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Fuel 94 (2012) 563–570

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Fuel
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Product distributions from isothermal co-pyrolysis of coal and biomass
Nathan T. Weiland a,b,⇑, Nicholas C. Means a,c, Bryan D. Morreale a
a

National Energy Technology Laboratory, Pittsburgh, PA, United States Mechanical & Aerospace Engineering Dept., West Virginia Univ., Morgantown, WV, United States c URS Corporation, Pittsburgh, PA, United States
b

a r t i c l e

i n f o

a b s t r a c t
Co-gasification and co-pyrolysis of coal and biomass are being studied as a means to reduce the carbon footprint of an IGCC plant. Co-feeding creates many challenges in the thermochemical conversion of coal/ biomass such as the variable nature of biomass feedstocks, potential nonlinear reaction rate effects during conversion and the varying composition of the products. An experimental study on isothermal copyrolysis of Illinois #6 coal and switchgrass was done in a drop reactor at 900 °C to investigate the effects of co-feeding on pyrolysis product distributions under conditions relevant to transport gasifiers. Coal/biomass mixtures were fed to the reactor in feed ratios of 100/0, 85/15, 70/30, 50/50, and 0/100, while primary gaseous products (CO, CO2, CH4, H2 and H2O) were monitored and analyzed online. Ultimate analysis of solid and liquid products is used to track the distribution of the feedstocks’ elements and energy content into its pyrolysis products, while GC–MS and ash elemental analyses are provided to more fully characterize these products. Experimental results show that under the conditions studied, product distributions do not display any non-linear effects, and can be estimated as a mass-weighted sum of the product distributions of the pure feedstocks. This result is likely due to the higher temperatures used in this study, though it is inherently useful in the development of higher-temperature gasification systems. Ó 2011 Elsevier Ltd. All rights reserved.

Article history: Received 3 June 2011 Received in revised form 5 October 2011 Accepted 20 October 2011 Available online 7 November 2011 Keywords: Pyrolysis Biomass Switchgrass Isothermal Products Coal

1. Introduction The thermochemical conversion of coal is a complex reaction process which takes advantage of an abundant natural resource. Recoverable coal reserves in the United States have been estimated at 260 billion short tons. This is approximately 27% of the total world recoverable coal reserves [1]. Coal can be burned to produce heat, coupled to gas turbines or fuel cells to produce electricity or converted into synthesis gas (syngas) to produce liquid fuels and other chemicals. The use of carbon–neutral biomass is one of the most attractive ways of reducing CO2 emissions from coal, since the carbon in biomass is generated from atmospheric CO2 by photosynthesis. Combined thermochemical conversion of coal and biomass for power may become a carbon-negative process with the use of carbon capture and sequestration (CCS) technologies. Biomass is the third largest energy resource in the world behind coal and oil [2,3]. Plant derived biomass material is commonly available from forestry and lumber waste, algae, crop residue and industrial waste [4,5]. Unfortunately, the majority of the potential energy from these biomass sources is not realized and is lost to natural decomposition [6].

⇑ Corresponding author at: Mechanical & Aerospace Engineering Dept., West Virginia Univ., Morgantown, WV, United States. Tel.: +1 412 386 4649. E-mail address: nathan.weiland@mail.wvu.edu (N.T. Weiland).
0016-2361/$ - see front matter Ó 2011 Elsevier Ltd. All rights reserved. doi:10.1016/j.fuel.2011.10.046

The addition of biomass to coal during thermal conversion may have various effects. The reaction of coal and biomass to syngas may be impacted due to synergistic interactions and may show variations in thermal reactivity or in the chemical or physical properties of the solid, liquid and gaseous products [4]. An overview of the thermochemical conversion process is shown in Fig. 1 [7]. During thermochemical conversion, a solid carbonaceous material first undergoes thermal decomposition (pyrolysis) to products such as syngas, tars, phenols and char. The volatile products can then take part in gas phase reactions such as cracking, reforming, combustion and shift. Finally, the solid char can react to produce syngas compounds in gasification, or CO2 and H2O in combustion. In many coal utilization processes, the pyrolysis reaction occurs separately from gasification or combustion. Because of this, understanding the pyrolysis reaction is important when analyzing thermochemical conversion technologies. The focus of this paper is on the pyrolysis reaction as a precursor to gasification, though the results apply equally well to combustion processes. Primary pyrolysis is a devolatilization reaction which involves the breakdown of the macromolecular structure of the solid fuel material and the release of volatile products. A secondary devolatilization occurs at higher temperatures resulting in the release of secondary volatile gases such as CH4, C2H4, and HCN [8]. Although much work has been done on the thermochemical conversion of coal, it is not well understood how co-feeding coal

Weiland et al. volatilization of alkali and alkaline earth metals from the biomass material will occur. This is nearly twice the volatile matter present in Illinois #6 coal. The increased quantity of hydrogen produced from biomass devolatilization may react with evolving species from coal. Illinois #6 coal is ranked as a high volatile C bituminous coal.24]. Volatile matter makes up about 75% of switchgrass by mass. CH4. Likewise. The pyrolysis of coal may be influenced by the presence of product gases (CO. in order to better approximate feed conditions in actual gasifier operation. much of this difference can be attributed to soil picked up by the switchgrass baler. Feedstocks Illinois #6 bituminous coal and switchgrass were used as the feedstocks in this study. electricity and heat production. however. however the amount of sulfur in switchgrass is only 0. high temperature pyrolysis. The thermochemical conversion of coal may also be influenced by ‘‘char–coal’’ interactions due to the presence of alkali and alkaline earth metal species (Ca. Mg and Na) which are in greater abundance in biomass relative to coal [5. .14. The coal was obtained from the Penn State Coal Sample Bank and Database. The results showed a positive effect on the reactivity of coal pyrolysis [14. Switchgrass (Panicum virgatum L. it is uncertain whether alkali and alkaline earth metals in biomass will contribute catalytic activity to coal during fast. catalytic effects of biomass ash components on coal gasification kinetics. H2. CO2. CH4. and differences in surface reactivity between coal and biomass constituents. The production of syngas from coal is impeded by a low H:C ratio. which may be a major contributor to the ‘‘gas–coal’’ interactions. The feedstock materials are fed into the reactor as: – – – – – 100% coal. CO2.17–19].15] and gasification [11. H2O.14. H2. This decrease in sulfur containing compounds is verified in qualitative product gas analysis and may help to reduce the impact of sulfur on downstream processes. 70 wt% coal. or recombine. CH4. It is also a known fact that at elevated temperatures. which is shown in Table 1 for both feedstocks. 1. H 2O and cracking products CO. mixtures of Illinois #6 coal and switchgrass will be co- fed into a drop-tube reactor at 900 °C under an inert atmosphere of argon. samples were not dried prior to testing. Because of this. The activity of the inorganic matter can be described as K $ Ca > Na for bituminous coal and Ca > K > Na for lignite [20].564 N. which is undesirable. other studies have demonstrated that inorganic species can influence the gasification of coal in a variety of gasifying environments including H2O. The switchgrass is a Forestburg cultivar from South Dakota that was baled in mid-September and later pelletized.12]. CO2. 15 wt% biomass. 50 wt% biomass. Currently.9.T. Combustion. conversion and product distributions [4. Typically. such as biomass [10]. detailed experimental investigation is required. it has been suggested that syngas yields may be improved by adding H2 from another source. Experimental details 2. Before computational models can reasonably predict the effects of coal-biomass pyrolysis and gasification/ combustion. The recombination reaction impairs the conversion of coal because free radicals produced from coal devolatilization can react. H 2O Char-gas reactions (Gasification. overall conversion and product distributions during gasification and pyrolysis.21. 85 wt% coal. etc. CO2 and O2 [11. etc. and biomass will influence the reaction kinetics.1. Biomass is composed of a much higher quantity of oxygen containing species compared to coal. which are more likely to be used in commercial gasifier operation. The mixtures are weighted towards lower biomass compositions. 30 wt% biomass. producing a lower aspect ratio feedstock than raw switchgrass that is more desirable for its feeding qualities. These pyrolysis gases may take part in ‘‘gas–coal’’ interactions resulting in variations in reaction kinetics. and coal containing more ash than in switchgrass. The effect of the wt% of biomass fed into the reactor will be investigated for variations and distributions of solid. 50 wt% coal. with char to produce a low reactivity char. Consol Energy supplied proximate and ultimate analyses for the coal and switchgrass. (reproduced from [7]). Previous studies have shown that the presence of these alkali and alkaline earth metals can have a catalytic effect on the reactivity and volatile product distribution during pyrolysis [13–16]. H2. These volatilized species may contribute catalytic activity to coal pyrolysis as well as gas phase reactions [12]. Other major differences in material composition include over three times more oxygen in switchgrass than Illinois #6 coal.10]. The proximity of these metal-containing functional groups in biomass relative to coal will be of great importance. K. H2. There is some debate in the gasification literature over whether or not there are nonlinear kinetic and product distribution effects when biomass is added to coal. The increased presence of hydrogen may prevent the recombination reaction and promote an increase in coal conversion [11]. Reforming. Coal/biomass thermochemical reaction sequence. CH4. Coal and biomass species pairing was done based on geographical proximity. Naphtha Oxygenated Compounds (Phenols) Char Gas phase reactions (Cracking. Combustion. Similarly. Oil. as ash analysis reveals unusually high Si content (>50%) in the switchgrass ash [23. 2. CO Shift) Fig. Ultimate analysis shows that sulfur is a dominant species ($5 wt%) present in Illinois #6 coal. The influence of metal species on coal pyrolysis varies between coal types. This feedstock was reground on site.) Tar.17–19]. / Fuel 94 (2012) 563–570 Solid Carbonaceous Pyrolysis Material Pyrolysis Gases (CO. CO Shift) CO. 100% biomass. In this study.22]. The coal and biomass samples were ground and sieved to À18 Â 50 mesh (297–1000 lm) and À16 Â 50 mesh (297–1190 lm).) which are rapidly evolved from the biomass at high temperature. respectively. Theories for the nonlinear dependence of co-feeding include increased reactivity of coals with biomass volatiles. liquid and gaseous products. the ash content in late-harvest switchgrass is less than half of the reported value of 9.12 wt%. H2O.) is a fast growing crop native to North America and is commonly used as a biomass source for ethanol. thus preventing the recombination reaction.08% [16.

25% CO. the quantitative gas species measurements are corrected accordingly and integrated over the course of the reaction to yield the total gas and water products. Tars from the other two triplicate tests are extracted with acetone for later ultimate analysis.06 Ash 11. allowing the coal and/or biomass material to fall onto the hot frit and pyrolyze in the center of the hot zone.29 74.76 0. is denoted as ‘‘heavy tar.1 mm OD Inconel 800H containment tube with a wall thickness of 2. Isothermal co-pyrolysis experiments are carried out at atmospheric pressure.’’ Heavy tars collected during one of the triplicate tests are extracted from the filter papers using a 2:1 vol% mixture of toluene and methanol for qualitative analysis in a separate GC–MS. CO2.152 m in height. Weiland et al. and H2O.3 mL/min. Sample Illinois #6 coal Switchgrass 6. Following the QMS sampling. condensable tar and water from the pyrolysis products. capillary column with a silica plot coating was used in the GC–MS with a helium carrier gas flow set at 1. 1. dry basis) Carbon 63. H2.41 Fixed carbon 46. Tar collected on the quartz wool (light tar) is extracted with acetone for later analysis. the product gases pass through copper coils and quartz wool in an ice bath to remove some of the Fig.T.32 mm i.91 m. The exit of the reactor is maintained at a temperature of 150 °C.87 Hydrogen 4. above the hot zone. and an argon sweep gas flow rate of 2000 sccm. This containment vessel is lined with a quartz inner tube with a 27. The reactor is made from a 38. dry basis) HHV (MJ/kg) 24. Mass accumulating in the cold trap and its following filters and Drierite is determined by weight difference. 2. which is opened to drop the sample onto a porous quartz frit of about 3 mm thickness. The QMS is calibrated to quantitatively measure the primary gas constituents. 10% CH4. Experimental setup and procedure A schematic of the experimental setup used in this study is shown in Fig. the purge gas bypass valve is closed and the hopper valve is opened.78 Nitrogen 1.31 565 Proximate analysis (wt%.98 9. just prior to the connection to the lab vent line is a valve for capturing the product gas evolved during the first $20 s of the reaction. pyrolysis products are transported out the bottom of the reactor by the sweep gas. dry basis) Moisture 3. prior to testing. The top two heaters of the reactor are heated to 900 °C under purge gas flow and maintained at this temperature for approximately one hour prior to introduction of the solid feed material.70 5. The QMS calibration is checked daily with a NIST-traceable calibration gas bottle containing 50% Ar. and 10% H2.87 Sulfur 4. Approximately 1. / Fuel 94 (2012) 563–570 Table 1 Proximate and ultimate analysis of coal and biomass used in this study.08 15. located in the center of the 45. 5% CO2.57 39. and 0. 2. and mass that condenses on these components.53 Ultimate analysis (wt%.6 cm hot zone defined by the height of the resistance heaters.20 Oxygen 13. All connections above this point are maintained at 150 °C by external heat tape to prevent condensation of pyrolysis products out of the product stream. . housed inside a set of three resistance heaters.94 44. The temperature profile for this analysis was an initial hold at 35 °C for 10 min. After the reactor has thermally reached a steady state. as determined by pre. Schematic of co-pyrolysis drop tube reactor. Although not representative of the total gas production over the $15 min reaction.12 18.705 m in length. the measured water fraction from the QMS is subtracted from this number.and post-test weight difference.0 g of coal and/or biomass material was loaded into the hopper valve. Below the heavy tar filters.55 Volatile 42.09 2. The reactor inlet consists of a coal/biomass hopper separated from the reactor by a ball valve. 10 °C/min to 200 °C and a final hold at 200 °C for 5 min. CO. the pyrolysis products are sampled at 1 Hz by a quadrupole mass spectrometer (QMS) until the reaction ceases (about 15 min). CH4. and the result is denoted as ‘‘light tar.78 0.5 mm wall thickness.d. the bag sample is useful for later qualitative analysis of its minor gas constituents using a PerkinElmer Clarus 500 GC–MS. The remainder of the condensable products is captured by another set of filter papers and a column of Drierite (anhydrous calcium sulfate) at room temperature. each 0.N.87 Higher heating value (calculated.’’ Lastly. A 30 m long and 0. The bottom of the quartz tube rests on a series of three 8 lm ashless filter papers supported by a metal screen.77 mm and a length of about 0.0 mm ID. including: argon.2. After dropping the sample onto the frit.

and the chars and raw feedstocks are all analyzed per ASTM standard D6349-98 for their ash content by Inductively Coupled Plasma Optical Emission Spectrometry (ICP OES). This number is likely to be lower than its actual energy content. This is likely due. The general production trend shows that as the quantity of switchgrass in the solid feed increases. a little at a time.T. Product yields from pyrolysis of switchgrass and Illinois #6 coal at 900 °C for varying feed blend ratios. to platinum foil sample holders. oxygen. water. H. 100% 75% 50% 0% 20% 40% 60% 80% 100% Wt% Biomass in Feedstock Fig. N. solid (char) and condensable products generated for various feed blend ratios during pyrolysis at 900 °C are shown in Fig. 4. the QMS calibration gas bottle was made to flow through the reactor as the reactor temperature was heated from ambient temperature to 900 °C. Element mass balances. Element mass closures are shown in Fig. The large difference in char and gas pyrolysis products is expected based on the proximate analysis reported in Table 1.8 1 Wt% Biomass in Feedstock Fig. In particular. as it does not account for contributions from unmeasured energy-containing species such as H2S.566 N. thus its oxygen content could not be determined by difference. Char residues also undergo ultimate analyses. O. which are integrated over about 1200 data points. The HHV (dry basis) of the feedstocks and their chars and tars are calculated from their ultimate analyses according to the formula developed by Channiwala and Parikh [25]: 60% Char 50% Wt% of Feedstock Gas Water Heavy Tar Light Tar 40% 30% 20% 10% 0% 0 0. and A are the ultimate analysis percentages of carbon. and the acetone allowed to evaporate at room temperature. and heavy tar products decrease linearly. and S from the ultimate analyses. qualitatively and quantitatively. however. The amount of heavy and light tars produced was not sufficient to obtain measurements of its sulfur content. and range from 75% to 108%. and C. HHV ¼ 0:3491C þ 1:1783H þ 0:1005S À 0:1034O À 0:0151N À 0:0211A ð1Þ 175% Carbon Hydrogen 150% Element Mass Closure Nitrogen Oxygen 125% where HHV is in units of MJ/kg. nitrogen and oxygen. while the char. Weiland et al. 3. which shows that switchgrass contains about twice as much volatile matter as Illinois #6 coal. is unfortunately sufficient to preclude the use of the QMS gas species data for evaluating the kinetics of the co-pyrolysis reaction. 3. which appear in the product gas. hydrogen. S. carbon and hydrogen balances are very good. and depend on the accuracy of the argon mass flow controller for quantitative measurements. while necessary to maximize product collection efficiency. with the results of Zhang et al. This is largely consistent. The energy content of the product gas is calculated directly from the Higher Heating Value (HHV) of its measured major fuel constituents. and noted a trend towards linear product distributions at higher temperatures. Overall product distribution Variations in gaseous. even when excluding the oxygen content in the tars. the amount of gaseous products and light tars increases linearly. a measure of the mineral matter in the feedstocks and chars (unavailable for the small quantities used in this study) would be . until enough tar residues remain to perform an ultimate analysis per ASTM D5373. sulfur. Kinetics of the copyrolysis of coal and switchgrass is the subject of ongoing work. in part.2. and less than half as much fixed carbon. [10]. and C. H. Nitrogen balances are lower.6 0. the heavy and light tars extracted with acetone. Overall. Prior to pyrolysis testing. to the fact that oxygen is determined by difference. who studied co-pyrolysis of legume straw and lignite in a drop tube reactor from 500 to 700 °C. and only those with mass closures between 90% and 105% are used in subsequent analyses. and this contribution to the element balance for oxygen is neglected. confirming that homogeneous gas phase reactions gas are negligible in the $4 s traverse time between the reaction location and the gas sampling location. N. Following the reactor tests. hydrogen. / Fuel 94 (2012) 563–570 Overall mass balances for each test are calculated. Results and discussion 3.4 0. as gaseous N-containing species are not measured by the QMS. 4 for carbon. The largest source of error in the total mass measurements is the QMS gas measurements. and is thus a function of the inaccuracies in the measurements of ash from the proximate analysis. Measurements of these gas species changed by less than 3% of their original compositions. In addition. nitrogen and ash on a dry basis. Elemental product distributions 3. and C2– C5 hydrocarbons. the operation of the reactor was characterized with a series of tests.1. are added. Ultimate analysis of the chars and tars produced in the pyrolysis experiments allows for detailed element balances to be performed. 3. Oxygen balances are often well over 100%. Varying the sweep gas flow rate showed that a minimum argon flow rate of 1500 sccm is required to avoid tar cracking and secondary char formation during the pyrolysis reaction. This time delay.2 0.

. 7. etc. (b) hydrogen.g.2 0. erroneous result in the ultimate analysis.T. oxide and sulfide formation. Carbon from coal is shown to more likely remain in the char following pyrolysis.8 1 Wt% Biomass in Feedstock more accurate for this purpose than the proximate analysis ash measurement. 0% 0 0. Energy content in the pyrolysis products as a function of: (a) energy content of original feedstock and (b) weight of pyrolysis product. Distribution of the C. . Hydrogen from both coal and switchgrass tends to form water and gases. which affects the energy analyses in Section 3. H and O components of the feedstock to the various pyrolysis products are shown in Fig. and contributes to the low C mass closure at this condition in Fig. which includes unknown mineral transformations (e. 5. The low carbon content of the coal char. / Fuel 94 (2012) 563–570 567 (a) Wt% C from Feedstock 60% Char 50% 40% 30% 20% 10% 0% 0% Heavy Tar Light Tar Gas (a) 60% Percent of Feedstock Energy 50% 40% 30% 20% 10% 0% 0% Char Gas Heavy Tar Light Tar 20% 40% 60% 80% 100% Wt% Biomass in Feedstock 20% 40% 60% 80% 100% (b) Wt% H from Feedstock Wt% Biomass in Feedstock 50% Char 40% 30% 20% 10% 0% 0% Heavy Tar Light Tar Water Gas (b) HHV of Product (MJ/kg) 40 35 30 25 20 15 10 5 Char Gas Feedstock 0 0% 20% 40% 60% 80% 100% Wt% Biomass in Feedstock Heavy Tar Light Tar 20% 40% 60% 80% 100% Wt% Biomass in Feedstock (c) 100% Char 80% Water Gas 60% 40% 20% 0% 0% -20% Wt% Biomass in Feedstock 20% 40% 60% 80% 100% Wt% of Feedstock 30% 40% CO2 CH4 Fig. 6.4 0. 5. biomass in feedstock. while O from switchgrass more typically yields gaseous products.6 0. Oxygen from coal is more likely to form water or remain in the char. while the carbon in switchgrass typically forms gaseous and light tar compounds. with slightly more H from switchgrass also forming light tars. release of carbonates.) that occur during the ashing process [26]. Distribution of feedstock major elements in pyrolysis products for: (a) carbon.3 below. 4.N. Wt% O from Feedstock CO H2 20% 10% Fig. Weiland et al. is likely due to an Fig. and (c) oxygen. Distribution of gaseous pyrolysis products vs.

. 7. which occur mostly in the switchgrass tar. Light hydrocarbons also appear in these gas bag samples. Pyrolysis product energy contents are largely linear with respect to wt% of switchgrass in the feedstock. Closure of the energy balances averages 87%. Energy content distributions Based on the ultimate analyses of the raw feedstocks and their pyrolysis tars and chars. Heavy tars appear to be the most energy-dense product. As discussed above. 3. Ash elemental analysis was performed via ICP OES on the raw feedstocks as well as the chars produced from pyrolysis at 900 °C. carbon disulfide (CS2).568 N. [10]. which only appears in the coal-derived tars. where major differences in identified species are observed. 6a shows the distribution of the feedstock energy content into the various pyrolysis products. 3. raw switchgrass contains significantly higher quantities of alkali and alkaline earth metals such as Ca. hydrogen sulfide (H2S). and again follow closely the results of Zhang et al. the energy content (HHV) of each of the parent and product components can be evaluated per Eq. and sulfur dioxide (SO2) that were not present in the pure switchgrass product gas. particularly for the high switchgrass blend ratios. Evaluation of liquid and solid products Qualitative GC–MS analysis of the heavy tars from co-pyrolysis of Illinois #6 coal and switchgrass are shown in Fig. as shown in Fig. the results of the ultimate analysis and the subsequent energy calculation are fairly uncertain. As shown in Fig. Gas energy density is the most variable. Weiland et al. this may explain the lack of any non-linear or synergistic effects occurring in the product distribution trends as a result of this ‘‘gas–coal’’ mechanism. Identification of these and other heavy tar species may be important in determining the influence of tar on downstream processes in a gasification system. Evaluation of gaseous products The gaseous products generated by co-pyrolysis of coal and switchgrass at 900 °C are presented in Fig. while biomass energy content is mostly transferred to gas and light tar products. This result agrees with expected species present based on the high quantity of sulfur in Illinois #6 coal compared to switchgrass as seen in the ultimate analysis and Table 1. CO. 8. Primary differences in the results of this work include higher methane content and lower hydrogen content than the results of Zhang et al. and sulfur-containing dibenzothiophene. while hydrogen decreases slightly. where the HHV of the char and light tar products do not vary considerably with feedstock content.T. and is largely due to the presence of more CO2 with increasing switchgrass blend ratio. (1). Chromatograms of switchgrass. which then prevents recombination reactions that decrease the reactivity of the coal char [11].5. though due to the small quantity of heavy tars available for ultimate analysis. where biomass is Ar. 3. CH4 CO2 C2H4 C2H6 C 2H 2 100% SG shown to produce about four times as much CO as coal. and thus constitute a portion of the unaccounted energy from pyrolysis of the feedstocks. where aromatic hydrocarbons are shown to be present in all of the tars. CO represents the largest single product from the isothermal pyrolysis of switchgrass. Carbon dioxide and methane likewise increase with switchgrass content. 10.3. At roughly 1/3 of the weight of the original feedstock. K and Mg. Coal mixtures mostly retain their energy in the char after pyrolysis. 6b. as seen in the following section. This may indicate an enhancement of the methanation reaction at the higher temperatures and closer particle spacing used in the present work. particularly for high switchgrass mixtures. Secondary volatile components are qualitatively analyzed by GC–MS. with the remaining 13% likely residing in either unmeasured light (C2–C5) hydrocarbons that appear in the product gas. Gaseous products from pyrolysis of Illinois #6 coal and its blends contained sulfur species such as carbonyl sulfide (COS). or in highly volatile light tar species that vaporize at room temperature. / Fuel 94 (2012) 563–570 It is interesting to note that as much hydrogen is present in gas from coal pyrolysis as from switchgrass pyrolysis. these species are not quantitatively measured but carry significant energy content. The theory behind non-linear ‘‘gas–coal’’ interactions supposes that an increase in hydrogen content surrounding the coal particle results from the use of biomass. The primary differences in the analyses are the presence of benzenediols.4. The presence of alkali and alkaline earth metals in switchgrass is significant due to known catalytic C 3H 6 C4H8 H2S 30% SG/70% Coal COS 15% SG/85% Coal 100% Coal CS2 SO2 0 2 4 6 8 10 Response time (min) 12 14 16 Fig. although the water content that is normally part of this condensable fraction is not included in this calculation. Fe and Ti. since only slightly more H is available in the switchgrass feedstock (see Table 1). The specific energy content of each of the products is shown in Fig. Light tars are more energy dense than the chars due to higher hydrogen concentrations and the absence of ash. though this would conflict with results from equilibrium gasification product studies. If the amount of hydrogen liberated from coal increases to the level of that of biomass at the higher temperatures investigated here. Fig. 8. while Illinois #6 coal contains greater amounts of transition metals such as Al. Illinois #6 coal and biomass/coal blends from GC–MS analysis of collected gas bag samples from pyrolysis at 900 °C. These results are largely linear with respect to biomass blend ratio. 9.

10. ultimate analysis of tar and char products.30% SG 10 50% ILL . ICP OES ash analysis of feedstocks and char material produced from pyrolysis of switchgrass and Illinois #6 coal at 900 °C. ICP OES elemental analysis of chars. 4. / Fuel 94 (2012) 563–570 Methyl Benzenediol 569 Diethyl Phthalate Methyl Anthracene Propoxy Phenol Methyl Pyrene Benzaldehyde Phenol Methyl Phenol Hydroquinone Naphthalenol Benzenediol Fluorene Solvent Solvent Triphenylene Biphenylene Anthracene Pyrene 100% SG 30% SG/ 70% Coal 15% SG/ 85% Coal 100% Coal 0 10 20 30 Time [min] 40 50 Fig. Contrary to some of . Removal of these catalysts from the solid char at 900 °C may explain. Comparison of the char ash contents with the raw feedstocks shows that some alkali and alkaline earth ash components are more likely to volatilize during pyrolysis.Char 85% ILL . These studies include primary gas analysis. in part. Conclusion The thermochemical conversion of coal and biomass mixtures by isothermal pyrolysis at 900 °C has been investigated for differences in solid. and to a lesser extent.Raw Wt % in Ash 1 0.N.Raw Illinois#6 Coal . and qualitative GC/MS analysis of trace gases and heavy tars. the lack of non-linear product distribution trends that might otherwise result from ‘‘char–coal’’ interactions.Char Switchgrass . activity of these metals during the thermochemical conversion of coal. 9. K and Mg. namely Na and Ba. 100 Illinois#6 Coal . Weiland et al. Chromatograms of switchgrass and Illinois #6 coal heavy tar from GC–MS analysis from pyrolysis at 900 °C.50% SG Switchgrass . liquid and gaseous product distributions.T.1 0.15% SG 70% ILL .01 Al Ba Ca Fe K Mg Mn Na Sr Ti Fig.

while switchgrass yields more gas and light tar products. Qualitative GC/MS analysis of the product gases show that isothermal coal pyrolysis yields sulfur containing species. Development of switchgrass (Panicum virgatum) as a bioenergy feedstock in the United States. [18] Veraa MJ. [7] Higman C. [20] Lemaignen L et al. Cai N-s.30:880–91. [5] Vassilev SV et al. which do not appear in the low-sulfur switchgrass product gas. Genotypic variability in mineral composition of switchgrass. As expected.81:315–26. Kszos LA.99:8022–6.86:353–9. Fuel 2007. Co-gasification reactivity of coal and woody biomass in hightemperature gasification. where product distributions must also be determined. The effects of these conditions are the subject of future work in this field. A TG-FTIR study on catalytic pyrolysis of coal. Effect of alkali metal catalysts on gasification of coal char. reed canarygrass. [11] Sjöström K et al. Yaman S. [16] Fahmi R et al.83:713–8. [17] Zhu W et al.34:48–53. such as H2S. one source of coal-biomass interaction is ‘‘gas–coal’’ reactions. Effects of volatile–char interactions on the volatilisation of alkali and alkaline earth metallic species during the pyrolysis of biomass.570 N. Energy Fuels 2010. A review on gasification of biomass. Fuel 2010. whereas the switchgrass tar contained some chlorine-containing compounds. [19] Kajitani S et al. Such a result is inherently useful in the development of copyrolysis and co-gasification processes.78:1189–94. Combustion of agricultural residues. New Jersey: Wiley. pyrolysis of coal tends to yield more char and heavy tar components than pyrolysis of switchgrass. This result may be due to the nature of fast pyrolysis experiments. The effect of alkali metals on combustion and pyrolysis of Lolium and Festuca grasses. 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