coming up !!) - Molecular modeling - Combinatorial approaches - Thermal hermal stability stab l ty for combust combustion on react reactions ons etc

Limitations:

- Surface area, microporosity (per unit SA activity !!) - Low temperature activity - Chemical stability ( S S and halogen halogen poisoning)

A3+ B3+ O3 A3+(1-x) A2+x B3+1-x B4+x O3 A3+(1-x) A2+x B3+ O3-(x/2) Vo(x/z) A3+(1-x) A2+x B3+1-2s B4+2s O3-(x/z)+s Vo(x/z) B4+ = Positive hole Vo = Oxide ion vacancy

(i) (ii) (iii) (iv)

Oxide ion vacancies = Mobility M bilit of f oxide id ions i = Increased ionic conductivity = Accommodation sites for extra O

C ti Continuously l Regenerating R ti Trap T (CRT)

CRT Particulate Filter Operating Principle

Diesel Particulate Filter

Johnson Matthey Continuously Regenerating ) Diesel Particulate Filter Technology gy (CRT (

Use of NOx Within CCRT System

CRT Filter System Continuously Regenerating Trap

Principle Oxidation of NO to NO2 inside Pt catalyst Conversion of stored soot in trap by NO2

Continuously Regenerating Trap (CRT)

Utilize the strong oxidizing property of NO2
Unit consists of Pt based catalyst y upstream p of Filter to oxidize NO to NO2 NO2 oxidizes the soot(C) into CO2 in the trap

C(s) + NO2(g) CO(g) + NO2(g)

---> > CO(g) + ---> CO2(g) +

NO(g) NO(g)

(1) (2) (3)

2 NO(g) + O2(g) ---> 2 NO2(g)

This system is very sensitive to

sulphur content of fuel (S<10 ppm)

Active Regeneration

B Burner regeneration i system

Electrical Regeneration

The Mitsubishi DPF System

A device that vastly y reduces emission of particulate matter (the main particle component p of black smoke) ) from diesel engines of buses

Mitsubishi DPF System

System y

Mitsubishi put this system for practical use first time in Japan in buses succeeded in removing 80 % of PM even removes 100 % of black smoke

Overview of the Mitsubishi DPF System System

The Mitsubishi DPF System traps particulate matter i a porous ceramic in i filter, fil and d this hi accumulated l d particulate matter is periodically burned. By regularly g y exchanging g g two filters to continuously y trap p and burn particulate matter, it can be continuously collected while the bus is running.

Overview of the Mitsubishi DPF System System

System Overview
Two filter assembly y Exhaust gas control valve Air flow sensor, temperature & pressure sensors Electric heater & convector

The Mitsubishi DPF System.

Overview of the Mitsubishi DPF System System

Particulate matter collection
The filters use a heat-resistant, finely porous ceramic material. These pores form parallel channels, channels Using 2 filters, exhaust gas is passed through one filter until the accumulation level reaches a specified point, at which the exhaust gas flow is switched automatically by the switching valve to resume particulate matter collection by the other filter

Overview of the Mitsubishi DPF System System

Particulate matter combustion
After the filter end is heated to 600C by y the electric heater, the exhaust gas control valve is opened and part of the exhaust gas is conducted into the filter. The accumulated particulate matter inside the filter is then gradually burned over about 25 minutes by flame propagation .

Overview of the Mitsubishi DPF System System

Particulate matter collection and combustion process

Effectiveness of exhaust gas cleaning

Approximately 80% of particulate matter is eliminated, achieving output levels of only half those specified in the 1988 long-term l t exhaust h t gas restriction(JIS) t i ti (JIS) t target. t Moreover, black smoke, which accounts for most (65%) particulate matter, , is 100% eliminated, , making g exhaust of p invisible to the eye.

Effectiveness of exhaust gas cleaning

Effectiveness of particulate matter reduction.

Effectiveness of black smoke reduction.

P i l Flow Partial Fl Filters Fil

Retrofitment Devices: Partial Flow Filter

Johnson Matthey Wi h Emitec With E i PFF

Fresh and Partially used Devices