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Journal of Analytical and Applied Pyrolysis 97 (2012) 123–129

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Journal of Analytical and Applied Pyrolysis
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Continuous high-temperature fluidized 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 fluidized bed reactor that fed coal and discharged char continuously at temperatures of 750–980 ◦ 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 influence from varying the atmospheric gas composition on the product distribution and pyrolysis gas composition was closely related to the oxidation or gasification 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 gasification Fluidized bed Staged conversion Atmospheric-gas influence 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 gasified 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 fluidized bottom to implement the pyrolysis of fine coal (<15 mm) to produce tar and char simultaneously. The relatively large-size coal is pyrolyzed or partially gasified in the oxygen-containing atmosphere at the fluidized 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: (S. Gao), (G. Xu). 0165-2370/$ – see front matter © 2012 Elsevier B.V. All rights reserved.

reaction atmosphere of the fine coal pyrolysis in the top transportbed section. In this process, the generated pyrolysis gas may be also fed back into the fluidized 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 gasification process which, as conceptualized in Fig. 1c, combines a fluidized bed pyrolyzer in oxygen-containing atmosphere at temperatures of about 900 ◦ C and a moving bed char gasifier 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 gasification 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 gasification occurs in a fluidized bed with continuous coal feed and char discharge. Consequently, their coal pyrolysis behavior is definitely 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.

Process schematic diagrams of a few pyrolysis technologies. The reactor was electrically heated to the preset temperature first without any gas flow through the bed and in turn with the required gas stream formulated by mixing the gas components from their cylinders under controls of mass flow meters. Three 0. implying a kind of synergetic effects among different atmospheric gas species. Zeng et al. 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. The fluidizing gas composition was varied to simulate particularly the conditions for the processes conceptualized in Fig.5 g/min. The coal pyrolysis in a laboratory fluidized bed reactor with continuous coal feed and char discharge was tested in this study. fluidized bed reactor. H2 . Experimental The adopted experimental apparatus was shown schematically in Fig. gas supplying parts. coal pyrolysis test was started by feeding coal continuously into the reactor at a rate of 7. char discharger/collector. CO2 and CH4 at 750–980 ◦ C in a laboratory fluidized bed with continuous coal feed and char discharge. [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 fixed bed reactor. CH4 and H2 affect the coal pyrolysis behavior at relatively high temperatures of up to 980 ◦ C in a continuous fluidized bed reactor. There are limited studies on coal pyrolysis in O2 -containing gases [13–15]. The produced char particles overflowed from the char discharging tube that was inserted into a glass container. [2] also tested the pyrolysis in a continuous fluidized 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 gasification process illustrated in Fig. 2. This indicated a kind of synergetic effect of the various gas components in the coke oven gas on coal pyrolysis. [8] clarified that the gas and liquid yields increased with increasing the temperature from 570 to 660 ◦ C. The superficial gas velocity in the reactor was fixed to fully fluidize the coal particles so that the produced char can be smoothly discharged (∼3 times of Umf ). it took about 20 min to obtain a steady state of operation after starting the coal feed. 1c. / Journal of Analytical and Applied Pyrolysis 97 (2012) 123–129 Fig. The results will be reported in three articles in series.17]. When both the particle-bed temperature and the atmospheric-gas composition reached their preset steady values. 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. [4. Also in a fixed bed reactor of atmospheric pressure. 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. 2.124 M. This study is devoted to investigating the continuous coal pyrolysis in various N2 -based complex atmospheres containing O2 . The present study succeeds to our previous investigation of coal pyrolysis in a quartz-sand bed fluidized with composition-varied gases but with an instantaneous coal sample drop (a few grams) into the temperature-preset reactor [16. Guo et al.0 l/min passed through the screw feeder to facilitate the coal particles to enter the reactor. CO2 . [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. while the overall conversion and oil yield were lower than in pure hydrogen but higher than in helium. and char was discharged from 125 mm above the distributor. These previous studies clarified that the pyrolysis in simulated pyrolysis gas atmosphere facilitated the formation of tar [16]. It consisted mainly of the continuous coal feeding micro screw feeder. Generally. 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]. . and this one is focused on characterization of the product distribution and pyrolysis gas composition. CO. 1. A N2 flow of 1. [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. Ariunaa et al. while the char yield decreased. 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. 1a and b. There was yet not report on how the reaction gas containing O2 . electric furnace. In a downer reactor for pyrolyzing very fine coal in a N2 atmosphere. Zhong et al. 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. The coal feeder was equipped with a speed-variable motor to adjust the feeding rate. CO. 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 3–4 mm was set to distribute and also preheat the fluidizing gas. [15] concluded that the char gasification 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.5] studied the influence of coke oven gas components on product yields and char characteristics in a fixed bed reactor. and the fluidized bed reactor was a stainless steel tube of 46 mm in inner diameter.3mm K-type thermocouples monitored the temperatures inside the fluidized particles and in the freeboard of the reactor. The major section excluding the connection part between the gas distributor and the expanded top freeboard was 450 mm long. Braekman-Danheux et al. Borrego et al. Liao et al. tar recovery sector and gas cleaner. Wang et al. There are some literature studies about the atmospheric-gas influence on coal pyrolysis [3–12].

thus resulting in the gradually increased yield of hydrogen [18].%. by dried further in a silica gel column. The total gas yield exhibited a gradual increase with elevating the temperature.% to 59. 4. gas mixer. the yields of char and tar decreased from 64. 8 ice-water bath. 2.95 Ultimate analysis (wt. 7. 2.% and 2. high pyrolysis temperature facilitated the cracking of aliphatic hydrocarbons and the condensation or polymerization reactions of aromatic hydrocarbons.%) Hdaf 3. but a part of the gas was sucked from the reactor exit to recover tar and analyze gas composition.46 Cdaf 77. The increase in the CO yield with raising the temperature should be attributed to the cracking of phenolic.98 Sdaf 0.064. In Fig. in succession. Results and discussion 3. Zhong et al. 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. thermocouple. respectively.5 m long) connected to the reactor exit and two condensers filled with condensate (glycol/water = 1:1) at about −20 ◦ C. fluidized bed. 3b. Proximate analysis (wt. char collector. electric furnace.28 dried in an atmospheric oven at 110 ◦ C for 3 h and further crashed into the sizes of 1–2 mm for experiment. / Journal of Analytical and Applied Pyrolysis 97 (2012) 123–129 125 Fig. The clean gas.74 Ndaf 1. while the decrease in the CO2 yield at relatively high temperatures was because of the enhanced Boudouard reactions between CO2 and char. 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. 3b this was mainly due to the rapid increases in the CO and H2 yields. 3. 10. gas and water was about 92–95% of the fed coal and O2 mass and the other 5–8% of the coal mass should be the elutriated fine char with the ventilated pyrolysis gas which could not be accurately determined in the test. was finally collected using gas bags and analyzed in a micro GC (Aligent 3000A) equipped with both TCD and FID detectors.72 wt. The total mass of tar.14 Vd 30.% and 3. the coal was .%) Ad 4. When the bed temperature was below 910 ◦ C. 3. screw feeder. 6. an air-cooled iron tube (0. making its yield first increase and then decrease with raising the reaction temperature. gas meter. The sucked gas was cooled down in. 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. Comparing the data at 750 and 980 ◦ C.% to 1.23 wt. one can see that. The pyrolysis gas yield was calculated on the basis of the gas molar composition and volume determined by taking a well-metered N2 flow as the tracer gas.40 FCd 65.1. 3 shows the yields of pyrolysis products varying with the fluidized bed temperature in 750–980 ◦ C at an excessive air ratio (ER) of 0. Variation with temperature Fig. 3b confirmed actually this interpretation. In fact.41 wt.05 Odaf 16. Table 1 Data of proximate and ultimate analyses for the tested coal. condenser. gas bag. 1. 5.% because raising the temperature promoted the char steam gasification. 9. micro GC. The gradually. 11. and according to Fig.92 wt.60 wt. The tested coal was a kind of sub-bituminous coal from Xinjiang Jimusaer of China. For the tests of this study. Schematic diagram of the laboratory scale fluidized bed pyrolyzer.M. and Table 1 lists the data of the proximate and ultimate analysis for the coal. The C2 hydrocarbons in pyrolysis were mainly from cracking some long-chain hydrocarbons.06 wt. The washed gas passed further through a fabric filter and was monitored in a wet gas meter for its flow rate. carbonyl and oxygenous heterocyclic compounds in tar [18]. but slightly increased CH4 content in Fig. Most of the experiments were performed for two times under the same conditions. The water yield also decreased from about 3. The mass of tar was determined by removing its mixed acetone with vaporization at 28 ± 2 ◦ C under slightly negative pressure. This showed essentially a competition between the formation and decomposition of such species. char. and the reproducibility of the two results was well so that their average was reported herein as the experimental data.

especially H2 and C2 . 4b shows that at ER = 0.107. 4a) would reduce the secondary cracking of tar to raise the tar yield. / Journal of Analytical and Applied Pyrolysis 97 (2012) 123–129 Fig. 4c corroborated this mechanism of oxygen effect on pyrolysis gas production. Freeboard temperature and pyrolysis product characterization at varied ER in N2 atmosphere at 850 ◦ C. 5 revealed that the presence of CO and CH4 in the atmosphere facilitated the production of tar. CH4 and C2 decreased obviously with raising ER. Compared with the pyrolysis in pure N2 .064. 3.1 ml/g at ER = 0. Hence. the freeboard temperature decreased from 898 to 785 ◦ C. 4a shows that the freeboard temperature decreased with raising ER when the temperature of particle bed was fixed at 850 ◦ C. 4. respectively. the char yield increased with raising the CH4 fraction in the atmosphere but decreased with increasing the CO2 amount.%) into the N2 -base reaction atmosphere. Fig. but this effect was much weaker than the oxygen-intensified tar oxidation at the raised ER. 4c increased linearly from 58. CO and CH4 at different amounts (6.% to 52.107. Adding H2 and CO into the reaction atmosphere affected little the char yield. However.3. Fig.4 ml/g at ER = 0 to 166. The compositions of their generated pyrolysis gases were shown in Table 2. the CO production in Fig. CO2 . Against the pyrolysis in N2 atmosphere. at higher ER.126 M. 3. Variation with other gases in O2 -free atmosphere Fig. Product distribution and pyrolysis gas composition varying with pyrolysis temperature at an ER of 0.69 wt. which was about 50% higher than that in N2 atmosphere.58 wt.86–31. Variation with ER The excessive air ratio ER significantly affected the pyrolyzer performance and the quality of pyrolysis products. 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.%.% and 3.17 to 14. but the gasification reaction of char (by reacting with O2 ) caused the gradually higher CO production Fig.22 vol.62 wt. whereas the inclusion of H2 and CO2 suppressed .107 the gas yield reached 33. Corresponding to the increase of ER from 0 to 0.72 MJ/Nm3 .% and 1. the LHV of the pyrolysis gas was gradually lower with higher ER in Fig. 4b shows that the char and tar yields decreased correspondingly from 68.23 wt.2. Especially. the presence of O2 in the pyrolysis atmosphere tended to consume combustible gases.15 MJ/Nm3 corresponding to the temperature rise from 750 ◦ C to 910 ◦ C and then decreased to 13. 4c. The relatively stable CO2 yield in Fig. The lower freeboard temperature at higher ER (see Fig. which complies well with the above-clarified gas composition variations. 13.18 wt. Fig. the yields of the other combustible gases including H2 .% of the coal at dry base. 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 . Elevating ER meant surely more char as well as more tar to be combusted or destroyed to lower thus their yields. 3. As a result. Zhong et al.

2 the tar production.1 23.6 12. (4) (1) (2) (3) The effect of CO2 on gas yield was resulted mainly from the CO2 gasification of char.56 31. steam and CO2 reforming of methane [23.56 to 21. CO2 and CH4 in O2 -free atmosphere on pyrolysis product distribution at 850 ◦ C.4 49.8 ml/g) in Table 2. which was about 3 times higher than Fig.% to elevate the freeboard temperature from 898 to 944 ◦ C. The increased production rate of C2 species in Table 2 verified 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. The involved reactions are [20.6 CH4 31.26].%) Freeboard temperature (◦ C) Gas production rate (ml/g) H2 N2 H2 CO CO2 CH4 – 11.6 132. 3.3 CO 58. 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].24. Table 3 shows the corresponding changes in production rates of the various pyrolysis gas components. while simultaneously the CH4 reforming by CO2 lowered the CO2 production. which was in accordance with the results of Zhang et al. 6.3 25.2 ml/g) when raising the CO2 fraction from 0 to 11. 2C(H) + H2 → 2C(H2 ) and C(H2 ) + H2 + Ci → CH4 + Cf .8 11. 5 and causing the pyrolysis gas to have high production rates of CO (58. [23]. 5).41 898 905 912 900 889 944 982 875 887 119. CH4 .2 – – 30. Table 3 shows also that the production rates of CO2 and H2 obviously increased when CO was into the atmosphere.2 ml/g when the atmospheric CO concentration was 31.5 9. Zhong et al. Some experiments were thus performed at 850 ◦ C in atmospheres containing O2 (ER = 0.2 168. C(H2 ) + Cf → 2C(H).g.41 11.4 143. This made a higher C2 production rate (from 9.2 – – 131. while both the CO and CO2 fractions slightly decreased due to probably the enhanced methanation reactions. thus lowering the char yield in Fig.21]: Cf + H2 → C(H2 ). .8 350. / Journal of Analytical and Applied Pyrolysis 97 (2012) 123–129 Table 2 Pyrolysis gas yield in different N2 -based atmospheres (“–” means no analysis for the gas component added to the reaction atmosphere).1 11. This increased consequently the H2 and CO production rates in Table 2. the deposited carbon from thermal cracking of CH4 increased the char yield (Fig.%. This was verified also by the increased freeboard temperature in Table 2.27]. Influence of H2 .% to make a rather higher freeboard temperature of 982 ◦ C.6 – – CO2 34.1 10.6 31. Variation with other gases in O2 -containing atmosphere For the autothermal pyrolysis conceptualized in Fig. As presented in Fig.2–160.41 vol.0 60.2 – – 297.3 30. On the other hand.4 50.0 160.% in the reaction atmosphere.7 33. the inclusion of H2 .9 57.4 27.19].2–9. methane may provide radicals.0 12.7 36. When coal was pyrolyzed in the N2 + CH4 atmosphere. 1. the coal pyrolysis may use the gas produced by gasification as its transport gas and meanwhile mixed with air or O2 to provide the heat required by the pyrolysis.56 21. and then a conversely lowered C2 production (11. 5.4 17.56 21. such as CH3 .91 vol.41 11.22 11.107) but with different other gas species. <950 ◦ C) the decomposition of high-C species would be dominant. The added H2 in the reaction atmosphere and its consequent H radicals tended to react with the nascent char via the hydrocracking or hydrogasification reaction to form more CH4 (Table 2) and highquality tar. Gas atmospthere Concentration (vol. The CO2 production reached 149.91 vol.0 to 11.0 ml/g) and H2 (119. 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.8 147. [22] and Sun et al. thus decreasing the amounts of tar and char combusted. 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 [16.2 22.6 73..4 to 268.56 vol.2 9. Table 2 shows that there was particularly more CH4 and C2 hydrocarbons when H2 was presented.M. CH2 and H to stabilize the coal radicals generated in pyrolysis and in turn to elevate the tar yield.56 21. 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. methane cracking. CH4 or CO into the base gas atmosphere of N2 + O2 increased both the char and tar yields.4–350.4. The presence of CH4 induced some complicated heterogeneous and homogeneous reactions including combustion.9 28.2 C2 127 9. whereas the rather higher temperature might cause the decomposition of C2 species overwhelming.7 ml/g accompanying with the increase of CH4 content from 0 to 34.1 ml/g) at the rise of the CO2 fraction from 11. The variation in the production rate of C2 species was subject to the freeboard temperature exclusively.23–25]. a result from increasing the endothermic heat need (for more char CO2 gasification) which caused a rather extensive electric heating for the reactor. At relatively low freeboard temperatures (e.4 52. These led to the rapid rise of H2 production rate from 76.

56 31. As shown in the satellite table.2 – – CO2 51. Gas atmospthere Concentration (vol.56 31.9 137. The supply of CO2 into the atmosphere Fig.5 22. making thus their higher production rates in Fig. 7a shows that adding H2 decreased the tar yield.%. respectively.2 149. Fig.5 – – 155.6 91. Comparison between atmospheres free of and with O2 Fig. These results complied well with the observation of Zhang et al. / Journal of Analytical and Applied Pyrolysis 97 (2012) 123–129 Table 3 Pyrolysis gas yield using N2 + O2 as the basic atmosphere at ER = 0.3 7.91 11.7 CO 166.2 38. CO and CH4 in O2 -containing atmosphere (ER = 0. caused lower tar yield.0 CH4 18.91 11. char.107 0.7 7. and thus one can find their implied mechanics from that literature study.4 – – 122.107 785 807 764 779 762 808 812 76.8 8.1 135.107) on pyrolysis product distribution at 850 ◦ C.107 0. The facilitated char gasification in the atmosphere with high CO2 concentration should be the cause. into the N2 + O2 atmosphere decreased obviously the productions of CO and CO2 . [17] in batch-wise coal pyrolysis test. 6 and Table 3. and the base atmosphere was N2 (7a) and N2 + O2 (7b). 7. 6 and Table 3).56 vol.6 82. that in the N2 + O2 atmosphere. .%) ER Freeboard temperature (◦ C) Gas production rate (ml/g) H2 O2 H2 CO CH4 – 11. Zhong et al. The production rate of H2 reached 122.3 7.107 0.9 ml/g at the CO content of 11. Adding H2 .107 0.107.1 Fig. and the inclusion of CO and CH4 into the N2 + H2 atmosphere was likely to increase the tar yield.5.6 36.7 6. the sequence of adding gas component was H2 . Influence of H2 .1 C2 3.1 22.8 30. 7 compares the tar and char yields varying with the atmospheric gas composition for the atmospheres free and with O2 in a and b. but one can still see that the addition of H2 and CO2 would lower the char yield.0 5. 6. The test was conducted by adding an individual gas component into the atmosphere gradually.5 268.107 0. The production of C2 species exhibited a rise as well with the presence of CO. The satellite table lists the composition of the plotted atmospheric gases G1–G10. Char and tar yields of pyrolysis in various O2 -free and O2 -containing reactions.6 167. should be responsible for the result.7 222. The char yield did not greatly vary with the changes of the gas composition shown above. CH4 and CO2 .91 0. 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. 3. which reduced the combustion for the other gas species. CO.107 0. This was related to the reduced oxidation for the C-containing species including tar. which was easier to be oxidized.9 46.8 19.1 23. The enhanced CO combustion. The continuous coal pyrolysis tests done here verified further the results and mechanism. CH4 and C2 species.128 M.4 ml/g in the atmosphere without CO. which was 76.56 31.

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This is true because the more combustible gas in the atmosphere would reduce the oxidation of tar and char to increase thus their yields. 7b showed obviously lower yields than Fig. S. [17] X. Daroux.G. Dong. Guo. X. Van Heek. Zhao.J.O. Alvarez. J. S. The addition of any combustible gas into the N2 + O2 atmosphere (ER = 0. Experimental study of coal topping process in a downer reactor.F. H.C. Nonetheless. CO2 and H2 O gasification kinetics of a coal char in the presence of methane. 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 . C. Braekman-Danheux. 4.J. H. [23] Z. Effects of calcium oxide on the cracking of coal tar in the freeboard of a fluidized bed. M. Sun. B. Bromly. Liao. X. [27] Z. CO2 and CO. Y. Zhang. P. Wang. the yields of char and tar were both evidently lower than in pure-N2 atmosphere. Ghosh. and its presence in the atmosphere thus facilitated the tar reforming and char gasification to lower their yields. Carbon dioxide is not a combustible gas but a gasification or reforming reagent. Fontana. D. Borah. hydrogen and nitrogen. B.J. M. 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 . Qian.J. Acknowledgments The authors are grateful to the financial support of the National Basic Research Program of China (2011CB201304). increasing the ER until 0. A.107) all increased the tar and char yields due to the suppressed oxidation or gasification of tar and char by O2 . [5] C. Hüttinger. H. G.W. [20] K. Munkhjargal. R. Jia. Y. Journal of East China University Science and Technology 24 (1998) 37–41.Q. CH4 and CO2 . Z. Li. P. Xu. Suo. Xu. [13] X. Z. S. J. Xu. Purevsuren. 1: influence of temperature on the pyrolysis yields. C. affirming further that it is the oxidation reactions which lowered those yields in the O2 -containing atmosphere. J. Zhong. Huang. Kinetic studies of steam gasification of char in the presence of H2 . [19] X. Rathnam.H. [25] C. Journal of Industrial and Engineering Chemistry 44 (2005) 463–470. H. F..L. In O2 -free atmospheres at the tested temperatures (up to 980 ◦ C). while elevating the CO2 content in the atmosphere obviously decreased the char yield because of the facilitated reaction of char with CO2 . Jüntgen. Coal hydromethanolysis with coke-oven gas. Journal of Fuel Chemistry and Technology 35 (2007) 1–4. [26] N. Zhang. Wall. Liu. Zhang. Y. Gao. The variation in the atmospheric CO and H2 concentrations affected little the char yield. Cao. Lian.Z. [4] C. Modern Chemical Industries 27 (2007) 37–43 (Chinese). Coal hydromethanolysis with coke-oven gas.K.G. A.R.P. The CO2 yield had only a slight increase with elevating ER. Matsuoka. Fixed-bed pyrolysis of coal under hydrogen pressure at low heating rates. As for the pyrolysis gas product. [16] R. Feng. [6] A. D. Kumagai. Energy Fuels 21 (2007) 1601–1605. Ng.B. Y. raising the reaction temperature (>700 ◦ C) evidently increased the pyrolysis gas yield. Fuel Processing Technology 91 (2010) 9–16. Fig. Zhang. Van Hoegaerden. R. S.064 in this article).S. Akiho. [11] W. Fuel 77 (1998) 847–851. [22] G. H2 . Gray. Zhu. L.J.F. The yields of C2 hydrocarbons first slightly increased and then decreased. whereas for H2 and hydrocarbons their yields slightly decreased. Laurent. Evidence for methane reactivity during coal pyrolysis and liquefaction. / Journal of Analytical and Applied Pyrolysis 97 (2012) 123–129 129 and the inclusion of CO and CH4 was likely to raise the char yield.G. B. Wu. L. Li. Fig.F. Li. Conclusions This paper investigated the pyrolysis characteristics of a subbituminous coal in a fluidized bed reactor with continuous coal feed and char discharge at temperatures of 750–980 ◦ C and in N2 -base atmospheres containing O2 . Wang. Cyprès. Coal flash pyrolysis. Fuel 63 (1984) 1716–1719. The heating value of the pyrolysis gas exhibited the same variation tendency as for the yield of C2 hydrocarbons.Q. Rao. Mühlen. Zhang. Coal pyrolysis under synthesis gas. over 850 ◦ C). D. Q.M. G. S. M.M. Chemical Engineering Science 52 (1997) 815–827. Chinese. Deng. Pyrolysis and combustion characteristics of an Indonesian low-rank coal under O2 /N2 and O2 /CO2 conditions. Wee. W.107 decreased the yields of char and tar but increased the yields of gas and water. A. Li.S. Zhang. J.W. 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 gasification) of char by reacting with the atmospheric gas containing H2 and CO2 .H. Dong. the National Natural Science Foundation of China (21076217). J. C. Fuel 64 (1985) 944–949. Chemical Engineering Journal 156 (2010) 519–523. Fuel Processing Technology 91 (2010) 810–817. P. Haghighi. 1: coal pyrolysis under coke-oven gas and synthesis gas. Yu. Xu. Coal hydromethanolysis with coke-oven gas. Yao.R. Methane pyrolysis: thermodynamics. J.