Journal of Analytical and Applied Pyrolysis 97 (2012) 123129

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Journal of Analytical and Applied Pyrolysis

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Continuous high-temperature uidized bed pyrolysis of coal in complex atmospheres: Product distribution and pyrolysis gas
Mei Zhong a,b , Zhikai Zhang a , Qi Zhou a , Junrong Yue a , Shiqiu Gao a, , Guangwen Xu a,
a b

State Key Laboratory of Multi-Phase Complex Systems, Institute of Process Engineering, Chinese Academy of Sciences, P.O. Box 353, Beijing 100190, China Chemistry and Chemical Engineering, Xinjiang University, Xinjiang 830046, China

a r t i c l e

i n f o

a b s t r a c t
This study is devoted to investigating the continuous coal pyrolysis in a laboratory uidized bed reactor that fed coal and discharged char continuously at temperatures of 750980 C and in N2 -base atmospheres containing O2 , H2 , CO, CH4 and CO2 at varied contents. The results showed that the designed continuous pyrolysis test provided a clear understanding of the coal pyrolysis behavior in various complex atmospheres free of and with O2 . The effect of adding H2 , CO, CH4 or CO2 into the atmosphere on the tar yield was related to the O2 content in the atmosphere. Without O2 in the atmosphere, adding H2 and CO2 decreased the pyrolysis tar yield, but the tar yield was conversely higher with raising the CO and CH4 contents in the atmosphere. In O2 -containing atmospheres, the inuence from varying the atmospheric gas composition on the product distribution and pyrolysis gas composition was closely related to the oxidation or gasication reactions occurring to char, tar and the tested gas. 2012 Elsevier B.V. All rights reserved.

Article history: Received 11 February 2012 Accepted 29 April 2012 Available online 5 May 2012 Keywords: Coal pyrolysis Partial gasication Fluidized bed Staged conversion Atmospheric-gas inuence Tar

1. Introduction Pyrolysis or carbonization represents the possible major way to convert low rank coal into high rank fuel and chemicals that can be transported and used economically. In addition to the well-known coal coking process, the so-called vertical rectangular carbonization furnace illustrated in Fig. 1a is being widely used in China to produce char and tar that are both for chemical applications (char is generally used for making calcium carbide or gasied for syngas of NH3 synthesis at low capacities). In this furnace, the pyrolysis gas is recycled into the bottom high-temperature zone to be a fuel that is combusted to provide at least partially the entailed endothermic heat and meanwhile suppress the combustion of solid char to realize the desired high yield of char [1]. Different from the moving bed process illustrated in Fig. 1a for converting only the coal particles with sizes above 20 mm (called lump coal), we proposed a fractionated pyrolysis process, as conceptualized in Fig. 1b, to treat the granular coal with sizes below 15 mm. A transport-bed top is integrated with a uidized bottom to implement the pyrolysis of ne coal (<15 mm) to produce tar and char simultaneously. The relatively large-size coal is pyrolyzed or partially gasied in the oxygen-containing atmosphere at the uidized bottom. This pyrolysis generates the reducing gas containing H2 and CO at high temperatures (900 C) to provide both the required heat and

Corresponding authors. E-mail addresses: sqgao@home.ipe.ac.cn (S. Gao), gwxu@home.ipe.ac.cn (G. Xu). 0165-2370/$ see front matter 2012 Elsevier B.V. All rights reserved. http://dx.doi.org/10.1016/j.jaap.2012.04.009

reaction atmosphere of the ne coal pyrolysis in the top transportbed section. In this process, the generated pyrolysis gas may be also fed back into the uidized bottom to increase the char yield, a means very similar to that adopted for Fig. 1a. Recently, we are also working on a new two-stage gasication process which, as conceptualized in Fig. 1c, combines a uidized bed pyrolyzer in oxygen-containing atmosphere at temperatures of about 900 C and a moving bed char gasier downstream the pyrolyzer [2]. This two-stage arrangement expects to produce low-tar fuel gas from either biomass or powder coal. Obviously, all the conversion processes conceptualized in Fig. 1 involve coal pyrolysis or partial gasication in the oxygencontaining gas (e.g., air) at relatively high temperatures. The coal pyrolysis refers usually to the thermal treatment of coal in atmospheres free of O2 , even by an indirect heating of the coal in a vessel without input of any external gas (e.g., coking or carbonization). For the processes in Fig. 1b and c, the partial gasication occurs in a uidized bed with continuous coal feed and char discharge. Consequently, their coal pyrolysis behavior is denitely different from the commonly investigated coal pyrolysis in inert gases (N2 or He) at relatively low temperatures, for example, below 800 C. The understanding of such a kind of pyrolysis is critical to the development of the processes highlighted in Fig. 1b and c, while this is also highly needed for understanding the coal conversion fundamentals occurring in the high-temperature bottom section of the rectangular coal carbonization reactor shown in Fig. 1a where the recycled pyrolysis gas is burnt.

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Fig. 1. Process schematic diagrams of a few pyrolysis technologies.

There are some literature studies about the atmospheric-gas inuence on coal pyrolysis [312]. Braekman-Danheux et al. [4,5] studied the inuence of coke oven gas components on product yields and char characteristics in a xed bed reactor. They reported that the char obtained in a coke oven gas atmosphere was not fundamentally different from those in pure hydrogen or pure inert atmosphere, while the overall conversion and oil yield were lower than in pure hydrogen but higher than in helium. Also in a xed bed reactor of atmospheric pressure, Ariunaa et al. [6] found that there was slight difference in the yields of char and tar under varied atmospheric-gas compositions for lignite at temperatures of 400 to 800 C. Liao et al. [7] revealed that the higher pressure and slower heating rate increased the pyrolysis oil yield and improved the oil quality when testing the pyrolysis in a pressurized xed bed reactor. They also concluded that the conversion and oil yield of coal pyrolysis in coke oven gas and synthesis gas were higher than those from hydropyrolysis at the same H2 partial pressure. This indicated a kind of synergetic effect of the various gas components in the coke oven gas on coal pyrolysis. In a downer reactor for pyrolyzing very ne coal in a N2 atmosphere, Wang et al. [8] claried that the gas and liquid yields increased with increasing the temperature from 570 to 660 C, while the char yield decreased. There are limited studies on coal pyrolysis in O2 -containing gases [1315]. Borrego et al. [14] reported that a small amount of O2 in the atmosphere inhibited the volatile release to a certain extent and the oxygen could involve in cross-linking the surfaces of the re-solidifying char particles and reduce the swelling of coal particles. Guo et al. [15] concluded that the char gasication rate in the mixture of 2000 ppm O2 and 15% H2 O was quicker than that in 2000 ppm O2 or 15% H2 O alone, implying a kind of synergetic effects among different atmospheric gas species. The key issue is that oxygen is preferential to react with gas species like volatiles so that the behavior of coal pyrolysis is different from that in O2 -free atmospheres. The present study succeeds to our previous investigation of coal pyrolysis in a quartz-sand bed uidized with composition-varied gases but with an instantaneous coal sample drop (a few grams) into the temperature-preset reactor [16,17]. The coal pyrolysis in a laboratory uidized bed reactor with continuous coal feed and char discharge was tested in this study. The uidizing gas composition was varied to simulate particularly the conditions for the processes conceptualized in Fig. 1a and b. Zeng et al. [2] also tested the pyrolysis in a continuous uidized bed reactor but their tested gas atmosphere was limited to the mixture of N2 and O2 with an intention to provide the needed pyrolysis fundamental data for the two-stage gasication process illustrated in Fig. 1c. These previous studies claried that the pyrolysis in simulated pyrolysis gas atmosphere facilitated the formation of tar [16], while the inclusion of O2 into the reaction atmosphere incurred an obvious decrease

in the tar yield and formed more polycyclic aromatic hydrocarbons (PAHs) [2]. There was yet not report on how the reaction gas containing O2 , CO, CO2 , CH4 and H2 affect the coal pyrolysis behavior at relatively high temperatures of up to 980 C in a continuous uidized bed reactor. This study is devoted to investigating the continuous coal pyrolysis in various N2 -based complex atmospheres containing O2 , H2 , CO, CO2 and CH4 at 750980 C in a laboratory uidized bed with continuous coal feed and char discharge. The results will be reported in three articles in series, and this one is focused on characterization of the product distribution and pyrolysis gas composition. 2. Experimental The adopted experimental apparatus was shown schematically in Fig. 2. It consisted mainly of the continuous coal feeding micro screw feeder, electric furnace, uidized bed reactor, gas supplying parts, char discharger/collector, tar recovery sector and gas cleaner. The coal feeder was equipped with a speed-variable motor to adjust the feeding rate, and the uidized bed reactor was a stainless steel tube of 46 mm in inner diameter. A stainless steel sintered plate was mounted in the reactor to be the gas distributor above which a layer of inert Al2 O3 ball in 34 mm was set to distribute and also preheat the uidizing gas. Below the gas distributor the reactor length was 300 mm and the top section of the bed was an expanded stainless steel freeboard of 100 mm in diameter and 150 mm in length. The major section excluding the connection part between the gas distributor and the expanded top freeboard was 450 mm long, and char was discharged from 125 mm above the distributor. Three 0.3mm K-type thermocouples monitored the temperatures inside the uidized particles and in the freeboard of the reactor. The supercial gas velocity in the reactor was xed to fully uidize the coal particles so that the produced char can be smoothly discharged (3 times of Umf ). The reactor was electrically heated to the preset temperature rst without any gas ow through the bed and in turn with the required gas stream formulated by mixing the gas components from their cylinders under controls of mass ow meters. When both the particle-bed temperature and the atmospheric-gas composition reached their preset steady values, coal pyrolysis test was started by feeding coal continuously into the reactor at a rate of 7.5 g/min. A N2 ow of 1.0 l/min passed through the screw feeder to facilitate the coal particles to enter the reactor. Generally, it took about 20 min to obtain a steady state of operation after starting the coal feed. The produced char particles overowed from the char discharging tube that was inserted into a glass container. The collected char was weighted to calculate the char yield when it was cooled to room temperature and preserved in a desiccator for its characterization after the experiment.

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Fig. 2. Schematic diagram of the laboratory scale uidized bed pyrolyzer. 1, screw feeder; 2, thermocouple; 3, electric furnace; 4, uidized bed; 5, gas mixer; 6, char collector; 7, condenser; 8 ice-water bath; 9, gas meter; 10, gas bag; 11, micro GC.

Table 1 Data of proximate and ultimate analyses for the tested coal. Proximate analysis (wt.%) Ad 4.14 Vd 30.40 FCd 65.46 Cdaf 77.95 Ultimate analysis (wt.%) Hdaf 3.98 Sdaf 0.74 Ndaf 1.05 Odaf 16.28

dried in an atmospheric oven at 110 C for 3 h and further crashed into the sizes of 12 mm for experiment.

3. Results and discussion 3.1. Variation with temperature Fig. 3 shows the yields of pyrolysis products varying with the uidized bed temperature in 750980 C at an excessive air ratio (ER) of 0.064. Comparing the data at 750 and 980 C, one can see that, the yields of char and tar decreased from 64.72 wt.% and 3.06 wt.% to 59.92 wt.% and 2.41 wt.%, respectively. The water yield also decreased from about 3.23 wt.% to 1.60 wt.% because raising the temperature promoted the char steam gasication. The total gas yield exhibited a gradual increase with elevating the temperature, and according to Fig. 3b this was mainly due to the rapid increases in the CO and H2 yields. In fact, high pyrolysis temperature facilitated the cracking of aliphatic hydrocarbons and the condensation or polymerization reactions of aromatic hydrocarbons, thus resulting in the gradually increased yield of hydrogen [18]. The increase in the CO yield with raising the temperature should be attributed to the cracking of phenolic, carbonyl and oxygenous heterocyclic compounds in tar [18], while the decrease in the CO2 yield at relatively high temperatures was because of the enhanced Boudouard reactions between CO2 and char. The C2 hydrocarbons in pyrolysis were mainly from cracking some long-chain hydrocarbons, making its yield rst increase and then decrease with raising the reaction temperature. This showed essentially a competition between the formation and decomposition of such species. When the bed temperature was below 910 C, the formation of C2 gases was dominant in comparison with the thermal cracking of C2 hydrocarbons (to form CH4 ). Raising further the temperature caused the latter to become dominant and led to the decrease in the yield of C2 species. The gradually, but slightly increased CH4 content in Fig. 3b conrmed actually this interpretation. In Fig. 3b, the lower heat value (LHV) of the generated pyrolysis gas (excluding N2 ) increased from

The generated gaseous pyrolysis product was ventilated into air without any treatment, but a part of the gas was sucked from the reactor exit to recover tar and analyze gas composition. The sucked gas was cooled down in, in succession, an air-cooled iron tube (0.5 m long) connected to the reactor exit and two condensers lled with condensate (glycol/water = 1:1) at about 20 C. The gas passed then through seven acetone-washing bottles immersed in an ice-water bath to gain the possible complete trapping of tar which was indicated by the little changed color in the last acetonewashing bottle. The washed gas passed further through a fabric lter and was monitored in a wet gas meter for its ow rate. The clean gas, by dried further in a silica gel column, was nally collected using gas bags and analyzed in a micro GC (Aligent 3000A) equipped with both TCD and FID detectors. The mass of tar was determined by removing its mixed acetone with vaporization at 28 2 C under slightly negative pressure. The pyrolysis gas yield was calculated on the basis of the gas molar composition and volume determined by taking a well-metered N2 ow as the tracer gas. Most of the experiments were performed for two times under the same conditions, and the reproducibility of the two results was well so that their average was reported herein as the experimental data. The total mass of tar, char, gas and water was about 9295% of the fed coal and O2 mass and the other 58% of the coal mass should be the elutriated ne char with the ventilated pyrolysis gas which could not be accurately determined in the test. The tested coal was a kind of sub-bituminous coal from Xinjiang Jimusaer of China, and Table 1 lists the data of the proximate and ultimate analysis for the coal. For the tests of this study, the coal was

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Fig. 3. Product distribution and pyrolysis gas composition varying with pyrolysis temperature at an ER of 0.064.

13.17 to 14.15 MJ/Nm3 corresponding to the temperature rise from 750 C to 910 C and then decreased to 13.72 MJ/Nm3 , which complies well with the above-claried gas composition variations. 3.2. Variation with ER The excessive air ratio ER signicantly affected the pyrolyzer performance and the quality of pyrolysis products. Fig. 4a shows that the freeboard temperature decreased with raising ER when the temperature of particle bed was xed at 850 C. Corresponding to the increase of ER from 0 to 0.107, the freeboard temperature decreased from 898 to 785 C. This referred to a result from decreasing the intensity of electric heating for the reactor when oxygen was fed into the reactor to create internally a part of the heat required for stabilizing the particle bed temperature. Fig. 4b shows that the char and tar yields decreased correspondingly from 68.62 wt.% and 3.18 wt.% to 52.58 wt.% and 1.69 wt.%, respectively. Elevating ER meant surely more char as well as more tar to be combusted or destroyed to lower thus their yields. The lower freeboard temperature at higher ER (see Fig. 4a) would reduce the secondary cracking of tar to raise the tar yield, but this effect was much weaker than the oxygen-intensied tar oxidation at the raised ER. Fig. 4b shows that at ER = 0.107 the gas yield reached 33.23 wt.% of the coal at dry base, which was about 50% higher than that in N2 atmosphere. Especially, the CO production in Fig. 4c increased linearly from 58.4 ml/g at ER = 0 to 166.1 ml/g at ER = 0.107. However, the yields of the other combustible gases including H2 , CH4 and C2 decreased obviously with raising ER. Hence, the presence of O2 in the pyrolysis atmosphere tended to consume combustible gases, especially H2 and C2 , but the gasication reaction of char (by reacting with O2 ) caused the gradually higher CO production

Fig. 4. Freeboard temperature and pyrolysis product characterization at varied ER in N2 atmosphere at 850 C.

at higher ER. The relatively stable CO2 yield in Fig. 4c corroborated this mechanism of oxygen effect on pyrolysis gas production. As a result, the LHV of the pyrolysis gas was gradually lower with higher ER in Fig. 4c. 3.3. Variation with other gases in O2 -free atmosphere Fig. 5 shows how the char yield (right ordinate) and tar yield (left ordinate) at 850 C varied with the addition of the gas components H2 , CO2 , CO and CH4 at different amounts (6.8631.22 vol.%) into the N2 -base reaction atmosphere. The compositions of their generated pyrolysis gases were shown in Table 2. Compared with the pyrolysis in pure N2 , the char yield increased with raising the CH4 fraction in the atmosphere but decreased with increasing the CO2 amount. Adding H2 and CO into the reaction atmosphere affected little the char yield. Against the pyrolysis in N2 atmosphere, Fig. 5 revealed that the presence of CO and CH4 in the atmosphere facilitated the production of tar, whereas the inclusion of H2 and CO2 suppressed

M. Zhong et al. / Journal of Analytical and Applied Pyrolysis 97 (2012) 123129 Table 2 Pyrolysis gas yield in different N2 -based atmospheres ( means no analysis for the gas component added to the reaction atmosphere). Gas atmospthere Concentration (vol.%) Freeboard temperature ( C) Gas production rate (ml/g) H2 N2 H2 CO CO2 CH4 11.56 21.41 11.56 31.22 11.56 21.41 11.56 21.41 898 905 912 900 889 944 982 875 887 119.2 131.4 143.6 132.0 160.8 147.2 168.3 CO 58.4 52.4 49.2 297.8 350.0 60.6 73.6 CH4 31.7 33.7 36.4 27.2 22.6 31.3 30.6 CO2 34.3 25.1 23.4 50.9 57.2 30.9 28.2 C2

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9.0 12.4 17.8 11.5 9.1 11.2 9.1 10.6 12.2

the tar production. The decrease of tar yield with the inclusion of H2 into the atmosphere was related possibly to the conversion of the tar-containing O into water and the H2 -promoted secondary cracking of volatile vapors that led to more pyrolysis gas [16,19]. Table 2 shows that there was particularly more CH4 and C2 hydrocarbons when H2 was presented, while both the CO and CO2 fractions slightly decreased due to probably the enhanced methanation reactions. The reduced tar production when including CO2 was attributed to both the higher freeboard temperature of the reactor (Table 2) at the increased CO2 fraction and its enhanced reforming reactions of tar [17]. The added H2 in the reaction atmosphere and its consequent H radicals tended to react with the nascent char via the hydrocracking or hydrogasication reaction to form more CH4 (Table 2) and highquality tar. The involved reactions are [20,21]: Cf + H2 C(H2 ), C(H2 ) + Cf 2C(H), 2C(H) + H2 2C(H2 ) and C(H2 ) + H2 + Ci CH4 + Cf . (4) (1) (2) (3)

The effect of CO2 on gas yield was resulted mainly from the CO2 gasication of char, thus lowering the char yield in Fig. 5 and causing the pyrolysis gas to have high production rates of CO (58.4350.0 ml/g) and H2 (119.2160.8 ml/g) in Table 2. This was veried also by the increased freeboard temperature in Table 2, a result from increasing the endothermic heat need (for more char

CO2 gasication) which caused a rather extensive electric heating for the reactor. The variation in the production rate of C2 species was subject to the freeboard temperature exclusively. At relatively low freeboard temperatures (e.g., <950 C) the decomposition of high-C species would be dominant, whereas the rather higher temperature might cause the decomposition of C2 species overwhelming. This made a higher C2 production rate (from 9.0 to 11.2 ml/g) when raising the CO2 fraction from 0 to 11.56 vol.% to elevate the freeboard temperature from 898 to 944 C, and then a conversely lowered C2 production (11.29.1 ml/g) at the rise of the CO2 fraction from 11.56 to 21.41 vol.% to make a rather higher freeboard temperature of 982 C. When coal was pyrolyzed in the N2 + CH4 atmosphere, the deposited carbon from thermal cracking of CH4 increased the char yield (Fig. 5), which was in accordance with the results of Zhang et al. [22] and Sun et al. [23]. It was widely recognized that the catalytic effect of coal/char can cause CH4 to decompose over the char surface at relatively low temperatures [9,2325]. This increased consequently the H2 and CO production rates in Table 2, while simultaneously the CH4 reforming by CO2 lowered the CO2 production. On the other hand, methane may provide radicals, such as CH3 , CH2 and H to stabilize the coal radicals generated in pyrolysis and in turn to elevate the tar yield. The increased production rate of C2 species in Table 2 veried actually the char-catalyzed cracking of CH4 and its resulting stabilization of the coal molecular fragments via the so-called condensation reactions under the participation of methyl and methylene radicals [22,24,26]. 3.4. Variation with other gases in O2 -containing atmosphere For the autothermal pyrolysis conceptualized in Fig. 1, the coal pyrolysis may use the gas produced by gasication as its transport gas and meanwhile mixed with air or O2 to provide the heat required by the pyrolysis. Some experiments were thus performed at 850 C in atmospheres containing O2 (ER = 0.107) but with different other gas species. As presented in Fig. 6, the inclusion of H2 , CH4 or CO into the base gas atmosphere of N2 + O2 increased both the char and tar yields. This is surely because that adding combustible gas into the atmosphere caused a part of O2 to react with the combustible gas fed to the atmosphere, thus decreasing the amounts of tar and char combusted. Table 3 shows the corresponding changes in production rates of the various pyrolysis gas components. The presence of CH4 induced some complicated heterogeneous and homogeneous reactions including combustion, methane cracking, steam and CO2 reforming of methane [23,27]. These led to the rapid rise of H2 production rate from 76.4 to 268.7 ml/g accompanying with the increase of CH4 content from 0 to 34.91 vol.% in the reaction atmosphere. Table 3 shows also that the production rates of CO2 and H2 obviously increased when CO was into the atmosphere. The CO2 production reached 149.2 ml/g when the atmospheric CO concentration was 31.91 vol.%, which was about 3 times higher than

Fig. 5. Inuence of H2 , CH4 , CO2 and CH4 in O2 -free atmosphere on pyrolysis product distribution at 850 C.

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Table 3 Pyrolysis gas yield using N2 + O2 as the basic atmosphere at ER = 0.107. Gas atmospthere Concentration (vol.%) ER Freeboard temperature ( C) Gas production rate (ml/g) H2 O2 H2 CO CH4 11.56 31.91 11.56 31.91 11.56 31.91 0.107 0.107 0.107 0.107 0.107 0.107 0.107 785 807 764 779 762 808 812 76.4 122.9 137.7 222.5 268.7 CO 166.1 135.6 82.5 155.6 167.0 CH4 18.5 22.1 23.8 19.1 22.2 CO2 51.9 46.6 36.6 91.2 149.2 38.8 30.1 C2 3.7 7.8 8.3 7.0 5.7 6.3 7.1

Fig. 6. Inuence of H2 , CO and CH4 in O2 -containing atmosphere (ER = 0.107) on pyrolysis product distribution at 850 C.

that in the N2 + O2 atmosphere. The production rate of H2 reached 122.9 ml/g at the CO content of 11.56 vol.%, which was 76.4 ml/g in the atmosphere without CO. The production of C2 species exhibited a rise as well with the presence of CO. The enhanced CO combustion, which reduced the combustion for the other gas species, should be responsible for the result. Adding H2 , which was easier to be oxidized, into the N2 + O2 atmosphere decreased obviously the productions of CO and CO2 . This was related to the reduced oxidation for the C-containing species including tar, char, CH4 and C2 species, making thus their higher production rates in Fig. 6 and Table 3. The results show also that the char yield decreased in the COcontaining atmosphere in comparison with that in the atmospheres with H2 and CH4 (data not presented in Fig. 6 and Table 3). The facilitated char gasication in the atmosphere with high CO2 concentration should be the cause. 3.5. Comparison between atmospheres free of and with O2 Fig. 7 compares the tar and char yields varying with the atmospheric gas composition for the atmospheres free and with O2 in a and b, respectively. The satellite table lists the composition of the plotted atmospheric gases G1G10. The test was conducted by adding an individual gas component into the atmosphere gradually, and the base atmosphere was N2 (7a) and N2 + O2 (7b). As shown in the satellite table, the sequence of adding gas component was H2 , CO, CH4 and CO2 . Fig. 7a shows that adding H2 decreased the tar yield, and the inclusion of CO and CH4 into the N2 + H2 atmosphere was likely to increase the tar yield. The supply of CO2 into the atmosphere
Fig. 7. Char and tar yields of pyrolysis in various O2 -free and O2 -containing reactions.

caused lower tar yield. These results complied well with the observation of Zhang et al. [17] in batch-wise coal pyrolysis test, and thus one can nd their implied mechanics from that literature study. The continuous coal pyrolysis tests done here veried further the results and mechanism. The char yield did not greatly vary with the changes of the gas composition shown above, but one can still see that the addition of H2 and CO2 would lower the char yield,

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and the inclusion of CO and CH4 was likely to raise the char yield. These were related to the preceding variations of tar yield with gas atmosphere and revealed in fact the occurrence of the C deposition on the char with the presence of CO and CH4 in the atmosphere and the enhanced volatilization (or gasication) of char by reacting with the atmospheric gas containing H2 and CO2 . Fig. 7b claried that in the O2 -containing atmosphere the addition of the combustible gas including H2 , CO and CH4 all increased the tar and char yields, while the inclusion of CO2 was likely to lower the yields of tar and char. This is true because the more combustible gas in the atmosphere would reduce the oxidation of tar and char to increase thus their yields. Carbon dioxide is not a combustible gas but a gasication or reforming reagent, and its presence in the atmosphere thus facilitated the tar reforming and char gasication to lower their yields. Fig. 7b showed obviously lower yields than Fig. 7a nearly for all the examined product species, afrming further that it is the oxidation reactions which lowered those yields in the O2 -containing atmosphere. 4. Conclusions This paper investigated the pyrolysis characteristics of a subbituminous coal in a uidized bed reactor with continuous coal feed and char discharge at temperatures of 750980 C and in N2 -base atmospheres containing O2 , H2 , CO, CH4 and CO2 . In O2 -containing atmospheres (ER = 0.064 in this article), raising the reaction temperature (>700 C) evidently increased the pyrolysis gas yield, and this increase in the gas yield resulted mainly from the increases in the productions of CO and H2 . The yields of C2 hydrocarbons rst slightly increased and then decreased, whereas that of CO2 kept a slight decrease with raising temperature. The heating value of the pyrolysis gas exhibited the same variation tendency as for the yield of C2 hydrocarbons. At the tested high pyrolysis temperatures (e.g., over 850 C), increasing the ER until 0.107 decreased the yields of char and tar but increased the yields of gas and water. The CO2 yield had only a slight increase with elevating ER, whereas for H2 and hydrocarbons their yields slightly decreased. The addition of any combustible gas into the N2 + O2 atmosphere (ER = 0.107) all increased the tar and char yields due to the suppressed oxidation or gasication of tar and char by O2 . Nonetheless, the yields of char and tar were both evidently lower than in pure-N2 atmosphere. When increasing the H2 content in the N2 + O2 atmosphere the production became higher for all combustible gases including CH4 and C2 species but lower for CO2 . Raising the atmospheric CH4 content lowered the CO2 yield but raised evidently the productions of H2 and C2 species. Adding CO elevated the yields of CO2 and H2 . In O2 -free atmospheres at the tested temperatures (up to 980 C), the tar yield increased with the addition of CH4 and CO but decreased with the presence of H2 and CO2 . Adding CH4 into the atmosphere caused slightly higher char yield due to the cracking of CH4 , while elevating the CO2 content in the atmosphere obviously decreased the char yield because of the facilitated reaction of char with CO2 . The variation in the atmospheric CO and H2 concentrations affected little the char yield. As for the pyrolysis gas product, the addition of H2 into the atmosphere caused gradually higher hydrocarbon yield (including CH4 ) but lowered the production of CO and CO2 . Raising the atmospheric CH4 content caused a slightly higher production of C2 species but it was slightly lowered by the inclusion of CO and CO2 . Acknowledgments The authors are grateful to the nancial support of the National Basic Research Program of China (2011CB201304), the National Natural Science Foundation of China (21076217), the Strategic

Priority Research Program Key technologies and demonstration for cleaning and highly efcient of low rank coal (XDA07010100) and the Young Teacher Scientic Research Cultivation Foundation of Xinjiang (XJEDU2011S03). References
[1] G.Q. Liu, S.P. Deng, X.R. Qian, Y.F. Jiang Y, H.S. Song, Research progress of coal pyrolysis technology in China, Modern Chemical Industries 27 (2007) 3743 (Chinese). [2] X. Zeng, Y. Wang, J. Yu, S.S. Wu, M. Zhong, S.P. Xu, G.W. Xu, Coal pyrolysis in a uidized bed for adapting to a two-stage gasication process, Energy Fuels 25 (2011) 10921098. [3] C. Braekman-Danheux, R. Cyprs, A. Fontana, P. Laurent, M. Van Hoegaerden, Coal hydromethanolysis with coke-oven gas. 1: inuence of temperature on the pyrolysis yields, Fuel 71 (1992) 251255. [4] C. Braekman-Danheux, R. Cyprs, A. Fontana, M. Van Hoegaerden, Coal hydromethanolysis with coke-oven gas. 2: inuence of the coke-oven gas components on pyrolysis yields, Fuel 74 (1995) 1719. [5] C. Braekman-Danheux, A. Fontana, A. Labani, P. Laurent, Coal hydromethanolysis with coke-oven gas. 3: inuence of the coke-oven gas components on the char characteristics, Fuel 75 (1996) 12741278. [6] A. Ariunaa, B.Q. Li, W. Li, B. Purevsuren, S. Munkhjargal, F.R. Liu, Z.Q. Bai, G. Wang, Coal pyrolysis under synthesis gas, hydrogen and nitrogen, Journal of Fuel Chemistry and Technology 35 (2007) 14. [7] H.Q. Liao, B.Q. Li, B.J. Zhang, Co-pyrolysis of coal with hydrogen-rich gases. 1: coal pyrolysis under coke-oven gas and synthesis gas, Fuel 77 (1998) 847851. [8] J.G. Wang, X.S. Lu, J.Z. Yao, W.G. Lin, L.J. Cui, Experimental study of coal topping process in a downer reactor, Journal of Industrial and Engineering Chemistry 44 (2005) 463470. [9] M.S. Gao, J.M. Zhang, M. Luo, Y. Suo, H. Lian, Study of weight loss characters and promoting function to sulfur release during lignite pyrolysis in methane, Coal Conversion 28 (2005) 710 (Chinese). [10] R. Cyprs, S. Furfari, Fixed-bed pyrolysis of coal under hydrogen pressure at low heating rates, Fuel 60 (1981) 768778. [11] W.C. Xu, K. Matsuoka, H. Akiho, M. Kumagai, A. Tomita, High pressure hydropyrolysis of coals by using a continuous free-fall reactor, Fuel 82 (2003) 677685. [12] R.C. Borah, P.G. Rao, P. Ghosh, Devolatilization of coals of northeastern India in inert atmosphere and in air under uidized bed conditions, Fuel Processing Technology 91 (2010) 916. [13] X. Li, R.K. Rathnam, J. Yu, Q. Wang, T. Wall, C. Meesri, Pyrolysis and combustion characteristics of an Indonesian low-rank coal under O2 /N2 and O2 /CO2 conditions, Energy Fuels 24 (2009) 160164. [14] A.G. Borrego, D. Alvarez, Comparison of chars obtained under oxy-fuel and conventional pulverized coal combustion atmospheres, Energy Fuels 21 (2007) 31713179. [15] X. Guo, H.L. Tay, S. Zhang, C.Z. Li, Changes in char structure during the gasication of a Victorian brown coal in steam and oxygen at 800 C, Energy Fuels 22 (2008) 40344038. [16] R. Xiong, L. Dong, J. Yu, X.F. Zhang, L. Jin, G.W. Xu, Fundamentals of coal topping gasication: characterization of pyrolysis topping in a uidized bed reactor, Fuel Processing Technology 91 (2010) 810817. [17] X.F. Zhang, L. Dong, J.W. Zhang, Y.J. Tian, G.W. Xu, Coal pyrolysis in a uidized bed reactor simulating the process conditions of coal topping in CFB boiler, Journal of Analytical and Applied Pyrolysis 91 (2011) 241250. [18] Y.B. Jia, J.J. Huang, Y. Wang, Effects of calcium oxide on the cracking of coal tar in the freeboard of a uidized bed, Energy Fuels 18 (2004) 16251632. [19] X.D. Zhu, Z.B. Zhu, L.H. Tang, C.F. Zhang, Fundamental study on the pyrolysis of coals I Effect of atmosphere and temperature on pyrolysis, Journal of East China University Science and Technology 24 (1998) 3741, Chinese. [20] K.J. Httinger, Mechanism of water vapor gasication at high hydrogen levels, Carbon 26 (1988) 7987. [21] H.J. Mhlen, K.H. Van Heek, H. Jntgen, Kinetic studies of steam gasication of char in the presence of H2 , CO2 and CO, Fuel 64 (1985) 944949. [22] G.J. Zhang, Y. Dong, M.R. Feng, Y.F. Zhang, W. Zhao, H.C. Cao, CO2 reforming of CH4 in coke oven gas to syngas over coal char catalyst, Chemical Engineering Journal 156 (2010) 519523. [23] Z.Q. Sun, J.H. Wu, M. Haghighi, J. Bromly, E. Ng, H.L. Wee, Y. Wang, D.K. Zhang, Methane cracking over a bituminous coal char, Energy Fuels 21 (2007) 16011605. [24] W.H. Calkins, C. Bonifaz, Coal ash pyrolysis. 5: pyrolysis in an atmosphere of methane, Fuel 63 (1984) 17161719. [25] C. Guret, M. Daroux, F. Billaud, Methane pyrolysis: thermodynamics, Chemical Engineering Science 52 (1997) 815827. [26] N.O. Egiebor, M.R. Gray, Evidence for methane reactivity during coal pyrolysis and liquefaction, Fuel 69 (1990) 12761282. [27] Z.Q. Sun, J.H. Wu, D.K. Zhang, CO2 and H2 O gasication kinetics of a coal char in the presence of methane, Energy Fuels 22 (2008) 21602165.