EVALUATION OF THE CO2 REACTIVITY OF CHARS OBTAINED UNDER CONVENTIONAL (O2/N2) AND OXY-FUEL (O2/CO2) ATMOSPHERES

Juliana G. Pohlmann, Eduardo Osrio, Antonio C. F. Vilela, Angeles G. Borrego** Iron and Steelmaking Laboratory, UFRGS, P.O. Box 15021, 91501-970, Porto Alegre, Brazil. E-mail address: Juliana.pohlmann@ufrgs.br ** National Institute of Carbon (INCAR), CSIC, P.O. Box 73, 33080, Oviedo, Spain. ABSTRACT New technologies have been studied to improve pulverized coal injection (PCI) and to make ironmaking process suitable to environmental requirements. Oxyfuel combustion technology consists of burning coal in an N2-free atmosphere, which is exchanged by a CO2rich gas. This technology has already been studied and developed for coal-fired power plants. It allows CO2 concentration in the flue gas and a significant portion of it could be recycled. Aiming at a possible application of oxy-fuel combustion in the blast furnace context, chars of three typical PCI coals of different ranks were obtained under conventional (O2/N2) and oxy-fuel (O2/CO2) atmospheres in a drop tube furnace (DTF). The aim of this work was to evaluate the CO2 reactivity of these chars via thermogravimetric analysis by isothermal method at 1000C. Coal burnouts, BET surface areas and the morphologies of the chars before gasification gave support on the results of the reactivity analysis. The chars behavior in all tests was strongly influenced by coal rank. In general, the higher reactivities were observed for the lower rank coal chars. The CO2 reactivity of chars increased when coal burnouts also increased. There was no effect in burnout because of the N2 replacement (conventional atmosphere) by CO2 (oxy-fuel atmosphere). As for the CO2 reactivity results, differences were only found between the conventional and oxy-fuel chars for the highly burnt lower rank coal chars due to the higher BET surface area of the oxy-fuel char. 1. INTRODUCTION Pulverized coal injection (PCI) is used in blast furnace tuyeres aiming at coke substitution and attempting to provide energy and reducing gases to the process. In high rates of PCI, due to extremely short residence time available for char combustion in the blast furnace, unburnt char will be carried from the combustion zone to the shaft, where it will compete with coke for CO21). Excessive amounts of unburnt material, leads to problems in the furnace permeability, decreasing productivity2). Nevertheless, high rates of PCI are desirable to reduce coke utilization and pig iron costs3). Then, an increase in the injection rate must be related to higher combustion efficiency to avoid an increase in unburnt char. Coal ranging from high to low rank, different injection lances design, different blast conditions (flame temperature and

stoichiometry oxygen ratio) and the injection of other fuels have been studied to improve combustion conditions4,5). There is international concern about substantial decrease in greenhouse gases emissions in ironmaking6). Increasing combustion efficiency and unburnt char consumption via solution loss reaction in the blast furnace shaft is important since it could lead to a decrease in fuel rate, increasing blast furnace productivity and releasing less CO2 to atmosphere. In this way, the optimization of PCI could decrease the environmental impact caused by ironmaking industries. Oxy-fuel combustion technology consists of burning coal in an N2-free atmosphere and oxygen is usually diluted by recycled flue gas rich in CO27). The characteristics of oxyfuel combustion differ from conventional combustion in several aspects8). Studies about oxy-fuel technology have mainly assessed the feasibility and economic aspects to applications in retrofits and new power plants. In this way, many studies have been done comparing char differences between conventional (O2/N2) and oxy-fuel atmospheres (O2/CO2). The reactivity of australian coal chars obtained under O2/N2 and O2/CO2 environments in DTF at 1400C and oxygen concentration ranging from 3 to 30% vol. was measured in a thermobalance by Rathnam and others9). They observed similar and higher burnouts in DTF when coals were produced under oxy-fuel conditions. The BET surface area of chars was also higher in the chars obtained under oxy-fuel conditions and SEM analysis of chars indicated more reacted particles in the O2/CO2 chars, because of the particle reaction of the carbon with CO2. Borrego and Alvarez10) have studied the influence of gas composition and oxygen concentration during the preparation of coal chars in a drop tube furnace. The chars were prepared under different O2/N2 and O2/CO2 ratios (ranging from 3 to 21% oxygen) in DTF at 1300C. Coal burnouts of both series (O2/N2 and O2/CO2) were higher for the lower rank parent coal and the conventional chars compared to the oxy-fuel chars obtained under the same oxygen content. The authors also observed higher maceral reflectances and surface areas in O2/CO2 chars compared to the conventional ones obtained with a similar O2 content. The reactivity evaluated in thermobalance between the samples obtained under conventional and oxy-fuel atmospheres at the same O2 concentration was similar. The literature on char characteristics and reactivity in relation to its behavior in power station boilers is likely to provide a substantial basis to investigate char reactivity in a blast furnace context. This approach could be useful if oxy-fuel PCI injection may be possible. Coal would be injected in the tuyeres with a mixture of oxygen and recycled CO2, thus avoiding N2 and minimizing the step of concentrating CO2 in the flue gases. Therefore CO2 capturing technologies could be implemented in the steel industry11). The effects of CO2 injection in blast furnace tuyeres was studied using mathematical models. Austin and others12) found that to replace some of the blast gas volume with recycled furnace top gas and additional enriching oxygen could lead to an increase in the fuel rate. However, Castro and others13) indicated that CO2 injection combined with

oxygen enrichment, in certain proportions, could lead to an increase in productivity of the blast furnace process. In order to apply oxy-fuel technology in PCI, research is being done on char combustion in conventional and oxy-fuel atmospheres. The first step14) comprised of chars being prepared under different O2/N2 and O2/CO2 atmospheres in a DTF, simulating different conditions within the combustion zone. Following the first research step, the aim of this work was to evaluate the CO2 reactivity of these chars by thermogravimetric analysis, simulating the solution loss reaction out of the combustion zone. Coal burnouts, BET surface areas and the morphologies of the chars before gasification gave support on the results of the reactivity analysis. 2. EXPERIMENTAL The three selected coals range from high to low volatile bituminous and they are typical of imported PCI coals used in Brazil: Guasare (GU) (Venezuela), Black Water (BW) and Jellinbah (JB) (Australia). The characterization of the coals is shown in Table 1. Table 1 Proximate, ultimate and petrographic analysis of the individual fuels GU BW JB Ash 6.9 9.5 9.8 VM % db 39.6 26.5 15.9 Cfix 53.5 64.0 74.3 C 80.9 83.4 87.2 H 5.1 4.3 3.8 % daf N 1.6 2.0 1.9 O 11.3 10.6 5.6 S 1.1 0.7 0.7 Rr % 0.63 1.02 1.56 V 77.2 2.4 20.4 % vol L 61.8 2.8 35.4 mmf I 69.3 30.7
VM = volatile matter; Rr = random vitrinite reflectance; V = vitrinite; L = liptinite; I = inertinite; db = dry basis; daf = dry-ash-free basis; vol = volume; mmf = mineral matter-free.

Fig. 1 Scheme of the experimental approach followed for char preparation in this study compare conventional and oxy-fuel conditions. These three samples will be referred as one step chars. The 2.5% O2 chars were again fed into the reactor using 5% O2 in both N2 and CO2 to obtain a result for char combustion without any interference from the volatiles emitted. An atmosphere rich in CO2 was selected to represent the enrichment in CO2 occurring higher up the blast furnace. Burnout (B) was calculated using the ash tracer expression showed in Equation 115):
Ashcoal 100 Ashchar comb 100 B(%) = 1 100 Ashcoal Ashchar comb.

(1)

As shown in Table 1, the coals ash and sulfur contents are suitable to blast furnace utilization. The coals have low liptinite content and moderate inertinite content. Coal chars were prepared in a drop tube furnace described elsewhere10) at 1300C. Drop tube furnaces were developed to simulate coal reaction in power plants, but they can approach some conditions that prevail in the combustion zone. The gas compositions and sequence of experiments used in this study are summarized in Fig. 1. The flow rate was 900 l.h-1 plus 300 l.h-1 for the feeder, the feeding rate 1 g.min-1 and the estimated residence time around 200 ms. Coal was injected under highly sub-stoichiometric conditions (2.5% O2 in N2) to produce the release of volatiles and minimize soot generation. Coal was also injected under conditions close to combustion reaction stoichiometry (10% O2 in N2) to represent highly burned coal. The experiment under 10% O2 in CO2 was conceived to

in which, Ashcoal is the ash content in parent coal and Ashchar-comb. is the ash content in the combustion residue. The char samples were embeddeb in polyester resin and polished for petrographic examination under incident polarized light. The pore surface areas of carbon from gas adsorption isotherms were evaluated using N2 at 77 K as adsorptive. The equipment used was a Micromeritics ASAP 2020. The Brunauer-Emmett-Teller (BET) theory was applied to the N2 adsorption data to obtain the surface area. As some of the samples contained large amounts of mineral matter with different adsorption properties than the organic fraction, the isotherms were corrected for mineral effect. The CO2 reactivity of the chars was evaluated by thermogravimetric analysis in a STA 409 PC Luxx apparatus. A small quantity of char (8mg) was homogeneously spread on the bottom of the crucible and heated up to 1000C under nitrogen flow (60 ml.min-1) at a heating rate of 30C.mim-1. Immediately the reactant gas was changed to CO2 at the same flow rate and the temperature was maintained until weight stabilization. The weights were corrected for buoyancy effects. The reactivity at 50% of conversion on an ash-free basis was calculated using the expression R50% = 1/w0 (dw/dt)50%, with w0 being the initial sample weight, in milligrams, and (dw/dt)50% the reaction rate at 50% of conversion, in mg.s1 . 3. RESULTS AND DISCUSSION 3.1 Coal burnouts Coal burnouts obtained in the drop tube furnace at conventional and oxy-fuel atmospheres under different oxygen contents are showed in Fig. 2.

100 80 Burnout (% ) 60 40 20 0

*For Guasare, oxygen content was 10%

GU

BW

50 m

GU 2.5

GU 10

JB

Char 2.5%

Char 10%

Oxy-char Ref-char Ref-oxy Ref-oxy 10% 5%* 5% 10%

Fig. 2 Coals burnouts in conventional and oxy-fuel atmospheres at different oxygen contents The coal burnouts decreased as the rank of the coal inceased (Fig. 2). As expected, 2.5% O2/N2 chars (lower O2 content) had the lowest burnouts9,10). For BW and JB chars obtained under 1 step and the with the same O2 content (Char 10% and Oxy-char 10%), the burnouts of oxy-chars were very similar to burnouts of conventional chars. There is no agreement about a trend in burnout behavior comparing chars obtained under O2/N2 and O2/CO2 and same oxygen content. Different research groups have also found lower16), similar9,10) or higher9,10) burnouts for chars obtained under oxy-fuel atmospheres compared to conventional atmosphere. Moreover, differences between research groups also occur due to experimental conditions such as equipment type, residence time and temperature. Regarding the 2 steps oxy-chars prepared under different oxygen content, the samples obtained 10% O2 (Ref-oxy 10% O2) had higher burnouts than the ones prepared under 5% O2 (Ref-oxy 5%).The burnouts of the refired-chars and refired-oxy samples which were prepared under the same oxygen content were very similar: for GU at 10% O2 and BW and JB at 5% O2. The samples refired in 10% O2, independent of atmosphere, showed the higher burnouts because they experienced a higher oxygen content (1st step 2.5% O2 + 2nd step 10% O2). The above observations indicate that for the three coals studied here, the most important parameter in the combustion efficiency was the oxygen content in DTF atmosphere, independent of conventional (O2/N2) or oxy-fuel combustion conditions (O2/CO2). 3.2 Chars appearence in optical microscope The chars appearence in optical microscope are showed in Fig. 3, highlighting the differences mainly due to the coal type and oxygen content in DTF. Accordingly to Fig. 3, the chars had a cenospherical shape, typical of high heating rates17). Qualitatively, it can be observed that as the rank of the parent coal increases, the porosity of the produced chars decrease due to the release of volatiles. In lower oxygen concentration, the lower rank coal (GU) yielded chars consisting of isotropic texture, expected for a low rank coal, and thick-walled particles. The medium rank coal (BW) yielded chars of mainly anisotropic texture, but

BW 2.5

BW 10

JB 2.5 JB 10 Fig. 3 Appearence of the coal chars obtained under 2.5% and 10% O2 in N2 in DTF small isotropic domains and tick-walled particles. Chars generated from the high rank coal (JB) showed mainly anisotropic domains, due to the highly organized structure of this coal18). When the oxygen concentration in the reactor was 10% O2, the three coals showed texture and thickness similar to the 2.5% O2 chars, but, with more reacted surfaces. Differences between chars and oxychars obtained under the same oxygen content were not observed. 3.3 Surface area BET surface areas of chars are shown in Table 2. Due to the high percentage of ash in the samples, mainly in the high conversion tests, some surface areas were not evaluated. Table 2 BET surface areas of chars (m2.g-1) GU Char 2.5% Char 10% Oxy-char 10% Ref-char 5% Ref-oxy 5%
a

BW

JB

13,08 12,65 12,16 48,48 40,66 23,59 n.d. 36,54

a

n.d.

22,70 n.d. 20,06

20,30 13,97 n.d.

27,11 20,89 75,80

Ref-oxy 10%

For Guasare, oxygen content was 10%. n.d. not determined.

Of the three coals, the BET surface area of Char 10% was higher than the one of Char 2.5% and this trend was more pronounced as coal rank decreased. The refiring of Char 2.5% in 5% O2/N2 led to the increase in BET surface area and this trend was less significant for the high rank coal. Other authors10) have also verified more significant differences in BET surface areas between high volatile coal chars obtained under different O2 contents. It was

assumed that there was an increase in surface area with combustion progress due to micropores coalescence or widening19). Comparing the samples of the JB, Char and Oxy-char, prepared under the same oxygen content, no significant difference was observed. This result was also observed with the BW Ref-char and Ref-oxy obtained under 5% O2. Regarding the GU refired samples obtained under 10%O2, the Ref-oxy sample showed higher BET surface area than the Ref-char sample. This higher BET surface area for oxy-fuel samples can be the result of internal surface area created by the char-CO2 gasification reaction9). 3.5 Char reactivity The CO2 reactivity at 50% conversion of the chars is showed in Fig. 5.

1,0E-03

O 2 /CO 2 chars R50% -CO 2 (s )

-1

8,0E-04 6,0E-04 4,0E-04 2,0E-04

0,0E+00 0,0E+00 2,0E-04 4,0E-04 6,0E-04 8,0E-04 1,0E-03

O2/N2 chars R50%-CO2(s )

-1

1,2E-03 1,0E-03 8,0E-04 6,0E-04 4,0E-04 2,0E-04 0,0E+00

R50% CO 2 (s-1)

*For Guasare, oxygen content was 10%

Fig. 7 Reactivity of chars obtained under conventional combustion (O2/N2) vs. Reactivity of chars of oxy-fuel conditions (O2/CO2) under the same oxygen concentration. Solid symbols = 1 step; void symbols = 2 step (refired); =GU; =BW; =JB.
GU BW JB

The burnout effect in the chars reactivity is showed in Fig. 8.

1,2E-03 GU BW JB R50% CO2 (s -1) 8,0E-04

Char 2.5%

Char 10%

Oxy-char Ref-char Ref-oxy Ref-oxy 10% 5%* 5% 10%

Fig. 5 CO2 reactivity at 50% conversion of chars prepared in DTF at different atmospheres. Similar to coals burnouts, there was a trend in reactivity increase with a decrease in coal rank for samples obtained under the same oxygen content in DTF (Fig. 5). It is also evident in Fig. 5 that reactivity of the lower rank coal char (GU) varied over a greater range when comparing all samples from the three coals. In the case of the chars obtained under 2.5% O2, the low rank coal GU was less reactive than expected when compared to the medium rank coal char BW. This may be due to the low ash deformation temperature of this coal20), 1280C, which could lead to a material deposition on the particle surface, blocking porosity and decreasing the active surface area and char reactivity21). The reactivity of the GU Char prepared with 2.5% O2 was lower than the reactivity of the GU Char 10% O2. As for BW and JB, the reactivity did not change with O2 content in DTF, despite the higher surface area of the 10% O2 samples. For the BW and JB samples, the reactivity of the O2/N2 chars was similar to the reactivity of the O2/CO2 chars in both one and two steps (Fig. 7). In the case of the GU chars obtained under 10% O2 in two steps (Ref-char 10% O2 vs. Ref-oxy 10% O2), the oxy-fuel sample was more reactive than conventional sample. The higher reactivity of this sample is associated with its higher BET surface area.

4,0E-04

0,0E+00 20 40 60 Burnout (%) 80 100

Figure 8 CO2 reactivity of the chars as a function of coal burnout The CO2 reactivity of the three coals increased with increasing burnout. This is due to the increase in BET surface area of the samples. This trend indicates that the char-CO2 reaction was controlled by both chemical reaction and the diffusion of the gas into the particle, because the higher surface area favors gas diffusion, increasing reactivity22). The similar reactivities obtained for the different coal chars at conventional and oxy-fuel atmospheres and the positive evolution of reactivity with burnout indicate that the chars tested have similar chances to completely react in the blast furnace stack. However, to better correlate the char behavior (reactivity) in the blast furnace shaft, its necessary to make combustion tests in conditions closer to those found in the raceway (atmospheres and temperatures). To

achieve this, the study will continue with new tests conducted in a raceway simulator (injection rig). This equipment is going to be built at LASID with the financial support of the Brasilian Coal Net. 5 CONCLUSIONS The chars behavior in all tests was strongly influenced by coal rank. Higher burnouts, BET surface areas and reactivities were reached as the coal rank decreased. Besides, among the three coals, the chars from the lowest rank coal had a greater range variance. Increasing oxygen content in DTF lead to an increase in burnout and BET surface area For the three coals, there was no effect in burnout because of the N2 replacement (conventional atmosphere) by CO2 (oxy-fuel atmosphere). As for BET surface area results, differences were only found between the conventional and oxy-fuel chars for the highly burnt lower rank coal chars. The CO2 reactivity of chars increased with an increase in burnout because of the greater surface area. The CO2 reactivity of conventional chars was similar to the CO2 reactivity of oxy-fuel chars for the medium and high rank coal samples from both one and two steps. For the greater burnt chars of the lower rank coal, the oxy-fuel sample was more reactive than the conventional one. This was because of the higher BET surface area of the oxy-fuel char. ACKNOWLEDGEMENTS The Brazilian team thanks CNPq and Brasilian Coal Net for the financial support. REFERENCES 1) M. Kawakami and K. Yamaguchi: Advanced pulverized coal injection technology and blast furnace operation, Pergamon - Elsevier Science, Oxford, (2000), 217. 2) A. Babich, D. Senk, H. W. Gudenau and K. Th. Mavrommantis: Ironmaking, RWTH Aachen University, Aachen, (2008), 402. 3) T. Deno and Y. Okuno: Advanced pulverized coal injection technology and blast furnace operation, Pergamon Elsevier Science, Oxford, (2000), 1. 4) T. Ariyama: Advanced pulverized coal injection technology and blast furnace operation, Pergamon Elsevier Science, Oxford, (2000), 123. 5) K. Yamaguchi; H. Ueno, K. Tamura. ISIJ International, 32, 6, (1992), 716). 6) T. Ariyama, M. Sato: ISIJ Int., 46, (2006), 1736. 7) B. J. P. Buhre, L. K. Elliot, C. D. Sheng, R. P. Gupta and T. F. Wall: Progr. Energy Comb. Sci., 31, (2005), 283. 8) T. F. Wall: Proc. Comb. Inst., 31, (2007), 31. 9) R. K Rathnam, L. K. Elliot, T. F. Wall, Y. Liu and B. Moghtaderi: Fuel Process. Technol., 90, (2009), 797.

10) A. G. Borrego and D. Alvarez: Energy Fuels, 21, (2007), 3171. 11) C. Hu, L. Chen, C. Zhang, Y. Qi and R. Win: Int. J. Iron Steel Res. 13, (2006), 38. 12) P. R. Austin, H. Nogami and J. Yagi: ISIJ Int., 38, (1998), 239. 13) J. A. Castro, E. N. Ferreira Junior and A. W. S. Baltazar: Proc. of 7th Japan-Brazil Symp. on Dust Processing-Energy-Environment in Metallurgical Industries, Brasilian Association of Metalurgy and Materials, Sao Paulo, (2009), 154. 14) A. G. Borrego, E. Osorio, M. D. Casal and A. C. F. Vilela: Fuel Process. Technol., 89, (2008), 1017. 15) A. Carpenter and N. Skorupska: Coal combustion Analysis and Testing IEACR/64, IEA Coal Research, London (1993), 97. 16) Q. Li, C. Zhao, X. Chen, W. Wu and B. Lin: Chem. Eng. Process. (2010). <doi: 10.1016/j.cep.2010.03.007>. 17) H. Marsh: Introduction to carbon technologies. Publicaciones de la Universidad de Alicantes. Spain, (1997). 18) M. J. G. Alonso, A. G. Borrego, D. Alvarez and R. Menendez : Fuel Process. Technol., 69, (2001), 257. 19) T. K. Gale, T. H. Fletcher and C. H. Bartholmew: Energy Fuels, 9(1995), 513. 20) M. C. Bagatini, M. L. F. Ghiggi, E. Osorio and A. C. F.Vilela, G. Defendi and R. Cruz Ironmaking Steelmaking, 36, (2009), 583. 21) L. R. Radovic et al: Fuel, 62, (1983), 849. 22) N. M. Laurendeau: Prog. Energy Combust. Sci., 4, (1978), 221.