Chemical Engineering Journal 207208 (2012) 616624

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Chemical Engineering Journal

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A model of biomass char gasication describing the change in catalytic activity of ash
Kentaro Umeki a,, Antero Moilanen b, Alberto Gmez-Barea c, Jukka Konttinen d
a

Division of Energy Science, Department of Engineering Sciences and Mathematics, Lule University of Technology, 971 87 Lule, Sweden VTT Technical Research Centre of Finland, P.O. Box 1000, 02044 VTT, Finland c Bioenergy Group, Chemical and Environmental Engineering Department, Escuela Superior de Ingenieros, University of Seville, Camino de los Descubrimientos s/n, 41092 Seville, Spain d Renewable Natural Resources and Chemistry of Living Environment, Department of Chemistry, University of Jyvskyl, P.O. Box 35, FI-40014 University of Jyvskyl, Finland
b

h i g h l i g h t s
" The model describes the change in catalytic activity during char gasication. " Three parallel reactions of catalytic and non-catalytic gasication were applied. " The model was validated by TGA measurements using nine different biomasses. " The model satisfactorily describes the reactivity with CO2 at 10231123 K and 0.13.0 MPa.

a r t i c l e

i n f o

a b s t r a c t
A comprehensive description of catalytic effects during char gasication under various conditions relevant to biomass gasication was made. A three-parallel reaction model was proposed to describe the dynamic change in catalytic activity of ash during gasication of biomass char particles. Three different regimes of conversion were identied by analyzing char reactivity experiments conducted in a vertical TGA with nine biomasses under a wide range of operating conditions (temperature: 10231123 K, pressure: 0.13.0 MPa and gasication mixtures of CO2COH2OH2): (1) catalytic char gasication with deactivation of catalyst, (2) non-catalytic char gasication, and (3) catalytic char gasication with small amount of stable ash, without suffering deactivation. A model including the three regimes was developed and the measurements were used to t the kinetic coefcients. It is shown that the model accurately predicts the reactivity of biomass char in CO2CO mixtures during the whole range of conversion. It was detected that char gasication maintains the catalytic activity during the entire conversion process when: (i) biomasses having small amount of silicon was used, and (ii) steam is used as part of the gasication agent. The model is still useful as predicting tool for these two conditions but its physical significance is contestable on the light of the model developed. For the conditions where the model is valid, it is shown that the model is a useful tool as sub-model in reactor simulations, predicting the conversion rate of single particles fast and accurately at different stages of conversion. The aspects that need to be further investigated for expanding the applicability of the model were identied. 2012 Elsevier B.V. All rights reserved.

Article history: Available online 16 July 2012 Keywords: Char gasication Biomass Alkali and alkaline earth metals Catalyst Modeling Silicon

1. Introduction Char gasication with steam and/or carbon dioxide is an important step during thermochemical conversion of lignocellulosic biomass because it often represents the rate-controlling phenomenon in the gasier. A great effort has been made to develop kinetic

Abbreviations: AAEM, alkali and alkaline earth metals; FBG, uidized-bed gasier; TGA, thermogravimetric analyzer. Corresponding author. Tel.: +46 920 492484; fax: +46 920 491074. E-mail address: kentaro.umeki@ltu.se (K. Umeki). 1385-8947/$ - see front matter 2012 Elsevier B.V. All rights reserved. http://dx.doi.org/10.1016/j.cej.2012.07.025

models to predict the rate of conversion of char particles during gasication, i.e. the reactivity. The gasication reactivity of a single char particle is mainly affected by char morphology, nature and content of ash-forming constituents, as well as diffusion of mass to and inside the particle. When the transport effects are negligible, for instance using ne particles, intrinsic reactivity is obtained. There are two ways of expressing intrinsic reactivity, and the following denitions are used in this paper: conversion rate, rcg = dXcg/dt, and instantaneous reaction rate, Rcg = 1/(1 Xcg)dXcg/ dt. The term reactivity is used in general to refer any of the two dened rates. Conversion rate is usually written as[1].

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Nomenclature dev k m Nexp R S r t X y n deviation rate coefcient, s1 mass, g number of data points, instantaneous reaction rate, s1 squared residual error, conversion rate, s1 time, s conversion, mass fraction of precursors in the original fuel, coefcients for JM and CLM2, Subscripts ccg,1 catalytic char gasication in the rst regime ccg,2 catalytic char gasication in the third regime cg char gasication ctloss deactivation of catalyst char char f nal i initial ncg non-catalytic char gasication in the second regime dev devolatilization t total vol volatiles

r cg kT ; pi f X cg

The rst function, k is a kinetic coefcient accounting for the effect of temperature and the partial pressure of gas species in the gasication reactions (CO, CO2, H2O, H2). LangmuirHinshelwood expressions have been utilized in the literature [1,2]. The second term in Eq. (1), f(Xcg), expresses the change of the conversion rate during char gasication and it has been often interpreted in terms of the change in reactive surface area (e.g. random pore model [3]). In fact, this vision lumps all the phenomena occurring during conversion that affects the conversion rate, for instance catalytic effects. In Eq. (1) the catalytic effects in f(Xcg) are assumed to be independent of operating conditions. Only variation of these effects with Xcg is allowed in Eq. (1). This is a reasonable approximation for reactor simulations where the variation of operating conditions in a given gasier is limited [1]. Though, in the present work we will consider that catalytic activity of the char during gasication can vary, so f will be assumed to vary with a more general form f(Xcg, g(T,pi)) where g is the factor in f accounting for the change in catalytic effects with operating conditions. Although a great number of measurements have been made suggesting the catalytic effects during char gasication, there are only a few kinetic models dealing with catalytic effect of ash content explicitly. In the present work the change of conversion rate due to catalytic activity of ash is investigated, i.e. the conversion rate behavior against char conversion at xed temperature and pressure of gasifying agents. Ash content, especially alkali and alkaline earth metals (AAEM) and iron, is known to act as catalyst in the gasication reactions of carbon [46]. Some studies [7,8] showed that the reactivity of char gasication can be correlated to the molar ratio of catalytic ash, i.e. AAEM, to carbon. Other inorganic substances such as silica, alumina and phosphates, on the other hand, lower the reactivity of char. Silica has been observed to reduce the reactivity [9] by reacting with potassium to form silicate, blocking the catalytic effect of potassium. Alumina has also shown the function to deactivate the catalytic activity of potassium [10]. Potassium phosphate has been observed inactive in the catalytic carbon gasication [11]. Dupont et al. [12] showed that the char reactivity is a linear function of the mass ratio of potassium to silicon. Moreover, the complicated effects of various ash components are often expressed by alkali index [13]. The dynamic change in catalytic activity of the inorganic compounds during high temperature gasication reactions is not well-known. Three deactivation processes of catalytic activity in char gasication have been proposed so far. First, the vaporization of AAEM content can reduce the catalytic ash content, i.e. reactivity [14,15]. Steep drop of AAEM retention in char was observed at early stage of char gasication. Second, calcium dispersion affects

the contact between the calcium-catalyst and carbon, and the reactivity may be reduced by agglomeration or sintering taking place during the char gasication reactions [16]. Finally, reactions between catalyst species (K, Ca, Na and Mg) and other inorganic substances (Si, Al and P) lower the reactivity of char as discussed in the previous paragraph. Several empirical models have been proposed to express the dynamic change in catalytic activity as shown in Table 1. Some studies [8,12,17,18] introduced empirical correction functions to be multiplied to the conventional rate formula such as that in Eq. (1). These models have shown good predictability for the conversion rate of char gasication obtained by TGA. Other models [10,15,19] employed parallel reaction model of non-catalytic and catalytic gasication. The predictability of these models was conrmed up to char conversion of 8090%, expressing well the initial decrease of conversion rate, which is due to the vaporization of catalysts at early stage of char gasication. The main drawback of empirical models is that they are difcult to apply to conditions other than those at which they have been obtained. Therefore, the char preparation and gasication experiments should be carried out at similar condition to that of the process to be applied. For instance in commercial uidized-bed gasication (FBG) units the conversion of mm-sized char particles occurs at temperature in the range of 10231173 K. Moreover, in FBG units the char is produced from coarse fuel particle that are rapidly devolatilized. Then, in situ char gasication (devolatilization and subsequent gasication of the char produced, i.e. without previous cooling) is important to be reproduced in the laboratory because signicant reduction in char reactivity after cooling the char has been reported [2022]. Only a few works have been conducted measuring gasication char reactivity applicable to commercial FBG [15,22]. A few models have obtained rate expressions as a function of time. This is inconvenient when the model is applied to reactor simulation because the time of stay of char particles varies greatly between the particles. Rate expression as a function of conversion is more convenient because the distribution variable is normalized (from 0 to 1) and also because the global rate in a fuel bed or calculation cells can be often approximated by average char conversion [23], allowing great simplications while maintaining the accuracy. In the present work, a theoretical model based on detailed understanding on microscopic phenomena is developed, but still with the aim of practical applications, i.e. in reactor simulations. The dynamic change in catalytic activity of ash particles during gasication of biomass char is studied by analyzing measurements conducted with a variety of biomass chars under wide range of operating conditions [24]. These data were obtained in a lab device

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Table 1 Empirical models for the dynamic change of conversion rate due to catalytic activity. Source [18] [8] [17] [12] [15] [10] [19] Fuel 14 biomasses Coal/activated carbon Wooda 21 Biomasses 2 Brown coals 2 Biomasses Brown coal
a

Char preparation 10 K/s, 1173 K, 1 min 10 K/s, 1173 K, 1 min 20 K/min, 873 K, 2.5 h <10 K/min, 723 K, 4 h In situ rapid pyrolysis 5 K/s, 773 K, 47 s 100 K/min, 1173 K, 1 h

Exp. TGA TGA TGA TGA DFR FBF TGA

Temp. 1123 K 1123 K 1073 K 10231173 K 1173 K 1123 K 10231373 K

Atmosphere H2O 0.05 Mpa CO2 0.1 MPa CO2 15 vol.% H2O 0.020.27 atm. H2O 53 vol.% Various H2OH2N2 H2O 1.04.0 MPa

Models p r k1 X cg 1 wln1 X cg 1 cX cg p p r k1 X cg 1 wln1 X cg 1 hp p r k1 X cg 1 wln1 X cg 1 p 1bt cg p r kamk =mSi b1 X cg 2=3 r k1 expk2 t k3 1 X cg r k1 k2 1 X cg

p r k1 1 k2 t2 k3 1 X cg 1 wln1 X cg

TGA, thermogravimetric analyzer. DFR, drop-tube xed-bed reactor with forced gas ow. FBF, xed-bed reactor with forced gas ow. a Samples were acid-washed and/or impregnated with alkali metals.

reproducing as much as possible the operation conditions in practice. The rate coefcients for all biomasses and the conditions for the applications of the proposed model are identied and discussed. Further improvements to be made to increase the understanding are proposed. 2. Experimental 2.1. Samples Nine biomass species were used in this study: barley straw (BS), forest residue of pine (FR), kenaf (Kn), miscanthus (Mc), pine bark (PB), pine sawdust (PS), reed canary grass (RC), wheat straw (WS), and willow (Wl). Table 2 shows the proximate and ultimate analyses as well as ash composition of raw biomass fuels. All the biomass species contain a large amount of AAEM. Some biomasses (Kn, PB, PS and Wl) contain negligible amount of SiO2 while SiO2 content is higher than the sum of AAEM species for other biomasses (BS, FR, Mc, RC and WS). 2.2. Experimental method The gasication tests were carried out by measuring the weight of the sample as a function of time in a pressurized thermobalance. The initial sample weight of raw biomass was in the range of 50
Table 2 List of samples and their properties (barley straw (BS), forest residue of pine (FR), kenaf (Kn), miscanthus (Mc), pine bark (PB), pine sawdust (PS), red canary grass (RC), wheat straw (WS), and willow (Wl)). BS Proximate V.M. F.C. Ash FR Kn Mc 78.5 18.2 3.3 47.9 6.0 0.6 41.6 0.6 42.8 0.5 0.4 7.6 4.8 25.3 0.7 0.03 2.1 5.3 PB 73.1 25.3 1.7 52.5 5.7 0.4 39.7 0.03 1.3 5.3 0.3 40.6 4.5 7.6 0.5 0.12 2.0 4.8 RC 73.5 17.6 8.9 45.0 5.7 1.4 38.9 0.14 89.8 1.4 1.1 3.5 1.5 3.1 0.1 0.05 1.1 4.1 PS 83.1 16.8 0.1 51.0 6.0 0.1 42.8 8.3 2.0 1.8 41.8 11.8 12.3 0.3 0.12 1.9 5.2 WS 77.7 17.6 4.7 47.5 5.9 0.6 41.5 0.07 59.9 0.8 0.5 7.3 1.8 16.9 0.5 0.04 1.1 2.3 Wl 79.9 18.9 1.2 49.7 6.1 0.4 42.6 0.03 0.4 0.3 0.2 30.8 5.1 26.5 0.3 0.02 3.0 11.5

and 60 mg with initial particle size less than 0.2 mm. It was conrmed that the measurements were conducted in the chemical regime [24]. Most of experiments were carried out at the temperature range of 10231123 K, total pressure of 0.1 MPa, and gas composition with 100 vol.% of CO2 or H2O. Additional experiments were carried out at total pressure of 3.0 MPa and using mixtures of CO2 and CO as gasication agent. Raw biomass sample was fed to a reactor after the reactor was kept at the desired conditions, which ensure the rapid heating of sample and in situ char gasication. Residual weight of sample basket was measured at constant time interval. The thermobalance setup and the principle of the measurement procedure are presented in detail elsewhere [24]. 2.3. Analysis method of experimental data and the denition of char gasication Overall fuel conversion was calculated as:

Xt

mi m mi mf

Since the experiments were carried out as in situ char gasication after rapid devolatilization, it is essential to divide the mass loss by char gasication from that due to devolatilization. Previous experiments under chemically controlled conditions showed that char gasication started after a short break following devolatilization [25]. It means that treating devolatilization and char gasication as parallel reactions with their own precursors makes no mathematical difference from the real reaction scheme, consecutive reactions. The overall fuel conversion can be expressed as:

1 X t yv ol 1 X dev ychar 1 X cg

analyses, wt.%-dry 76.1 79.3 79.4 18 19.4 17.0 5.9 1.3 3.6

100 Conversion [], conversion rate [s1 ] 1-Xt ychar(1Xcg)

Ultimate analyses, wt.%-dry C 46.2 51.3 46.6 H 5.7 5.8 5.8 N 0.6 0.4 1.0 O (diff.) 41.5 40.9 42.8 S 0.08 0.02 0.1 Ash content, wt.% SiO2 62.0 Al2O3 0.2 Fe2O3 0.2 CaO 4.5 MgO 2.2 K2O 19.3 Na2O 0.5 TiO2 0.02 SO3 1.4 P2O5 2.5 in ash 38.5 4.7 3.7 15.4 4.0 8.3 0.4 0.5 1.6 3.2 6.6 1.8 1.2 30.8 6.0 13.3 1.3 0.08 5.7 2.7

10

rcg x 100

yvol(1Xpy)
2

tcg,i 20 40 60 time [s] 80 100 120

10

Fig. 1. The analysis procedure to obtain tcg vs. (1 Xcg) from experimental data.

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By assuming that devolatilization can be represented by a single rst-order reaction the following can be written as:

10

r dev kdev 1 X dev

2nd regime 10 1-Xcg []

1

By integrating Eq. (4) and after substitution of Xdev into Eq. (3), this equation can be written as

1st regime

1 X t yv ol expkdev t ychar 1 X cg

10

3rd regime 10
3

Fig. 1 shows the procedure to derive char conversion, Xcg, as a function of time. First, experimental data of total fuel conversion was plotted on a logarithmic scale against time. During the rst several data plots, log(1 Xt) decreased linearly against time, which means that devolatilization proceeded as a rst order reactions. Second, these data were used to obtain the parameters of devolatilization term in Eq. (5). Since we can assume that Xcg remains zero during pyrolysis, Eq. (5) can be rewritten as:

(a)
10
4

0
0

1000

2000 3000 Time, tcg [s]

4000

5000

10

1 X t 1 yv ol 1 expkdev t

Instantaneous reaction rate, Rcg x 100 [s1 ]

considering that the sum of initial mass fractions of volatiles and char is one. The parameters in Eq. (6) were obtained by the least square method. Next, mass loss prole due to char gasication in Eq. (5), ychar(1 Xcg), was obtained. By using the obtained parameters and experimental value of overall fuel conversion, Xt, mass loss prole by char gasication, ychar(1 Xcg), can be calculated by the difference between the left hand side and the rst term of right hand side of Eq. (5). The result is shown as diamond symbols in Fig. 1. Then, the initial time for char gasication (t = tcg,i) was dened as the time when the derivative of ychar(1 Xcg) showed maximum. The value of ychar(1 Xcg) at the initial time of char gasication should be equal to (1 yvol), which determines the constraint of the least square calculation in the second step. After the iterative calculation, elapsed time of char gasication, tcg = t tcg,i, and char conversion, 1 Xcg = (1 Xt yvolexp(kdev t))/(1 yvol), were obtained. 3. Model In this section, the model of biomass char gasication describing change in catalytic activity of ash is introduced based on the experimental observation. Fig. 2a plots the typical prole of char conversion obtained in the present study plotted as logarithm of 1 Xcg against time. Fig. 2b shows the same plots for the zero-order reaction, rst-order reaction, and the parallel reaction of zeroand rst-order reactions. The conversion prole in Fig. 2a can be divided into three regimes. In the rst regime, log(1 Xcg) decreased linearly against time. It means that char gasication in the rst region followed rst-order kinetics as shown in Fig. 2b. After the short period, ca. 150 s in Fig. 2a, char gasication was transformed to another rst-order reaction, which was slower than the initial reaction (smaller slope in Fig. 2a). Then, char gasication was accelerated (sharp increase in the slope shown in Fig. 2a) at the last stage of char gasication, i.e. around 3000 s and above 90% of char conversion. As shown by comparison of the results from Fig. 2a with Fig. 2b, the reaction in the last region seems to follow zero-order kinetics. This visual observation is in agreement with that commonly observed for catalytic char gasication [26]. Fig. 2c shows the plot of instantaneous reaction rate of char gasication, Rcg, against char conversion. If the reaction is rst-order with respect to char, the instantaneous reaction rate should be parallel to the horizontal axis. Here, the instantaneous reaction rate of the second regime was parallel to the horizontal axis. Considering the instantaneous reaction rate of the second regime is lower than that in the rst regime, the reaction in the second regime can be thought to be non-catalytic reaction or reaction with a reduced catalytic activity where the catalytic material is stable. In fact, the

(b)
10 1-Xcg []
1

zero-order reaction parallel reaction

10

first-order reaction

10

0.2 0.4 0.6 0.8 Normalized time, tcg/tcg,Xcg=0.001 [-]

(c)

0.8

0.6

1st regime

3rd regime

0.4

0.2

2nd regime 0 0.2 0.4 0.6 Char conversion [] 0.8 1

Fig. 2. (a) tcg vs. log(1 Xcg) of experiments with reed canary grass at T = 1123 K and P CO2 0:1 MPa; (b) tcg vs. log(1 Xcg) for zero-order, rst-order, and their parallel reactions; and (c) Rcg. vs. char conversion (Xcg).

instantaneous reaction rate of initial rst-order reaction (Xcg < 0.4) decreased at higher char conversion in agreement with previous studies [15,19], where these observations were explained on the basis of vaporization of catalytic ash. Then they introduced a rst-order reaction independent from char conversion assuming that the reaction was a rst-order with respect to the amount of catalyst [15,19]. The zero-order reaction at the nal stage of reaction can be explained by assuming that small amount of catalytic ash remains in the ash and deactivation/vaporization process is negligible. On the basis of the visual ndings discussed and the past results from literature it seems reasonable to assume that during the second regime non-catalytic char gasication governed the overall conversion rate because of the negligible fraction of catalytic ash. However, catalytic gasication mechanism became dominant since

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(a)
0.8 Conversion, Xcg []

0.6
Exp. CLM1 JM CLM2

0.4

0.2

1500

Time, tcg [s]

3000

4500

7 6 Conversion rate, rcg [s 1] 5 4 3 2 1 0

x10

(b)
Exp. CLM 1 JM CLM 2

0.2

0.4 0.6 Conversion, Xcg []

0.8

Fig. 4. Comparison of the proposed models with experimental data. (a) Conversion vs. time, (b) conversion rate vs. conversion. Operating conditions: red canary grass at T = 1123 K and P CO2 0:1 MPa. Fig. 3. Suggested mechanisms describing the dynamic change in catalytic activity during char gasication.

Table 3 Comparison of the three models developed for catalytic char gasication with deactivation (regime 1 in Fig. 2): CLM1 (Eq. (8)), JM (Eq. (9)) and CLM2 (Eq. (10)). CLM1 kccg,1 kctloss, n kncg kccg,2 Nexp Deviation (%) 5.27 103 1.44 102 4.86 104 3.18 105 545 0.50 JM 6.01 103 15.3 4.36 104 3.82 105 545 0.28 CLM2 5.65 103 17.0 4.39 104 3.78 105 545 0.28

the fraction of catalyst in char that hardly deactivate/vaporize increased due to the carbon consumption. A proposed physical interpretation of the dynamic change in catalytic activity during char gasication is summarized in Fig. 3. As shown in Fig. 2b, transition from the second to third regimes can be expressed by applying parallel reaction mechanism of zero- and rst-order reactions. On the basis of the above discussion a three-parallel reaction model is assumed to describe the overall conversion rate of biomass char gasication.

rccg ;1JM kccg;1 1 X cg 2=3 expnX 2 cg

2/3

r cg r ccg;1 r ncg r ccg;2

rccg,1 corresponds to the part of conversion rate in rst regime, where catalytic char gasication with the deactivation of catalyst occurs (CCG1). rccg,1 is independent from char conversion because its dynamic change is governed by the loss of catalytic activity. The loss of catalytic activity has been expressed by exponential function of time in previous studies [15] as shown in Eq. (8). We call this model Catalyst Loss Model 1 (CLM1) in this paper.

r ccg;1CLM1 kccg ;1 expkctloss tcg

The drawback of CLM1 is, as discussed above, that it is less suitable for the application to reactor simulation because the expression includes the residence time of char particle explicitly. Therefore, model accounting catalytic effects during gasication as a function of conversion is preferred. Johnson model [27] (JM: Eq. (9)) fullls this conditions, so that it is considered in this work.

Here, the term, (1 Xcg) , expresses the change of surface area for char gasication, which can be introduced according to the shrinking core model without the formation of ash layer. The exponential term represents the relative reactivity of the surface area, which is, in our case, deactivation of catalyst. Although the deactivation rate of catalyst is independent of char conversion, it can be expressed by applying a correlation factor, n. However, the reactivity of catalytic char gasication is known to be independent of the char conversion [15,26], but of the reactive surface area of catalyst [16,28]. Therefore, we modied JM to exclude the surface area term, and examined its predictability as shown in Eq. (10) (CLM2: catalyst loss model 2).

rccg ;1CLM2 kccg;1 expnX 2 cg

10

The ability of the three models presented for the regime 1 (catalytic char gasication with deactivation) will be assessed in the results in order to select the most appropriate one.

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1.2

(a)
Conversion rate, rcg/rcg,0 [-] 1 0.8 0.6 0.4 0.2 0 1.2 Conversion rate, rcg/rcg,0 [-] 1 0.8 0.6 0.4 0.2 0

1023 K, 0.1 MPa CO2 1123 K, 0.1 MPa CO2 1123 K, 3.0 MPa CO2 1123 K, 2.7 MPa CO2+0.3 MPa CO

(b)

1123 K, 0.1 MPa H2O 1123 K, 3.0 MPa H2O

(c)

1023 K, 0.1 MPa CO2 1123 K, 0.1 MPa CO2 1123 K, 3.0 MPa CO2 1123 K, 2.7 MPa CO2+0.3 MPa CO

(d)

1123 K, 0.1 MPa H2O 1123 K, 3.0 MPa H2O 1123 K, 2.7 MPa H2O+0.3 MPa H2

0.2

0.4 0.6 Conversion, Xcg []

0.8

10

0.2

0.4 0.6 Conversion, Xcg []

0.8

Fig. 5. Xcg vs. rcg/rcg,i by the experiments under various reaction conditions. (a) Barley straw under CO2 atmosphere, (b) barley straw under H2O atmosphere, (c) miscanthus under CO2 atmosphere, and (d) miscanthus under H2O atmosphere.

Table 4 Rate coefcients for various reaction conditions according the three-parallel model given by Eqs. (6), (9), (10), (11). Temp. Barley straw 1023 K 1123 K Pressure 0.1 MPa 0.1 MPa 3.0 MPa 0.1 MPa 0.1 MPa 3.0 MPa Atmosphere CO2 CO2 CO2 CO2:CO = 9:1 CO2 CO2 CO2 CO2:CO = 9:1 kccg,1 5.07 104 6.16 103 3.99 103 8.36 104 3.64 103 2.69 103 3.44 103 5.70 103 n 37.9 48.3 124.0 30.4 344.9 120.5 276.3 110.2 kncg 2.15 104 3.27 103 5.33 103 2.27 103 4.29 104 2.68 103 3.28 103 1.76 103 kccg,2 2.75 106 1.27 105 4.21 104 1.37 104 1.05 105 8.62 105 9.96 104 2.08 104 Dev. (%) 0.75 0.40 1.36 0.20 1.72 1.11 2.06 1.03

Miscanthus

1023 K 1123 K

The second term in Eq. (7) represents the part of conversion rate by non-catalytic gasication. As observed from Fig. 2a and c, conversion rate corresponding to the second regime was expressed by the rst-order with respect to char conversion.

X cg;exp X cg;cal

13

4. Results and discussion 4.1. Comparison of models for the catalytic gasication with deactivation The ability of the three models developed to t the measurements in the regime 1 (catalytic char gasication with deactivation, i.e. CLM1, JM and CLM2) was assessed. The aim was to select the most suitable model for the application in reactor simulation. Fig. 4 compares the results from these three models with the experimental data at T = 1123 K with 100 vol.% of CO2 under atmospheric pressure. Experimental data shown in Fig. 4 was obtained with reed canary grass as fuel. All three models tted sufciently well with experimental prole of char conversion against time. Table 3 shows the rate coefcients and deviation, dev = (S/Nexp)1/2, for three models. All the models showed very small deviation although JM and CLM2 showed slightly better tting. Fig. 4b shows char conversion vs. conversion rate curve with three suggested models and

r ncg kncg 1 X cg

11

The third term in Eq. (7), i.e. conversion rate corresponding to the third regime, represents catalytic char gasication by stable catalyst. It was expressed by zero-order reaction.

r ccg;2 kccg;2

12

Substitution of Eqs. (8)(12) in Eq. (7) yields the overall conversion rate of char gasication. There are four unknown rate coefcients in the proposed model. These rate coefcients were calculated by minimizing the error between the experimental and calculated values of char conversion. Analytical solution for the integration of Eq. (7) was found only when CLM1 is assumed, so numerical integration is applied when using JM and CLM2. Minimization of the sum of squared residual error between the experimental data and calculated value was applied.

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1 Barley Straw (BS) Conversion rate, rcg x100 [s -1] 0.8 Forest residue (FR) Kenaf (Kn)

0.6

0.4

0.2 0 1

Miscanthus (Mc)

Pine bark (PB)

Pine sawdust (PS)

Conversion rate, rcg x100 [s -1]

0.8

0.6

0.4

0.2 0 1

Reed canary grass (RCG)

Wheat straw (WS)

Willow (Wl)

Conversion rate, rcg x100 [s -1]

0.8

0.6

0.4

0.2

0.2

0.4 0.6 Conversion, Xcg []

0.8

10

0.2

0.4 0.6 Conversion, Xcg []

0.8

1 0

0.2

0.4 0.6 Conversion, Xcg []

0.8

Fig. 6. Char conversion vs. conversion rate curves with experiments and the proposed model for various biomass species. Operating conditions: T = 1123 K and P CO2 0:1 MPa.

Table 5 Rate coefcients for various biomasses according the three-parallel model given by Eqs. (6), (9), (10), (11) (T = 1123 K, CO2 0.1 MPa). kccg,1 Barley straw Forest residue Kenaf Miscanthus Pine bark Reed canary grass Pine sawdust Wheat straw Willow 6.16 103 4.58 103 1.21 102 2.69 103 2.13 103 5.65 103 9.84 103 3.36 103 3.22 103 n 48.3 14.8 2.97 120.5 16.6 17.0 1.70 9.52 38.3 kncg 3.27 103 2.19 103 2.07 102 2.68 103 5.46 104 4.39 104 1.13 102 3.00 103 3.44 103 kccg,2 1.27 105 3.39 104 8.18 104 8.62 105 4.33 104 3.78 105 1.89 103 1.59 105 1.07 103 Dev. (%) 0.40 0.45 0.45 1.11 0.62 0.28 0.26 0.29 1.19

experiments with the rate coefcients that gave the best tting for time vs. char conversion curves. Here, the difference is more significant: conversion rate prediction by JM and CLM2 agreed with the experimental data for the entire range of char conversion while CLM1 showed considerable error for char conversion below 0.4, i.e. during the rst catalytic char gasication regime. Besides the good tting, an important aspect is the computational cost. During the estimation of rate coefcients, computa-

tional times to calculate a certain number of numerical integration were measured. The exact number is not shown here because it varies with the environment of computation and other factors. However, the computational time of CLM2 was 25 times lower than that of JM. The three models were compared for all the reaction conditions discussed in the following sections, and the same tendency with the example (Fig. 4 and Table 3) was observed. Therefore, CLM2 was identied as the most suitable model

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for the application in reactor simulation. In the following sections we shall call suggested/proposed model to mean the three-parallel reaction model (Eq. (7)) with rccg,1 given by CLM2 in Eq. (10) the other two regime rates in Eq. (7) are represented by Eq. (11) (rncg) and Eq. (12) ((rccg,2)). 4.2. Model validity under various reaction conditions Fig. 5 shows the char conversion vs. normalized conversion rate (rcg/rcg,i) curves obtained by the experiments under various reaction conditions. Two biomass species, barley straw and miscanthus, were selected for the analysis of Fig. 5. At all reaction conditions under CO2 and CO2/CO atmosphere, typical rcg/rcg,i curves like those presented in Fig. 4b were observed. On the other hand, rcg/rcg,i curve under H2O and H2O/H2 atmosphere showed no sign of initial conversion rate drop, showing instead, rather similar shape of the random pore model. The proposed model seems to be, therefore, applicable only under CO2 and CO2/CO atmosphere under examined conditions. There is no clear evidence for the difference of rcg/rcg,i curve under H2O based atmosphere and CO2 based atmosphere. Though, it is known that the reaction atmosphere affects the release of Na and K from fuel particles [29]. Then it can be argued that chemical reactions occurring in the ash were decisively inuenced by the atmosphere, resulting in different deactivation mechanism of catalyst. Apparently, the deactivation of catalytic activity was not signicant under steam based atmosphere in the present study. Further study on AAEM behavior under various atmospheres is necessary to understand the different shape of conversion rate curves under different atmosphere. The shape of rcg/rcg,i vs. Xcg curve, i.e. f(Xcg) in Eq. (1), varied with composition of the gasication mixture (CO2/CO). In general, having the same f(Xcg) for different reaction condition is necessary to apply conventional char gasication models such as random pore model. On the other hand, the proposed model does not require to have the same f(Xcg) for different reaction conditions. Since four rate coefcients represent the different processes, each coefcient has different temperature and pressure dependence, meaning that it is acceptable for the model to have different f(Xcg) at different reaction conditions. In Fig. 5a and c, the increase of temperature resulted in relatively slower deactivation of catalyst than char conversion process, meaning that the deactivation of catalyst is less sensitive to the reaction temperature than to catalytic effect itself. Table 4 shows the rate coefcients and the deviation under CO2 and CO2/CO atmosphere. The proposed model showed good tting ability for all the reaction conditions. 4.3. Model validity for various biomasses Fig. 6 shows the char conversion vs. conversion rate curves with experiments and the proposed model for various biomass species. Table 5 shows the rate coefcient and the deviation for these data. Experimental conditions of these gures were at the reaction temperature of 1123 K, with 100 vol.% of CO2, and under atmospheric pressure. The proposed model showed good tting ability to nine biomass species examined. However, kenaf and pine sawdust did not show the typical conversion rate curve. In fact, the parameters with best t for these two biomass species included negative values, which physically mean the char conversion decreased with reaction. A common physical property of these two biomass species is that they contain less silicon in ash-forming elements than other biomass (see Table 2). Other two biomasses with less silicon contents, pine bark and willow, showed typical shape of conversion rate, but they showed slightly higher deviation than other biomasses. It is concluded that silicon might have played a signicant role on catalyst deactivation process in the present study by forming silicates

[9]. To generalize the conclusion it is recommended to validate with larger number of biomass species. 5. Conclusions This work was aimed to identify a comprehensive description of catalytic effects during char gasication under various conditions relevant for biomass gasiers. Based on measurements conducted in a thermobalance, a reaction model of char gasication was proposed to describe the dynamic change in catalytic activity, comprising three regimes of reaction (1) catalytic char gasication with the deactivation of catalyst, (2) non-catalytic char gasication, and (3) catalytic char gasication with small amount of stable catalyst, i.e. without deactivation. Three functions describing the deactivation of catalyst were compared, and the model with the best tting ability requiring the less computational time was selected. The ability to describe the conversion rate obtained by experiments under various conditions (temperature: 1023 1123 K, pressure: 0.13.0 MPa and gasication mixtures of CO2 COH2OH2) was examined. The proposed model described the conversion rate of char gasication well with most biomass samples examined. However, biomass samples with small amount of silicon in their ash-forming elements maintained its catalytic activity for the entire gasication process. The model was still able to describe the conversion rate for these biomass species when the catalytic activity was maintained, but the best t parameters gave negative rate coefcient for the rst regime. For high silicon content biomass species the model was shown to work for gasication using mixtures of CO2 and CO for the ranges of temperature of 10231123 K and pressure of 0.13.0 MPa. Char gasication under steam atmosphere was observed to maintain its catalytic activity (like biomass with low silicon content) so the model seems to be not applicable for steam gasication for the operating conditions investigated. To further strengthen the application of the model, some issues to be further investigated were identied (i) the AAEM transformation behavior during char gasication; (ii) the reactions affecting the catalytic activity of the char during steam to be able to apply the model (or a modied model) under steam atmosphere; (iii) the dependency of rate coefcients on the reaction conditions in order to make the model more generally applicable. Acknowledgments The authors acknowledge the nancial support of Nordic Energy Research Top-level Research Initiative for supporting this work through Nordsyngas project. The support of the project GASIFREAC, nanced by the Academy of Finland, is also gratefully acknowledged. KU thanks Bio4Energy, a strategic research environment appointed by the Swedish government, for supporting this work. References
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