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Energy & Fuels 2006, 20, 532-539

Prediction of the Autoignition Delay Time of Producer Gas from Biomass Gasification
Juan J. Hernandez,* Clara Serrano, and Javier Perez
UniVersidad de Castilla-La Mancha, Escuela Te cnica Superior de Ingenieros Industriales, Edificio Polite cnico, AVenida Camilo Jose Cela S/N, 13071 Ciudad Real, Spain ReceiVed June 30, 2005. ReVised Manuscript ReceiVed NoVember 14, 2005

The greenhouse effect and the increasing demand for energy have encouraged the use of alternative fuels, with agricultural and forestry biomass waste being two of the main renewable sources that European and Spanish policies have been promoting during the last several years. In this article, theoretical results for the chemical autoignition delay time of producer gas obtained from the gasification of lignocellulosic biomass are presented. These results, together with those obtained in a previous work related to the laminar flame speed of the gas, are of great interest both for understanding the chemical kinetic mechanisms that control the fuel oxidation process and for the development of combustion models that provide significant information to be used as a tool for the optimization and design of internal combustion engines. The CHEMKIN software, in conjunction with the GRI-Mech chemical reaction mechanism, has been used to compute the autoignition delay time for different producer gas compositions, different values of pressure and temperature, and different producer gas/air equivalence ratios. Correlations of the delay time as a function of those variables are proposed, and a sensitivity analysis of the main reactions affecting the autoignition process has been carried out. The results have been compared with those obtained for conventional fuels (isooctane and methane), showing the potential of producer gas to reduce the knock tendency in a spark ignition engine and to allow homogeneous charge compression ignition (HCCI) combustion conditions at intake temperatures lower than those typically used in a natural gas HCCI engine. The reliability of the Livengood-Wu integral method, as a way to estimate the ignition timing under engine conditions (variable pressure and temperature), has also been checked. Differences lower than 6% between the Livengood-Wu integral and the CHEMKIN method, the latter using a complete chemical kinetic scheme, have been obtained for different engine operating conditions.

Introduction Recent European and Spanish energy strongly encourage the use of biomass waste for energy purposes. These policies have three targets: the reduction of CO2 emissions, the removal of wastes, and the use of indigenous fuels. Due to the low heating value and the high geographic dispersion of forestry and agricultural lignocellulosic waste, gasification constitutes an efficient technology that permits use of those wastes at the same location where they are produced, thus eliminating the cost derived from storage and transportation to power plants. The low energy content gas (producer gas), which consists mainly of CO, H2, N2, CO2, H2O, and CH4, can be directly used as a fuel in internal combustion engines, such as spark ignition (SI) or homogeneous charge compression ignition (HCCI) engines,3-5 or it can be used in dual fuel engine operation to reduce the pollutant emissions mainly due to its hydrogen content.6,7
* Corresponding author. Phone: (34)926295300 ext. 3880. E-mail: JuanJose.Hernandez@uclm.es. (1) Green paper: Towards a European strategy for the security of energy supply; Commission of the European Communities, Luxembourg, 2002. (2) Plan de Fomento de las Energ as RenoVables en Espan a; Instituto para la Diversificacio n y Ahorro de la Energ a: Madrid, Spain, 1999; in Spanish. (3) Barisano, D.; De Bari, I.; Nanna, F.; Cardinale, F.; Matera, D.; Cavalere, S.; Viggiano, D.; Fanny, Y. Proceedings of the First World Conference on Biomass for Energy and Industry, First World Conference and Technology Exhibition for Energy and Industry, Sevilla, Spain, June 5-9, 2000; James & James: London, 2001; Vol. 1, 384-389. (4) Ahrenfeldt, J.; Schramm, J.; Jensen, T. K. SAE Tech. Pap. Ser. 2001, 2001-01-3681. (5) Sridhar, G.; Paul, P. J.; Mukunda, H. S. Biomass Bioenergy 2001, 21, 61-72.

policies1,2

The laminar flame speed and the autoignition delay time of the producer gas constitute two of the most relevant thermochemical properties affecting the engine performance and pollutant emissions, and our knowledge of them allows us to optimize the engine efficiency. Laminar flame speed correlations for producer gas were proposed in a previous work,8 showing values lower than that of isooctane and higher than that of methane at typical engine conditions. Comparison between experimental and theoretical results proved that the experimental measurement of the laminar flame speed at high pressure was not possible due to the wrinkling of flame front, this favoring the theoretical methods as a more reliable way to obtain laminar flame speed values over a wide range of operating conditions. The autoignition delay time of a fuel/air mixture is defined as the time interval required for the mixture to spontaneously ignite at some prescribed conditions. Although several research works can be found in the literature related to the experimental and theoretical determination of the ignition delay time of conventional fuels9,10 and pure components,11-14 the autoignition process of the producer gas is still not well-known, and its thermochemical properties cannot be gathered from pure component data.
(6) Jensen, T. K.; Schramm, J.; Narusawa, K. SAE Tech. Pap. Ser. 2001, 2001-01-3532. (7) Tsolakis, A.; Hernandez, J. J.; Megaritis, A.; Crampton, M. Energy Fuels 2005, 19, 418-425. (8) Hernandez, J. J.; Lapuerta, M.; Serrano, C.; Melgar, A. Energy Fuels 2005, 19, 2172-2178. (9) Gauthier, B. M.; Davidson, D. F.; Hanson, R. K. Combust. Flame 2004, 139, 300-311. (10) Eckert, P.; Kong, S.; Reitz, R. D. SAE Tech. Pap. Ser. 2003, 200301-0011.

10.1021/ef058025c CCC: $33.50 2006 American Chemical Society Published on Web 12/21/2005

Autoignition Delay Time of Gas from Biomass Gasification

Table 1. Mole Fractions of the Producer Gas Components for Different Frg Values Frg ) 3 XH2O XN2 XCO2 XCH4 XH2 XCO 0.05857 0.41195 0.09003 0.00049 0.19937 0.23958 Frg ) 3.5 0.04220 0.38699 0.10166 0.01613 0.20917 0.24385 Frg ) 4 0.03745 0.37195 0.11458 0.04022 0.19355 0.24226 Frg ) 4.5 0.03418 0.35901 0.12719 0.06402 0.17584 0.23976 Frg ) 5 0.03127 0.34719 0.13928 0.08663 0.15861 0.23701

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Figure 1. Definition of the fuel/air ratios in the gasifier-engine system.

As an extension of the laminar flame speed work and to supplement the limited information currently available in the literature, this article presents a computational study of the chemical autoignition process of producer gas/air mixtures. Correlations quantifying the influence of the thermodynamic conditions (pressure and temperature), the producer gas composition (depending on the relative biomass/air ratio inside the gasifier), and the relative producer gas/air ratio in the engine have been obtained, and a chemical kinetic analysis of the main reactions involved in the process has also been carried out. The additivity of the producer gas delay time values, obtained under stationary conditions through the correlations provided, has been analyzed to check the Livengood-Wu integral method15,16 as a way to predict the ignition delay period in an engine, where pressure and temperature change due to the compression and expansion resulting from the piston motion and due to the heat release from fuel. Theoretical Calculations
The lignocellulosic biomass used in this work consists of waste from felling and pruning of Mediterranean pine (Pinus pinaster), dominant in the central areas of Spain (Castilla-Leon, CastillaLa Mancha, and Extremadura).17 The ultimate composition of this typical biomass can be directly obtained from the empirical formula: CH1.57O0.78N0.0056S0.0001. The biomass/air equivalence ratio inside the gasifier, Frg, is defined with respect to the stoichiometric ratio as shown in eq 1. Frg ) mbiomass/mair (mbiomass/mair)st (1)

H2O, N2O, NO2, HO2, S2, SO, SO2, SO3, NH, CO, H2, NO, OH, N, H, O, Ar, S, NH3, COS, H2S, HS, HCN, CN, NCO, NH2, CH4, H2O2, CHO, CH2O, CH3, and CH3O). Table 1 shows the mole fractions of the main species in the producer gas, obtained with different values of the relative biomass/air ratio, Frg. Producer gas consists of hydrogen and carbon monoxide as the main fuel species, followed by methane in the case of high values of Frg. The modeled producer gas composition is in agreement with typical experimental compositions obtained in other work.18,20 Additionally, the autoignition delay time depends on the producer gas composition and on the producer gas/air ratio in the engine. While Frg represents the relative biomass/air ratio in the gasifier, the relative gas/air ratio in the engine is defined in eq 2 as Fr. The difference between both ratios is shown in Figure 1. Results have been obtained for an Frg ratio ranging from 3 to 5 and for Fr values ranging from lean conditions (Fr ) 0.6) to rich mixtures (Fr ) 1.8). Fr ) mproducer gas/mair (mproducer gas/mair)st (2)

An equilibrium model18 derived by the authors has been used to calculate the producer gas composition for different biomass/air ratios. The assumption of chemical equilibrium allows very reliable results to be obtained, due to the long residence time of the gas at high temperature inside the gasifier.19 The model is based on the equilibrium constant method and comprises 29 equilibrium reactions that, together with the six mass conservation equations for the six elements considered (C, H, O, N, S, and Ar), allow us to calculate the equilibrium concentration of 35 chemical species (N2, O2, CO2,
(11) Bozhenkov, S. A.; Starikovskaia, S. M.; Starikovskii, A. Yu. Space Planes and Hypersonic Systems and Technologies, 11th AIAA/AAAF International Conference, Orleans, France, Sept 29-Oct 4, 2002; Association Aeronautique et Astronautique de France: Verneuil-sur-Seine, France, 2002; p 2002-5185. (12) Petersen, E. L.; Davidson, D. F.; Hanson, R. K. Combust. Flame 1999, 117, 272-290. (13) Oran, E. S.; Boris, J. P.; Young, T.; Flanigan, M.; Burks, T.; Picone, M. Eighteenth Symposium (International) on Combustion, Waterloo, Canada, Aug 17-22, 1980; The Combustion Institute: Pittsburgh, PA, 1981; pp 1641-1647. (14) Oran, E. S.; Boris, J. P. Combust. Flame 1982, 48, 149-161. (15) Heywood, J. B. Internal Combustion Engine Fundamentals; McGrawHill: New York, 1988. (16) Livengood, J. C.; Wu, P. C. Proceedings of the 5th International Symposium on Combustion 1955, 347-356. (17) Melgar, A.; D ez, A.; Lapuerta, M.; Herna ndez, J. J.; Alkassir, A. Energ a 2003, 171, 50. (18) Lapuerta, M.; Hernandez, J. J.; Tinaut, F.; Horrillo, A. SAE Tech. Pap. Ser. 2001, 2001-01-3586.

The CHEMKIN software21 and the GRI-Mech22 chemical reaction mechanism have been used to obtain the autoignition delay time of producer gas. GRI-Mech 3.0 is a detailed kinetic mechanism that describes the oxidation of methane and natural gas through 325 elementary reactions and 53 species. Several works prove the validity of this mechanism to obtain the autoignition delay time of some gaseous fuels through comparison with experimental results obtained using different devices. Bozhenkov et al.11 used a shock tube to determine the ignition delay of CH4/air and H2/air mixtures at wide pressure (3-450 atm) and temperature (1200-1750 K) ranges, using the OH emission technique. The experimental data were in agreement with the theoretical data obtained using GRIMech at the whole range. Vandebroek et al.23 measured the autoignition limits of CH4/air mixtures using a closed spherical vessel, and the results were compared to the computed ones obtained using different chemical reaction mechanisms, showing a good coincidence when the GRI-Mech mechanism was considered. Moreover, the suitability of GRI-Mech to simulate the laminar flame speed of the producer gas has been validated in previous work8,24 through comparison with the experimental speed obtained from the instantaneous pressure signal measured in a constant volume combustion vessel. CHEMKIN 4.0 consists of a set of applications for solving chemical kinetics problems. The homogeneous 0-D reactor model
(19) Li, X.; Grace, J. R.; Watkinson, A. P.; Lim, C. J.; Ergu denler, A. Fuel 2001, 80, 196. (20) Sridhar, G.; Paul, P.; Mukunda, H. Proc. Inst. Mech. Eng., Part A: J. Power Energy 2005, 219, 195-201. (21) Kee, R. J.; Rupley, F. M.; Miller, J. A.; Coltrin, M. E.; Grcar, J. F.; Meeks, E.; Moffat, H. K.; Lutz, A. E.; Dixon-Lewis, G.; Smooke, M. D.; Warnatz, J.; Evans, G. H.; Larson, R. S.; Mitchell, R. E.; Petzold, L. R.; Reynolds, W. C.; Caracotsios, M.; Stewart, W. E.; Glarborg, P.; Wang, C.; Adigun, O.; Houf, W. G.; Chou, C. P.; Miller, S. F.; Ho, P.; Young, D. J. CHEMKIN Software, release 4.0; Reaction Design, Inc.: San Diego, CA, 2004. (22) Smith, G. P.; Golden, D. M.; Frenklach, M.; Moriarty, N. W.; Eiteneer, B.; Goldenberg, M.; Bowman, C. T.; Hanson, R. K.; Song, S.; Gardiner, W. C., Jr.; Lissianski, V. V.; Qin, Z. GRI-Mech home page. http:// www.me.berkeley.edu/gri_mech/ (accessed June 2005). (23) Vandebroek, L.; Winter, H.; Berghmans, J. Second Internet Conference on Process Safety, March 20-24, 2000. http://www.safetynet.de/seiten/ 10.html. (24) Hernandez, J. J.; Serrano, C.; Perez, J.; Horrillo, A. Inf. Tecnol. 2004, 15, 19-22.

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Figure 2. Computed temperature, pressure, and H and OH profiles corresponding to a stoichiometric producer gas/air mixture, initially at 1100 K and 20 bar. Ignition delay equals 0.00054 s (when T ) 1500 K is reached).

application predicts the time-dependent chemical kinetic behavior of a homogeneous mixture in a closed system. An adiabatic constant volume system is assumed, which allows both the temperature and pressure to change during the process. The criterion used to define the ignition time is not unique, and it can be inferred either from the pressure or temperature trace or from the time-history of an intermediate species (e.g., OH, CH). In this work, the time at which the temperature has reached the initial value plus 400 K has been used to define the delay time. Simultaneously, as Figure 2 shows, a strong change in pressure and an increase in the H and OH concentrations also take place at that time. Different values of initial temperature and pressure, ranging from 900 to 1800 K and from 20 to 80 bar, respectively, have been considered. The calculated values of the autoignition delay time have been fitted to an Arrhenius-derived expression (eq 3): ) A p-n exp E (RT ) (3)

where p and T are pressure and temperature, E is the activation energy, R is the gas constant, and A and n are adjustable constants.

Results and Discussion Effect of Thermodynamic Conditions. For a stoichiometric producer gas/air mixture (Fr ) 1), Figure 3 shows that the predicted autoignition delay time is strongly affected by temperature, showing an exponential decrease when temperature increases. The effect of pressure on the autoignition behavior is not as clear as that obtained for conventional fuels, such as isooctane or methane, for which higher pressure values lead to lower values of the delay time.15 In the case of the producer gas, this trend can also be observed (with variations up to 80% at high temperature values), except in the intermediate temperature range (1200 K < T < 1500 K), where the delay time remains roughly constant when pressure is modified (with variations lower than 10% when pressure varies from 20 to 80 bar). This complex pressure-dependent behavior, also presented in Figure 4, is due to the H2 producer gas content.14,25 In the sensitivity study presented below, three temperature ranges (900-1200, 1200-1500, and 1500-1800 K), in which the reactions controlling the autoignition process are different, were distinguished. It was found that, while HO2 is the main radical affecting the ignition process at low temperature and the H atom is the main species favoring this process at high temperature, in the intermediate temperature range both species play important roles. Effect of the Gas Composition (Frg) and of the Relative Producer Gas/Air Ratio (Fr). As can be observed in Figure
(25) Gelfand, B. E.; Medvedev, S. P.; Khomik, S. V.; Popov, O. E.; Agafonov, G. L. Dokl. Phys. Chem. 1996, 349, 183.

Figure 3. Autoignition delay time (in microseconds) of a stoichiometric producer gas/air mixture vs pressure at different temperature values (Frg ) 3.5).

4, the predicted effect of the producer gas composition (Frg) is not as significant as the effect of temperature, although Frg variations become more relevant at high temperatures. At any pressure and temperature, the shortest autoignition delay time is reached for an Frg value around 3, for which the H2 content in the producer gas/air mixture is highest (Table 2). Having set the producer gas composition at constant values resulting from Frg equal to 3.5, Figure 5 shows that the influence of the relative producer gas/air ratio (Fr) on the autoignition delay time is not very significant. As Figure 5 also shows, the predicted autoignition delay time decreases when Fr increases in the low-temperature range (T < 1200 K), where the autoignition of a rich mixture is accelerated by means of the main propagating reactions taking place at those conditions (HO2 + CO ) OH + CO2 and HO2 + H2 ) H + H2O2). However, the predicted delay time is not much influenced by Fr variations when temperature is higher than 1200 K, due to the more important role of the reaction H + O2 ) OH + O. At high temperature, the effect of an increase in the Fr ratio (higher H2 and CO concentration in the producer gas/air mixture) is

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considered in the middle temperature range, while the effect of Fr has been only considered at temperatures lower than 1200 K. The delay time data fit the Arrhenius expression with a correlation coefficient (R2) equal to 99.9% for eq 4 and 97% for eqs 5 and 6.

(s) ) 1.189E - 11 exp

(21 T277)p ( )

-0.64

Frg0.42Fr-0.51

900 e T e 1200 K (4) 21 279 0.97 (s) ) 5.177E - 13 exp Frg T 1200 < T e 1500 K (5) (s) ) 3.980E - 11 exp

(13 T552)p

-0.50

Frg2.85

1500 < T e 1800 K (6)

Figure 4. Autoignition delay time (in microseconds) of a stoichiometric producer gas/air mixture vs Frg at different pressure and temperature values.
Table 2. Mole Fractions of the Components of a Producer Gas/Air Stoichiometric Mixture for Different Frg Values
Frg ) 3 XO2 XH2O XN2 XAr XCO2 XCH4 XH2 XCO 0.10715 0.02847 0.60208 0.00479 0.04393 0.00024 0.09690 0.11644 Frg ) 3.5 0.11551 0.01884 0.60549 0.00517 0.04556 0.00720 0.09338 0.10885 Frg ) 4 0.12283 0.01542 0.61291 0.00549 0.04737 0.01656 0.07969 0.09974 Frg ) 4.5 0.12879 0.01311 0.61945 0.00576 0.04898 0.02455 0.06743 0.09194 Frg ) 5 0.13368 0.01127 0.62495 0.00598 0.05039 0.03121 0.05714 0.08539

compensated by the lack of oxygen, which is necessary to promote the reaction H + O2 ) OH + O. As has been shown in the literature for other fuels,9 the influence of varying Fr is more significant when the mixture moves from lean conditions (Fr ) 0.6) to the stoichiometric ones (Fr ) 1). Three different correlations for the calculation of the producer gas autoignition delay time (eqs 4, 5, and 6), corresponding to the temperature ranges considered, have been obtained. In those equations, is the autoignition delay time (seconds), T is the initial temperature (K), and p is the initial pressure (bar). As has been mentioned before, the effect of pressure has not been

Sensitivity Analysis of the Producer Gas Autoignition Delay Time. To study the main species and reactions affecting the producer gas autoignition process, a sensitivity analysis has been performed at different pressures (20 and 80 bar) and temperature values (900, 1400, and 1800 K). The relative gasifier biomass/air ratio and the relative producer gas/air ratio in the engine have been set at Frg ) 3.5 and Fr ) 1, respectively. This analysis has been carried out by using the homogeneous 0-D reactor model of CHEMKIN. Due to the large number of reactions constituting the GRI-Mech reaction mechanism, a rateof-production analysis has been previously made to determine the contribution of each reaction to the net production or destruction rate of the main propagating species (HO2, H2O2, H, OH, O). Through this rate-of-production analysis, carried out at each of the temperature and pressure values considered, 34 of the 325 reactions that constitute the GRI-Mech were selected as the most important ones that may affect the autoignition process of the producer gas. After that, a manual sensitivity analysis was performed over this set of 34 reactions, and a sensitivity coefficient (C) was calculated through the expression

p,i - p,i - ) C) 2k0i - k0i k0i

(7)

where k0i is the pre-exponential factor of the reaction rate

Figure 5. Autoignition delay time (in microseconds) of producer gas/air mixtures (Frg ) 3.5) vs temperature, at 80 bar and different Fr values.

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Figure 6. Sensitivity coefficient of the delay time with respect to the main reactions, at 20 bar and different temperature values (Frg ) 3.5, Fr ) 1).

Figure 7. Sensitivity coefficient of the delay time with respect to the main reactions, at 80 bar and different temperature values (Frg ) 3.5, Fr ) 1).

constant corresponding to reaction i in the GRI-Mech mechanism, is the nonperturbed delay time of the producer gas at each pressure and temperature value, and p,i is the related perturbed delay time, resulting from multiplying the preexponential factor of reaction i by a factor of 2. Results for the nine reactions with a C value greater than 0.01 (this meaning a 1% change in ) are shown in Figures 6 and 7. If the sensitivity coefficient exhibits a negative value, that would indicate an increase in the overall reactivity of the chemical system (a lower delay time), and a positive value would imply a decrease in the overall reactivity. A large sensitivity coefficient value indicates a strong influence of the reaction on the producer gas autoignition process. The first conclusion that can be obtained from Figures 6 and 7 is that, at temperatures around 900 K, the radical HO2 becomes the main propagating species, which reacts as follows:

autoignition process at high temperatures (1800 K) are those involving the very reactive H, O, and OH radicals:

H + O2 ) O + OH OH + H2 ) H + H2O O + H2 ) H + OH
At intermediate temperature values (around 1400 K), kinetics determining the propagating chain and thus the autoignition process involve both sets of reactions. When pressure increases from 20 to 80 bar, the HO2 reactions become more important compared with the H kinetics, which would retard the autoignition process. However, the much lower sensitivity coefficient of the reaction H + O2 + N2 ) HO2 + N2 at 80 bar, which inhibits that process, compensates for such a retarding effect. This is the reason the producer gas delay time remains roughly constant with pressure at temperatures around 1400 K (Figure 3). Additionally, the time history of the representative species, H and HO2, is shown in Figures 8 and 9. In each figure, separate charts have been made for 20 and 80 bar, with the delay time indicated by a dotted line. As can be observed, the H mole fraction is nearly zero before the delay time at low temperature (900 K), and only when the delay time is reached does the HO2 species vanish and the H radical appear. However, increases in temperature provoke the H kinetics to be more important, the H radical appears earlier, and a higher H peak value is also reached. The effect of pressure on the above-mentioned switch

HO2 + CO ) OH + CO2 HO2 + H2 ) H + H2O2 H2O2 + M ) 2OH + M

The temperatures at which this particular sequence is important are in the range 900-1200 K. As Figures 6 and 7 also show, the main reactions predicted as promoting the

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Figure 8. Time evolution of the HO2 and H concentrations at 900 K (Frg ) 3.5, Fr ) 1). Delay time: 56 ms at 20 bar, 23 ms at 80 bar.

Figure 9. Time evolution of the HO2 and H concentrations at 1800 K (Frg ) 3.5, Fr ) 1). Delay time: 5.88 10-4 ms at 20 bar, 2.94 10-4 ms at 80 bar.

Figure 10. Autoignition delay time (in microseconds) of stoichiometric mixtures of methane, isooctane and producer gas (Frg ) 3.5) with air at different temperature and pressure values.

in the propagating species from H to HO2 is the opposite of that observed for temperature. While increases on temperature cause the H radical to become more significant, higher pressures favor the slower HO2 kinetics. Comparison with Conventional Fuels. To analyze the potential of the producer gas to be used as a fuel in internal combustion engines, a comparison between the predicted autoignition delay time of producer gas, methane (as representative of natural gas), and isooctane (representative of gasolinelike fuels) is shown in Figure 10. The isooctane delay time correlation has been taken from the literature,15 whereas the predicted methane values have been obtained from CHEMKIN computations. As Figure 10 shows, the autoignition delay time of isooctane is more sensitive to pressure variations than those predicted for methane and producer gas, but it shows lower sensitivity to cylinder temperature variations. At a constant pressure of 20 bar, autoignition time with producer gas is much longer than that with isooctane in the low-temperature range (below around 950 K), but it becomes much shorter in the hightemperature range. However, as pressure increases, the inversion

temperature (where autoignition time for producer gas and isooctane are equal) also increases (about 1100 K at 50 bar), and the differences between the producer gas and the isooctane autoignition time are less significant in the high-temperature range. However, the autoignition time of methane is higher than that of producer gas in the whole thermodynamic conditions range. Although the laminar flame speed of producer gas is lower than that of isooctane and higher than that of methane,8 the use of producer gas from biomass gasification has been proved4,5 to reduce the knock tendency with respect to gasoline or natural gas under typical pressure and temperature conditions in an SI engine (unburned temperature below 1100 K and high pressure). Thus, a producer gas-fuelled engine would permit some optimization of the thermal efficiency through a certain increase of the compression ratio, with similar knock tendency and NOx emission level (due to the lower combustion temperature of the producer gas18). Additionally, and due to the shorter delay time of producer gas compared with methane, the use of producer gas as a fuel

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rc )

Vd + Vc Vc

(8)

Comparison with the Livengood-Wu Integral Method. In this paragraph, the reliability of the widely used LivengoodWu integral method16 as a way to predict the ignition timing or the knock tendency of a fuel/air mixture under engine conditions has been described. The method assumes that autoignition takes place when

dt )1 t t (p ,T)
i 0

(9)

Figure 11. Ignition delay time (in milliseconds) of a producer gas/air and a methane/air mixture (Fr ) 0.6) under engine conditions (intake pressure ) 1.5 bar).

or as a fuel component in a natural gas HCCI engine would permit us to achieve stable temperature-controlled autoignition at lower charge intake temperature values, thus reducing the need for the preheating methods (residual gas trapping, electrical heating, etc.) typically used in this kind of engine.26,27 Figure 11 shows the ignition delay time (ti), calculated by using the close internal combustion engine simulator of CHEMKIN and assuming an adiabatic compression process of a lean producer gas/air and methane/air mixture (Fr ) 0.6) under engine conditions (pressure and temperature changing instantaneously) at two different volumetric compression ratios (rc ) 12 and rc ) 16) and different intake temperature values (Tin). The volumetric compression ratio has been defined as eq 8 shows, where Vd is the swept volume and Vc is the clearance volume. The engine characteristics used for the calculations have been the following: supercharging up to an absolute intake pressure ) 1.5 bar, bore ) 82.7 mm, stroke ) 93 mm, connecting rod length ) 144 mm, swept volume ) 499.5 cm3, and speed ) 3000 rpm. As can be observed, the predicted ignition delay time of a producer gas fuelled engine is lower than that for methane for the whole intake temperature range, and the minimum intake temperature to achieve autoignition is also lower when producer gas is used (around 460 K for producer gas and 520 K for methane at rc ) 12, and around 400 K for producer gas and 460 K for methane at rc ) 16).

where ti is the ignition delay period, is the ignition delay at the pressure and temperature conditions pertaining at time t (calculated assuming stationary conditions by using eq 4, 5, or 6), and t0 is the initial time used for calculations (usually corresponding to the start of injection in a diesel engine or to the end of the gas compression stroke, around the TDC, in a SI engine). Equation 9 assumes the following hypothesis: the overall rate of production of the critical species in the delay period chemistry, for a given mixture, depends only on the gas state, the concentration of the critical species during the delay period is conservative and additive, and the concentration required to initiate autoignition is fixed. Figure 12 shows the predicted ignition delay time of a producer gas/air mixture for different gas composition, different Fr values, and different engine compression ratios (rc). The engine characteristics considered have been the same as those used in the previous section, and all the calculations have been carried out for an intake temperature equal to 480 K. The delay time values have been obtained both by using the LivengoodWu method and by using the close internal combustion engine simulator of CHEMKIN, the latter considering the variations on the species concentration caused by the chemical reactions taking place during the compression process (pressure and temperature changing instantaneously). No significant discrepancies between the CHEMKIN procedure and the LivengoodWu method have been observed, although the latter seems to be less sensitive to the producer gas composition (corresponding to different Frg values) and more sensitive to Fr variations. When the compression ratio increases, the maximum error resulting from the use of the Livengood-Wu method decreases due to the shorter period to achieve autoignition (6 and 4% for Frg ) 5 when rc equals to 12 and 16, respectively).

Figure 12. Ignition delay time (in milliseconds) of producer gas/air mixtures under engine conditions (intake pressure ) 1.5 bar). Solid lines: Livengood-Wu values. Dashed lines: CHEMKIN values.

Autoignition Delay Time of Gas from Biomass Gasification

Energy & Fuels, Vol. 20, No. 2, 2006 539

Conclusions The effect of the main parameters (producer gas composition, temperature, pressure, and relative producer gas/air ratio in the engine) affecting the autoignition delay time of producer gas coming from forestry biomass gasification under typical engine conditions has been studied theoretically. Results predicted by the CHEMKIN software have been fitted to an Arrhenius expression to be used in combustion models. While the predicted autoignition delay time decreases exponentially when temperature increases, the influence of pressure is not so clear, due to the pressure dependency balance between the reactions involving the HO2 radical and those involving the H atom. While in a low (T < 1200 K) and in a high temperature (T > 1500 K) range the producer gas autoignition delay time decreases when pressure increases, at intermediate temperature values (1200 < T < 1500) a displacement from the most reactive H kinetics to the HO2 chemistry when pressure increases caused no significant variations on the delay time. A minimum autoignition delay time value was calculated for a gas composition corresponding to Frg ) 3, for which the H2 concentration in the producer gas/air mixture was maximum. The effect of the producer gas/air ratio in the engine (Fr) appeared to be significant only for temperature values lower than 1200 K and in the lean mixture range (Fr < 1). At higher temperatures, the effect of an increase in the Fr ratio (higher H2 and CO concentration in the mixture) is compensated by the lack of O2, which is necessary to promote reaction H + O2 ) OH + O. The simulated autoigniton behavior of producer gas presented a very high sensitivity to cylinder temperature variations and much lower sensitivity to cylinder pressure changes than those obtained for isooctane. The lower combustion temperature and knock tendency of producer gas compared with isooctane would
(26) Yap, D.; Megaritis, A.; Wyszynski, M. L. Energy Fuels 2004, 18, 1315-1323. (27) Ando, T.; Isobe, Y.; Sunohara, D.; Daisho, Y.; Kusaka, J. JSAE ReV. 2003, 24, 33-40.

permit some optimization of the SI engine thermal efficiency through an increase of the compression ratio without affecting NOx emissions. It has also been suggested from calculations that the use of producer gas as a fuel in a HCCI engine would also allow achieving temperature-controlled autoignition at charge intake temperatures lower than those usually required when natural gas is used. The Livengood-Wu integral method has been checked as a reliable way to calculate the ignition delay time under engine conditions, although errors around 6% have been observed for low compression ratios. Nomenclature
A ) adjustable constant in the Arrhenius expression of the delay time C ) sensitivity coefficient of the delay time with respect to a reaction E ) activation energy Fr ) relative producer gas/air ratio in the engine Frg ) relative biomass/air ratio in the gasifier koi ) pre-exponential factor of the reaction rate constant corresponding to reaction i mair ) mass of air mbiomass ) mass of biomass mproducer gas ) mass of producer gas n ) pressure exponent in the Arrhenius expression p ) pressure rc ) volumetric compression ratio R ) gas constant t ) time ti ) ignition delay time under engine conditions t0 ) initial time for calculations in the Livengood-Wu equation T ) temperature Tin ) intake temperature TDC ) Top Dead Center ) autoignition delay time p,i ) perturbed autoignition delay time Vd ) swept volume Vc ) clearance volume Xi ) mole fraction of component i
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