Fuel 94 (2012) 563570

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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-gasication 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 gasiers. 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 GCMS 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 gasication systems. 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 carbonneutral 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 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 rst 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 gasication, or CO2 and H2O in combustion. In many coal utilization processes, the pyrolysis reaction occurs separately from gasication 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 gasication, 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

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Solid Carbonaceous Pyrolysis Material

Pyrolysis Gases (CO, H2, CH4, H2O, etc.) Tar, Oil, Naphtha Oxygenated Compounds (Phenols) Char

Gas phase reactions

(Cracking, Reforming, Combustion, CO Shift)

CO, H2, CH4, CO2, H 2O and cracking products CO, H2, CH4, CO2, H 2O

Char-gas reactions
(Gasification, Combustion, CO Shift)
Fig. 1. Coal/biomass thermochemical reaction sequence. (reproduced from [7]).

and biomass will inuence the reaction kinetics, overall conversion and product distributions during gasication and pyrolysis. There is some debate in the gasication literature over whether or not there are nonlinear kinetic and product distribution effects when biomass is added to coal. Before computational models can reasonably predict the effects of coal-biomass pyrolysis and gasication/ combustion, detailed experimental investigation is required. Theories for the nonlinear dependence of co-feeding include increased reactivity of coals with biomass volatiles, catalytic effects of biomass ash components on coal gasication kinetics, and differences in surface reactivity between coal and biomass constituents. The pyrolysis of coal may be inuenced by the presence of product gases (CO, CO2, H2, CH4, H2O, etc.) which are rapidly evolved from the biomass at high temperature. These pyrolysis gases may take part in gascoal interactions resulting in variations in reaction kinetics, conversion and product distributions [4,9,10]. Biomass is composed of a much higher quantity of oxygen containing species compared to coal, which may be a major contributor to the gascoal interactions. The production of syngas from coal is impeded by a low H:C ratio. Because of this, it has been suggested that syngas yields may be improved by adding H2 from another source, such as biomass [10]. The increased quantity of hydrogen produced from biomass devolatilization may react with evolving species from coal, thus preventing the recombination reaction. The recombination reaction impairs the conversion of coal because free radicals produced from coal devolatilization can react, or recombine, with char to produce a low reactivity char, which is undesirable. The increased presence of hydrogen may prevent the recombination reaction and promote an increase in coal conversion [11]. The thermochemical conversion of coal may also be inuenced by charcoal interactions due to the presence of alkali and alkaline earth metal species (Ca, K, Mg and Na) which are in greater abundance in biomass relative to coal [5,12]. 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 [1316]. Similarly, other studies have demonstrated that inorganic species can inuence the gasication of coal in a variety of gasifying environments including H2O, CO2 and O2 [11,14,1719]. The results showed a positive effect on the reactivity of coal pyrolysis [14,15] and gasication [11,14,1719]. The inuence of metal species on coal pyrolysis varies between coal types. The activity of the inorganic matter can be described as K $ Ca > Na for bituminous coal and Ca > K > Na for lignite [20]. Currently, it is uncertain whether alkali and alkaline earth metals in biomass will contribute catalytic activity to coal during fast, high temperature pyrolysis. The proximity of these metal-containing functional groups in biomass relative to coal will be of great importance. It is also a known fact that at elevated temperatures, volatilization of alkali and alkaline earth metals from the biomass material will occur. These volatilized species may contribute catalytic activity to coal pyrolysis as well as gas phase reactions [12]. In this study, 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. Coal and biomass species pairing was done based on geographical proximity. Illinois #6 coal is ranked as a high volatile C bituminous coal. Switchgrass (Panicum virgatum L.) is a fast growing crop native to North America and is commonly used as a biomass source for ethanol, electricity and heat production. The effect of the wt% of biomass fed into the reactor will be investigated for variations and distributions of solid, liquid and gaseous products.

2. Experimental details 2.1. Feedstocks Illinois #6 bituminous coal and switchgrass were used as the feedstocks in this study. The coal was obtained from the Penn State Coal Sample Bank and Database. The switchgrass is a Forestburg cultivar from South Dakota that was baled in mid-September and later pelletized. This feedstock was reground on site, producing a lower aspect ratio feedstock than raw switchgrass that is more desirable for its feeding qualities. The coal and biomass samples were ground and sieved to 18 50 mesh (2971000 lm) and 16 50 mesh (2971190 lm), respectively. The feedstock materials are fed into the reactor as: 100% coal. 50 wt% coal, 50 wt% biomass. 70 wt% coal, 30 wt% biomass. 85 wt% coal, 15 wt% biomass. 100% biomass.

The mixtures are weighted towards lower biomass compositions, which are more likely to be used in commercial gasier operation. Likewise, samples were not dried prior to testing, in order to better approximate feed conditions in actual gasier operation. Consol Energy supplied proximate and ultimate analyses for the coal and switchgrass, which is shown in Table 1 for both feedstocks. Volatile matter makes up about 75% of switchgrass by mass. This is nearly twice the volatile matter present in Illinois #6 coal. Ultimate analysis shows that sulfur is a dominant species ($5 wt%) present in Illinois #6 coal, however the amount of sulfur in switchgrass is only 0.12 wt%. This decrease in sulfur containing compounds is veried in qualitative product gas analysis and may help to reduce the impact of sulfur on downstream processes. Other major differences in material composition include over three times more oxygen in switchgrass than Illinois #6 coal, and coal containing more ash than in switchgrass. Typically, the ash content in late-harvest switchgrass is less than half of the reported value of 9.08% [16,21,22], however, much of this difference can be attributed to soil picked up by the switchgrass baler, as ash analysis reveals unusually high Si content (>50%) in the switchgrass ash [23,24].

N.T. Weiland et al. / Fuel 94 (2012) 563570 Table 1 Proximate and ultimate analysis of coal and biomass used in this study. Sample Illinois #6 coal Switchgrass 6.29 74.98 9.08 15.94 44.70 5.78 0.57 39.76 0.12 18.31

565

Proximate analysis (wt%, dry basis) Moisture 3.55 Volatile 42.06 Ash 11.41 Fixed carbon 46.53 Ultimate analysis (wt%, dry basis) Carbon 63.87 Hydrogen 4.78 Nitrogen 1.20 Oxygen 13.87 Sulfur 4.87 Higher heating value (calculated, dry basis) HHV (MJ/kg) 24.09

2.2. Experimental setup and procedure A schematic of the experimental setup used in this study is shown in Fig. 2. The reactor is made from a 38.1 mm OD Inconel 800H containment tube with a wall thickness of 2.77 mm and a length of about 0.91 m, housed inside a set of three resistance heaters, each 0.152 m in height. This containment vessel is lined with a quartz inner tube with a 27.0 mm ID, 1.5 mm wall thickness, and 0.705 m in length. The reactor inlet consists of a coal/biomass hopper separated from the reactor by a ball valve, which is opened to drop the sample onto a porous quartz frit of about 3 mm thickness, located in the center of the 45.6 cm hot zone dened by the height of the resistance heaters. Isothermal co-pyrolysis experiments are carried out at atmospheric pressure, and an argon sweep gas ow rate of 2000 sccm. Approximately 1.0 g of coal and/or biomass material was loaded into the hopper valve, above the hot zone, prior to testing. The top two heaters of the reactor are heated to 900 C under purge gas ow and maintained at this temperature for approximately one hour prior to introduction of the solid feed material. After the reactor has thermally reached a steady state, the purge gas bypass valve is closed and the hopper valve is opened, allowing the coal and/or biomass material to fall onto the hot frit and pyrolyze in the center of the hot zone. After dropping the sample onto the frit, pyrolysis products are transported out the bottom of the reactor by the sweep gas. The bottom of the quartz tube rests on a series of three 8 lm ashless lter papers supported by a metal screen. The exit of the reactor is maintained at a temperature of 150 C, and mass that condenses on these components, as determined by pre- and post-test weight difference, is denoted as heavy tar. Heavy tars collected during one of the triplicate tests are extracted from the lter papers using a 2:1 vol% mixture of toluene and methanol for qualitative analysis in a separate GCMS. Tars from the other two triplicate tests are extracted with acetone for later ultimate analysis. Below the heavy tar lters, the pyrolysis products are sampled at 1 Hz by a quadrupole mass spectrometer (QMS) until the reaction ceases (about 15 min). 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. The QMS is calibrated to quantitatively measure the primary gas constituents, including: argon, CO, CO2, CH4, H2, and H2O. The QMS calibration is checked daily with a NIST-traceable calibration gas bottle containing 50% Ar, 25% CO, 5% CO2, 10% CH4, and 10% H2, the quantitative gas species measurements are corrected accordingly and integrated over the course of the reaction to yield the total gas and water products. Following the QMS sampling, the product gases pass through copper coils and quartz wool in an ice bath to remove some of the

Fig. 2. Schematic of co-pyrolysis drop tube reactor.

condensable tar and water from the pyrolysis products. Tar collected on the quartz wool (light tar) is extracted with acetone for later analysis. The remainder of the condensable products is captured by another set of lter papers and a column of Drierite (anhydrous calcium sulfate) at room temperature. Mass accumulating in the cold trap and its following lters and Drierite is determined by weight difference, the measured water fraction from the QMS is subtracted from this number, and the result is denoted as light tar. Lastly, just prior to the connection to the lab vent line is a valve for capturing the product gas evolved during the rst $20 s of the reaction. Although not representative of the total gas production over the $15 min reaction, the bag sample is useful for later qualitative analysis of its minor gas constituents using a PerkinElmer Clarus 500 GCMS. A 30 m long and 0.32 mm i.d. capillary column with a silica plot coating was used in the GCMS with a helium carrier gas ow set at 1.3 mL/min. The temperature prole for this analysis was an initial hold at 35 C for 10 min, 10 C/min to 200 C and a nal hold at 200 C for 5 min.

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Overall mass balances for each test are calculated, and only those with mass closures between 90% and 105% are used in subsequent analyses. The largest source of error in the total mass measurements is the QMS gas measurements, which are integrated over about 1200 data points, and depend on the accuracy of the argon mass ow controller for quantitative measurements. Following the reactor tests, the heavy and light tars extracted with acetone, are added, a little at a time, to platinum foil sample holders, and the acetone allowed to evaporate at room temperature, until enough tar residues remain to perform an ultimate analysis per ASTM D5373. Char residues also undergo ultimate analyses, 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). The energy content of the product gas is calculated directly from the Higher Heating Value (HHV) of its measured major fuel constituents. This number is likely to be lower than its actual energy content, however, as it does not account for contributions from unmeasured energy-containing species such as H2S, and C2 C5 hydrocarbons, which appear in the product gas. 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 0.2 0.4 0.6 0.8 1 Wt% Biomass in Feedstock

Fig. 3. Product yields from pyrolysis of switchgrass and Illinois #6 coal at 900 C for varying feed blend ratios.

HHV 0:3491C 1:1783H 0:1005S 0:1034O 0:0151N 0:0211A 1

175% Carbon Hydrogen 150% Element Mass Closure Nitrogen Oxygen 125%

where HHV is in units of MJ/kg, and C, H, S, O, N, and A are the ultimate analysis percentages of carbon, hydrogen, sulfur, oxygen, nitrogen and ash on a dry basis. Prior to pyrolysis testing, the operation of the reactor was characterized with a series of tests. Varying the sweep gas ow rate showed that a minimum argon ow rate of 1500 sccm is required to avoid tar cracking and secondary char formation during the pyrolysis reaction. In addition, the QMS calibration gas bottle was made to ow through the reactor as the reactor temperature was heated from ambient temperature to 900 C. Measurements of these gas species changed by less than 3% of their original compositions, conrming that homogeneous gas phase reactions gas are negligible in the $4 s traverse time between the reaction location and the gas sampling location. This time delay, while necessary to maximize product collection efciency, is unfortunately sufcient to preclude the use of the QMS gas species data for evaluating the kinetics of the co-pyrolysis reaction. Kinetics of the copyrolysis of coal and switchgrass is the subject of ongoing work.

100%

75%

50% 0% 20% 40% 60% 80% 100% Wt% Biomass in Feedstock

Fig. 4. Element mass balances.

3.2. Elemental product distributions 3. Results and discussion 3.1. Overall product distribution Variations in gaseous, solid (char) and condensable products generated for various feed blend ratios during pyrolysis at 900 C are shown in Fig. 3. The general production trend shows that as the quantity of switchgrass in the solid feed increases, the amount of gaseous products and light tars increases linearly, while the char, water, and heavy tar products decrease linearly. This is largely consistent, qualitatively and quantitatively, with the results of Zhang et al. [10], who studied co-pyrolysis of legume straw and lignite in a drop tube reactor from 500 to 700 C, and noted a trend towards linear product distributions at higher temperatures. The large difference in char and gas pyrolysis products is expected based on the proximate analysis reported in Table 1, which shows that switchgrass contains about twice as much volatile matter as Illinois #6 coal, and less than half as much xed carbon. Ultimate analysis of the chars and tars produced in the pyrolysis experiments allows for detailed element balances to be performed. Element mass closures are shown in Fig. 4 for carbon, hydrogen, nitrogen and oxygen. The amount of heavy and light tars produced was not sufcient to obtain measurements of its sulfur content, thus its oxygen content could not be determined by difference, and this contribution to the element balance for oxygen is neglected. Overall, carbon and hydrogen balances are very good, and range from 75% to 108%. Nitrogen balances are lower, as gaseous N-containing species are not measured by the QMS. Oxygen balances are often well over 100%, even when excluding the oxygen content in the tars. This is likely due, in part, to the fact that oxygen is determined by difference, and is thus a function of the inaccuracies in the measurements of ash from the proximate analysis, and C, H, N, and S from the ultimate analyses. In particular, a measure of the mineral matter in the feedstocks and chars (unavailable for the small quantities used in this study) would be

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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. Energy content in the pyrolysis products as a function of: (a) energy content of original feedstock and (b) weight of pyrolysis product.

Wt% O from Feedstock

CO H2

20%

10%

Fig. 5. Distribution of feedstock major elements in pyrolysis products for: (a) carbon, (b) hydrogen, and (c) oxygen.

0% 0 0.2 0.4 0.6 0.8 1 Wt% Biomass in Feedstock

more accurate for this purpose than the proximate analysis ash measurement, which includes unknown mineral transformations (e.g., oxide and sulde formation, release of carbonates, etc.) that occur during the ashing process [26]. Distribution of the C, H and O components of the feedstock to the various pyrolysis products are shown in Fig. 5. Carbon from coal is shown to more likely remain in the char following pyrolysis, while the carbon in switchgrass typically forms gaseous and light tar compounds. The low carbon content of the coal char, which affects the energy analyses in Section 3.3 below, is likely due to an

Fig. 7. Distribution of gaseous pyrolysis products vs. biomass in feedstock.

erroneous result in the ultimate analysis, and contributes to the low C mass closure at this condition in Fig. 4. Hydrogen from both coal and switchgrass tends to form water and gases, with slightly more H from switchgrass also forming light tars. Oxygen from coal is more likely to form water or remain in the char, while O from switchgrass more typically yields gaseous products.

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It is interesting to note that as much hydrogen is present in gas from coal pyrolysis as from switchgrass pyrolysis, since only slightly more H is available in the switchgrass feedstock (see Table 1). The theory behind non-linear gascoal interactions supposes that an increase in hydrogen content surrounding the coal particle results from the use of biomass, which then prevents recombination reactions that decrease the reactivity of the coal char [11]. If the amount of hydrogen liberated from coal increases to the level of that of biomass at the higher temperatures investigated here, this may explain the lack of any non-linear or synergistic effects occurring in the product distribution trends as a result of this gascoal mechanism. 3.3. Energy content distributions Based on the ultimate analyses of the raw feedstocks and their pyrolysis tars and chars, the energy content (HHV) of each of the parent and product components can be evaluated per Eq. (1). Fig. 6a shows the distribution of the feedstock energy content into the various pyrolysis products. Closure of the energy balances averages 87%, with the remaining 13% likely residing in either unmeasured light (C2C5) hydrocarbons that appear in the product gas, or in highly volatile light tar species that vaporize at room temperature. Pyrolysis product energy contents are largely linear with respect to wt% of switchgrass in the feedstock. Coal mixtures mostly retain their energy in the char after pyrolysis, while biomass energy content is mostly transferred to gas and light tar products. The specic energy content of each of the products is shown in Fig. 6b, where the HHV of the char and light tar products do not vary considerably with feedstock content. Light tars are more energy dense than the chars due to higher hydrogen concentrations and the absence of ash, although the water content that is normally part of this condensable fraction is not included in this calculation. Heavy tars appear to be the most energy-dense product, though due to the small quantity of heavy tars available for ultimate analysis, particularly for high switchgrass mixtures, the results of the ultimate analysis and the subsequent energy calculation are fairly uncertain. Gas energy density is the most variable, and is largely due to the presence of more CO2 with increasing switchgrass blend ratio, as seen in the following section. 3.4. Evaluation of gaseous products The gaseous products generated by co-pyrolysis of coal and switchgrass at 900 C are presented in Fig. 7, where biomass is
Ar, CO, CH4 CO2 C2H4 C2H6 C 2H 2 100% SG

shown to produce about four times as much CO as coal. At roughly 1/3 of the weight of the original feedstock, CO represents the largest single product from the isothermal pyrolysis of switchgrass. Carbon dioxide and methane likewise increase with switchgrass content, while hydrogen decreases slightly. These results are largely linear with respect to biomass blend ratio, and again follow closely the results of Zhang et al. [10]. Primary differences in the results of this work include higher methane content and lower hydrogen content than the results of Zhang et al. This may indicate an enhancement of the methanation reaction at the higher temperatures and closer particle spacing used in the present work, though this would conict with results from equilibrium gasication product studies. Secondary volatile components are qualitatively analyzed by GCMS, as shown in Fig. 8, where major differences in identied species are observed. Gaseous products from pyrolysis of Illinois #6 coal and its blends contained sulfur species such as carbonyl sulde (COS), hydrogen sulde (H2S), carbon disulde (CS2), and sulfur dioxide (SO2) that were not present in the pure switchgrass product gas. 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. Light hydrocarbons also appear in these gas bag samples, particularly for the high switchgrass blend ratios. As discussed above, these species are not quantitatively measured but carry signicant energy content, and thus constitute a portion of the unaccounted energy from pyrolysis of the feedstocks. 3.5. Evaluation of liquid and solid products Qualitative GCMS analysis of the heavy tars from co-pyrolysis of Illinois #6 coal and switchgrass are shown in Fig. 9, where aromatic hydrocarbons are shown to be present in all of the tars. The primary differences in the analyses are the presence of benzenediols, which occur mostly in the switchgrass tar, and sulfur-containing dibenzothiophene, which only appears in the coal-derived tars. Identication of these and other heavy tar species may be important in determining the inuence of tar on downstream processes in a gasication system. Ash elemental analysis was performed via ICP OES on the raw feedstocks as well as the chars produced from pyrolysis at 900 C. As shown in Fig. 10, raw switchgrass contains signicantly higher quantities of alkali and alkaline earth metals such as Ca, K and Mg, while Illinois #6 coal contains greater amounts of transition metals such as Al, Fe and Ti. The presence of alkali and alkaline earth metals in switchgrass is signicant due to known catalytic

C 3H 6

C4H8

H2S 30% SG/70% Coal COS

15% SG/85% Coal

100% Coal

CS2

SO2

8 10 Response time (min)

12

14

16

Fig. 8. Chromatograms of switchgrass, Illinois #6 coal and biomass/coal blends from GCMS analysis of collected gas bag samples from pyrolysis at 900 C.

N.T. Weiland et al. / Fuel 94 (2012) 563570

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

10

20

30 Time [min]

40

50

Fig. 9. Chromatograms of switchgrass and Illinois #6 coal heavy tar from GCMS analysis from pyrolysis at 900 C.

100 Illinois#6 Coal - Raw Illinois#6 Coal - Char 85% ILL - 15% SG 70% ILL - 30% SG 10 50% ILL - 50% SG Switchgrass - Char Switchgrass - Raw Wt % in Ash

0.1

0.01 Al Ba Ca Fe K Mg Mn Na Sr Ti
Fig. 10. ICP OES ash analysis of feedstocks and char material produced from pyrolysis of switchgrass and Illinois #6 coal at 900 C.

activity of these metals during the thermochemical conversion of coal. 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, namely Na and Ba, and to a lesser extent, K and Mg. Removal of these catalysts from the solid char at 900 C may explain, in part, the lack of non-linear product distribution trends that might otherwise result from charcoal interactions.

4. Conclusion The thermochemical conversion of coal and biomass mixtures by isothermal pyrolysis at 900 C has been investigated for differences in solid, liquid and gaseous product distributions. These studies include primary gas analysis, ultimate analysis of tar and char products, ICP OES elemental analysis of chars, and qualitative GC/MS analysis of trace gases and heavy tars. Contrary to some of

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the existing literature on coal/biomass co-pyrolysis, product distributions appear to be linear with respect to the wt% of switchgrass in the feedstock. This linear relationship extends to individual major product gas species, heavy and light tar fractions, water production, and energy content in the pyrolysis products. This result may be due to the nature of fast pyrolysis experiments. As expected, pyrolysis of coal tends to yield more char and heavy tar components than pyrolysis of switchgrass, while switchgrass yields more gas and light tar products. As previously discussed, one source of coal-biomass interaction is gascoal reactions. These interactions may be more pronounced in a slow pyrolysis reaction typically observed during thermogravimetric experiments. Alternately, catalytic interactions may have greater inuence on co-gasication and do not appear to have a major impact on the product distributions during fast co-pyrolysis. Qualitative GC/MS analysis of the product gases show that isothermal coal pyrolysis yields sulfur containing species, such as H2S, COS, which do not appear in the low-sulfur switchgrass product gas, while low molecular weight aliphatic hydrocarbons (C2C4 species) were more prevalent in the biomass product gas. In the heavy tar analysis, the coal tar contained more aromatic hydrocarbons, whereas the switchgrass tar contained some chlorine-containing compounds. This work demonstrates that the product distributions from isothermal co-pyrolysis of a coal/biomass mixture can be estimated as a mass-weighted sum of the product distributions of the pure feedstocks. Such a result is inherently useful in the development of copyrolysis and co-gasication processes, where knowledge of the char, tar, and gas compositions are critical in the development of downstream processing and gas cleaning systems. This result also holds value in the determination of co-pyrolysis kinetics, where product distributions must also be determined. These results may not hold, however, under slower heating rate conditions, at lower temperatures, or under reactive (gasication) atmospheres. The effects of these conditions are the subject of future work in this eld. Acknowledgements This technical effort was performed in support of the National Energy Technology Laboratorys ongoing research in Advanced Gasication Technologies under the RES Contract DE-FE0004000.

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