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Is Elevated Pressure Required To Achieve a High Fixed-Carbon Yield of Charcoal from Biomass? Part 1: Round-Robin Results for Three Different Corncob Materials
Liang Wang, Marta Trninic, yvind Skreiberg, Morten Gronli, Roland Considine,|| and Michael Jerry Antal, Jr.*,||

Department of Energy and Process Engineering, Norwegian University of Science and Technology (NTNU), Kolbjrn Hejes vei 1B, NO-7491 Trondheim, Norway Department of Process Engineering, Faculty of Mechanical Engineering, University of Belgrade, Kraljice Marije 16, 11000 Belgrade, Serbia SINTEF Energy Research, Sem Saelands vei 11, NO-7465 Trondheim, Norway Hawaii Natural Energy Institute, School of Ocean and Earth Science and Technology, University of Hawaii at Manoa, Honolulu, Hawaii 96822, United States ABSTRACT: Elevated pressure secures the highest xed-carbon yields of charcoal from corncob. Operating at a pressure of 0.8 MPa, a ash-carbonization reactor realizes xed-carbon yields that range from 70 to 85% of the theoretical thermochemical equilibrium value from Waimanalo corncob. The xed-carbon yield is reduced to a range from 68 to 75% of the theoretical value when whole Waimanalo corncobs are carbonized under nitrogen at atmospheric pressure in an electrically heated mue furnace. The lowest xed-carbon yields are obtained by the standard proximate analysis procedure for biomass feedstocks; this yield falls in a range from 49 to 54% of the theoretical value. A round-robin study of corncob charcoal and xed-carbon yields involving three dierent thermogravimetric analyzers (TGAs) revealed the impact of vapor-phase reactions on the formation of charcoal. Deep crucibles that limit the egress of volatiles from the pyrolyzing solid greatly enhance charcoal and xed-carbon yields. Likewise, capped crucibles with pinholes increase the charcoal and xed-carbon yields compared to values obtained from open crucibles. Large corncob particles oer much higher yields than small particles. These ndings show that secondary reactions involving vapor-phase species (or nascent vapor-phase species) are at least as inuential as primary reactions in the formation of charcoal. Our results oer considerable guidance to industry for its development of ecient biomass carbonization technologies. Size reduction handling of biomass (e.g., tub grinders and chippers), which can be a necessity in the eld, signicantly reduces the xed-carbon yield of charcoal. Fluidized-bed and transport reactors, which require small particles and minimize the interaction of pyrolytic volatiles with solid charcoal, cannot realize high yields of charcoal from biomass. When a high yield of corncob charcoal is desired, whole corncobs should be carbonized at elevated pressure. Under these circumstances, carbonization is both ecient and quick.

INTRODUCTION Coal combustion is the largest source of carbon dioxide emissions in the U.S.A.1 Alternatives to coal-red powerplants (e.g., wind, photovoltaics, solar thermal, natural gas, etc.) are now being deployed, but cost-competitive substitutes for coal as a reductant (i.e., coke) are lacking. CO2 emissions from the iron and steel industries represented 16% of energy-related coal CO2 emissions in 2000.2 During that year, coal use was responsible for 8.7 Gt or 37% of global CO2 emissions from fossil fuels. In 2008, CO2 emissions because of coal grew to 12.6 Gt (i.e., 42% of global CO2 emissions).3 This growth of emissions was (in part) due to world crude steel production that increased from 848 Mt in 2000 to 1.3 Gt in 2008.4 Most of the CO2 emissions associated with conventional crude steelmaking result from the reduction process in a blast furnace,5 whereby coke made from hard coal and/or pulverized coal made from steam coal are used to convert iron ore into iron. The substitution of biocarbon (i.e., charcoal) for coal in the iron and steel industry can reduce CO2 emissions6 if the biocarbon is manufactured eciently from sustainably grown
r 2011 American Chemical Society

biomass. This use of biocarbon is not novel; before the dawn of recorded history, mankind employed charcoal to smelt tin for the manufacture of bronze tools,7 and today in Brazil, blast furnaces use charcoal produced from Eucalyptus wood that is cultivated nearby.8 Likewise, the Norwegian ferroalloy industry makes heavy use of charcoal imports from the Pacic.9 Unfortunately, biocarbon is not produced eciently by conventional technology;1012 consequently, greenhouse gas emissions associated with biocarbon production are unnecessarily large and worrisome.1315 The goal of this work is to learn what reaction conditions oer the highest yields of biocarbon from biomass. Anxiety about the ecient production of charcoal and its resultant properties motivated one of the earliest publications concerned with industrial chemistry research. In 1851, Violette, who was Commissioner of Gunpowder Production in France, the same post that was held earlier by Lavoisier, released the
Received: March 23, 2011 Revised: June 2, 2011 Published: June 02, 2011
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Energy & Fuels rst16 of two important papers16,17 concerning the production and properties of charcoal. Violette observed very high yields of charcoal when carbonization was conducted at high pressure. His observations were conrmed by Palmer18 in 1914 and Bergstrom19,20 in 1915. Almost 7 decades passed before Mok and Antal21,22 reported an increase from 12 to 22% in the yield of charcoal from cellulose when the gas pressure was increased from 0.1 to 2.5 MPa. Their ndings concerning improvements in charcoal yields at elevated pressures were corroborated by Blackadder and Rensfelt,23 Richard and Antal,24 and Mok et al.25 Thus, there can be no doubt that elevated pressures enhance charcoal yields. In 1909, Klason and his co-workers used their experimental results to deduce a stoichiometric equation for the pyrolytic production of charcoal from cellulose26 and wood27 at 400 C. For cellulose, they found C6 H10 O5 f 3:75CH0:60 O0:13 + 2:88H2 O + 0:5CO2 + 0:25CO + C1:5 H1:25 O0:38 1

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where the rst product is charcoal with a carbon content of 81.7 wt %. If we employ the usual denition of charcoal yield: ychar = Mchar/Mbio, where Mchar is the dry mass of charcoal and Mbio is the dry mass of the feedstock, then Klason et al. realized a value ychar = 34.0% from cellulose as represented by eq 1. For wood, Klason et al. reported a charcoal yield of 36.7% with a carbon content of 68.1%. The ndings by Klason et al.26,27 (summarized above) illustrate the fact that charcoal is not a well-dened chemical compound with an explicit chemical formula. To further emphasize this point, we note that Schenkel in his Ph.D. thesis10,12,28 reported a steady increase from 70 to 95% in the carbon content of the charcoal product of beech wood pyrolysis as the pyrolysis temperature increased from 400 to 800 C. This increase in carbon content was accompanied by a decrease in ychar from 35 to 24%. The notion of charcoal yield as a moving target is further illustrated by our own experience. In 1990, Antal et al.29 coauthored a review that listed charcoal yields ranging from 27.9 to 50 wt % together with proximate analyses when available. In 1996, Antal et al.30 speculated that corncob could oer a charcoal yield of 55 wt % and reported an experimental value of the charcoal yield from kukui nut shell of 62.1 wt % with a xed carbon content of 78.1 wt %. These ndings cause us to conclude that, although the value of the charcoal yield is a convenient metric for qualitative discussions, it is meaningless as a quantitative measure of the eciency of a carbonization process. In our previous work,10,3135 we introduced the xed-carbon yield yfC as a meaningful metric of carbonization eciency   % fC yfC ychar 2 100 % feed ash where % fC and % feed ash represent the percentage of xedcarbon contained in the charcoal and the percentage of ash in the feedstock, respectively. Note that the xed-carbon content of a charcoal approximates the fraction of carbon that is eective as a metallurgical reductant. From a dierent perspective, the xedcarbon content approximates the amount of pure carbon that can be obtained by further thermal treatment of the charcoal and yfC serves as a measure of the eciency of the pyrolysis process in converting biomass into pure carbon. Modern thermochemical equilibrium software (e.g., StanJan36 software or the NASA computer program Chemical Equilibrium

Figure 1. (a) Eects of the temperature on the products of cellulose pyrolysis, following the attainment of thermochemical equilibrium at 1 MPa. (b) Eects of the pressure on the products of cellulose pyrolysis, following the attainment of thermochemical equilibrium at 400 C.

with Applications37) enables calculations of the equilibrium yields of the products of biomass pyrolysis as a function of the reaction temperature and pressure. Figure 1 displays theoretical equilibrium yields of the products of cellulose pyrolysis at 1.0 MPa as a function of the temperature and at 400 C as a function of the pressure. Although carbon yields increase somewhat at temperatures below 400 C, the reaction rate at low temperatures is very slow. In Figure 1, the yield of H2 is represented, despite its small value that caused us to omit its display (but not its presence) in our previous publications.10,32 Although the mass fraction yields of H2 are small, hydrogen plays an important role in the equilibrium chemistry, as evidenced by its yield on a mole basis. Figure 1 shows that the maximum yield of carbon from cellulose is 28 wt % at 400 C (i.e., 62 mol % of cellulose carbon is converted into biocarbon). Note that the pyrolytic conversion of cellulose into carbon is an exothermic reaction with a large increase in entropy when equilibrium is reached; consequently, the carbonization process is irreversible, and pressure has little eect on the yield of carbon at 400 C, while higher temperatures evoke a small decrease in the carbon yield.32 Ten years ago, we published comparisons for many dierent biomass feedstocks of experimental values of yfC with theoretical values of yfC obtained using StanJan software and the elemental compositions of the feedstocks.31 The experimental values of yfC
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Energy & Fuels were obtained at both atmospheric and elevated pressures using electrically heated carbonization retorts. In all cases, the values of yfC obtained at elevated pressure exceeded those obtained at atmospheric pressure, and in some cases, the yfC values approached the theoretical, limiting, equilibrium values calculated using StanJan. Three years later, a ash-carbonization (FC) reactor at the University of Hawaii (UH), which eected carbonization by air oxidation at elevated pressure (see below), realized comparably high xed-carbon yields using various biomass feedstocks. Furthermore, the ame speeds at elevated pressure in the FC reactor were very high; consequently, the time required for carbonization of a bed of feedstock was very short (see below). Together, these ndings indicate that charcoal can be produced very eciently and quickly at elevated pressure in practical equipment. Nevertheless, pressurized equipment is costly to purchase and operate and demands special operational expertise. Also, it is a curious fact that most fundamental studies of biomass pyrolysis at atmospheric pressure have employed small samples or the thermal ablation of a large sample. Could the relatively low xedcarbon yield obtained at atmospheric pressure be a result of small particles and facile mass transfer of volatiles away from the hot, pyrolyzing solid? This question is not new; in 1991, Hancox et al.38 proposed studies of the systematic eect of a reduction in particle size on pyrolysis chemistry, with the goal of detailing the vaporsolid secondary reactions and their impact on char yields. However, to the best of our knowledge they did not accomplish such studies. Could large particles provide high xed-carbon yields of charcoal at atmospheric pressure? This question is especially important because tub-grinders are increasingly used by industry to shred waste biomass. Is shredded biomass suitable for carbonization? Similarly, some carbonization processes employ uidized-bed reactors that require particulate feedstocks. Can uidized-bed reactors realize high xed-carbon yields of charcoal? The aim of this paper is to elucidate the eects of particle size on xed-carbon yields at atmospheric pressure and elevated pressure in FC equipment. We hypothesize that increasing particle size substantially improves xed-carbon yields. This improvement in yield is a result of increasing heterogeneous interactions between the pyrolytic vapors and the solid charcoal together with its mineral matter, both of which may be catalytic for the formation of charcoal. Also, we hypothesize that elevated pressure enables the carbonization of liquid bio-oil before it can vaporize and escape the solid matrix. In this paper, we examine the validity of these hypotheses using corncob samples sourced from three dierent locations. Corncob is particularly well-suited for this work because of its widespread availability and complementary results that are now becoming available from other laboratories.3942 Subsequent papers will examine other feedstocks of interest to industry. The use of chemical dehydration agents to produce charcoal is not a focus of our work but was discussed in a previous review.29

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Figure 2. Cross-sectioned view of (a) Pcob and (b) Scob.

Table 1. Specications of Instruments and Their Crucibles/ Pans

crucible/ instruments TA Q600 Mettler Toledo TGA 851e TA Q5000 crucible/pan crucible geometry (d h, mm) 64 7 4.5 10 1 pan number volume (L) 1 2 3 crucible (90) crucible (150) pan (100)

Figure 3. Crucibles/pans used in pyrolysis experiments. experiment labeled 101014 that used white Wcob. No pretreatments (except for drying and grinding) were applied to the feedstocks to enhance carbon yields. At NTNU, each sample of corncob was prepared for carbonization tests in two dierent ways: either the cob was ground in a cutting mill mounted with a 1 mm sieve, or using a sharp knife, a thin cross-section was sliced from a whole cob, as shown in Figure 2. This cross-section included representative amounts of pith, woody ring, and cha material. Also, in some cases, cubic samples were cut from the woody ring of Pcob and Scob cross-sections. The cubic particles weighed 5, 10, 20, and 40 mg, corresponding to cube sizes from 2 to 6 mm. At NTNU, all cob samples were dried in an oven at 105 C for 24 h prior to carbonization. At the UH, the cobs were used as received, following storage in the open air. Three atmospheric pressure, thermogravimetric analyzers (TGAs) were employed in this work: models TA Q5000 and TA Q600 of TA Instruments and a Mettler Toledo model TGA/SDTA 851e. Table 1 and Figure 3 summarize the geometry and depth of the crucibles and the pans used with each TGA. All TGA runs employed nitrogen (99.999% pure) as purge gas with a ow rate of 100 mL min1. Prior to each experiment, a measured amount of corncob material (5, 10, 20, and 40 mg in single particle or powder form) was loaded into the appropriate crucible/sample pan. Each experiment was initiated with a 30 min purge at room temperature, followed by 30 min of drying at 105 C. Then, the sample was heated from 105 to 950 C at a heating rate of 10 C min1. This temperature program is summarized in Table 2. For some experiments conducted in the TA Q600 and Mettler Toledo model TGA/ SDTA 851e instruments, a lid with a small pinhole was used to cover the crucible with loaded sample. These runs are identied as closed crucible experiments. The char yield ychar was calculated by dividing the
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APPARATUS AND EXPERIMENTAL PROCEDURES

Grab samples of corncobs were obtained from Surcin, Belgrades municipality in Serbia (Scob; ZP Maize Hybrid, ZP 505), Pioneer HiBred International (Pcob), Oahu, Hawaii, and the Waimanalo farm of the UH College of Tropical Agriculture and Human Resources, Oahu, Hawaii (Wcob). There are two varieties of Wcob: red and white. All of the work described in this paper employed red Wcob, except the FC

Energy & Fuels Table 2. Temperature Programs

pyrolysis method time step 1 2 3 4 30 10 dynamic isothermal (min) 30 jump heating rate (K/min) temperature (C) 25 25 f 105 105 105 f 950 feed Pcob Wcob Scob proximate analyses (wt %) VM 79.64 80.32 81.08 fC 17.75 17.64 17.47 ash 2.61 2.04 1.45 yfC (wt %) 18.23 18.01 17.73

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Table 3. Proximate Analysis, Heating Value, and Fixed Carbon Yield of Feed Materials

HHV (MJ/kg) 18.87 18.43 18.63

nal sample mass by the mass measured at the end of the drying period at 105 C. A temperature controllable mue furnace (approximately 0.009 m3), a stainless-steel retort (approximately 0.004 m3), and two ceramic crucibles (approximately 200 mL) with lids were employed by NTNU to determine the maximum charcoal and xed-carbon yields that can be realized at atmospheric pressure from untreated whole corncob samples. Cob samples were placed in each crucible and thereafter covered with a lid. Then, the crucibles were placed in the retort that was covered with a metal lid prior to insertion into the mue furnace. The retort was purged with nitrogen for 30 min before heating as well as during the run to ensure carbonization in an inert atmosphere. The furnace was heated from room temperature to 950 C with a heating rate of 5 C/min. A thermocouple was placed in the retort to monitor the temperature history during the experiment. At NTNU, all corncob feed samples were subjected to proximate analysis according to American Society for Testing and Materials (ASTM) E 871 and 872; however, the ash content of the feeds was determined according to ASTM D 1102. Both NTNU and UH employed the ASTM D 1762-84 procedure for proximate analyses of the charcoal products. However, at UH, the charcoal volatile matter content was determined by preheating the covered crucible with sample for 2 min on the outer ledge of the furnace and 3 min on the edge of the furnace with the furnace door open and then heating the covered crucible with sample at the rear of the furnace for 6 min at 950 C with the furnace door closed. At NTNU, the covered crucibe with sample was immediately placed at the rear of the furnace and heated for 6 min at 950 C. The greater overall heating time used by UH suggests that the UH values for volatile matter content may be somewhat larger than those of NTNU. We oer our readers the following explanation for the dierences in our procedures for proximate analysis. The NTNU researchers altered the standard procedure because of the practical diculty in following it exactly. In the standard procedure, the measurement of volatile content requires the mue furnace to be heated to 950 C. Then, with the furnace door open, the crucible with the sample is set on the outer ledge of the furnace (300 C) and then for 3 min on the edge of the furnace (500 C). Then, the sample is moved to the rear of the furnace for 6 min with the mue furnace closed. There are two practical diculties that may cause misleading volatile content measurements: (1) It is hard to ensure the temperatures on the outer ledge and edge of the furnace are 300 and 500 C. (2) When the furnace door is open, the temperature in the furnace drops quickly and requires a relatively long time to return to 950 C. This means that, after the crucible with the sample is placed in the back of the furnace with its door closed, during the rst several minutes, the temperature in the furnace is lower than 950 C. It is possible that the temperature is still lower than 950 C after 6 min. This would mean that the sample is not heated at 950 C for 6 min. To perform the volatile content measurement more eciently and to ensure that the sample is heated at 950 C for 6 min, NTNU places the crucible with the sample directly in the rear of the furnace without preheating on the outer ledge and edge of the furnace.

Elemental analyses of the samples by NTNU were conducted by use of an elemental analyzer (Vario MACRO Elementar) according to standards ASTM E 777 (carbon and hydrogen), ASTM E 778 (nitrogen), and ASTM E 775 (sulfur). The oxygen content was determined by the dierence of 100% and the sum of the ash, C, H, N, and S contents. Also, elemental analyses were obtained from two commercial laboratories in the U.S.A. The microstructure and surface topography of the char particles were investigated using a Zeiss Supra-55 variable-pressure eld emission scanning electron microscope (LV FE-SEM). Samples were mounted on carbon tape without further preparation and scanned by a SEM. The SEM is equipped with an energy-dispersive X-ray spectroscope (Bruker Quantax) that enables the detection of the elemental compositions of selected spots. At UH, the biomass feed was placed in a canister that was subsequently loaded into the top of a pressure vessel (the FC reactor) that was then pressurized with air to 0.8 MPa (100 psig). Electric heating coils at the bottom of the pressure vessel ignited the lower portion of the biomass. After the specied ignition time, compressed air was delivered to the top of the pressure vessel and owed through the packed bed of feed to sustain the carbonization process. The pressure within the reactor was continuously monitored and maintained at 0.8 MPa by a valve located downstream of the reactor. After sucient air was delivered to carbonize the corncob, the airow was halted and the reactor cooled overnight. The charcoal was removed from the reactor and allowed to equilibrate under a fume hood for 2 days before proximate analysis (i.e., ASTM D 1762-84) was performed. For moisture content determination, the charcoal samples were dried in a Fisher Scientic Isotemp model 282A vacuum oven evacuated below 0.015 MPa (4 in. Hg). The volatile matter and ash analyses were performed using a Thermolyne 1300 mue furnace.

RESULTS
Fixed-Carbon Yields. In Table 3, we see that all three cobs enjoy similar proximate analyses. The proximate analysis procedure can be viewed to be a type of carbonization process. From this perspective, we can calculate the fixed-carbon yields that are offered by proximate analysis: 18.2 wt % (Pcob) versus 17.7 wt % (Scob) versus 18.0 wt % (Wcob). In this context, the proximate analysis offers a benchmark value for the fixed-carbon yield that can be obtained at atmospheric pressure. Throughout this paper, we will be comparing fixed-carbon yields obtained under different conditions with the values obtained from the proximate analysis procedure. Table 4 displays ultimate (i.e., dry, elemental) analyses of the cobs used in this work as determined by three dierent laboratories, together with published analyses of cobs used in our earlier studies. Considering the fact that the Pcob and Wcob both originated in Hawaii, whereas the Scob originated in Europe, their elemental analyses are remarkably similar. Note that both NTNU and Hazen determine oxygen content by dierence (i.e., they normalize their analyses to 100%), whereas Human does not. Because of the normalization, we lack a metric of the
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Table 4. Ultimate Analyses of Avicel Cellulose, Waimanalo (Wcob), Pioneer (Pcob), and Serbian (Scob) Corncobs and the Calculated Theoretical Fixed-Carbon Yield yfC
ultimate analysisa (wt %) MCb (wt %) Avicel cellulose (Hazen) Avicel cellulose (Human) corncob (2000)c Pcob (NTNU)d Pcob (Hazen)d Pcob (Human) Wcob (NTNU)d Wcob (2003, Human)c Wcob (Hazen)d Wcob (Human) Scob (NTNU)d
a

C 44.50 44.37 48.22 46.98 49.66 46.79 47.79 48.79 50.27 48.55 47.61

H 6.02 6.15 6.20 6.39 5.74 5.80 6.37 5.72 5.58 5.81 6.27

O 49.07 49.23 42.92 43.38 41.82 44.80 43.19 41.48 43.12 43.23 43.89

N 0.25 0.01 1.57 0.54 0.44 0.40 0.52 0.75 0.43 0.56 0.55

S 0.01 0.00 0.13 0.10 0.05 0.04 0.09 0.08 0.00 0.04 0.23

ash 0.15 0.01 3.48 2.61 2.29 1.88 2.04 1.31 0.60 1.61 1.45

total 100.00 99.77 102.52 100.00 100.00 99.71 100.00 98.13 100.00 99.80 100.00

yfC (wt %) 28.7 28.4 34.1 32.4 36.5 32.8 33.1 36.1 36.4 34.8 32.8

5.20 5.48 6.40 7.37 6.69 4.18 11.01 9.69 10.64 5.18

Dry mass basis. b Moisture content on a wet mass basis. c From ref 32. d By dierence.

Figure 4. Eects of pressure on Waimanalo cob pyrolysis following the attainment of thermochemical equilibrium at 400 C.

Figure 5. Inuence of dierent instruments on one Pcob single particle sample char yield in an open crucible.

absolute accuracy of the two measurements. Values of C, H, and O listed in Table 4 for the Hazen analysis of Avicel microcrystalline cellulose suggest an accuracy of at least two signicant gures, but the Hazen values for N, S, and ash are high (unless the sample was somehow contaminated). The large range in values of the C, H, and O contents reported by the three laboratories for the same cob material was unexpected. When the nitrogen, sulfur, and ash contents of the cobs are neglected, these elemental analyses can be used to calculate the yields of the pyrolysis products as a function of the pressure when thermochemical equilibrium is achieved at 400 C using StanJan software. Figure 4 displays these yields for the Wcob ultimate analysis as a function of the pressure at 400 C. Note that the value of the xed-carbon yield is largely independent of the pressure. Returning to Table 4, we see that the theoretical xedcarbon yield of Pcob ranges from 32.4 to 36.5 wt %, that the theoretical xed-carbon yield of Wcob ranges from 33.1 to 36.4 wt %, and that the theoretical xed-carbon yield of Scob is 32.8 wt % based on only the NTNU analysis. Note the impact of the higher oxygen content (43.23 wt %) in Humans analysis of Wcob on the theoretical value of yfC (34.8 wt %), relative to Humans 2003 value (41.48 wt %) for Wcob and the resultant

value of yfC (36.1 wt %). The oxygen measurements by Human displayed in Table 4 were direct measurements, whereas the Hazen and NTNU measurements were by dierence. Clearly, the value of the theoretical xed-carbon yield is quite sensitive to the accuracy of oxygen determination of the feed. We note that, in Table 4, we correct an error in our earlier publication32 of the analysis of Wcob (i.e., the Wcob (2003, Human) values). In the 2003 laboratory report, Human included the moisture content (11.01%) of the sample in the elemental analysis (i.e., its elemental analysis was on a wet basis), but this was not clearly declared in its laboratory report. For this reason, the 2003 values of the H and O contents of the Wcob, which we published under the impression that they were dry basis values,32 were high and the C content was low relative to dry basis values. In our paper, we noted these anomalies but incorrectly ascribed them to natural variations in the cob composition. The low value of C together with the high values of O and H resulted in a low value of the thermochemical equilibrium theoretical xed-carbon yield and caused us to believe that our experimental value of the xed-carbon yield was equal to the theoretical value. Table 4 presents the corrected,
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Figure 6. Inuence of dierent instruments on one Scob single particle sample char yield in an open crucible.

Figure 8. Inuence of dierent instruments on Scob powder sample char yield in an open crucible/pan.

Figure 7. Inuence of dierent instruments on Pcob powder sample char yield in an open crucible/pan.

dry-weight elemental analysis values for the theoretical xedcarbon yield of the 2003 data (i.e., 36.1 wt %). When the experimental value is compared to this corrected value, the experimental value obtained by the FC process in 2003 was 78% of the theoretical value (see below). We emphasize that the chief point of Table 4 is the surprising ineciency of conventional pyrolysis procedures (e.g., proximate analysis); the theoretical xed-carbon yield values are double the actual xed-carbon yields obtained by the proximate analysis procedure! This disparity between practice and theory indicates the improvements in yield that can potentially be realized by informed chemical reaction engineering of the carbonization process. The availability of three dierent TGA instruments enabled us to conduct an internal round-robin study of char and xedcarbon yields from two of the three cob samples. Figures 5 and 6 display the eects of particle size on char yields at 950 C as measured by the three instruments. These results represent TGA runs of a single, nominally cubic particle with varying

sizes (to achieve the indicated mass) cut from the woody ring annulus of each cob. Because the composition of the woody ring is not representative of the composition of the whole cob, the char and xed-carbon yields displayed in these gures cannot be directly compared to those of whole cobs (see below). Nevertheless, the trends displayed in these gures are meaningful. For all of the cobs in all of the instruments, the char yield increases with an increase in particle size. Furthermore, the TA Q600 instrument realizes a signicantly higher char yield than the other instruments. As noted previously, the TA Q600 employs a narrow, deep crucible that isolates the sample from the ow of purge gas and thereby enhances secondary reactions. We expand upon this nding below. Figures 7 and 8 display similar results representing the eects of sample size with two of the three cob powders (not cubes) on their respective char yields. In this case, the sample size represents the amount of powder loaded into the open TGA crucible/ pan. In agreement with Figures 5 and 6, higher char yields are obtained from larger samples and the TA Q600 instrument provides the highest char yields. However, in these gures, the char yields from the powders are lower than the comparable yield from single cubes. Because the powder is representative of the composition of the whole cob, whereas the cubes are not, the lower yields may reect compositional dierences, as well as the reduced dimensions of the particles (see below). The char sample remaining in the TGA from these runs was too small to ash. To obtain an estimate of the xed-carbon yield, we employed the volatile matter and ash contents of charcoals heated to the same nal temperature in the N2-purged mue furnace (see below; Table 6). With this additional information, values of the estimated xed-carbon yields for the TA Q600 as a function of the sample size with open and closed crucibles are listed in Table 5. All estimated values exceed the comparable yfC obtained by the proximate analysis procedure. In all cases, larger sample sizes oered enhanced charcoal and estimated xedcarbon yields. In all cases, the closed crucible increased the estimated xed-carbon yield by about 1520%; nevertheless, even the closed crucible yields are much lower than the theoretical xed-carbon yield. Note that, in some cases, the crucible/ pan was not able to accommodate the largest sample; consequently, the measurement was not made.
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Energy & Fuels Table 5. Charcoal and Fixed-Carbon Yields Realized at Atmospheric Pressure (0.1 MPa) in the TA Q600 Micro-TGA
ychar (wt %)a open crucible PCobc PCobd PCobe SCobc SCobd SCobe PCobf SCobf WCobf
a

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yfC (wt %)b open crucible 19.27 20.41 21.50 19.14 19.84 21.04 25.76 25.29 24.73 closed crucible 23.12 23.46 24.20 22.81 23.44 23.89

closed crucible 24.51 24.87 25.66 24.46 25.14 25.62

20.43 21.64 22.80 20.52 21.28 22.56 27.31 27.12 26.47

Percent of dried feed material. b yfC = charcoal yield (100 % volatile matter % char ash)/(100 % feed ash). Here, the volatile matter for char produced at 950 C and ash content measured from the mue-furnace-produced charcoal is used. c A total of 5 mg of powder sample. d A total of 10 mg of powder sample. e A total of 20 mg of powder sample. f A 180190 mg thin cross-sectioned sample.

Figure 9. Particle size distributions of ground Pcob and Scob samples.

Table 6. Charcoal and Fixed-Carbon Yields Realized at Atmospheric Pressure (0.1 MPa) in a N2-Purged Mue Furnace
proximate analysis (wt %) VM Pcob charcoal Wcob charcoal Scob charcoal 4.61 4.85 4.69 FC 91.85 92.07 91.90 ash 3.54 3.08 3.41 ychar (wt %) yfC (wt %) 26.77 26.45 26.52 25.25 24.86 24.73

To further explore the eects of the particle size on char yield, we sieved 10 g samples of the ground Pcob and Scob and measured the char yield from each of the sieved samples (eight dierent particle sizes) using the MT T851e instrument. Figure 9 displays the particle size distributions obtained from the two ground cob samples, while Figure 10 displays the char yields. The results are startling; both cobs provide evidence of nearly identical behavior, with a steady increase in the char yield from 15.2 to 23.5 wt % as the particle size increased from 0.0630.125 to 2.53.0 mm. Clearly, the particle size has a strong eect on the char yield. We remark that smaller (<90 m) particles of two energy crops (switchgrass and reed canary grass) are known to have higher concentrations of minerals than larger (90600 m) particles because of ash speciation by grinding, and the catalytic nature of the mineral matter caused the pyrolysis temperature of the smaller particles of the grasses to decrease.43 These observations might cause one to attribute our observations of particle size eects on char yields to mineral speciation. However, minerals catalyze the formation of charcoal (see below); consequently, a putative increase in the mineral content of the smaller particles in our work would cause an increase in their char yield and not a decrease. Plainly, smaller particles oer lower yields of charcoal. Our observations concerning the inuence of crucible/pan geometry on char yields are not new; earlier work (see the Discussion below) used open versus closed crucibles to accentuate the impact of vapor-phase conditions on char yields.

Figure 10. Inuence of the particle size on Pcob and Scob char yield (sample mass of 10 mg). (a) Representing char yields from Pcob and Scob as single particle samples with a particle size of 2.53 mm.

Figures 1114 display the inuence of closed crucibles with a small pinhole opening on char yields for Pcob and Scob cubes and powder samples in the TA Q600 and MT T851e instruments. In virtually all cases, the closure of the crucible substantially enhances the char yield. Nevertheless, the yields remain signicantly below the theoretical xed-carbon yields. These observations corroborate earlier work and reveal the importance of secondary reactions involving vapor-phase species in the formation of charcoal. Conditions that improve or prolong the contact of vapor-phase pyrolysis species with the solid serve to enhance the char yield. As the thermodynamic equilibrium calculations suggest, fragmentary compounds (e.g., levoglucosan, glycolaldehyde, 5-hydroxymethyl furfural, etc.) born by pyrolysis of biomass are not stable species at elevated temperatures. In a hot environment, they quickly decompose into carbon and gases, especially in the presence of catalytic mineral matter or solid carbon. As noted above, the char yields from the cob woody ring are not representative of yields obtained from the whole cob. Figures 15 and 16 are weight loss curves to 550 C (not 950 C) for the inner (pith), middle (woody ring), and outer
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Figure 11. Eects of open versus closed crucible on one Pcob single particle sample char yield.

Figure 13. Eects of open versus closed crucible on Pcob powder sample char yield.

Figure 12. Eects of open versus closed crucible on one Scob single particle sample char yield.

Figure 14. Eects of open versus closed crucible on Scob powder sample char yield.

(ne cha) parts of Pcob and Scob compared to the relevant powder sample. The results are consistent with earlier ndings; the Pcob and the Scob woody rings give the highest char yields, whereas the powders give average yields between those of the woody rings and the inner piths that oer the lowest yields. Table 5 displays char and xed-carbon yields from thin crosssections of each cob as measured by the MT T851e. Note that the large cob cross-section signicantly augments the xed-carbon yield relative to the comparable powder yield; nevertheless, the highest xed-carbon yield (25.66 wt % from Pcob) is much lower than theoretical values predicted using thermodynamics. Table 6 displays comparable charcoal yields obtained from whole cobs in closed crucibles under nitrogen in a mue furnace at 950 C. In Table 6, all values represent the mean of triplicate measurements. Table 6 also displays proximate analyses of the mue furnace charcoals that allow us to calculate the xedcarbon yields obtained from whole cobs at atmospheric pressure. Note the good agreement of the mue furnace results with those of the cob cross-sections (see Table 5). The Wcob values given in Table 6 can be compared to those for Wcob displayed in Table 7

that were obtained by the FC process at elevated pressure. The atmospheric pressure value of 24.86 wt % is less than the FC xed-carbon yields that range from 25.5 to 28.0 wt %. In agreement with our previous work,31 pyrolysis at elevated pressure representing practical conditions oers a nominal 10% increase in the xed-carbon yield above that which can be obtained under nitrogen at atmospheric pressure using an externally heated electrical furnace. We remark that Scob was not tested in Hawaii because of importation diculties. On the other hand, we have extensive experience with Pcob feedstocks; unlike any other biomass which we have tested, Pcob ignites prematurely at elevated pressures in FC equipment. Special procedures are needed to deal with its high reactivity, and these procedures are beyond the scope of this paper. The parity plot displayed in Figure 17 summarizes our ndings. Ordinate values of the parity plot represent the theoretical xed-carbon yields predicted by thermodynamics for each of the four Wcob ultimate analyses listed in Table 4. Abscissa values represent experimental measurements of the xed-carbon yields
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Figure 15. Pyrolysis and char yield behavior of dierent constituents of a Pcob thin cross-section in an open crucible.

Figure 17. Parity plot displaying the experimental FC, mue furnace (MF), proximate analysis (PA), and thermogravimetric analysis (TGA) xed-carbon yields for open and closed crucibles (o and c) with various sample sizes in mg versus the theoretical values calculated using the ultimate elemental analyses (4 and 2, Wcob; ] and [, Pcob; and +, Pcob TGA; 0 and 9, Scob; and /, Scob TGA).

Figure 16. Pyrolysis and char yield behavior of dierent constituents of a Scob thin cross-section in an open crucible.

Table 7. Charcoal and Fixed-Carbon Yields Realized at 1 MPa in the FC Reactor

proximate analysis (wt %) ID Wcob 90303 Wcob 90224 Wcob 101014 VM 15.25 10.87 7.11 FC 80.62 84.74 89.06 ash 4.13 4.39 3.83 ychar (wt %) yfC (wt %) 30.55 30.40 30.66 25.52 26.70 28.01

obtained in this work. The dashed diagonal lines indicate the percentage attainment of the theoretical yield. The highest yields obtained in this work were delivered by the FC process operating at elevated pressure, realizing xed-carbon yields ranging from 70 to almost 90% of the theoretical limit. Note the impact of the range of uncertainty in the ultimate analysis values on the percentage attainment results. Somewhat lower xed-carbon yields were realized from whole cobs in the mue furnace under nitrogen, and these yields were nearly identical to the yields obtained from cob cross-sections under nitrogen in the microTGA. Still lower yields were obtained from powders in closed crucibles under nitrogen. Even lower yields were obtained from

powders in open crucibles under nitrogen. The lowest yields were delivered by the proximate analysis laboratory procedure; these were about 2/3 of those obtained at elevated pressure in practical equipment. There is some irony here; practical equipment employing air at elevated pressure realized higher pyrolysis xed-carbon yields than can be obtained under the best of circumstances under nitrogen in laboratory instruments at atmospheric pressure. SEM Micrographs and EDX Analyses. Recall that the FC process behaves like a downdraft gasifier; air flows downward as the flaming pyrolysis front moves upward. Tarry vapors born by flaming pyrolysis are carried downward through the hot charcoal bed where they suffer further pyrolysis and deposit secondary carbon onto the charcoal formed earlier in the process. Also, mineral vapors can be condensed and deposited in the lower parts of the bed. The intensity of the flame increases as it moves up the bed; consequently, temperatures toward the top of the bed are usually higher than those near the bottom. In what follows, we compare representative SEM photos of samples of FC charcoal taken from the top and bottom sections of the bed to photos of atmospheric pressure charcoals, together with semi-quantitative EDX analyses of various interesting locations visible in the SEM photo. Figure 18a displays a SEM micrograph of a grab sample of Wcob charcoal particles taken from the top of the canister. The arrow indicates the point of increased magnication given in Figure 18b, likewise in 18c. The surface of the pore shown in Figure 18d is littered with tiny balls of various shapes. Similar balls were displayed in the SEM photos by Bourke et al.44 and unpublished photos by Dr. Jim E. Amonette (Pacic Northwest National Laboratory). This prior work caused us to think that the balls were commonplace in FC charcoal, but in fact, they were observed only in the one particle shown in Figure 18a. Figure 18d displays numbered points where EDX analysis was accomplished. The results of the EDX analyses are given in Table 8 under top section. This sample typies charcoal with low ash content. Analyses of the cell wall (e.g., points 24) were high (>80 wt %) in carbon content, whereas analyses of the balls (e.g., points 1, 9, 10, and 11) were lower in carbon content (<80 wt %) but still rich in carbon. All of the points were rich in oxygen. The ash content (K and Mg) was higher in the tiny balls, and a very small amount of Cl was detected at all points.
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Figure 18. SEM micrographs of various charcoal samples. (ad) 2040 mesh Wcob charcoal from the top section of the FC reactor.

Table 8. SEMEDX Analyses of Wcob Charcoal from the FC Reactor (Elemental Compositions in wt %)
top section spot element C O K Cl Mg Ca Na P S Si 1 2 3 4 5 6 7 8 9 10 11 12 1 2 3 bottom section 4 5 6 7 8

76.94 85.14 83.63 84.48 80.09 76.24 81.47 77.67 74.18 77.66 74.67 76.59 82.01 80.35 73.64 86.99 76.69 87.15 84.57 81.60 20.28 13.60 15.65 14.57 18.66 21.88 16.92 20.28 23.30 20.28 22.72 21.53 6.35 5.12 7.18 8.87 5.76 10.02 9.47 5.43 0.70 0.05 1.29 0.30 0.00 0.10 0.01 0.33 0.89 0.06 0.00 0.20 0.00 0.06 0.02 0.04 0.52 0.06 0.00 0.07 0.00 0.02 0.02 0.03 0.71 0.05 0.00 0.13 0.00 0.02 0.01 0.02 0.67 0.07 0.00 0.10 0.01 0.03 0.02 0.35 0.59 0.06 0.60 0.12 0.00 0.03 0.01 0.47 0.62 0.06 0.74 0.16 0.00 0.02 0.01 0.00 0.66 0.04 1.06 0.23 0.00 0.06 0.00 0.00 0.65 0.04 1.35 0.33 0.00 0.12 0.01 0.00 0.65 0.04 1.06 0.23 0.01 0.06 0.00 0.00 0.59 0.04 1.47 0.32 0.00 0.11 0.01 0.07 0.55 0.07 0.94 0.19 0.00 0.09 0.02 0.01 5.83 5.30 0.00 0.10 0.00 0.20 0.10 0.11 7.79 10.33 6.37 0.00 0.07 0.00 0.13 0.06 0.10 8.61 0.00 0.08 0.02 0.05 0.04 0.05 2.18 1.24 0.00 0.13 0.00 0.31 0.06 0.22 9.15 7.60 0.00 0.15 0.01 0.23 0.12 0.28 1.86 0.63 0.00 0.11 0.00 0.17 0.01 0.05 3.95 6.89 0.93 5.71 0.00 0.00 0.31 0.11 0.00 0.01 0.62 0.12 0.06 0.05 0.10 0.08

In Figure 19, the particle of Wcob from the bottom of the canister typies higher ash charcoals; its oxygen content is very low at all points (see Figure 19b and Table 8 under bottom section), and it is littered with crystals that are rich in K and Cl (points 13, 5, and 8). In this case, often the Cl content is close to that of K, suggesting that these are crystals of KCl. These crystals may appear to be the tiny balls of Figure 18; however, the crystals have a white color (not the gray color of the balls in Figure 18), and their high mineral content as indicated by the EDX analysis is quite dierent from that of the balls. The cell walls in Figure 19 appear thinner and more uid compared to those of Figure 18. These dierences relative to Figure 18 may result from the position of the cob in the canister, or the particles may be derived from dierent parts of the cob.

Representative surfaces of the pores of Scob charcoal particles produced at atmospheric pressure in open and closed crucibles are shown in Figures 20 and 21. No tiny balls are found in the open crucible sample (Figure 20), but balls with high carbon and low oxygen contents are visible in the closed crucible sample (Figure 21). The bright crystals present in the open crucible charcoal (Figure 20) are relatively low in C and high in K with little accompanying Cl (points 1, 3, 5, and 6 in Table 9 under open crucible). These crystals may be K2O and/or K2CO3.45,46 The high carbon content (see Table 9) of the closed crucible sample (Figure 21) may result from carbonization of the tarry vapors that could coat the surface with carbon. Note the low Cl content relative to the K content of all of the measured points. Remarkably, the surfaces of both Scob particles produced at 1 atm
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Figure 19. SEM micrographs of various charcoal samples. (a and b) 2040 mesh Wcob charcoal from the bottom section of the FC reactor.

Figure 20. SEM micrographs of a Scob charcoal sample from the microTGA (TA Q600) with an open crucible.

Figure 21. SEM micrographs of a Scob charcoal sample from the microTGA (TA Q600) with a closed crucible.

appear more rounded than ash-carbonized particles shown previously, as though the Scob particles experienced a brief period of partial liquidity prior to carbonization. The question of liquidity during carbonization is among the most controversial in the eld of biomass pyrolysis. We discuss this question further below.

DISCUSSION It is well-known that the char yield from dierent pure cellulose samples can vary substantially, even when the samples

are heated under identical conditions. For example, Antal et al.47 reported char yields of 6.8, 7.0, 9.1, and 10.2 wt % for small samples of four, dierent, pure, ash-free celluloses heated to 520 C at 1 C/min. Consequently, any comparison of char yields must involve identical substrates, and this constraint limits our ability to make comparisons among yields reported in the prior literature. Nevertheless, earlier workers have reported ndings similar to ours. For example, Varhegyi et al. observed a decrease from 3.3 to 2.8 wt % in the char yield at 400 C (5 C/min) when the Avicel cellulose sample size decreased from 0.94 to 0.11 mg.48 Stiles in his Ph.D. thesis49 described a sharp fall in char yields for particle diameters below 300 m. Likewise for whole biomass materials, the gasication of Maritime pine wood chips produced more char than that of the pine wood sawdust50 and more char was obtained from hazelnut shells51 and almond shells52 than their respective powders. Even in the case of fast pyrolysis, large particles were reported to produce more charcoal than small particles.53 Why is more charcoal formed from larger particles? More than 20 years ago, Varhegyi et al.54 described an increase in the char yield from 5 to 19 wt % when the pyrolysis of 1 mg samples of Avicel cellulose was conducted in covered (with pinhole) versus open crucibles. This perspicuous nding revealed the role of secondary reactions involving the interactions of pyrolytic volatile matter with the solid sample in the formation of charcoal and conrmed the speculation of Bradbury et al. that the residence time of the volatiles in the cellulose during the pyrolysis reaction largely inuences the extent of char formation.55 Other evidence corroborating the importance of secondary reactions in charcoal formation includes (i) the reduction in char yield when pyrolysis is conducted in vacuum,56 (ii) the reduction in char yield when gas ow is increased,21,22,24,57 and (iii) the increase in char yield with increasing pressure.10,24,25,3032,58 In particular, an important recent study by Shen et al.59 described an increase in the particle size of Australian Eucalyptus loxophleba wood particles from 0.18 to 1.5 mm that caused an increase in the charcoal yield from 14 to 20 wt %. The preponderance of this evidence evoked the following conclusion in a review paper: Vaporsolid interactions (secondary reactions) are eectively the only source of char formed during the pyrolysis of pure cellulose. These heterogeneous reactions alone can increase the char yield from 0% to more than 40%.60 However, in the case of whole biomass (not pure cellulose), it is likely that the primary, solid-phase pyrolysis reactions contribute to the formation of charcoal.
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Energy & Fuels Table 9. SEMEDX Analyses of Scob Charcoal from the Micro-TGA (Elemental Compositions in wt %)
open crucible spot element C O K Cl Mg Ca Na P S Si 1 82.17 11.34 5.10 0.07 0.60 0.28 0.17 0.11 0.08 0.08 2 85.85 12.71 1.20 0.01 0.11 0.08 0.04 0.00 0.00 0.00 3 74.51 13.83 8.76 0.11 1.06 0.43 0.33 0.34 0.18 0.45 4 82.71 14.28 1.94 0.01 0.39 0.09 0.45 0.02 0.04 0.07 5 68.26 5.37 19.02 0.39 1.58 1.00 0.76 1.51 0.78 1.34 6 82.85 8.99 5.44 0.15 0.63 0.48 0.31 0.34 0.35 0.46 7 87.66 9.13 2.63 0.03 0.31 0.14 0.09 0.00 0.01 0.00 1 80.89 13.84 2.74 0.10 0.67 0.17 0.37 0.03 0.03 1.18 2 86.70 10.40 2.62 0.04 0.05 0.13 0.04 0.00 0.00 0.00 closed crucible 3 88.66 9.16 2.06 0.01 0.01 0.09 0.01 0.00 0.00 0.00 4 85.96 10.81 2.86 0.04 0.13 0.15 0.04 0.00 0.00 0.00 5 86.12 10.92 2.65 0.02 0.05 0.13 0.08 0.01 0.00 0.00

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6 88.86 9.61 1.39 0.03 0.04 0.06 0.01 0.00 0.00 0.00

The foregoing observations concerning the eects of particle size and secondary reactions are in part a reection of the catalytic nature of charcoal and its mineral matter content. Since the 1800s, it has been known that downdraft reactors deliver a tar-free gas because the tar-laden gas born by pyrolysis ows through the hot bed of charcoal at the bottom of the reactor that catalyzes the decomposition of the tars to more gas and char.61 Recently, this insight has been employed to enhance the removal of tar from the euent of supercritical water biomass gasiers,6264 as well as more conventional systems.6568 In his Ph.D. thesis, Abu El-Rub et al.69 showed that biomass chars gave the highest naphthalene conversion among low-cost catalysts used for tar removal from biomass gasiers. Very recently, Abu El-Rubs ndings were questioned by Gilbert et al.,70 whose work showed that the main mode of tar conversion in the presence of charcoal at 800 C was homogeneous vapor-phase cracking. The importance of the homogeneous cracking chemistry should be no surprise, because its role in tar conversion was elucidated 3 decades ago.7176 In particular, competitive vapor-phase reactions7176 (largely ignored by the research community) play a key role in the formation at 800 C of the heavy, refractory, condensable phase described by Gilbert et al.70 In any case, the temperature range for charcoal formation of 250450 C is much lower than that studied by Abu El-Rub et al.69 and Gilbert et al.;70 consequently, true, low-temperature primary tars are the reactants, and their sensitivity to the catalytic action of charcoal or mineral matter is not well-understood. The catalytic action of the charcoal results (at least in part) from its mineral matter content. The metal ions K, Li, Ca, Fe, and Cu, typically present as mineral matter in biomass, greatly enhance the formation of char from both cellulose and wood.60 In the case of corn straw, the removal of K+ and Ca2+ ions by water or acid washing lowers the yield of charcoal obtained from the straw.77 Larger particles enhance the retention of alkali and alkaline earth metal species, thereby retaining catalytic species that enhance charcoal yields.78 It is well-known that charcoal maintains the morphology of its precursor.10 It is also well-known that fast pyrolysis causes the biomass to pass through a liquid phase prior to the formation of tarry vapors.60,7981 Oering insight into this apparent contradiction, Haas et al.82 report that some parts of the cell wall become molten at temperatures between 350 and 500 C during the pyrolytic contraction of the cell wall structure. Nevertheless, Haas et al.82 conclude that the overall three-dimensional tissue structure of the biomass is preserved following pyrolysis (i.e., the

char structure closely resembles that of its parent material). They also note that some pyrolysis products become trapped within the cell walls. These observations are in harmony with our SEM photos.

CONCLUSION (1) The yield of charcoal from biomass is not a meaningful metric of the eciency of a carbonization process. Instead, the xed-carbon yield should be used to characterize carbonization eciency. (2) When an elemental analysis of the feedstock is available, it can be used to calculate the yield of pure carbon that can be realized when thermochemical equilibrium is reached in a carbonizer. This theoretical yield of pure carbon can be compared to the experimental value of the xed-carbon yield and thereby used as a meaningful metric of the eciency of the carbonization process. (3) The standard proximate analysis procedure oers a very low xed-carbon yield of charcoal from corncob. The xed-carbon yields of chars produced by the proximate analysis procedure are about 1/2 of the theoretical value. (4) The xed-carbon yields of char obtained from the pyrolysis of corncob in analytic thermogravimetric analyzers is low but somewhat higher that that of the proximate analysis procedure. A deep TGA sample pan/crucible improves the yield. (5) Ordinarily TGA studies employ small particles. Large particles oer signicantly higher xed-carbon yields than small particles within TGA instruments. This signature of the importance of secondary reactions to charcoal formation has not been given adequate emphasis in prior work, especially in research involving TGA. (6) The xed-carbon yield is improved when carbonization occurs in a vessel with a lid. Any restriction of the ability of the pyrolytic vapors to escape from the vicinity of the char product increases the xed-carbon yield. (7) Relatively high xed-carbon yields are obtained from whole corncobs heated under N2 in closed vessels in a mue furnace. This is not a practical way to manufacture charcoal; electrical heat is too expensive to be used for carbonization. (8) With operation at elevated pressure with whole corncob, the FC process realized the highest xed-carbon yields observed in this work, approaching 90% of the theoretical limiting values. This satisfying result nevertheless oers opportunities for improvement. (9) Increasingly, tub grinders and other size-reduction equipment are being used to handle biomass. If the goal is to maximize biocarbon production, size reduction of this sort is worse than useless because it substantially reduces biocarbon yields while needlessly
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Energy & Fuels consuming energy and occupying capital. (10) Likewise, uidized beds and transport reactors,12 which demand ne particles as feedstocks, cannot give high xed-carbon yields of charcoal. (11) If biocarbon is the desired product, carbonization equipment that does not require size reduction is best suited to maximize the biocarbon yield. Biomass is not easy to grind, shred, sliver, or chip. Size reduction demands considerable capital investment and wastefully consumes power. The fact that biocarbons are produced most eciently without size reduction gives carbonization processes a considerable advantage over other technologies that convert biomass into higher value fuels. (12) We emphasize that our TGA studies employed ne particles because ne particles are increasingly used in commercial practice (see 911 above). Our goal was to open industrys eyes to the detriments of their use of ne particles in carbonization equipment. These detriments are unequivocally illustrated by the state-of-the-art TGA data displayed in this paper. (13) Our ndings show that secondary reactions involving vapor-phase species (or nascent vapor-phase species) are at least as inuential as primary reactions in the formation of charcoal. Conditions that improve or prolong the contact of vapor-phase pyrolysis species with the solid enhance the xed-carbon yield of charcoal. As thermodynamic equilibrium calculations suggest, fragmentary compounds (e.g., levoglucosan, glycolaldehyde, 5-hydroxymethyl furfural, etc.) born by pyrolysis of biomass are not stable species at elevated temperatures. In a hot environment, they quickly decompose into carbon and gases, especially in the presence of catalytic mineral matter or solid carbon.

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AUTHOR INFORMATION
Corresponding Author

*Telephone: 808-956-7267. Fax: 808-956-2336. E-mail: mantal@ hawaii.edu.

ACKNOWLEDGMENT Michael Jerry Antal, Jr. acknowledges support by the National Science Foundation (NSF, Award CBET08-28006), the Oce of Naval Research under the Hawaii Energy and Environmental Technologies (HEET) initiative, and the Coral Industries Endowment of the University of Hawaii. He thanks Dr. Maria Burka (NSF) and Ms. Bonnie Thompson (NSF) for their continuing interest in biocarbons, Dr. Woraphat Arthayukti for alerting him to the need for improving the yield of charcoal from biomass,30 and Prof. Jim Brewbaker and Pioneer Hi-Bred for providing needed corncob. The Norwegian team acknowledges support by the Bioenergy Innovation Centre (CenBio), which is funded by the Research Council of Norway, 19 Norwegian industry partners and 7 research and development institutes. Finally, we thank ve reviewers for their insightful comments on our work. REFERENCES
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