Fuel 78 (1999) 335340

Combustion of Spanish coals under simulated pressurized-uidized-bed-combustion conditions

Elena Alvarez*, Juan F. Gonzalez
ENDESA, Prncipe de Vergara 187, E-28002 Madrid, Spain Received 20 April 1998; accepted 24 August 1998

Abstract Coal reactivity is an important parameter related to efciency of boilers, and learning how to predict it can reduce costs when screening for new fuels. We have measured the reactivity of Spanish coals in a high pressure thermogravimetric analyzer, under operational conditions similar to those found in Pressurized-Fluidized-Bed-Combustion (PFBC). The results obtained from non-isothermal tests were used to look for correlations between the reactivity and the physical and chemical properties of the coals. Reactivity increased with increasing rank, but no relationship was found with the initial pore or surface characteristics of either the coals or the chars. We found a correlation between the true density of the chars and their reactivity. We also observed a decrease in the reactivity, calculated from isothermal tests, as the pressure was increased, while there was a slight increase in reactivity with increasing temperature. q 1999 Elsevier Science Ltd. All rights reserved. Keywords: Coal combustion; High pressure; Thermogravimetric analysis

1. Introduction The production of steam for electric power by burning coal seems likely to remain an important energy conversion route until well into the next century. Coals are heterogeneous solids that can vary widely in their properties; hence their combustion behavior in power stations can differ signicantly. This has been particularly accentuated with the increasing trade in thermal coals. The international market has provided utility operators with a wide selection of coals. In many cases, expensive full-scale test burns are required to conrm the suitability of a coal. There is therefore a need to develop methods for assessing coal characteristics so that combustion plant performance can be predicted more effectively. A common technique for coal characterization is thermal analysis [1,2]. This is a fast, cheap and reliable technique for reactivity measurement. The usual method in thermal analysis involves continuously measuring a physical or chemical change in a substance whilst it is being subjected to a controlled temperature program. The measured variable in thermogravimetric analysis (TG) is the change in weight of the sample, which is plotted as a function of furnace
* Corresponding author. Present address: Energy Science Laboratories, Inc., 6888 Nancy Ridge Dr., San Diego, CA 92121, USA. Tel.: 1 1-619552-2033; Fax: 1 1-619-587-7092; e-mail: ealvarez@fda.net.

temperature (non-isothermal mode) or time (isothermal mode). With the derivative thermogravimetric analysis (DTG), a plot of the rate of weight change is produced. When the coal is heated in an atmosphere of owing air, the graphical plot produced is known as the burning prole, which can provide a comparative evaluation of the characteristics of the coal. The order of reactivity of the coal is assessed on the peak temperature, with less reactive coals showing higher peak temperature. The reactivity of coals has been widely studied because of its importance for the efcient combustion of coals and for the screening of candidate fuels [3,4]. The ability to screen candidate fuels quickly and cheaply is essential when the construction of a new plant is considered, or in order to reduce fuel costs or emission in an existing one. General relationships between the physical and chemical characteristics and reactivity of coals and the nature of the combustion process are usually established based on the study of the thermal behavior of coals in atmospheric conditions [5]. However, the reactivity values obtained would be specially meaningful if the conditions in the simulated test could mimic those in the plant. One of the reasons for concern is that pressure and temperature inuence substantially the extent and the control of the combustion process. Because of the complexity of the reactions involved, combustion is considered as two separate stages: devolatilization, and the subsequent char combustion. Since char

0016-2361/99/$ - see front matter q 1999 Elsevier Science Ltd. All rights reserved. PII: S 0016-236 1(98)00160-4

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Table 1 Immediate and ultimate analysis of the coals used in this study Coal Virgen del Pilar Oportuna Barrabasa Luengo Segre Compostilla Sudafrica Moisture (%) 20.3 14.0 14.8 13.2 14.4 1.0 4.0 Volatile matter (%,d) 49.8 31.9 34.6 32.3 49.8 10.4 29.5 Fixed carbon (%,d) 25.0 30.5 27.4 33.0 16.5 64.4 57.7 Ash (%,d) 25.3 37.6 38.0 34.7 33.7 25.2 12.7 C (%,d) 52.7 42.8 41.3 45.4 48.0 68.8 72.8 S (%,d) 10.7 9.8 8.2 7.1 9.6 1.6 0.6 N (%,d) 0.8 0.4 0.4 0.6 0.6 1.0 1.8 H (%,d) 4.0 2.9 3.1 3.2 3.6 2.0 4.1 O (%,d) 6.4 6.5 9.0 9.0 4.5 1.4 7.9

gasication or combustion is the slower step, it usually controls the overall conversion process. A better understanding of the kinetics of this step under plant conditions is therefore essential for optimum design and operation of coal gasiers. In this work, we have focused on the study of the combustion of six Spanish coals at high pressure and high temperature conditions, using a thermogravimetric analyzer. All of these coals are under consideration for usage at the Puertollano station, which generates electric power through the gasication in combined cycle technology, or at the pressur ized uidized bed combustion (PFBC) station of Escatron. We have been able to establish correlations between the true density of the coals and their reactivity in plant conditions. Furthermore, we have investigated the nature of the reaction controlling the combustion process and the effect of varying pressure and temperature.

analyses of coals are presented in Table 1. Char samples were prepared by crushing and screening the coal to 100 200 mm diameter and heating 20 g of each coal at 8508C in a ow of inert gas N2 during 30 min in a vertical reactor. The surface area of coals and chars was determined by the single-point BrunnauerEmmetTeller (BET) method using liquid N2 in a Micromeritics Flowsorb 2200. Porosity and pore size distribution were measured by a Micromeritics PoreSizer 9300 mercury porosimeter and corrected for coal compressibility effect [6]. Helium density was obtained by means of a picnometer Micromeritics Accupyc 1300. Samples for textural analysis were rst degassed at 1408C for 12 h under vacuum. Surface areas, density and porosity results are reported in Table 2. Coals were screened to 100200 mm diameter for thermogravimetric tests. 2.2. Thermobalance

2. Experimental 2.1. Coal samples and analysis Seven coal samples of different rank and origin were chosen for this study. Five of them (Virgen del Pilar, Oportuna, Segre, Luengo and Barrabasa) are sub-bituminous Type C coals from the Teruel and Mequinenza areas (Spain); the antracitic Compostilla (Leon, Spain) and the imported bituminous Sudafrica coals are being used in different pulverized fuel (PF) power plants. The as received coal was crushed and screened to less than 200 mm for analysis. The ultimate and proximate
Table 2 Textural analysis of coals and chars Coal Virgen del Pilar Oportuna Barrabasa Luengo Segre Compostilla Sudafrica Density (g cm 23) Original 1.62 1.77 1.82 1.70 1.61 1.71 1.53 Pyrolized 2.11 2.29 2.31 2.23 2.20 1.96 1.97

The pressurized thermogravimetric apparatus used in this study has been previously described [7]. The main parts are the microbalance, housed in a steel block, and the reactor. Both are constructed for a maximum working pressure of 100 bar. The sample holder, connected to the balance with a chain, was made of Incoloy net and can be smoothly lowered and lifted up to the hot chamber of the reactor by a driven winch system. The reaction tube can be heated electrically up to 11008C. As reaction atmosphere, air and N2 were used for combustion tests, as indicated. The temperature is measured by means of a PtRh thermocouple located below the sample holder, thus representing the furnace temperature. The data acquisition system allows

Surface (m 2 g 21) Original 12.6 6.7 11 36 5.5 4.2 3.6

Pyrolized 83 54 61 29 100 2.2 4.9

Vp (cm 3 g 21) Original 0.110 0.108 0.156 0.104 0.146 0.030 0.069

Pyrolized 0.118 0.159 0.193 1.125 0.176 0.039 0.084

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Fig. 1. Non-isothermal weight loss curve () and burning prole, R, ( ) of the sub-bituminous coal Virgen del Pilar. R values are normalized by W0. The peak temperature is indicated by Tm and the burnout temperature by Tb.

The weight loss of the sample was continuously monitored as a function of temperature. Fig. 1 represents a typical nonisothermal thermogram and the plot of the rate of weight loss versus temperature, i.e. the burning prole. The different regions in the curve represent: (1) loss of moisture at temperature below 1008C; (2) volatile loss; (3) abrupt increase of slope as the combustion becomes the major mechanism; (4) maximum of weight loss at the peak temperature (Tm), which is the main characteristic point of the curve; (5) rate decrease to zero at another characteristic point of the burning prole, the burnout temperature (Tb). This point represents the temperature at which the rate of weight loss is 1% min 21, and the oxidation of the sample is considered to be complete [8]. Arrhenius plots obtained from burning proles have been used to derive apparent activation energies. The intrinsic reaction rate, k, is given by the relationship: k Ae2E=Rg T 1

storing of the signals of the microbalance and the thermocouple in preset intervals of time. The measured weight values are further corrected for the buoyancy. 2.3. Coal combustion tests To monitor coal combustion reactivity, isothermal and non-isothermal thermogravimetric methods were used. Mass transfer effects were eliminated by using a sufciently high ow rate of gas and a small sample size. Preliminary tests showed that when sample weights were lower than 25 mg and gas ow rate was about 1 l min 21, the reaction rate remained unchanged with the experimental uncertainty. Thus, under these conditions, the effect of external mass transfer is negligible. In the non-isothermal tests, a sample of 25 mg of coal was heated in a owing atmosphere of 2 l min 21 of a mixture of composition 4.5% O2 in N2 at a heating rate of 108C min 21.

where E is the activation energy (J mol 21), A the pre-exponential factor (mol min 21), T the temperature (K) and Rg the universal gas constant. In the isothermal combustion tests, samples of 25 mg of coal were quickly introduced into the reaction tube at the reaction temperature in a ow of 1 l min 21 of N2 until devolatilization was nished. Once the reaction temperature was attained under N2, combustion was performed in a ow of 1 l min 21 of air until constant weight. A typical weight loss history and the rate of weight loss for a coal are shown in Fig. 2. There are four distinct regions in the combustion curve, that represent: (1) devolatilization; (2) built up of oxygen complexes on the surface of the char, as an increase in weight is observed and an increase in reaction rate as the char undergoes activation; (3) rectilinear portion of the burn-off plot, in which about 40% of the material is burned; (4) reduction of reaction rate as the surface per unit of weight decreases. In zone 3, the increase in burn-off is directly proportional to time. It was from this portion of the plots that the reactivity parameter was calculated. The maximum rate of char weight loss, calculated by; Rmax   21 dW W0 dt max mg mg21 h21 2

Fig. 2. Isothermal weight loss () and rate of weight loss, R, curves ( ) of the combustion of the sub-bituminous coal Virgen del Pilar. R values are normalized by W0. The maximum rate of weight loss is indicated by Rmax.

was used as an index of coal reactivity [9,10], where W0 is the initial weight of char in a dry-ash free basis (mg) and (dW/dt)max is the maximum rate of weight loss in a dry-ash free basis (mg h 21). Non-isothermal reactivity measurements were performed to determine the relative reactivities of the different coals used in this study in order to identify possible relationships between combustibility and characteristics of coals. The isothermal reactivity parameter was used to evaluate the effect of varying operating conditions (temperature, pressure) on coal behavior.

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Table 3 Peak (Tm) and burnout (Tb) temperatures derived from the burning prole of the coals Coal Virgen del Pilar Oportuna Barrabasa Luengo Segre Compostilla Sudafrica Tm (8C) 387 380 355 372 387 459 460 Tb (8C) 495 524 492 473 487 549 554

3. Results and discussion The rst objective of this study was to investigate the correlation between the physical and chemical properties of several coals (shown in Tables 1 and 2) and their reactivity at high pressure and temperature. The reactivity parameters for each coal are listed in Table 3. Multiple determinations were made for the Virgen del Pilar coal at 12 bar and 108C min 21. The results were found reproducible within a maximum spread of 0.2% and 0.8% for the Tm and Tb parameters, respectively. The parameter burnout temperature, Tb, could not be correlated with any characteristics of coals or chars. As expected, peak temperature of combustion, Tm, increased with increasing rank: coals with a lower carbon content and a high content of volatile matter were more reactive. The same relationship was observed for chars. No apparent relationship was found between reactivity and initial pore or surface characteristics of parent coals or chars, although the changes in surface area were not determined as a function burn-off. No conclusions can be inferred on how the development of porosity could affect reactivity for a particular char, or if correlations might exist for conversions other than 0%. On the other hand, a good correlation was obtained with the initial absolute He-density of chars, as shown in Fig. 3. Helium displacement is often
Fig. 4. Arrhenius plot for the combustion of the coal Virgen del Pilar.

used to determine the true densities of solids, since this gas is not easily absorbed on the internal surfaces of coal at room temperature, and it is believed to penetrate pores greater than 34 A. The correlation with Tm could indicate that the structure at the micropore level plays an important role in combustion rates, although could indicate a relation between reactivity and mineral matter content, since the true density reported in Table 2 comprises both density of the carbon and the mineral matter. To express density in ash-free basis, the following relationship is used: rHe r 1 ASH r HHe 3 1 2 XASH XASH where r H He is the specic volume of coal or coal char solids (cm 3 g 21), XASH the ash mass fraction, rASH the true density of ash, and rHe the specic volume in ash-free basis (cm 3 g 21). Since there is no available data on the true density of the ashes contained in the different coals, an average value of 2.7 g cm 23 has been used [11]. When the recalculated true densities were plotted vs. the reactivities, no correlation could be found, which might indicate that reactivity would depend on a property of the mineral matter. However, if this was the case, the lack of correlation between the reactivity and total ash would suggest that only a certain type of impurity is involved in the catalytic effect. For low rank coals (C , 80%), a catalytic effect of Ca, Mg, Na, and K has been reported [12]. In that study, not only the amount of the coal minerals was important, but also their state and distribution. For example, the catalytic properties of Ca can be masked in coals with high sulfur content, due to the formation of inactive suldes [13]. To study the combustion reaction under high pressure conditions, we rst identied the different processes controlling reaction and estimated the activation energies for each of them. Then we investigated the inuence of different operational parameters, temperature and pressure, on coal combustion reactivity. These parameters were modied within the workable levels in a PFBC combustor.

Fig. 3. Correlation between the He-density of the chars studied (r He) and the peak temperature (Tm) obtained from the burning prole.

 E. Alvarez, J.F. Gonzalez / Fuel 78 (1999) 335340 Table 4 Apparent activation energies (kJ mol 21) for the chemical (E1) and diffusion (E2) reaction rate control Coal Virgen del Pilar Oportuna Barrabasa Luengo Segre Compostilla Sudafrica E1 110.2 143.7 107.0 167.9 174.0 246.0 156.0 E2 61.7 98.6 91.1 107.4 87.3 86.5 88.2

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Table 5 Inuence of temperature on the reactivity of different coals Coal Virgen del Pilar Oportuna Barrabasa Luengo Segre Compostilla Sudafrica
a

Rmax (mg mg 21 h 21) a 8008C 8508C 80.5 74.3 81.7 68.7 86.2 49.5 50.6 82.9 72.8 82.2 66.2 87.0 51.2 50.2

Fig. 5. Isothermal combustion of the coal Oportuna at 12 bar and temperatures () 8008C, ( ) 8508C and () 9258C. 9258C 100.9 78.1 94.8 84.8 99.2 54.5 49.2

The results are the average obtained from three different runs.

Table 6 Infuence of pressure on the reactivity of different coals Coal Virgen del Pilar Oportuna Barrabasa Luengo Segre Compostilla Sudafrica
a

Rmax (mg mg 21 h 21) a 12 bar 20 bar 82.9 72.8 82.2 66.2 87.0 51.2 50.2 70.4 56.9 64.8 58.9 62.6 36.8 40.2

25 bar 59.5 49.8 57.0 51.8 64.4 37.2 34.3 Fig. 6. Isothermal combustion of the coal Oportuna at 8508C and pressures () 12 bar, ( ) 20 bar and () 25 bar.

The results are the average obtained from three different runs.

A typical Arrhenius plot is shown in Fig. 4. Different linear portions can be drawn in this curve, which can be interpreted as a series of separate events. The linear fraction number 1 was found at low temperatures and is related to the chemical control of the reaction rate [14]. As the temperature rises, the consumption rate exceeds the rate of diffusion, and the rate is controlled by diffusion effects [14]. The energies of activation corresponding to each linear portion for each coal are indicated in Table 4. The values obtained at high pressure are in accordance with the ones obtained by other authors for the chemical reaction [15,16] and the diffusion process [14] at atmospheric pressure. In most of the cases, the energy E2 is approximately half the value of energy E1, which indicates

a transition to pore diffusion control [14], being the transition point around 5208C. Different isothermal combustion tests were performed under various temperatures between 800 and 9258C. The effect of temperature on the reactivity at a pressure of 12 bar for one of the coals tested is shown in Fig. 5. The evolution of the reaction rate is represented as a function of conversion. After an initial phase during which char activation occurs, the reaction rate increased linearly with time. The reaction rate reached a maximum level which is usually interpreted as the point that corresponds to the highest value of surface area in the burning char [17]. The conversion at that point varied between 25% and 50% depending on the coal studied. The rates showed little change with conversion until reaching high levels of conversion after which they dropped to zero. This decrease in rate could be due to loss in the surface area. Table 5 lists the reactivity result for all coals examined in these conditions. All the samples were found to exhibit similar behavior, showing an increase in reactivity with increasing combustion temperature.

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The effect of pressure on the reactivity of the same coal as above at a temperature of 8508C is shown in Fig. 6. The total pressure was varied between 12 and 25 bar in different isothermal combustion tests with air. Table 6 lists the reactivity results for all coals. A decrease in reactivity was observed as the pressure increased within the limits and conditions studied. To explain this effect, two events have to be considered: the increase in the O2 partial pressure, and the increase in total pressure. The oxygen partial pressure is the major driving force for the O2 transfer from bulk gas to particle surface and for the chemical reaction. Kinetic studies of the reaction between char and oxygen have yielded orders of reaction of 1 to 1/2 during pulverized coal combustion, and 1 during AFBC conditions [18]. According to these reports, a positive effect of the increasing pressure on the reactivity should be expected. However, the true reaction order has been found to be close to 0 during combustion at high pressure under high oxygen partial pressure in experiments using a shock tube [19], and between 0.3 and 0.9 during laboratory-scale PFBC studies [20], which would explain why the reactivity did not increase with increasing pressure in our studies. The most likely explanation for the reduced reactivity at higher pressures is the reduction in the oxygen diffusion coefcient, as well as the increase in the resistance of gaseous products arising from the char. Since the reaction is under diffusional control, small changes in pressure are likely to affect reactivity in an inversely proportional manner. It has been recognized that the apparent order of reaction respect O2 under pore diffusion control is 0.5, leading to a true order of reaction of zero [14,21]. As this order is lower than the unity, the increase in O2 concentration can not compensate for the decreasing diffusion coefcients and thus the observed rate decrease. On the other hand, a result found in studies of combustion of pulverized coal, and that is common also to gasication processes, is that pressure can also affect the reaction by reducing the heat transfer and

heating rate, so that the total efciency of combustion drops as pressure increases [14]. Acknowledgements This investigation was carried out under ECSC funds (project 7220-EC-761) in the facilities of Tecnologa y Gestion de la Innovacion, S.A. (Madrid, Spain). We thank J.A. Pitarch for excellent technical assistance, and M.A. Blazquez for critical reading of the manuscript. References
[1] Warne SSJ. Thermochimica Acta 1991; 192:19. [2] Carpenter AM, Skorupsa NM, Coal Combustion-analysis and testing, Report IEACR/65. IEA Coal Research: London, 1993. [3] Ma S, Hill JO, Heng S. Journal of Thermal Analysis 1989;35:1985. [4] Benfell KE, Beaumish BB, Rodgers KA. Thermochimica Acta 1977; 297:97. [5] Wells WF, Smoot LD. Fuel 1991; 70:454. [6] Toda Y, Toyoda S. Fuel 1972; 51:199. [7] Muhlen HJ, Sulimma A. Fuel Processing Technology 1987; 15:145. [8] Morgan PA, Robertson SD, Unsworth JF. Fuel 1986; 65:1546. [9] Jenkins RG, Nandi SP, Walker PL. Fuel 1973; 52:288. [10] Fung DPC, Fairbridge C, Anderson R. Fuel 1988; 67:753. [11] Johnson JL. Fundamentals of coal gasication. Chemistry of Coal Utilization, 2. NY: John Wiley and Sons, 1981. [12] Miura K, Hashimoto K, Silveston PL. Fuel 1989; 68:1461. [13] Calemma V, Radovic LR. Fuel 1991; 70:1027. [14] Essenhigh RH. Fundamentals of coal combustion. Chemistry of Coal Utilization, 2. NY: John Wiley and Sons, 1981. [15] Patel MM, Grow DT, Young BC. Fuel 1988; 67:165. [16] Alvarez T, Fuertes AB, Pis JJ, Ehrburger P. Fuel 1995; 74:729. [17] Su JL, Perlmutter DD. AIChE Journal 1985; 31:973. [18] Shiao SY, Warchol JJ, Perna MA, Chandran RR. Proceedings of the 10 th International Conference on Fluidized Bed Combustion. San Francisco, 1989. p. 23. [19] Bannin VE, Moors R, Veekind B. Fuel 1997; 76:945. [20] Lu Y. Energy and Fuels 1996; 10:248. [21] Smith IW, Tyler RJ. Combustion Science and Technology 1974; 9:7.