EXHAUST EMISSIONS FROM A SI ENGINE FUELED WITH PYROLYSIS GAS

M. Ratcliff*, C. Baca-Overly, S. Deutch, C. Feik, J. Graham and S. Phillips National Renewable Energy Laboratory, 1617 Cole Blvd, Golden, Colorado, USA 80401 Fax: 303-384-6363; matthew_ratcliff@nrel.gov Introduction A 4-cylinder, 4-stroke, spark ignition (SI) engine of 2.5L displacement and 9.4 compression ratio was operated for over 100 hours on wood-derived pyrolysis gas to measure exhaust emissions and performance characteristics. The pyrolysis gas (15-16.5 MJ/Nm3) was produced from mixed hardwood and softwood pellets, in NRELs Thermochemical Process Development Unit (TCPDU) using a two-step, indirect gasification process [1]. A typical fuel gas composition is shown in Table 1. In addition, light gasifier tar that escaped the pyrolysis gas clean-up train was consumed as fuel. These tar components were principally benzene (~1 vol. %) and smaller amounts of toluene, naphthalene and related aromatics. Table 1. Pyrolysis Gas Composition from TCPDU in Volume % H2 17.9 CO 34.9 CH4 15.8 C2H4 4.7 C2H2 1.0 C2H6 0.5 CO2 17.3 N2 6.0

port temperature was measured despite the presence of ~17% CO2 in the pyrolysis gas. The CO2 would be expected to reduce the combustion and exhaust temperatures relative to natural gas, due to its high heat capacity. This is the key mechanism by which exhaust gas recirculation (EGR) affects NOx reductions in reciprocating internal combustion engines [3]. Finally, the prompt NOx mechanism may be the principal explanation for the higher NOx emissions from pyrolysis gas, due to the presence of ethylene and acetylene in the fuel, typically 5% and 1%, respectively. The prompt NOx chemistry depends on the presence of CH radicals, which may arise in significant amounts from cleavage reactions of unsaturated hydrocarbons [4].
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Figure 1. Regulated exhaust emissions from natural gas (NG) and pyrolysis gas (PG) at a load of 13 kW and ignition timing of 30o BTDC. Figure 1 also shows that could be increased with pyrolysis gas to a lean operability limit of 1.49 (generator frequency = 60 0.3 Hz), resulting in a NOx emission of 22.4 lb/MWh. At this condition, the averaged exhaust port temperature was 541oC, or 50oC lower than at = 1.22. Both CO and THC emissions from pyrolysis gas began to increase with increasing . This trend was expected, because unburned-fuel emissions increase as combustion temperatures decrease, or the engine enters lean-misfire conditions [5]. Because carbon monoxide is a major fuel component in pyrolysis gas, and CO oxidation kinetics are relatively slow, much of the CO in the exhaust should be considered to be unburned fuel. In order to reduce NOx emissions, the limits of lean-burn operation and ignition timing were explored. Figure 2 shows NOx versus load curves from pyrolysis gas and natural gas. The top pyrolysis gas curve is from = 1.30, and 24o BTDC. Up to approximately 9 kW, the pyrolysis gas NOx emissions from this setting were very similar to the best natural gas results ( = 1.03, 24o BTDC). At higher loads there was an increase in NOx compared to natural gas, despite the much leaner air-fuel mixture. The next lower pyrolysis gas curve in Figure 2 was obtained by optimizing the airfuel ratio and ignition timing for each load tested. These data show that reducing NOx from pyrolysis gas combustion was most effectively done by lean operation, even when the ignition timing had to be advanced to maintain stable engine operation. The broad air flammability limits of pyrolysis gas are due to the presence of hydrogen in the fuel, as well as the relatively low concentration of nitrogen (compared to producer-gas). By exploiting this quality with lean-burn operation, we were able to achieve significantly lower, part-load NOx emissions using pyrolysis gas. Nevertheless, it appears that some form of exhaust after-treatment will be necessary

The manufacturers rated output for the engine-generator on natural gas (~37 MJ/Nm3) was 17 kW. The engine-generator also achieved 17 kW on pyrolysis gas, albeit with slightly less stable performance. This is in contrast to spark ignition engines fueled with producer gas (5.5-7.0 MJ/Nm3), which typically must be derated 3040% compared to natural gas [2]. At loads # 13 kW, the gensets performance on pyrolysis gas was as good or better than natural gas, as measured by the ability to maintain 60 0.3 Hz. Results and Discussion The regulated exhaust emissions from both natural and pyrolysis gas are compared in Figure 1, as a function of Lambda ( = actual Air/Fuel ) stoichiometric Air/Fuel) at a load of 13 kW and ignition timing of 30o Before Top Dead Center (BTDC). NOx from natural gas peaked (44.3 lb/MWh) at = 1.10, then decreased with leaner air/fuel mixtures. The lean operating limit for natural gas (i.e. for a generator frequency = 60 0.3 Hz) was = 1.18. At this setting, the CO and total hydrocarbon (THC) exhaust emissions were similar to those from pyrolysis gas. However, the NOx emitted from natural gas was 29.2 lb/MWh, in contrast to 82 lb/MWh from pyrolysis gas. There are three possible explanations for this large, fuel dependent, difference in NOx. Fuel-bound nitrogen in the wood, which produces NOx upon combustion, contributes to the total. However, given that the nitrogen content in the wood pellet feedstock was < 0.03 wt %, this can not explain a significant amount. Thermal NOx enhancement, due to higher localized flame temperatures within the combustion chambers, is another contributing mechanism. This hypothesis may be supported by the exhaust port temperature data. For the comparison in Figure 1, the average exhaust port temperature from natural gas at = 1.18 was 588oC; while the average was 592oC from pyrolysis gas at = 1.22. The slightly higher average exhaust

Fuel Chemistry Division Preprints 2002, 47(1), 385

for both pyrolysis and natural gas fueled, spark ignition enginegenerator systems, in order to achieve some existing and proposed NOx standards [6]. The Lean-NOx catalysts being developed for diesel engines may be ideal for pyrolysis gas, in order to achieve NOx standards and maintain high energy efficiency. However, those catalytic converters are not commercially available. Therefore, stoichiometric operation with conventional 3-way catalysts is the best approach.
40 NG,1.03 Lambda, 24 35 NG, 3-way Catalyst PG,1.3 Lambda, 24 PG, NOx optimized 30 PG, 3-way Catalyst

3) 4) 5) 6)

Tomazic, D. A Primer on Exhaust Gas Recirculation. Diesel Progress. October 2001, 26-30. Miller, J. A.; Bowman, C. T. Prog. Energy Combust. Sci. 1989, 15, 287-338. Abdel-Rahman, A.A. Int. J. Energy Res. 1998, 22, 483-513. Air Quality Standard Permit for Electric Generating Units. Air Permits Division, Office of Permitting, Registration & Remediation. Texas Natural Resource Conservation Commission. 2001.

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Figure 2. NOx emissions from pyrolysis gas and natural gas as a function of load, Lambda, ignition timing and 3-way exhaust catalyst. At the bottom of Figure 2 is a two-point NOx line from pyrolysis gas fueled operation with a 3-way catalyst. Difficulties maintaining stoichiometric operation prevented collection of quality data, especially at higher loads. This was principally due to a lack of feedback air-fuel ratio control. The data presented suggest that NOx levels similar to those from natural gas with the 3-way catalyst (also shown in Figure 2) are possible using this strategy. A larger catalytic converter would perhaps be necessary, because of the higher raw NOx emissions from pyrolysis gas during stoichiometric operation. In either fuel case, a larger 3-way catalyst, or additional engine NOx control, such as EGR, would be required to meet present and future NOx standards for states such as Texas (0.14 lb/MWh in east Texas after January 1, 2005) [6]. At a given , NOx from pyrolysis gas fueling was higher than from natural gas. However, because the of the ability to operate the engine at higher air/fuel ratios on pyrolysis gas at comparable outputs, the differences in NOx emissions between the two fuels can be negligible. Regardless, the lowest measured NOx value at a load of 9 kW is still an order of magnitude higher than proposed U.S. emissions standards for small generators. Further reductions in NOx emissions from SI engines will have to come from enhanced leanburn performance and/or addition of exhaust after-treatment technologies. Alternatively, engines could run stoichiometrically with feedback control and a 3-way exhaust catalyst, as developed by the automotive industry. References 1) 2) Ratcliff, M. A.; et. al. Biosyngas Characterization Tests, NREL/TP-510-31224. 1998. Shashikantha, Parikh, P. P. Spark Ignition Producer Gas Engine and Dedicated Compressed Natural Gas Engine Technology Development and Experimental Performance Optimization. SAE 1999-01-3515, 1999.

Fuel Chemistry Division Preprints 2002, 47(1), 386