J. Anal. Appl.

Pyrolysis 79 (2007) 86–90

www.elsevier.com/locate/jaap

Biocarbon production from Hungarian sunflower shells

Michael Jerry Antal Jr.*, Samuel Robert Wade, Teppei Nunoura
Hawaii Natural Energy Institute, School of Ocean and Earth Science and Technology, University of Hawaii at Manoa, Honolulu, HI, USA
Received 12 June 2006; accepted 16 September 2006
Available online 13 November 2006

Abstract
The production of biodiesel and bioethanol fuels is often accompanied by the co-production of lignocellulosic ‘‘waste’’ byproducts. For
example, the oil from sunflower seeds (that can be used to manufacture biodiesel fuel) has as ‘‘waste’’ co-products the sunflower shell and its stem.
In this paper we examine the production of biocarbon (charcoal) from sunflower shells produced in Hungary. The conversion of these shells to
biocarbon via the University of Hawaii’s Flash CarbonizationTM process is efficient and very quick. An increase in reaction pressure from 1.27 to
2.17 MPa causes a reduction in reaction time that results in a significant increase in charcoal production and profitability. These findings justify
further study of the benefits of charcoal production at pressures above 2 MPa.
# 2006 Elsevier B.V. All rights reserved.

Keywords: Flash CarbonizationTM process; Sunflower shell; Charcoal; Biocarbon; Biodiesel; Pyrolysis; Pressure

1. Introduction The FC process [3–5] involves the ignition and control of a

Once again, the rapidly escalating price of transportation
fuels has engendered intense interest in the production of
biodiesel and other liquid fuels (e.g. ethanol) from renewable
biomass. Biodiesel is an expensive fuel because it is
manufactured from vegetable oils. Fortunately, the plants that
produce vegetable oils often also produce copious amounts of
lignocellulosic byproducts. For example, in addition to
sunflower oil the sunflower plant produces shells, a blossom,
and a stem. Anyone, who has seen fields of sunflowers in bloom
in Hungary, appreciates the abundance of lignocellulosic
biomass that accompanies the precious sunflower seeds. It is
often erroneously assumed that these lignocellulosic bypro-
ducts have no value. In a visionary paper Varhegyi et al. [1]
described the production of biocarbon (i.e. charcoal) from the
sunflower stem. In this paper we describe the yields and
properties of biocarbons that can be derived from the sunflower
shell by use of the University of Hawaii’s Flash Carboniza-
tionTM (FC) process. Biocarbons enjoy many lucrative markets.
A review of technical information concerning their properties
and production is available [2].
* Corresponding author. Tel.: +1 808 956 7267; fax: +1 808 956 2336.
E-mail address: mantal@hawaii.edu (M.J. Antal Jr.).
0165-2370/$ – see front matter # 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.jaap.2006.09.005
flash fire at about 1 MPa within a packed bed of biomass. Heat,
released by the fire, triggers the transformation of biomass into
carbon with yields that can reach the thermochemical
equilibrium ‘‘limit’’ in less than 30 min of reaction time.
Typically, the FC process realizes charcoal yields in the range of
30–40%, fixed-carbon yields (see below) from 28 to 31%, and
energy conversion efficiencies of biomass to charcoal from 55 to
66%. In many cases between 59 and 63% of the carbon in the
biomass feedstock is transformed into carbon in the charcoal.
About two-third of the feedstock’s moist mass is converted into a
combustible gas at elevated pressure. This gas can be burned to
generate heat for drying the moist biomass feedstock.
For example, corn stover (including cobs) is the most plentiful
agricultural residue in the USA. In a previous paper [3] we
showed that the cob is a particularly attractive feedstock for
carbonization: at 1.2 MPa it ignited after 2 min of heating, and
airflow to the FC reactor was halted after 18 min. All
temperatures in the bed reached 500 8C before the run was
terminated. In this run 63% of the cob’s carbon was converted to
charcoal fixed-carbon, the cob charcoal product retained 60% of
the energy content of the cob feedstock, and 71% of the cob’s
moist mass was gasified. The fixed-carbon yield of this run was
100% of the thermochemical equilibrium limiting value.
In this paper we detail the effects of pressure and air delivery
on the performance metrics (reaction time, charcoal and fixed-
carbon yields) of the FC process with Hungarian sunflower
 M.J. Antal Jr. et al. / J. Anal. Appl. Pyrolysis 79 (2007) 86–90 87

shell feedstock. These metrics enable a comparison of the
economic benefits of operation at low (1.27 MPa) versus
moderate (2.17 MPa) pressure. This comparison indicates that
higher operating pressures will improve the economics of
charcoal production from sunflower shells.
2. Experimental
Sunflower seed shells (hulls) grown and milled in Hungary
were obtained from the Hungaro-Sol Co. Mahogany wood
chips (a readily available waste product of cabinet manu-
facture in Hawaii) were provided by the Carbon Diversion
Corp. and used as tinder. The shells were carbonized as
received without treatment of any sort, whereas wood chips
that had been exposed to rain were oven-dried before
carbonization.
In a typical FC run [3–5] a measured amount of feedstock
was placed inside a cylindrical canister (see Fig. 1). Then the
canister was loaded into a vertical pressure vessel that was
subsequently pressurized at 1.27 MPa (170 psig) or 2.17 MPa
(300 psig) by air. Electric power was delivered to an electric
heater at the bottom of the autoclave. Ignition occurred after a
few minutes and the heater was turned off. Gas was released
from the bottom of the pressure vessel to maintain the pressure
below the vessel’s limit while the temperature of the bottom of
the bed rose to a maximum value. This starved-air ignition step
created a shallow bed of carbon at the bottom of the canister.
Then air was released from the vessel to establish the desired
operating pressure, and pressurized air was delivered to the top
of the reactor while combustion gas was vented from the
bottom. The flame front moved up the bed, against the flow of
air, triggering the conversion of biomass into carbon. When
sufficient air had been delivered to assure carbonization of the
bed, the airflow was halted, the pressure vessel was
depressurized and permitted to cool. Subsequently, the charcoal
in the bed was divided into three sections (one section of
mahogany charcoal and two sections of sunflower shell
charcoal), equilibrated in the open air, weighed, and a
representative carbon sub-sample was taken from each section
for proximate analysis according to ASTM D1762-84. More
details concerning these procedures are described in previous
publications [3–5].
3. Results and discussion
Table 1 displays the elemental analysis of a grab sample of
the sunflower shells employed in this work, and an analysis of a
grab sample of the same batch of sunflower shells that was
reported in a previous publication [6]. The agreement of the two
analyses is good. We remark that the sunflower shells have
about the same oxygen content as corncob [3] (another
interesting agricultural residue), but the shell’s carbon content

Fig. 1. Schematic diagram of the laboratory-scale Flash CarbonizationTM reactor. A, air accumulator; C, compressor; CI, canister with insulation; DDV, downdraft
valve; H, electric heater; IV, isolation valve; MMV, micrometer valve; O, oxygen analyzer; PAV, pneumatically activated valve; PG, pressure gauge; PRV, pressure
relief valve; PS, power source; PT, pressure transducer; PV, pressure vessel; R, regulator; SRD, safety rapture disk; TC, Thermocouple; UDV, updraft valve; VAT,
variable auto transformer; WT, water trap.
88 M.J. Antal Jr. et al. / J. Anal. Appl. Pyrolysis 79 (2007) 86–90

Table 1
Sunflower shell analyses
ID mca (%) Ashb (%) Ultimate analysisc (%) SABRd (kg/kg)
C H O N S Ash
e
SF1 11.22 1.35 50.48 5.82 43.33 0.49 0.11 1.60 5.9
SF2 f NA NA 50.37 5.62 42.64 0.33 0.05 1.62 NA
a
Dry basis moisture content using ASTM E 1756-95.
b
ASTM E 1755-95.
c
Measured by Huffman Laboratories Inc., USA.
d
Stoichiometric air/biomass ratio.
e
Value for experiment 060324; 10.94% for experiment 060217.
f
Values taken from Antal et al. [6].

is higher than cob, whereas its hydrogen, nitrogen, sulfur, and
ash contents are lower. Table 1 also displays the stoichiometric
air–biomass ratio (i.e. the amount of air required to completely
combust the dry biomass). Because of its high carbon content,
this value (5.9 kg/kg) is somewhat larger than that of corncob
(5.14 kg/kg).
Thermochemical equilibrium calculations [3,6] based on the
elemental analysis of the biomass feedstock indicate that
carbon is a preferred product of biomass pyrolysis at moderate
temperatures, with byproducts of carbon dioxide, water,
methane, and traces of carbon monoxide. Depending upon
its elemental composition, the ‘‘theoretical yield’’ of carbon
from biomass (as determined by the thermochemical equili-
brium calculations) ranges from about 27 to 46 wt% (on a dry
weight basis) [6]. In the case of sunflower shells the theoretical
carbon yield is 36% [6], whereas for corncob the theoretical
yield is 28% [3].
The pyrolytic conversion of biomass to charcoal does not
produce a pure carbon; consequently to assess the efficiency of
a carbonization process we employ metrics that have practical
value and can be compared with a theoretical prediction of the
yield realized when thermochemical equilibrium is established.
First we define the charcoal yield: ychar = mchar/mbio, where
mchar the dry mass of product charcoal and mbio is the dry mass
of the feedstock. Unfortunately, this measure of the carboniza-
tion efficiency is intrinsically vague because the chemical
composition of charcoal is not defined. A more meaningful
metric is given by the fixed-carbon yield yfC = ychar  {% fC/
(100 % feed ash)}, where % fC is the percentage fixed-
carbon content of the charcoal, and % feed ash is the percentage
ash content of the feed [3,4]. The fixed-carbon yield represents
the efficiency realized by the pyrolytic conversion of ash-free
organic matter in the feedstock into a relatively pure, ash-free
carbon. For example, with corncob feedstock the FC process
realizes the theoretical fixed-carbon yield (28%) derived from
thermochemical equilibrium calculations as discussed above.
Note that the percentage volatile matter content of a charcoal is
defined by % VM = 100 % fC % char ash, where % char
ash is the percentage ash content of the charcoal.
Table 2 displays the results of three FC runs with sunflower
shell feed and mahogany wood tinder. Many other runs were
conducted as part of this study, but these runs employed either
too little or too much air delivery; consequently they did not
realize optimum fixed-carbon yields. Runs SF170a and SF300
realized nearly identical fixed-carbon yields (28.7 and 28.0%,
respectively) and produced charcoals with agreeably low VM
contents (<18.1% for the sunflower shell charcoal). These
fixed-carbon yields were nearly identical to that obtained in our
earlier work (involving a purely pyrolytic production of
charcoal at elevated pressure) and do not seem to be susceptible
to further improvement. Recall that the FC process realizes
100% of the theoretical fixed-carbon yield from corncob. In this
case the fixed-carbon yield (28.7%) is only about 80% of the
theoretical limit for sunflower shells (36%). At present we have
no good explanation for the relatively low fixed-carbon yield
from sunflower shells as compared to corncob feedstock.

Table 2
Results of the Flash CarbonizationTM treatment of Hungarian sunflower shells (SF) with Mahogany wood tinder
ID Section Proximate analysis (%) ychara (%) yfCa (%)
VM fC Ash
SF170a SF top 7.88 86.7 5.4 34.0 28.7
060412 SF middle 16.5 80.2 3.4
Mahogany 11.0 87.6 1.4 31.3 27.6
SF170b SF top 37.9 58.3 3.9 31.4 21.7
060217 SF middle 10.3 84.0 5.8
Mahogany 10.8 87.8 1.3 29.3 25.9
SF300 SF top 8.42 85.3 6.3 34.2 28.0
060324 SF middle 18.1 78.0 3.9
Mahogany 18.5 80.5 1.1 31.2 25.3
a
For sunflower the listed yield represents both the combined value of the top and middle sections.
 M.J. Antal Jr. et al. / J. Anal. Appl. Pyrolysis 79 (2007) 86–90 89

Table 3
Summary of reaction conditions
ID Feedstock dry basis (kg) Pressure (MPa) Delivered aira Total airb Superficial velocitye Flame velocityf
(mm/s) (mm/s)
ABRc (kg/kg) ld ABR (kg/kg) l
SF170a 1.01 1.27 1.41 0.238 1.47 0.248 13.0 0.83
SF170b 1.01 1.27 0.972 0.164 1.03 0.174 15.0 1.44
SF300 1.01 2.17 0.851 0.144 0.952 0.161 8.1 1.51
a
Following ignition.
b
Initial amount in reactor + delivered.
c
Air–biomass ratio.
d
l = ABR/SABR.
e
Superficial velocity of the airflow at 298 K and reactor pressure.
f
Upward velocity of the flaming pyrolysis reaction through the packed bed of biomass.

Data for run SF170b are included to illustrate the effect of
VM content on fixed-carbon yield. A few small lumps of
partially pyrolyzed feed were discovered in the product of this
run. These lumps were the cause of the high VM content of the
top section. Note the dramatic effect of the high VM content of
this run (relative to that of SF170a) on its fixed-carbon yield.
Table 3 offers a summary of the reaction conditions
associated with the three experiments. The focus of these
experiments was the effect of pressure on the fixed-carbon
yield, the reaction time, and the air demand. Experiments
SF170a and SF300 realized nearly identical fixed-carbon
yields, and we believe that this yield represents the limiting
value that can be achieved by the FC process. The flame
velocity is the average speed at which the flaming pyrolysis
reaction moves upward through the packed bed of biomass,
converting the biomass into charcoal. Conditions that realize a
higher flame velocity require less reaction time and result in a
higher throughput. Note that an increase in pressure from 1.27
to 2.17 MPa nearly doubled the flame velocity (0.83 mm/s in
SF170a versus 1.51 mm/s in SF300) within the reactor. In
addition to the improvement in flame velocity, Table 3 shows
that an increase in pressure also decreased the air demand of the
process. Both the amount of air delivered following ignition,
and the total air (including that needed to pressurize the reactor)
were significantly decreased by the increase in pressure from
1.27 to 2.17 MPa.
The superficial velocity [7] displayed in Table 3 is the speed at
which air moves downward through the top of the canister (above
the bed of biomass) at 298 K and the reactor pressure following
ignition of the flash fire. Experiment SF170b was an attempt to
increase the flame velocity at 1.27 MPa by an increase in the rate
of air delivery; hence its superficial velocity. The experiment was
a partial success: the flame velocity increased from 0.83 to
1.44 mm/s – only slightly below the value of the flame velocity at
2.17 MPa. Unfortunately, at this ‘‘high speed’’ the flaming
pyrolysis reaction was unable to completely carbonize the
feedstock (see Table 2 and the discussion above). From this result
we conclude that at a given pressure there is a limit to the speed at
which the flaming pyrolysis reaction can move while fully
carbonizing the feedstock. Values of the superficial velocity in
Table 3 offer an explanation for this limiting behavior. At
2.17 MPa the superficial velocity of the air was much less than
that at 1.27 MPa. Consequently, the tarry vapors produced by the
pyrolysis reactions had more time to react via secondary
reactions before they exited the reactor. In addition the increased
pressure increased the intensity of heat release by the combustion
reactions. These effects of elevated pressure enabled a higher
flame velocity with complete carbonization of the feed.
The benefits of increased pressure are not obtained for free.
Air compressors with an outlet pressure of 1.27 MPa (170 psig)
are much less costly than those with an outlet pressure of
2.17 MPa (300 psig). One goal of this work was to learn if more
research at pressures above 1.27 MPa is justifiable. To answer
this question we made a simple economic assessment of the two
cases that was intended for comparison purposes (only). Cost
estimates were based on actual costs incurred in the fabrication
and setup of a FC Demonstration reactor on the campus of the
University of Hawaii. Important aspects of the estimate include
the size of the reactor (1.73 m D  2.74 m H), the capital
investment (US$ 270,000 exclusive of the air compressor), the
cost of the feedstock (US$ 30/tonne), the selling price of fixed-
carbon in the charcoal product (US$ 437/tonne of fixed-
carbon), the salary of the two operators (US$ 29.93/h) and the
operating schedule (24 h/day, 7 days/week, 50 weeks/year).
The cost of an appropriately sized 1.27 MPa air compressor is
about US$ 30,000, whereas the cost of a 2.17 MPa air
compressor is about US$ 120,000. Table 4 displays a succinct
summary of the results. Because of the higher flame velocity the
2.17 MPa system is able to process 26 canisters/day with an
output of 8.4 tonnes/day of fixed-carbon, whereas the 1.27 MPa
system processes 18 canisters/day with an output of 6.1 tonnes/
day of fixed-carbon. The increased output of product charcoal

Table 4
Economic comparison for operation at 1.27 MPa (170 psig) vs. 2.17 MPa (300 psig)
Pressure (MPa) yfC Batches/day Production (tonnes/day) Capital investment (US$) Payback time (year)
1.27 0.287 18 6.1 300,000 3.7
2.17 0.280 26 8.4 390,000 1.3
90 M.J. Antal Jr. et al. / J. Anal. Appl. Pyrolysis 79 (2007) 86–90
results in a decrease in payback time (for the capital
investment) from 3.7 to 1.3 years. We emphasize that this
economic calculation is highly dependent upon the availability
of electric power from a grid, the cost of land and labor, and
other factors. The exact value of the payback time is not a focus
of this discussion. The surprising conclusion is that the increase
in flame speed by operation at 2.17 MPa results in increased
production of charcoal that dramatically improves the profit-
ability of the process relative to its operation at 1.27 MPa.
Further research on the performance of the FC process at
elevated moderate pressures (e.g. 2 MPa) is well justified.
Acknowledgments
We thank following sponsors of our work for their support:
The Consortium on Plant Biotechnology Research (CPBR),
Carbon Diversion Corp. (Michael Lurvey); the Coral Industries
Endowment of the University of Hawaii Foundation, and the
University of Hawaii. We also thank Lloyd Paredes (Hawaii
Natural Energy Institute) for his assistance with the experi-
mental work, Dr. Gabor Varhegyi for obtaining and shipping the
sunflower shell feedstock, and Richard Cox of the UH Office of
Technology Transfer and Economic Development for his
continued support. One of us (Antal) thanks Dr. Gabor
Varhegyi, Dr. Emma Jakab and their co-workers with the
Institute of Materials and Environmental Chemistry of the
Hungarian Academy of Sciences for collaboration during the
past 20 years. This collaboration has resulted in the publication
of 24 co-authored papers.
References
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[3] M.J. Antal, K. Mochidzuki, L.S. Paredes, Ind. Eng. Chem. Res. 42 (2003)
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[4] T. Nunoura, S.R. Wade, J.P. Bourke, M.J. Antal, Ind. Eng. Chem. Res. 45
(2006) 585.
[5] S.R. Wade, T. Nunoura, M.J. Antal Jr., Ind. Eng. Chem. Res. 45 (2006)
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[6] M.J. Antal, S.G. Allen, X. Dai, B. Shimizu, M.S. Tam, M.G. Gronli, Ind.
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[7] T.B. Reed, R. Walt, S. Ellis, A. Das, S. Deutch, Fourth Biomass Conference
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