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Journal of Analytical and Applied Pyrolysis 91 (2011) 241–250

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Journal of Analytical and Applied Pyrolysis
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Coal pyrolysis in a fluidized bed reactor simulating the process conditions of coal topping in CFB boiler
Xiaofang Zhang, Li Dong, Juwei Zhang, Yajun Tian, Guangwen Xu ∗
State Key Laboratory of Multi-Phase Complex System, Institute of Process Engineering, Chinese Academy of Sciences, ZhongGuanCun Bei’ertiao 1, Haidian District, Beijing 100080, China

a r t i c l e

i n f o

a b s t r a c t
Simulating the conditions of pyrolytic topping in a fluidized bed reactor integrated into a CFB boiler, the study was devoted to the reaction fundamentals of coal pyrolysis in terms of the production characteristics of pyrolysis oil in fluidized bed reactors, including pyrolysis oil yield, required reaction time and the chemical species presented in the pyrolysis oil. The results demonstrated that the maximal pyrolysis oil yield occurred on conditions of 873 K, with a reaction time of 3 min and in a reaction atmosphere gas simulating the composition of pyrolysis gas. Adding H2 and CO2 into the reaction atmosphere decreased the pyrolysis oil yield, while the oil yield increased with increasing the CO and CH4 contents in the atmosphere. TG-FTIR analysis was conducted to reveal the effects of reaction atmosphere on the chemical species present in the pyrolysis oil. The results clarified that the pyrolysis oil yield reached its maximum when the simulated pyrolysis gas was the reaction atmosphere, but there were slightly fewer volatile matters in the pyrolysis oil than the oil generated in the N2 atmosphere. All of these results are expected not only to reveal the composition characteristics of the pyrolysis oil from different conditions of the coal topping process but also to optimize the pyrolysis conditions in terms of maximizing the light pyrolysis oil yield and quality. © 2011 Elsevier B.V. All rights reserved.

Article history: Received 14 September 2010 Accepted 18 February 2011 Available online 26 February 2011 Keywords: Coal topping CFB boiler Fluidized bed Reaction atmosphere Pyrolysis oil TG-FTIR

1. Introduction “Coal topping” (pyrolytic topping) process was proposed by Yao and Kwauk [1,2] to achieve high-value utilization of coal consumed in CFB boilers. As shown schematically in Fig. 1, light liquid product in this process is produced by flash pyrolysis of coal in a pyrolyzer integrated into a circulating fluidized bed boiler which burns the pyrolysis-generated char to generate heat and electricity. Previous studies showed that the pyrolysis is necessary to proceed with rapid heating and in turn the quick separation (from solids) and quench of the gaseous product in order to minimize the secondary reactions like cracking and polymerization [2,3]. A few, although limited studies have been done regarding pyrolytic topping. Wang et al. [4] found that downer is a suitable reactor for implementing the pyrolysis of coal through mixing with the hot ash particles during their fall in the reactor via gravity. Those authors further investigated the influences of pyrolysis temperature and particle size on the topping performance [5,6]. Because the coal particle residence time is short (only a few seconds), the downer reactor only adapts to coal in micrometers. Moving bed is

another kind of reactor used to implement the pyrolytic topping, and Bi [7] employed this reactor to integrate the coal pyrolysis with a riser combustor. Comparing to the downer reactor, a special effort is needed to scale up the reactor to achieve high-efficiency mixing with coal particles for industrial application. Fluidized bed allows easier scale-up and also adapts wide-size particles (<10 mm), and it should be highly appropriate for pyrolytic topping. However, almost no related study has been conducted before under this concern. Thus, this work is devoted to investigating the coal pyrolysis characteristics in terms of pyrolysis oil yield and quality under conditions simulating the pyrolytic topping process. The effects of temperature, bed height, reaction time and reaction atmosphere were studied to deepen the understanding of coal pyrolysis and to provide fundamental data for the process and operation optimizations of the pyrolytic topping. 2. Experimental 2.1. Apparatus and test procedure The experiments were performed in a quartz-made fluidized bed reactor of 0.06 m in diameter and 0.7 m in height. The schematic diagram of the experimental apparatus is shown in Fig. 2. The coal particles were fed from the top of the bed into the reactor in which quartz sand particles of 212–380 m were fluidized. The height of

∗ Corresponding author. Tel.: +86 10 62550075; fax: +86 10 62550075. E-mail address: (G. Xu). 0165-2370/$ – see front matter © 2011 Elsevier B.V. All rights reserved. doi:10.1016/j.jaap.2011.02.013

wt. The reaction atmosphere (N2 or mixture of H2 .15 m/min (2 times of minimum fluidization velocity) to achieve the full fluidization of the quartz sand particles. A thermocouple was immersed in the quartz sand bed to monitor and measure the temperature of the fluidized bed. The collected liquid was first treated in an atmospheric rotary evaporator at 318 K and then in a vacuum oven at 318 K.1 O: 9. The liquid collected from washing the cooler and pyrolysis gas was treated to recover pyrolysis oil (tar) through filtration and remove both acetone and water. The yield of pyrolysis oil (Yoil . Table 2 lists the characteristic peaks in FTIR spectra and their implicated functional groups. The bed was heated to the desired temperature in N2 atmosphere and then the fluidizing gas was switched to the required reaction atmosphere. a thermo gravimetric analyzer (Netzsch STA 449C) coupled with a FTIR (i. the cleaned gas was sampled at the end of the gas line at an interval of about 20 s. N2 . At the end of gas sampling. 2. TG-FTIR) was employed to analyse the recovered pyrolysis oil. After passing through a filter and drier further. The sampled gas was analysed using a micro GC (Agilent 3000) to determine its composition. the sand bed in the reactor was adjusted according to the experimental needs. which was usually a few minutes after the coal feeding. and Table 1 shows the major properties of the tested coal. The quality of the pyrolysis oil was determined by a thermal gravity analyzer integrated with a Fourier transform infrared spectrometer (FTIR). L/g) with a dry ash-free basis were calculated with Yoil = moil × 100% mcoal × (100 − Mad − Aad ) (1) Table 1 Proximate and ultimate analyses of the tested coal.9 LHV [MJ kg−1 ] 24.2 Ash: 18.6 H: 4. / Journal of Analytical and Applied Pyrolysis 91 (2011) 241–250 Table 2 Typical FTIR absorption peaks and their implicated functional groups [8].7 and 22. The volume of the gas was measured by a wet gas meter after the washing bath. 1.e. 10 g of lignite were added into the reactor from the bed top through a valve-hopper. CO. Zhang et al. CH2 . When the bed temperature in the new atmosphere reached the specified steady value. CO2 and CH4 ) was formed by mixing gases from different cylinders and the flow rate was kept at 1. the gas from the reactor was switched to a bypass line to vent without passing through the above-mentioned gas cooling and washing vessels. Therefore. the pyrolysis oil sample was heated from 303 K to 1173 K at 30 K/min in TG. The generated pyrolysis gas was cooled immediately in a water cooler and then washed with water and acetone in succession cooled via an ice-water bath. A micro GC was used to measure the molar concentrations of H2 . O2 . Nitrogen at 80 mL/min was adopted to carry the evolved volatile gas from TG to the gas cell of FTIR heated to 573 K.2 Fixed C: 48. Principle of the coal pyrolytic topping process in CFB boiler. CO. CO2 and hydrocarbons up to C3 in the gaseous product. Schematic diagram of the adopted experimental apparatus.96 Ultimate analysis [db-wt.%] Water (arrival base): 1. The reactor was first heated to 673 K before the fluidizing gas (N2 ) was introduced into the reactor. 1430–1470 1405–1465 1500 1740 2800–3100 2000–2250 2250–2400 2920 3500 3650 Function group –CH3 –CH2 C C C O CH4 CO CO2 –CH3 . the time to sample the gas also represented the reaction time measured for the pyrolysis.%] C: 65.7 Volatile: 31.1 S: 0.242 X. 2. –O–H(a) –O–H(b) Characteristic chemicals Methyl Methylene Single ring aromahydrocarbon Acid ketone Methane Carbon monoxide Carbon dioxide Aliphatic Phenolic hydroxyl Alcoholic hydroxyl C–H Fig.4 × Ygas = i t 0 Fmt Ci dt × 100% (2) mcoal × (100 − Mad − Aad ) .. Absorbance [cm−1 ] 1355–1395. The particle sizes of the tested lignite were 4–6 mm. In order to gain composition information of pyrolysis oil. A three-zone electric furnace heated the reactor and the heating conditions for each zone could be independently controlled. The FTIR analysis was conducted at TG temperatures between 373 K and 1273 K. Proximate analysis [db-wt. The resulting intensity of FTIR spectrum was mass-normalized to eliminate the influence of sample mass. In the TG-FTIR analysis.%) and the production rate of pyrolysis gas (Ygas . Analysis approach and mass balance Fig.6 N: 1.2.

and this error also represented the repeatability of the tests reported herein. The pyrolysis gas concentrations (excluding N2 ) varying with the reaction time in Fig. Fig. Then. Carbon balance examination for the experimental system via gasification (temperature: 1133 K. Zhang et al. One can see that the release of CO and CH4 was only at a short initial stage. and Fmt is the mole flow rate of gas at the time t (mol/s). 5. The result implies that the measurement error would be in 4% in this article. / Journal of Analytical and Applied Pyrolysis 91 (2011) 241–250 243 Fig. The ash collected at the reactor exit by a filter was found to contain about 2. showing a good reliability of the testing system.X. Fig. The tests were performed at two different static bed heights. CO2 and CH4 ) and the correspondingly calculated accumulative C conversion obtained in a gasification test that was particularly performed to examine the mass balance in the adopted experimental system. the tests were performed to identify the suitable reaction time firstly and then to clarify the influences of reaction temperature and atmosphere on the oil yield and composition features. The gasification was tested at 1133 K in a gas mixture of air (80 vol%) and steam (20 vol%). 3 shows the time-series concentrations of the C-containing gas components (CO. Effect of reaction time on yields of pyrolysis oil and gas (temperature: 923 K. Figs. where Mad and Aad are the contents of water and ash in coal (wt. both CO and H2 had Fig. 4 one can judge that the pyrolysis at 923 K would finish in about 200 s to allow the major part of the coal volatiles to be released. Ci is the concentration of gas species i in pyrolysis gas (vol%). . respectively. the C balance in this test reached about 96%.8% of the fed C. 3. 4 and 5 show the production characteristics of pyrolysis gas and oil varying with the reaction time. 3. demonstrates that up to 93. Time series of the concentrations for major gas components at the static bed heights of 85 mm and 350 mm (temperature: 923 K. atmosphere: air + H2 O). but the analysis in this section will be based on the data from the 350-mm bed test exclusively.%). The accumulative C conversion. atmosphere: N2 ).0% C was present in the gas product within the tested 3500 s. Before the peaks the gradually increased concentrations with prolonging the reaction time show essentially the quickly deepened degree of the pyrolysis reaction. 4. From the gas concentration profiles in Fig. atmosphere: N2 ). 4 clarify that the concentrations for all the gaseous components had their peaks at certain time. denoting actually the period with coal pyrolysis. 3. Necessary reaction time determination By presetting the pyrolysis temperature at 923 K. Fig. the char gasification and in turn the combustion of the formed combustible gas (CO) led to the long-time release of CO2 . the yields of gas and oil in pyrolysis were measured in N2 to determine the necessarily required reaction time or the time from feeding coal into the reactor. 85 mm and 350 mm.1. Consequently. while the successive decrease in the gas concentrations denotes actually the approach to the end of the pyrolysis reaction. 4 clarifies also that the pyrolysis gas was rich in CH4 and had its lowest concentration for CO2 . moil and mcoal are the masses of the produced pyrolysis oil and coal fed into the reactor (kg). In-between. defined from the molar ratio of the released gaseous C over the fed C in the coal. t is the time that the pyrolysis reaction lasts for or the time for collecting pyrolysis oil (s). Results and discussion In terms of maximizing the pyrolysis oil yield and meanwhile understanding the oil composition features.

It was reported that in pyrolysis the disruption of H–H bonds occurs first to produce radical H. TG-FTIR spectra of pyrolysis oil produced with different reaction times. These different gas concentration and release features for different gas species revealed essentially the different mechanisms for forming different gas species in coal pyrolysis [9–13]. The time to appear the concentration peak was different for different gas components. both ether and quinone in coal provides the major source of CO2 . and its release also ends earlier than H2 . It was equivalently earliest for CH4 and CO. Zhang et al.244 X. and the polymerization of the free radicals H generates the molecule H2 . The peak for CO2 was shown up nearly at the reaction end. The cracking of aliphatic and aromatic compounds con- taining methyl function group produces CH2 or CH3 . Hydrocarbons can be derived from cracking fatty matters and aliphatic side-chains of aromatic molecules. and some weak bonds of aromatic and carboxylic groups. while all hydrocarbons other than CH4 manifested a total concentration higher than that of CO2 but lower than that of CO and H2 . . 6. while CO would be mainly from the cracking of aliphatic matters. and in succession it was hydrocarbons (excluding CH4 ) and H2 . The cracked carboxylic groups can react with O to form CO2 as well. The involved major reactions are: H–H → 2H R–CH2 –R → R–R + –CH2 CH2 + 2H → CH4 (3) (4) (5) The decomposition of oxygen heterocyclic ring. which in turn react with H to form CH4 . / Journal of Analytical and Applied Pyrolysis 91 (2011) 241–250 Fig. Methane evolves earlier than H2 . the equivalent concentrations.

5 displays further the yields of pyrolysis gas and oil varying with the reaction time. and vary with the second reactions occurring to the primary species. The higher particle bed height caused the concentration peaks to come earlier. 4 that for CO and hydrocarbons their releasing sequence and concentration values are between those of CH4 and H2 . The abscissa in Fig. while the later period of pyrolysis mainly involves the reactions of carbonaceous residues. more fundamental studies are definitely needed in order identify further the real causes for the results shown in Fig.2. For the particle bed height of 350 mm Fig. In pyrolysis. As expected. Taking CH4 and CO as the examples. Similar to the gas product characterized in Fig. 5. one can believe that in Fig. Zhang et al. Fig. the higher production of aliphatic species for lignite pyrolysis in the longer reaction time can also lower the contents of the other chemical species containing in the pyrolysis oil. the yields of pyrolysis oil and gas increased rapidly with time in a period after feeding the coal sample into the reactor. the various gaseous and liquid compounds come directly from the breakage of side chains of large molecules and aromatics. 4. Considering all of these. Coal consists of many kinds of functional groups. Although the higher freeboard for 85-mm particle bed would cause deeper secondary cracking of tar to lower the oil yield and elevate the gas yield [14]. carboxylic acids (C O). This ensures consequently a quick pyrolysis in the reactor. single-ring aromatics (C C). Ether is easier to crack and CO2 can thus be formed almost at the start of the pyrolysis reaction. 6 characterizes the pyrolysis oil composition with the TGFTIR spectra of the liquid products recovered at different reaction time. the composition of pyrolysis oil should also vary with reaction time. With the longer reaction time of 180 s. indicating that the result was mainly related to the quicker heating for coal particles in the 350-mm particle bed. The lower particle bed height caused the lower yields for both gas and oil. Effect of temperature on yields of pyrolysis oil and gas (atmosphere: N2 . But the decomposition of quinine requires rather severe conditions so that the CO2 concentration is low and its release preserves for long time in pyrolysis. 3. Cracking aliphatic matters would occur at intermediate temperatures. In practice. 5 compares the yields of pyrolysis gas and oil realized at the two tested particle bed heights of 85 and 350 mm at the reaction time of 190 s that led to the maximal oil yields. The latter complies well with the data in Fig. the pyrolysis oil is produced mainly at the initial stage of pyrolysis. while those with the lower contents for the 180-s pyrolysis referred actually to the obvious occurrence of the secondary reactions of those primary volatile species. justifying the result in Fig. 3. Fig. 4 where the release of pyrolysis gas reached almost the end at the reaction time of 200 s. and the decomposition of these functional groups in pyrolysis [15] generates the pyrolysis gas and oil products. 7. The compared pyrolysis oils had the similar FTIR spectra. Meanwhile. but varying the height affected the time reaching the gas concentration peaks. this effect is not dominant because the gas yield was actually lower for the tested lower particle bed height. 6 compares the FTIR spectra of the pyrolysis oils collected at the reaction time of 25 s and 180 s. the time corresponding to their concentration peaks were about 85 s and 110 s for the particle bed heights of 350 and 85 mm. The FTIR data show that the oil from the pyrolysis for 180 s contained more aliphatic hydrocarbons and phenols but less singlering aromatic chemicals. causing the H2 release to appear at high temperatures. Fig.%. the coal pyrolysis is still in progress but the generated product is mainly gas through the reactions of polymerization or cracking of carbonaceous matters. Hence. Nonetheless. reaction time: 180 s). CH). Consequently. CH2 . After 3 min. the particle bed height is generally decided by the permitted pressure drop through the reactor. 7 shows how the yields of pyrolysis oil and gas in the tested fluidized bed reactor varied .X. 4 that the general features were similar. 6 the chemical species with higher contents for the pyrolysis by 180 s were generated mainly through the higher production of the primary volatiles in the longer reaction time. The identified absorption peaks in the FTIR spectra were shown in Table 2. 6 refers to the temperature of TG. According to Fig. This should be the case especially for the carboxylic acids and hydroxide compounds that are easy to decompose. One can see from Fig. Fig.3 wt.09 L/g. Further insight into the time-series behavior The time-series pyrolysis gas release behavior is further analysed for the tested two particle bed heights in the reactor. while the corresponding gas yield was 0. and the analysed composition species include aliphatic hydrocarbons (–CH3 . The generated H would prefer to react with some other active radials. respectively. The time of 3 min was also proved to be sufficient for realizing the maximal oil yield in the pyrolysis at the tested lower particle bed height of 85 mm (referring further to the inset table comparison in Fig. one can suggest that the particle bed height should be above 350 mm to balance the reaction kinetics (heating rate) and the pressure drop conditions. 5). the tested lignite is rich in aliphatic hydrocarbons [16]. 4 one can see that the side-chains are easier to break to make CH4 release earlier of pyrolysis reaction. Fig. The oil yield reached its maximal value at about 200 s. 5 clarifies also that for the tested coal at the examined temperature of 973 K and in N2 atmosphere. from the viewpoint of maximizing the pyrolysis liquid product.3. while only one peak appeared for the carboxylic compounds. carboxylic acids and alcoholic hydroxyl compounds than the oil from the pyrolysis for 25 s. phenol (–OH (a)). the tar yield with respect to coal mass of dry ash-free basis reached about 12. and alcohol (–OH (b)). 6. the more primary volatiles were surely released but for the tested 25 s the volatile release had to be in process. while the gas yield exhibited only a small increment (less than 20% of total gas production) in the period from 200 s to 350 s. Pyrolysis temperature optimization Reaction temperature is the critical parameter affecting the pyrolysis product distribution and many studies have been conducted to clarify the effect of temperature on the yields of gas and liquid products in pyrolysis [5. The inset table in Fig. a reaction time of 3 min would be enough.18]. There are two peaks for aliphatic hydrocarbons and single-ring aromatics. / Journal of Analytical and Applied Pyrolysis 91 (2011) 241–250 245 Correlating the preceding reaction pathways with Fig. Furthermore.17. The result complies with the fact that more hot particles in the higher bed can enhance the interaction between the hot bed material and the coal sample particles to lead to a quicker rise of the coal particle temperature.

such as around 873 K according to Fig. causing thus the gas yield to increase gradually from low to high temperatures. As one of the major secondary reactions. In the tested temperature range. Zhang et al. whereas there was a peak yield for the pyrolysis oil at about 923 K. From the viewpoint of achieving high light pyrolysis oil production. 8. / Journal of Analytical and Applied Pyrolysis 91 (2011) 241–250 Fig. Fig. 823 K and . the coal pyrolysis should thus be at temperatures below but close to the one leading to the maximal pyrolysis oil yield. with the pyrolysis temperature. the polymerization reaction is likely to occur to increase the semi-coke production and to cause more heavy oil components. the pyrolysis gas yield increased continuously with the rise in the temperature. The former reaction is dominant at lower temperatures to allow gradually increased pyrolysis oil production. 8 shows the FTIR spectra measured via TG-FTIR for the pyrolysis oils obtained at two different pyrolysis temperatures. while the latter turns to be overwhelming at higher temperatures to reduce the oil yield with raising the temperature.246 X. Accompanying the cracking. These two types of reactions all increase the gas production. [5] who performed flash pyrolysis of lignite in a fast-entrained bed reactor. 7. the cracking of the pyrolysis oil would occur first to the naphthenic hydrocarbon and macromolecule polar aromatics. The appearance of a peak pyrolysis oil yield with varying the reaction temperature shows in fact the competition between deepening the pyrolysis reaction and enhancing the secondary reactions such as cracking and reforming of the pyrolysis oil during elevating the temperature. This temperature leading to the maximal oil yield consisted with the result of Cui et al. TG-FTIR spectra of pyrolysis oil produced at different temperatures. and then to the ring-opening for aromatic compounds at higher temperatures.

Furthermore. Effect of reaction atmosphere on yield of pyrolysis oil (temperature: 873 K. For all the tests. 10. Fig. In the fixed bed reactor.X. By noting that the four datum points on the left side were obtained through raising the H2 content and the other three points on the right side were from further adding CO2 into the atmosphere. No. and alcoholic hydroxyl group compounds. For the testing system of this work. whereas further inclusion of CO and CH4 into the atmospheric gas increased the oil yield conversely. the pyrolysis oil yield reached its maximum at 873–923 K. 1023 K. / Journal of Analytical and Applied Pyrolysis 91 (2011) 241–250 247 Fig. The rather higher temperatures caused not only the lower pyrolysis oil yield but also the reduction in the contents of the valuable species in the oil product (due to the deep secondary reactions occurring to the primary pyrolysis oil). 1. Treating N2 as the basic atmosphere (see the inset table). phenols. Comparatively. This further verifies that coal pyrolysis for high-quality pyrolysis oil should not be at high temperatures. [18] for coal pyrolysis in an entrained flow reactor. It can be seen that increasing the H2 content in the reaction atmosphere increased the pyrolysis oil yield in all the reported fixed bed pyrolysis tests but decreased the yields for the tests in entrained flow or drop tube furnace reactors. in terms of producing high-quality pyrolysis oil. Reactor Swept fixed bed reactor Fixed bed reactor Fixed-bed reactor Fixed-bed reactor Tube reactor Continuous free-fall reactor Heating rate 3 K/min 5 K/min 10 K/min 150 K/min 1000 K/s 2000 K/s Pyrolysis oil yield ↑ ↑ ↑ ↑ ↓ ↓ Ref. Therefore. Fig. completely opposite reports are available in the literature. 8 displays multiple peaks in the FTIR spectra for single-ring chemicals. the presence of CO in the atmosphere would enhance the formation of pyrolysis oil. showing that there are possibly different sorts of molecules for one kind of chemicals. . the obtained result complied with the literature finding in the entrained flow and drop tube reactors. In summary. Fig. 10 replots the experimental data through correlating the oil yield and the fraction of (H2 + CO2 ) in the atmosphere. Decreasing the pyrolysis oil yield with adding CO2 into he atmosphere was reported by Cui et al. Fig. alcoholic hydroxide and single-ring aromatics.e.24] [19] [14] [25] Note: the arrows ↑ and ↓ mean increase and decrease of pyrolysis oil yield with raising H2 content in the atmosphere. the heating rate is limited to 10 K/min. respectively. As for the effects of H2 . Because the heating rate of fluidized bed reactor adopted in this study was up to 1000 K/s. reaction time: 180 s). carboxylic acids. Most of the above-mentioned results are consistent with the literature studies. [19] in their fixed bed coal pyrolysis tests at 400–750 ◦ C. the pyrolysis oil from the test at 1023 K was characterized with obviously reduced spectrum intensity for the plotted functional groups including hydrocarbons. Thus. phenol. but there is no literature report yet regarding this influence. we can believe that the specific decrease in the oil yield with raising the gas content (i. the reaction time or the time collecting pyrolysis oil after feeding coal sample into the reactor was 180 s and the temperature was fixed at 873 K. Table 3 compares the major literature reports and working conditions (including reactor type and heating rate) for investigating the influence of H2 on pyrolysis oil yield. while others [14.. meanwhile somehow reasonable yields of aliphatic hydrocarbons and cyclane hydro-aromatics were also ensured. while the heating rate in the entrained flow reactor and drop tube furnace can be as high as 1000–2000 K/s. while increasing the volatile production with including CH4 into the reaction atmosphere was reported by Gao et al. Figs. a series of tests were conducted to clarify the influences of various gas components containing in the pyrolysis gas on pyrolysis behaviors. This fact suggests that the influence of H2 on pyrolysis performance is closely related to the heating rate for the coal sample. the slope of the two lines in Fig. 9 and 10 show the variation of pyrolysis oil yield with the changes of the atmospheric gas composition.4. Influence of H2 and CO2 contents in the reaction atmosphere on pyrolysis oil yield (temperature: 873 K. Several research groups [20–25] reported an obvious increase of the pyrolysis oil yield with increasing the H2 content in the reaction atmosphere. it is critical to control the temperature at reasonably low values that can ensure both high oil yield and high oil quality. The distinctive difference for these two groups of reactors is the heating rate of the coal sample particles inside the reactor. Product distribution in varied reaction atmospheres In the coal topping process illustrated in Fig. 9 and 10. Zhang et al. 10) was almost the same for both H2 and CO2 . Table 3 Results of literature studies on influence of H2 on pyrolysis oil yield. 3. [23] [22] [21. 9 demonstrates that adding H2 and CO2 into the atmosphere decreased the pyrolysis oil yield. It is clarified that raising the contents of both these components decreased monotonically the pyrolysis oil yield. According to Figs. although it improved the quality of the pyrolysis oil. coal pyrolysis is likely to occur in pyrolysis gas atmosphere. the pyrolysis temperature determines not only the pyrolysis oil yield but also the oil composition. 9.26] found that the inclusion of H2 decreased the pyrolysis oil yield. reaction time: 180 s).

Meanwhile. the increase of the fraction of the gas in the atmosphere should decrease the oil yield. the influence of atmospheric gas on pyrolysis behavior is subject to two opposite types of essential interactions [26–29]. while CO and CH4 are easy to form free radicals in comparison with the direct reaction with oil species. whereas the supply of additional free radicals for coal-radical stabilization would be dominant for CO and CH4 present in the reaction atmosphere. Zhang et al. 9 simulates the pyrolysis gas composition. 9 and 10. especially the condensable species (forming pyrolysis oil) which have relatively large and long-chain molecules via the reactions of hydrogenation. it is thought that in the tested fluidized bed reactor (heating rate ∼1000 K/s).248 X. Notwithstanding. The gas G5 in Fig. the pyrolysis oil would be more with the inclusion of a gas into the atmosphere. more studies are needed to clarify the mechanisms of the preceding different effects of different gas species. The gas may provide radicals. When the former reaction is overwhelming. reforming and gasification to lower the oil yield. Otherwise. to enhance the stabilization of coal-base radicals generated in coal thermal cracking to increase the pyrolysis oil yield. such as methyl. the gas components of CO2 and H2 would mainly participate in the pyrolysis oil hydrogenation and reforming reactions. 11. dimethyl. the gas may also interact with the formed gaseous products. According to Figs. / Journal of Analytical and Applied Pyrolysis 91 (2011) 241–250 Fig. The fact is that both H2 and CO2 are good reactant for reformation and gasification. H and carboxyl. It is shown that the compensative effects of (H2 + CO2 ) and (CO + CH4 ) on pyrolysis made the pyrolysis oil yield in the simulated pyrolysis . TG-FTIR spectra of pyrolysis oil produced in different reaction atmospheres. Fundamentally.

G.B. Chinese. Chin. the composition of the resulting oil became closer to that from the pyrolysis in N2 but with slightly higher contents for carboxylic acids. J. this increased the pyrolysis oil yield and the contents of light components including aliphatic hydrocarbons. G2. Consequently. the heating rate had a great impact on the effect of H2 for coal pyrolysis. G. Both CO and CH4 affected the pyrolysis principally via providing free radicals to stabilize the coal radicals generated in coal molecular cracking and breakage. Besides. Chinese.5. The result shows in fact that using the pyrolysis gas as the reaction atmosphere would not affect greatly the pyrolysis oil yield in comparison with the pyrolysis in N2 . in order to get high-quality pyrolysis oil.%). 30. J. demonstrated actually a promotion effect of CH4 on the pyrolysis oil yield and quality. It is interesting to note that the pyrolysis in atmospheres of N2 and the simulated pyrolysis gas (H2 + CO2 + CO + CH4 ) had very close pyrolysis oil yields. phenols. Especially. alcohols and phenols. many overall features of the FTIR spectra were the same for all the cases tested. References [1] X. Therefore. / Journal of Analytical and Applied Pyrolysis 91 (2011) 241–250 249 gas atmosphere reach 13. The contents of aliphatic hydrocarbons and aromatics are equivalent for both reaction atmospheres. Mixing behavior between coal and hot circulation ash in down flow of coal topping process. alcohols and phenols. It is obvious that the reaction atmosphere greatly affected the FTIR spectrum of the pyrolysis oil in the TG-FTIR analysis. including hydrogenation and reformation. alcohols and phenols.Z. while the pyrolysis in the simulated pyrolysis gas has led to some slightly higher productions of the carboxylic acids. Comparing to the (N2 + H2 ) atmosphere.X. at about 700 K there was a peak absorbance for aliphatic hydrocarbons and at about 500 K the absorbance of carboxylic acids reached the maximum. Pyrolysis oil composition versus reaction atmospheres The FTIR spectra in Fig. [3] G. dramatically decreased the contents of aliphatic hydrocarbons. Consequently. Therefore. Zhao. we can see that the pyrolysis in both N2 and the simulated pyrolysis gas (H2 + CO2 + CO + CH4 ) had not only very close pyrolysis oil yields (Fig. Yao. the aliphatic hydrocarbons and aromatics manifested very similar FTIR spectra in the TG-FTIR analysis. pp. The TG-FTIR analysis for the pyrolysis oil collected in different time period from coal sample feeding clarified that the oil generated in the early time of pyrolysis contained more aromatics. 11 display the composition features of the pyrolysis oils made by the tests shown in Figs. Chinese. The effects allowed by CO and CO2 in the reaction atmosphere possibly compensated each other to make the composition of FTIR spectra in Fig. G4 and G5.21 wt. using pyrolysis gas as the reaction atmosphere in coal topping process is technical feasible. Process Eng. 4. while the rather high temperature. [31]. while this meanwhile led to more acid species to present in the liquid.%. Yao. technology and progress.Q. phenol hydroxide. 11 for the various atmospheric gas components on the pyrolysis oil composition reflected as well the influential essence clarified in the Section 3. Process Chem. Gao.H. Kwauk. [2] J. Conclusions Pyrolysis of a kind of lignite in a laboratory fluidized bed reactor under conditions simulating the so-called coal topping process in a CFB boiler led to the following conclusions. Chinese. in: The 4th Joint China/Japan Chemical Engineering Symposium. 9 and 10. Coal Conv. In summary. Prog. Yao. X. alcohols and mono-aromatics in Fig. 2007. to decrease the production of light components. The compared atmospheres included G1. alcoholic hydroxide and aromatics in the pyrolysis oil. Total distribution and liquid composition of products from coal topping process in a downer Reactor. Meanwhile. the presence of (CO + CO2 ) increased the formation of aliphatic hydrocarbons. whereas the resulting oil in the latter case contained slightly more carboxylic acids. 11 have no big difference between the pyrolysis oils produced in the atmospheres of (N2 + H2 ) and (N2 + H2 + CO + CO2 ).Z. Wu. the pyrolysis time should not be too short or too long. and 773–900 K should be the recommended values. the pyrolysis temperature for the highest oil yield was shown to be about 873 K (823–923 K). such as at 1023 K. 2011CB201304) and National Key Technology R&D Project of China (2009BAC64B05). 21–31.4. (1) The time to ensure the highest pyrolysis oil yield appeared to be 180 s in a fluidized bed reactor at about 873 K. Further addition of (CO + CO2 ) into (N2 + H2 ) influenced the pyrolysis oil composition but the variation degree was much smaller than changing the atmospheric gas from N2 to (N2 + H2 ). phenols and aromatics but little affected the contents of alcoholic hydroxide and carboxylic acid. M. The figure intends to clarify further how the gas atmosphere affects the composition feature of the produced pyrolysis oil.E. M. Zhang et al.S. . 30 (2007) 36–41. (2) In terms of pyrolysis oil yield and quality. alcohols and phenols. The facilitated coal radial stabilization by the additional free radicals generated from CH4 should be responsible for the formation of the identified more light components including aliphatic oil. National Basic Research Project of China (No. Wang. which even improves the pyrolysis oil quality by causing more phenol production. 11. [30] and Liu et al. This. Including H2 into N2 atmosphere obviously decreased the contents of aliphatic hydrocarbons. aromatics (mono-ring). Liu. J. The preceding effects from Fig. 7 (1995) 206–210. Therefore.. 3. and both CO2 and H2 had similar specific effect on decreasing the pyrolysis oil yields with raising their contents in the reaction atmosphere. By further including CH4 in the gas to make the atmosphere simulate the pyrolysis gas. Z. Further including CH4 into the (N2 + H2 + CO + CO2 ) atmosphere obviously increased all the chemical species characterized in Fig. which even allows slight upgrading of the pyrolysis oil product. as a result of its induced enhancement on the reformation and hydrogenation of the oil species. Chem. Xu.9 wt.W. Value-added comprehensive processing of coal with topping: strategy. J. (3) The effects H2 and CO2 in the reaction atmosphere on the coal pyrolysis were proved to be mainly through their participation in the secondary reactions of generated nascent pyrolysis oil. J. phenols and alcohols in the resulting pyrolysis oil. Acknowledgements The authors are grateful to the financial support from National Natural Science Foundation of China (No. 5 (2005) 241–245. Kuxmk. [4] J. 9) but also similar oil composition features. It appeared that too high temperature would lead to more acid species.B. the use of pyrolysis gas as the reaction atmosphere in the fluidized bed pyrolytic topping process is technical feasible. Adding H2 decreased the yields of all the major oil components. which was shown to be between 50 and 180 s. which was even higher than the yield realized in N2 (about 12. carboxylic acids and alcohols but less aliphatic hydrocarbons and phenols. the high-quality pyrolysis oil characterized by high contents of light components (short C chain and mono-aromatics) should be generated at relatively low pyrolysis temperature. Lu. S. This article also demonstrated that the different pyrolysis gas species have different gas evolution characteristics. China. 11. 20776144). et al. Lin. mono-aromatics. S. complying with the literature reports of Liao et al. For example. A new process of coal topping for extracting liquid fuels.

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