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Fuel Processing Technology 87 (2006) 531 538 www.elsevier.

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Fuel conversion from oxy-fuel combustion in a circulating fluidized bed


T. Czakiert a , Z. Bis b , W. Muskala a , W. Nowak a,
a

Department of Heating, Ventilation and Air Protection, Czestochowa University of Technology, Dabrowskigo 73, 42-200 Czestochowa, Poland b Department of Energy Engineering, Czestochowa University of Technology, Brzeznicka 60A, 42-200 Czestochowa, Poland Received 17 October 2005; received in revised form 20 October 2005; accepted 14 December 2005

Abstract The study of the combustion process carried out in an oxygen-enriched atmosphere in a circulating fluidized bed (CFB) combustor is presented. The experiments were focused on fuel behavior in the conditions of increased oxygen concentration, at a different temperature and a different fuel load in the combustion chamber. The tests were performed in a laboratory-scale CFB combustor. Brown coal was used as the fuel. The values of variable parameters were in the following ranges: the oxygen concentration in the delivered stream of gas substrates (mixtures of O2 + N2 and O2 + CO2): 21 60%; the combustor's temperature: 973 1133 K; the mass of fuel portions: 4 8 g. Based on the obtained data, carbon, sulfur and nitrogen conversion ratios were calculated. 2006 Elsevier B.V. All rights reserved.
Keywords: Circulating fluidized bed; Oxygen-enriched; Conversion ratio

1. Introduction The main purpose of the oxygen-enriched combustion process is to obtain the highest CO2 concentration in the flue gas that lead to easier and cheaper CO2 separation from the flue gas [13]. Other advantages of oxygen-enriched combustion include, for example, a higher combustion efficiency resulting from the higher oxygen concentration in the combustion chamber [4,5], or a higher thermal efficiency of the boiler owing to the reduction in the volume of the flue gas leaving the combustion chamber [6,7]. A positive feature of the oxygenenriched combustion, which is especially important in the case of the CFB boilers, is also a possibility of utilizing different kinds of fuels, especially low-rank fuels. Apart from the economical advantage, the use of low calorific-value fuels has an additional advantage, i.e. the capability to obtain a lower adiabatic combustion temperature. This is important because the difficulties with temperature control and heat transfer are the major problems connected with this combustion process [810]. In fact, there are well known solutions applied in pulverizedfuel boilers, where flue gas recirculation is used for temperature control [1113]. However, such a method requires a prelimi Corresponding author. E-mail address: wnowak@is.pcz.czest.pl (W. Nowak). 0378-3820/$ - see front matter 2006 Elsevier B.V. All rights reserved. doi:10.1016/j.fuproc.2005.12.003

nary treatment of the recirculated gases, i.e. the elimination of gaseous pollutants and fly ash, as well as the moisture. On the one hand, the flue gas treatment is quite difficult and, on the other hand, it is also rather expensive. Because of that, it can be anticipated that CFB boilers, with their specific feature, will successfully face the problems, where the presence of the bed material makes the temperature control easier [14]. However, due to the nature of oxygen-enriched combustion, the construction of CFB boilers, as well as the organization of the fluidization process and fuel combustion, would be significantly different from those in the conventional CFB systems. Moreover, it is characteristic of PC boilers that the total fuel conversion ratio depends in this case directly on the time during which a coal particle covers the path along the combustion chamber once. Whereas, in CFB systems, where the cyclicality of the process concerns both the bed material and the fuel, the coal particle has the possibility of being burn-up during its successive residences in the combustion chamber [15]. However, considering the fuel as the volatile matter and the char separately, it should be noted that only char recycled to the combustion chamber as one of the components of the circulating fluidized-bed material has the possibility of being secondarily burn-up; whereas, for the volatile matter the first cycle of the circulation loop is the only one, at the same time (as is the case in PC boilers), thus being crucial from the point of

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view of their combustion. Hence, as the research methodology considers the separate analysis of the process of combustion of the volatile matter and the char, the below-described results of the carbon, sulfur and nitrogen conversion ratios refer only to the first cycle of the combustion chamber return system combustion chamber circulation loop. In fact, many papers [1620] deal with fuel conversion as well as pollutant emissions from oxygen-enriched combustion, however the studies are closely related to PC boiler technology. Whereas, the below-described results treat about fuel behavior in CFB combustion under oxygen-enriched conditions. 2. Control of C, S, N conversion For a solid fuel it can be assumed that its components (including C, S, N) are distributed in its structure between the volatile matter and the char [21,22]. The process of combustion of such a fuel usually follows the following time scheme: i) heating of the particle and evaporation of moisture, ii) release and combustion of volatile matter, iii) combustion of char. In practice, the end of combustion of volatile matter and the beginning of char combustion overlap, which is determined chiefly by the particle size. For the fuel in a dry state it can be assumed that the conversion ratio of its main components (sulfur, nitrogen) contained in the volatile matter and the char depends directly on the carbon conversion ratio identified with the fuel conversion ratio. This assumption provides grounds for the creation of the graphical relationship, which is shown in Fig. 1. The above-mentioned relations are described by the line: i) 0-S1-3 when the volatile matter contains a larger part of the total fuel sulfur, ii) 0-S2-3 when the volatile matter contains a smaller part of the fuel S, iii) 0-3 when the distribution of sulfur in the volatile matter and in the char is uniform. The coordinates of points S1 and S2 correspond to the carbon (horizontal axes) and the sulfur (vertical axes) fraction of the volatile matter for the majority and the minority sulfur share in the volatile matter, respectively. Points of the coordinates (XC, XS) represent the obtained results for the S to SO2 conversion ratio at a given fuel conversion ratio. In turn,

lines 0-1-2-3 and 0-1-2-3 describe the fuel combustion process, respectively, for the majority and the minority sulfur share in the volatile matter, where, at a certain stage, the processes of conversion of the volatile matter and the char progress in parallel. Thus, the contour of triangle 0-S1-3-0, for the case under analysis where a larger part of the total fuel sulfur is contained in the volatile matter (see Table 2), delineates the region for possible locations of the points representing the sulfur conversion ratio. When the measurement point lies: i) on line 0-S1, this means that only sulfur contained in the volatile matter has undergone conversion; ii) on line 0-S3, this means that the sulfur contained in the volatile matter has undergone complete conversion and the combustion of the char is underway; iii) within triangle 0-S1-3-0, this means that the sulfur contained in the volatile matter and in the char has undergone partial conversion; iv) above line 0-S1-3, this means that the values of coordinates XC or/and XS are burdened with error; and v) below line 0-3, this may indicate a delayed release of sulfur during fuel devolatilization (at the end of volatile matter liberation). In fact, the coal nature has a great influence on combustion of sulfur contained in both: the volatile matter and the char. In the event of fuels where majority of total-S is contained in the char for instance, the process of char combustion can effect V the sulfur conversion. Thus, the estimated values of XS and Char XS can be burden with error. However in case of selected fuel, the distribution of sulfur in the volatile matter and in the char is almost uniform, therefore the described method of calculations can be apply. The diagram in Fig. 1 can also be used in the analysis of the conversion ratio of fuel nitrogen. In that case, only point S (XC, XS) needs to be substituted with point N of coordinates (XC, XN), where XN represents the nitrogen fraction of the volatile matter. The only difference in the interpretation of the results in this case is the possibility of the measurement point taking on a position above line 0-N1-3, which would indicate the conversion of the nitrogen from the gas supplied (NOx-thermal). 3. Experimental 3.1. Experimental apparatus

1,0 0,9 0,8 0,7

2 XS 1
1

XS, (-)

0,6 0,5 0,4 0,3 0,2 0,1

S1

2' XS 1'
0,1 0,2
2

0,0 0 0,0

S2 1 2 XC XC
0,3 0,4 0,5 0,6 0,7 0,8 0,9 1,0

XC, (-)
Fig. 1. Diagram of C, S, N conversion.

The tests dealt with the emissions of main gases originating from the combustion of coal, i.e. CO2 and CO, as well as SO2 and NOx. The investigations were conducted in a laboratoryscale on a test stand with a circulating fluidized bed, as shown in Fig. 2. The main element of the test stand is a vertical column made from a cylindrical quartz glass tube, 1.7 m high and with an inner diameter of 0.05 m, which is encased in three segments of heaters. The whole construction is based on an electrically heated ceramic grid. The upper part of the column is connected to a return system, which comprises a cyclone used for solids separation (bed material, ash and unburned fuel) from the exhaust gas going out of the system and three valves: a feed valve, a drain valve and a flow regulating valve. Component gases for making the gas mixtures are delivered from gas

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22 23 T4 19 5 20 21 T3 4 6 AIR 7 1 9 10 11 12 EXHAUST GAS

533

O2

N2

CO2

T2 3 8 FUEL 13 T1 15

17

18 2 T0

16

14

Fig. 2. Schematic diagram of the experimental apparatus for CFB. 1. combustion chamber, 2. grid, 3. heaters, 4. thermal insulation, 5. cyclone, 6. feed valve, 7. drain valve, 8. flow regulating valve, 9. air compressor, 10. gas cylinders, 11(14). ball valves, 12(15,17). flow meter, 13. flow mixer, 16. preheater, 18. fuel feeder, 19. temperature measuring system, 20. heater power system, 21. heater control system, 22. probe, 23. gas analyzer, T0T4 thermocouples.

cylinders to a mixer, and then through a main heater directly to the CFB system. The gas mixture is fed to two different points, below the grid, and to the return system. In the present experiments the gas mixtures were based on N2 and CO2 with oxygen, where the O2 concentrations amounted to 21%, 40% and 60% in the consecutive variants. The fuel was fed in a pulse manner by a feeder located immediately above the grid. Brown coal was selected as the fuel, and its properties are presented in Tables 1 and 2. For successive variants, the mass of fuel portions fed into the combustor was 4, 6 and 8 g, respectively. The coal samples were fed periodically, i.e. the sample was fed after completed burnout of the previous portion. The temperature measurement along the CFB column was carried out at four different levels, and the whole heating system was controlled by a computer. For the measurements taken, the temperature was in the range from 973 to 1133 K. For the determination of the exhaust gas components, two Mahiak analyzers were employed (Multor 610 and Finor 710), which enabled a continuous measurement of flue gas con-

centration changes in respect of such substances, as O2, CO2, CO, NOx and SO2. 3.2. Combustion experiments At the beginning, the combustion of fuel samples of the smallest mass (4 g) was investigated. The reactor was operating with air at the temperature of 973 K. For the following tests the reactor's temperature was raised up to 1053 K and then to 1133 K. After that, the gas mixture of 40% O2 + 60% N2 was delivered into the reactor and the measurements were taken for each temperatures i.e. 973, 1053 and 1133 K, respectively. The last tests were carried out with 60% O240% N2 mixture at different temperature levels as above. The whole experimental procedure was repeated first for fuel sample mass of 6 and 8 g and then for gas mixtures based on O2 + CO2. Several repetitions were done in each case. During the tests, the on-line determination of the flue gas components (CO2, CO, SO2 and NOx) was applied.

Table 1 Proximate and ultimate analyses of brown coal Size [m] CV [kJ/ kg] Proximate [wt.%, DB] FC VM ASH Ultimate [wt.%, DAF] C H S N O (by diff.)

Table 2 Distribution of total carbon, sulfur and nitrogen in the volatile matter and in the char (dry-ash-free basis) Carbon [wt.%] Volatile matter Char 37 63 Sulfur [wt.%] 60 40 Nitrogen [wt.%] 55 45

01200 11,953 37.58 36.36 26.06 71.95 8.48 0.74 0.45 18.38

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measurement

flue gases

CO2 concentration (%)

CFB
4

1'

1 O2, CO2, CO, NOx, SO2 analyzers

t 0-1 - t delay t 0-1'-0 - t n-cycle


t 1st cycle t 2nd cycle

coal

1
tdelay

inlet gas
20 30 40 50 60 70 80 90 100

0 0 10

Time (s)
Fig. 3. Example of CO2 fluctuations in the flue gas.

The fluctuations in the concentration of all abovementioned flue gas components, as recorded during the tests, confirmed a cyclic nature of circulating fluidization processes. An example of CO2 fluctuation is shown in Fig. 3. Such behaviour of the combustion process is a result of the bed material being recycled to the combustion chamber, which includes unburned coal separated from the flue gas in the cyclone. As can be seen in Fig. 3, the first cycle is significantly different from the others, and this remains true for all flue gas components analyzed. The above-mentioned relationship has a direct impact on the coal conversion ratio, which was each time considerably high in the first cycle of the circulation loop, compared to the total fuel conversion ratio. Furthermore, it is worthy of noting that the final calculation of the total conversion ratio for the following tests usually showed values lower than 100%, which was chiefly a consequence of the cyclone separation efficiency in the CFB system. Additionally, and what is also very important especially in respect of the present analysis, the first cycle combines the conversion of both the volatile matter and the char, whereas the appearance of the subsequent cycles can only provide evidence for further burning up of the char. The above-mentioned relationships are the main reasons for the present analysis being only focused on the first cycle of the fuel sample passing over the circulation loop. 3.3. Calculations of the conversion ratios The emissions of CO2 and CO were recalculated into the conversion ratio of carbon (XC) included in the fuel portion fed into the combustor, and the emissions of SO2 and NOx were recalculated into the conversion ratio of sulfur (XS) and nitrogen (XN), respectively. In each of the cases, the conversion ratio was expressed in [kmol] of carbon, sulfur or nitrogen (contained in the released CO2 and CO, SO2, NOx) related to [kmol] of C, S, N in the fed fuel sample for XC, XS and XN, respectively. The calculations were based on the following equations (where x stands for C, S or N and A stands for

CO2 + CO, SO2 or NOx in the case of XC, XS and XN, respectively): XX nW X V nX 1

where:

n"X

N V SP = [ A] [kmol], 22,41

[ ]

V mp d nX

x kmol; MX

[A] =

1 t

[A()]d.
0

4. Results and discussion 4.1. Carbon conversion ratio The carbon conversion ratio for mixtures based on CO2 with different oxygen concentrations and at a different temperature of the reactor is presented in Fig. 4. On the one hand, it can be seen that the carbon conversion ratio increases with an increase of oxygen concentration in the gas mixture delivered into the combustion chamber, and this relationship maintains regardless the reactor's temperature level. The reason for this is the increase in the combustion rate caused by an increase in partial oxygen pressure. On the other hand, it can be noticed that irrespective of the oxygen concentration in the combustion chamber, increasing temperature of the reactor has no effect on the carbon conversion ratio. The obtained data show that the oxygen concentration in the gas delivered into the reactor is crucial for the investigated process of fuel sample combustion in such conditions. The O2 fraction of the gas mixture determines

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1,0 0,9 0,8 0,7
21% O2 + 79% CO2, 4g 40% O2 + 60% CO2, 4g 60% O2 + 40% CO2, 4g

535

1,0 0,9
21% O2 + 79% CO2, 1133K 40% O2 + 60% CO2, 1133K 60% O2 + 40% CO2, 1133K 21% O2 + 79% N2, 1133K 40% O2 + 60% N2, 1133K 60% O2 + 40% N2, 1133K

CHAR

0,7

XC (-)

0,6 0,5 0,4 0,3

XC (-)

0,6 0,5 0,4 0,3

VM

0,2 0,1 0,0 973 1053 1133

0,2 0,1 0,0 0,0 0,1 0,2 0,3 0,4 0,5 0,6

Temperature (K)
Fig. 4. Effect of temperature and oxygen concentration on the carbon conversion ratio.

(-)
Fig. 5. Effect of fuel sample mass and inlet gas mixture composition on the carbon conversion ratio.

both: effectiveness and rate of diffusion of oxygen molecules towards a coal particle. In the first stage, higher concentration of oxygen molecules close to a surface of fuel particle is conductive to reaction of C with O2 to CO that leads to higher temperature of the fuel particle. Furthermore because of facilitated diffusion of oxygen, the distance between the fuel particle surface and the zone where CO reacts with O2 is shorter that results in further increase of temperature of the fuel particle. Finally, the increase of temperature of coal particle surrounded by gas of high oxygen concentration leads to the increase in combustion rate. It can also be seen in Fig. 4 that in each of the variants the carbon conversion ratio reaches (or is close to) the values exceeding the level defined by the carbon fraction of the volatile matter. It is also known that in the case of fine fuel particles (as in the tests described see Table 1), their gradient-less heating can be assumed, where the whole amount of volatile matter releases at once in the process of fuel devolatilization. Thus, this suggests that in the first cycle of circulation loop, analyzed here, the whole amount of volatile matter releases from the fuel matrix (which, however, does not necessary mean its complete burning) and the char conversion starts. The effect of fuel sample mass and the composition of the gas mixture delivered to the CFB combustor on the carbon conversion ratio is represented by the XC relationship (Fig. 5), where fuel ratio is defined (Eq. (5)) such that it increases with increasing fuel sample mass, but decreases with increasing oxygen concentration in the gas mixture. u mp n Omin d : s nsub V d zO 5

overall effect led to the appearance of so-called thermal wave which carried away part of the bed material (including the unburned fuel) from the combustion chamber to the return system where, due to the lack of oxygen, the combustion process ceased. Thus, the decrease of fuel conversion ratio was obtained because of shortening the time of fuel residence in the combustion zone. It can be also noticed that the carbon conversion ratio is slightly lower, when the combustion process is conducted in gas mixtures based on CO2 with an oxygen concentration identical to the one in the case of N2-based mixtures. Reasons for this can be found in Boudouard's reaction, where, at a high CO2 concentration and in the presence of elementary carbon, the carbon dioxide is reduced to CO, which leads to slowing down the combustion process. This might cause a decomposition of CO2 as an inlet gas constituent, or CO2 as the final product of the combustion process, where the endothermic nature of this reaction has the effect of lowering the temperature in the combustion zone. Thus, regarding the kinetics of this reaction, the required energy is drawn from the hot flue gases. 4.2. Sulfur conversion ratio In fact, 90% (or even 95%) of total sulfur contained in the fuel is converted to SOx in case of conventional CFB boilers operating with air. However, several percent of fuelS fixed strongly in some mineral components of ash is found in the bottom/fly ash removing from the boiler. In contrast for oxygen-enriched combustion, the completed conversion of sulfur can be expected because of higher temperature of fuel particles as mentioned above. The relation of the sulfur conversion ratio with the carbon conversion ratio was used as a basis for analyses of the sulfur conversion ratio, as defined in Eq. (1). This approach made also possible to perform separate analyses for the conversion ratio of sulfur both contained in the volatile matter and combined in the char. Thus, in addition to the ultimate analysis of coal (Table 1), it was necessary to determine the contents of S, N and carbon combined in the char (see Table 2). For the specimen test, a LECO analyzer was employed.

It can be seen that the carbon conversion ratio decreases with increasing fuel sample mass. This effect is greater, when there is a higher O2 concentration in the gas mixture. This can be caused by a local increase in temperature, whose value depends directly on the mass of the fuel fed and the oxygen concentration in the delivered gas mixture (an increase in the combustion rate). The local increase of the temperature in the combustion zone results in a local increase in both the volume of gas and its velocity. The

VM

CHAR

0,8

536
1,0 0,9 0,8 0,7
char XS

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1,0
XS = 1
V

1'
C (O2 )

B 2

0,9 0,8 0,7

O2+ N2 mp = 6g XS XS
Char V

2' = 2

XS (-)

0,6 0,5 0,4 0,3 0,2 0,1

(-)
2' 1
V

S1 O2+ N2 mp= 4g Tw 973 K 1053 K 1133 K

Char

0,6 0,5 0,4 0,3 0,2 0,1 0,0 21 40 60


T T T

1'

0,0 A 0,0 0,1 0,2 0,3 0,4 0,5 0,6 0,7 0,8 0,9 1,0

XC (-)
Fig. 6. Sulfur conversion ratio (O2 + N2 mixtures).

XS ,XS

O2 (%)
Fig. 8. Sulfur conversion ratio for the volatile matter and for the char (O2 + N2 mixtures).

The sulfur conversion ratio for mixtures based on N2 with a different oxygen concentration and at a different temperature is shown in Fig. 6. The results for O2 + CO2 mixtures are presented in Fig. 7. As can be seen in most of the cases, the measurement points lie within triangle AS1B. In fact, thus defined area should include all points of sulfurcarbon conversion ratios. In one of the cases, however, for the lowest fuel sample mass, the lowest temperature and the highest oxygen concentration in the gas mixture, a measurement point was outside the triangle. One of the causes could be sought in the low combustor temperature, which favours the emission of sulfur in the form of other compounds (e.g. H2S). Another cause could be the high oxygen concentration, which may lead to the formation of SO3. However, none of the above-mentioned compounds (H2S, SO3) was measured in the tests. The location of the measurement points suggests also that an increased oxygen concentration in the gas mixture improves the conversion of sulfur to SO2. Furthermore, the effect of increasing temperature on the increase of the sulfur conversion ratio can be seen, whereby at a temperature of 1133 K almost complete conversion of sulfur takes place. V Based on the assumption (XS = 1 : 1 and XS char = 2 : 2) presented in Fig. 6, it was possible to estimate the sulfur conversion ratio separately for the volatile matter and for the V char (as defined according to the description in Fig. 6). Both XS char and XS are shown in Figs. 8 and 9, for O2 + N2 and O2 + CO2
1,0 0,9 0,8 0,7
S1 O2+ CO2 mp = 4g Tw 973 K 1053 K 1133 K C (O2) B

mixtures, respectively. It is easy to notice the effect of temperature on the conversion ratio of sulfur contained in the V volatile matter (XS ). Whereas, it is rather difficult to see a V relation between XS and the oxygen concentration in the gas mixture. The above-mentioned trends provide evidence for a kinetic behaviour of volatile matter combustion. This statement was also confirmed by the observation of the combustion process, whereby it was easy to notice that the combustion of the volatile matter took place immediately on the surface of devolatilized coal particles. It is understandable, because the rate of combustion of volatile matter is in this case higher than the rate of its formation and release from the fuel particle. Different relationships can be observed for the ratio of conversion of sulfur combined in the char (XS Char). The values of XS Char increase with increasing O2 concentration in the gas mixture delivered to the combustion chamber. This trend indicates diffusion behaviour of char combustion. Furthermore, the opposite relationship between XS Char and temperature is observed. As has been mentioned above, with increasing combustor temperature the volatile matter burn-up also increases. This resulted in higher local increases in temperature. As a result, a local increase in the volume of gas and its velocity and

1,0 0,9 0,8 0,7


O2+ CO2 mp = 6g XS XS
Char V

(-)
Char V

0,6 0,5 0,4 0,3 0,2 0,1 0,0 21 40 60


T T T

XS (-)

0,6 0,5 0,4 0,3 0,2 0,1 0,0 A 0,0

0,1 0,2 0,3 0,4 0,5 0,6 0,7 0,8 0,9 1,0

XS ,XS

XC (-)
Fig. 7. Sulfur conversion ratio (O2 + CO2 mixtures).

O2 (%)
Fig. 9. Sulfur conversion ratio for the volatile matter and for the char (O2 + CO2 mixtures).

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an increase in the power of so-called thermal wave could be observed, which had the effect of shortening the time of char residence in the combustion chamber. It should be noticed that the relationships between the sulfur conversion ratios for the O2 + N2 and O2 + CO2 mixtures, as shown in Figs. 6 and 7, as well as in Figs. 8 and 9, show a qualitative similarity of the processes described, and suggest that the quantitative differences stem from the different fuel burn-up resulted from the different inlet gas composition (Fig. 5). 4.3. Nitrogen conversion ratio Taking into consideration the assumptions taken for the analyses of sulfur conversion, the nitrogen conversion ratio (XN) was calculated (Eqs. (1)(4)). The values of XN in the function of XC with different oxygen concentrations and at different temperatures are presented in Fig. 10 (O2 + N2 mixture) and Fig. 11 (O2 + CO2 mixture). It is easy to notice significant differences in the location of measurement points compared to the sulfur conversion ratio analyzed previously. It is worthy of noting that there are no measurement points in the area above triangle AN1B. This means that it is impossible to demonstrate the presence of the NOx thermal mechanism. Furthermore, it can be seen that the points describing the nitrogen conversion do not lie within the borders delimited by triangle AN1B, as was observed for sulfur. In fact, all measurement points are located below the base of the triangle. This behavior suggests a partial nitrogen conversion and the fact that it is intensified at the stage of fuel particle devolatilization and volatile matter combustion. This might result from the assumption that on the first stage of devolatilization the volatile matter only includes a small amount of fuelnitrogen, while most of or the whole amount of the fuelN appears in the volatile matter on the second stage of devolatilization. This possibility of fuel nitrogen conversion to NOx is represented by the dashed line in Fig. 10. The abovementioned behaviour causes also a superposition of fuel nitrogen conversion on the char combustion process. Thus, the presence of high-temperature char particles results in the reduction of NOx to N2, and so released oxygen is used again in the combustion process. It can be easily noticed that the
1,0 0,9 0,8 0,7
O2+ N2 mp= 8g Tw 973 K 1053 K 1133 K N1 C (O2) B

1,0 0,9 0,8 0,7


O2+ CO2 mp= 8g Tw 973 K 1053 K 1133 K N1 C (O2) B

XN (-)

0,6 0,5 0,4 0,3 0,2 0,1

0,0 A 0,0 0,1 0,2 0,3 0,4

0,5 0,6 0,7 0,8 0,9 1,0

XC (-)
Fig. 11. Nitrogen conversion ratio (O2 + CO2 mixtures).

distance between the points representing the calculated sulfur conversion ratio and the region (triangle AN1BA) for locations of the points representing the expected sulfur conversion ratio is longer for lower fuel conversion ratios (the beginning of the combustion), it means for coarse fuel particle where combustion of volatile matter close to the particle surface leads to the increase of temperature of fuel particle. Whereas, the distance is shorter for higher XC (the progress of char conversion), i.e. for shrank fuel particle when the combustion of volatile matter is almost finished. Such behavior could confirm the reduction of NOx to N2 in the presence of char in the initial phase of combustion. Other explanation of such low level of NOx can be NOCO reaction, since it is assumed that Boudouard's reaction takes place under experimental conditions. The higher concentration of CO (as the product of Boudouard's reaction) can lead to the reduction of NO to N2. Similarly as for the analyses of the sulfur conversion ratio, also in the case of nitrogen conversion a qualitative similarity can be observed for mixtures based on nitrogen and CO2 (Figs. 10 and 11, respectively), with the quantitative differences being caused by a different fuel burn-up for the O2 + N2 and O2 + CO2 inlet gases. 5. Conclusions The results of the experiments have enabled us to formulate the following conclusions: 1. The ratio of carbon conversion to CO2 and CO in the first cycle of the fuel sample passing through the circulation loop increases with an increase of oxygen concentration in the combustion chamber, and it does not practically change with the variations in combustor temperature. Thus, the oxygen concentration is crucial. This improves conditions of oxygen diffusion as well as influences on the increase of temperature of fuel particles, thereby the combustion rate increases. 2. The ratio of carbon conversion in O2 + N2 mixtures is always higher than for O2 + CO2 mixtures, at the same oxygen concentration and combustor temperature. 3. Coal combustion under oxygen-enriched conditions promotes the increase of the conversion of sulfur combined in

XN (-)

0,6 0,5 0,4 0,3 0,2 0,1

0,0 A 0,0 0,1 0,2 0,3 0,4

0,5 0,6 0,7 0,8 0,9 1,0

XC (-)
Fig. 10. Nitrogen conversion ratio (O2 + N2 mixtures).

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T. Czakiert et al. / Fuel Processing Technology 87 (2006) 531538 [5] N. Kimura, K. Omata, T. Kiga, S. Takano, S. Shikisima, The characteristics of pulverized coal combustion in O2/CO2 mixtures for CO2 recovery, Energy Conversion and Management 36 (1995) 805808. [6] S. Takano, T. Kiga, Y. Endo, S. Miyamae, K. Suzuki, CO2 recovery from PCF power plant with O2/CO2 combustion process, IHI Engineering Review 28 (1995) 160164. [7] Y. Tan, M.A. Douglas, K.V. Thambimuthu, CO2 capture using oxygen enhanced combustion strategies for natural gas power plants, Fuel 81 (2002) 10071016. [8] C.E. Baukal, Oxygen-Enhanced Combustion, CRC Press LLC, USA, 1998. [9] T. Kiga, S. Takano, N. Kimura, K. Omata, M. Okawa, T. Mori, M. Kato, Characteristics of pulverized-coal combustion in the system of oxygen/ recycled flue gas combustion, Energy Conversion and Management 38 (1997) S129S134 (Supplement). [10] Y. Shao, D. Golomb, Power plants with CO2 capture using integrated air separation and flue gas recycling, Energy Conversion and Management 37 (1996) 903908. [11] E. Croiset, K.V. Thambimuthu, NOx and SO2 emissions from O2/CO2 recycle coal combustion, Fuel 80 (2001) 21172121. [12] L. Hao, K. Okazaki, Simultaneous easy CO2 recovery and drastic reduction of SOx and NOx in O2/CO2 coal combustion with heat recirculation, Fuel 82 (2003) 14271436. [13] Y.Q. Hu, N. Kobayashi, M. Hasatani, Effects of coal properties on recycled-NOx reduction in coal combustion with O2/recycled flue gas, Energy Conversion and Management 44 (2003) 23312340. [14] T. Czakiert, R. Kobylecki, Z. Bis, W. Nowak, Oxy-fuel combustion, The 2nd International Conference on Contemporary Problems of Thermal Engineering, Ustron, Poland, 2004, pp. 7582. [15] W. Lin, C.E. Weinell, P.F.B. Hansen, K. Dam-Johansen, Hydrodynamics of a commercial scale CFB boiler-study with radioactive tracer particles, Chemical Engineering Science 54 (1999) 54955506. [16] C.E. Baukal, V.Y. Gershtein, P.B. Eleazer, Low NOx with oxygen-enriched combustion in high N2 environments, The JFRC/AFRC Symposium on Combustion, Hawaii, USA, 1998, pp. 112. [17] K. Kimura, S. Takano, T. Kiga, S. Miyamae, Experimental studies on pulverized coal combustion with oxygen/flue gas recycle for CO2 recovery, The JSME-ASME International Conference on Power Engineering-93, Tokyo, Japan, 1993, pp. 487492. [18] T. Nozaki, S. Takano, T. Kiga, K. Omata, N. Kimura, Analysis of the flame formed during oxidation of pulverized coal by an O2CO2 mixture, Energy 22 (1997) 199205. [19] K. Okazaki, T. Ando, NOx reduction mechanism in coal combustion with recycled CO2, Energy 22 (1997) 207215. [20] L. Zheng, E. Furimsky, Assessment of coal combustion in O2+CO2 by equilibrium calculations, Fuel Processing Technology 81 (2003) 2334. [21] S. Chaiklangmuang, J.M. Jones, M. Pourkashanian, A. Williams, Conversion of volatile-nitrogen and char-nitrogen to NO during combustion, Fuel 81 (2002) 23632369. [22] P. Kilpinen, S. Kallio, J. Konttinnen, V. Barisic, Char-nitrogen oxidation under fluidised bed combustion conditions: single particle studies, Fuel 81 (2002) 23492362.

the fuel. Because of higher temperature of fuel particles, there is a little probability of sulfur-to-mineral components of ash (contained in the fuel) bonding. 4. A positive phenomenon found during the oxy-fuel combustion process is a significant limitation of fuelnitrogen conversion to NOx. Denotations m mass, kg M molar mass of the substance, kmol kg 1 n stoichiometric amount of the substance, kmol kg 1 n amount of the substance in the fuel sample, kmol n amount of the substance in the flue gas, kmol nsub V inlet gas mixture flow rate, kmol s 1 t time, s 3 1 VN flue gas flow rate, mN s SP X conversion ratio of the substance, Xchar conversion ratio of the substances combined in the char, XV conversion ratio of the substance contained in the volatile matter, z concentration of the substances in the inlet gas mixture, % fuel ratio, combustion time, s average concentration of the substance in flue gas, % [] Subscripts c carbon n nitrogen min minimal o oxygen p fuel s sulfur References
[1] E. Croiset, K.V. Thambimuthu, A novel strategy for greenhouse gas abatement in coal-fired power plants: enriched oxygen combustion, The Combustion Canada' 99, Calgary, Canada, 1999. [2] Y. Hu, S. Naito, N. Kobayashi, M. Hasatani, CO2, NOx and SO2 emissions from the combustion of coal with high oxygen concentration gases, Fuel 79 (2000) 19251932. [3] Y.Q. Hu, N. Kobayashi, M. Hasatani, The reduction of recycled-NOx in coal combustion with O2/recycled flue gas under low recycling ratio, Fuel 80 (2001) 18511855. [4] Y.Q. Hu, H. Nikzat, M. Nawata, N. Kobayashi, M. Hasatani, The characteristics of coal-char oxidation under high partial pressure of oxygen, Fuel 80 (2001) 21112116.