Beruflich Dokumente
Kultur Dokumente
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 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.
Fig 1 Priority listed PAHs. *Not included in priority list, D (not listed as to human carcinogenicity), B2 (probable human carcinogen). [Ravindra et al7]
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.
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
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 Co pos o on o Unregulated U egu ed Emission ss o
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
SO2 emission increases with increasing sulfur content As the fuel injection quantity increases, the emission of SO2 will i r increase.
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.
Fig 10: Effect of ethanol and engine load on unburned ethanol 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.
Ethene and ethyne are the products of pyrolysis between diesel and ethanol. C2H2 and C2H4 emission decreases with the increase of engine load.
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.
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
Carbon Soot
Carbon Soot
Note: Soluble Organic Fraction, Sulfates and Water are in Vapor form.
L-H;
E-R;
MVK Mechanisms
Diesel
Limitations
- De-NOx applications - Indoor heating - Automobiles ?? - VOCs ?? - Promoter - Oxygen storage - catalyst
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
Oxide ion vacancies = Mobility M bilit of f oxide id ions i = Increased ionic conductivity = Accommodation sites for extra O
Principle Oxidation of NO to NO2 inside Pt catalyst Conversion of stored soot in trap by NO2
NO(g) NO(g)
Active Regeneration
Electrical Regeneration
A device that vastly y reduces emission of particulate matter (the main particle component p of black smoke) ) from diesel engines of buses
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
System Overview
Two filter assembly y Exhaust gas control valve Air flow sensor, temperature & pressure sensors Electric heater & convector
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.