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J. Anal. Appl.

Pyrolysis 85 (2009) 142–144

Contents lists available at ScienceDirect

Journal of Analytical and Applied Pyrolysis

journal homepage: www.elsevier.com/locate/jaap

Pyrolysis of agricultural residues from rape and sunflowers: Production and

characterization of bio-fuels and biochar soil management
M.E. Sánchez *, E. Lindao, D. Margaleff, O. Martı́nez, A. Morán
Natural Resources Institute, Chemical Engineering Area, University of León, Avda de Portugal 41, 24071 León, Spain


Article history: This research explores the opportunities of combining energy production with a biochar soil
Received 1 July 2008 management using a pyrolysis process. Real-world issues justify this approach: the need to provide
Accepted 3 November 2008 sustainable production systems that minimize on- and off-site pollution and soil degradation; and the
Available online 11 November 2008
demand for solutions to global warming. The proposed technology is a pyrolysis process that yields gas,
bio-oil and biochar. The composition and heating value of the gas makes it suitable for use as a fuel. The
Keywords: bio-oil obtained may be evaluated as an environmentally friendly green biofuel candidate. The biochar
product is carbon-rich and a potential solid biofuel. Other ways it might be used as a C and N source in soil
amendment. This is a key to securing environmental benefits: the production of a biochar which can be
Bio-oil applied to soil.
Bio-char ß 2008 Elsevier B.V. All rights reserved.

1. Introduction nities for sustainable soil management. The benefits of biochar rest on
two pillars: the extremely high affinity of nutrients to biochar and the
Rape and sunflower are one of the most commonly cultivated extremely high persistence of biochar (slow microbial degradation
plants worldwide. Biomass sources, such as agricultural residues, are and chemical oxidation). These two properties can be used effectively
good precursors for the production of biosyngas, bio-oil and bio-char to address some of the most urgent environmental problems of our
fuels [1]. These new and renewable fuels are the major alternatives to time: soil degradation and food insecurity, water pollution from agro-
conventional fossil fuels [2]. The recovery of energy from these solid chemicals and climate change [9]. The key for securing environ-
wastes has focused on thermochemical processes such as direct mental benefits is the production of a biochar by-product during
combustion [3], gasification [4] and pyrolysis [5]. Of these processes, pyrolysis which can be applied to soil [10].
pyrolysis has been receiving increasing attention in recent years as an The aim of this work is to study the gas, liquid and solid fraction
acceptable route for waste disposal. The main reason for this is that in production of two biomass wastes when they are using for
the pyrolysis process, which consists of heating the material in pyrolysis approach giving special attention to char study.
absence of air to produce gas, liquid and solid products, the conditions
can be optimised to maximize the production of either gases, oils or 2. Experimental
chars depending on the product required [6].
The main components of the gas samples are H2, CO, CO2, and CH4. 2.1. Materials
In the pyrolysis process the heavier hydrocarbons are cracked giving
rise to lighter ones; these are the greatest interest as their heating The starting material consisted of two biomasses supplied from
values are higher [7]. Bio-oil is a complex mixture, highly oxygenated León (Spain): rape and sunflower, which were dried and crushed to
with a great number of large size molecules, which nearly involve all a particle size of 2–3 mm.
species of oxygenated organics, such as esters, ethers, aldehydes,
ketones, phenols, carboxylic acids and alcohols [8]. The biochar 2.2. Experimental set-up in the laboratory
product is carbon-rich and a potential solid biofuel. Biochar
(charcoal) is also considered a soil amendment that has very specific The experimental design used in the laboratory pyrolysis tests
and unique properties that make it stand out among the opportu- is shown in Fig. 1. Pyrolysis was carried out in a reactor consisting
of a quartz tube 40 cm long with a diameter of 7 cm placed in an
electrically heated horizontal oven [11].
* Corresponding author. A 30 g sample was pyrolysed. Helium was fed into the front of
E-mail address: mesanm@unileon.es (M.E. Sánchez). the reactor, and, before heating began, it was fed through at a flow

0165-2370/$ – see front matter ß 2008 Elsevier B.V. All rights reserved.
M.E. Sánchez et al. / J. Anal. Appl. Pyrolysis 85 (2009) 142–144 143

Fig. 1. Laboratory experimental set-up.

rate of 200 mL/min for 60 min to remove the air from the system. ASTM D-3286-91a. These analyses were repeated at least three
Pyrolysis conditions were a maximum heating ramp of 30 8C/min, times for good accuracy, the results differing by 0.1 wt%.
starting from room temperature to a final temperature of 550 8C
and at a He flow rate of 100 mL/min. When the reactor reached 2.5. Characterization of biochar
550 8C, this temperature was maintained for approximately 1 min
and then the process was stopped. As for the heating ramp, the In the characterization of the solid materials, both the original
maximum allowed by the oven was used, and no tests were made biomass and biochar, a proximate analysis was run. Moisture was
with other gradients, as the bibliographical references showed that determined in a SELECTA THREOVEN with forced ventilation.
within the range 5–30 8C/min no variation in the heating gradient Volatile matter and ash were analysed with a THERMOLYNE 48000
significantly affected product formation [12]. The final tempera- muffle furnace with automatic temperature control. Regulations
ture was chosen from a previous thermogravimetric study, as the UNE 32 002, 32 019 and 32 004 were followed for moisture, volatile
heating gradient was within the range studied [13]. It was matter and ash, respectively. Fixed carbon was determined by
observed that the range of temperatures over which devolatiliza- difference.
tion of the residue occurs was quite large, running from 200 8C to An elemental analysis was also run to determine the main
550 8C, with devolatilization in thermobalance being almost chemical elements present in the sample: carbon, hydrogen,
complete. The gases produced in the pyrolysis process were nitrogen, sulphur, and oxygen, the last by subtraction. For the first
carried by the He through the lower part of the reactor, where they three elements, a LECO CHN-600 apparatus was used and ASTM
passed through a number of ‘‘traps’’, where the oils (condensable standard D-5373 was followed. Total sulphur was determined with
gas fraction) were collected. The traps comprised a balloon and two a LECO SC-132 according to ASTM standard D-4239.
U-shaped glass tubes packed in ice and filled with Raschig rings. Heating value was determined with a LECO AC-300 using the
Finally, the gases were fed into a methyl methacrylate container adiabatic method in accordance with regulation UNE 32 006.
with water inside, which was displaced, and a sample taken for gas These analyses were repeated at least three times for good
analysis. The gas yield was checked by directly measurement of the accuracy, the results differing by 0.1 wt%.
volume of gas produced in the pyrolysis process.

2.3. Characterization of gas 3. Results and discussion

The gas fraction was analysed by GC with an HP-5890 series 3.1. Materials
II with a flame ionization detector (FID) and a thermal
conductivity detector (TCD). Different pyrolysis experiments The two biomasses were characterized after dried (Table 1).
established that the relative values of gas composition do not Rape and sunflower are carbon and oxygen rich feedstock,
deviate more than 5%. To analyse hydrocarbons (CxHy), an HP-
AL/S semi-capillary column with a length of 50 m and an Table 1
internal diameter of 0.53 mm was used, with He as carrier gas Chemical analyses (%) and heating values of rape and sunflower original and
and the FID detector was used. H2, O2, N2, CH4 and CO were carbonized residues (char).
analysed in a 5 Å molecular exclusion packed column of 1/8’’ Rape CharRape Sunflower CharSunflower
outer diameter, 6-ft long, with a mesh of 60/80 and He as carrier
Moisture 8.8 3.2 8.1 4.73
gas and the TCD detector was used. CO2 was analysed in a
Volatile mattera 78.7 13.6 74.5 13.4
Chromosob 102 packed column specific for this substance with Asha 7.3 21.8 8.3 28.9
an outer diameter of 1/8’’ and a length of 6 ft, with a mesh of 80/ Fixed carbona,c 14.0 64.6 17.2 57.7
100 and He as carrier gas, the TCD also being used. For the Carbonb 44.7 72.2 43.6 63.4
identification and quantification of the gaseous species, three Hydrogenb 5.8 0.9 5.8 0.7
Nitrogenb 0.8 1.3 1.0 1.6
SUPELCO gas reference standards were used. Sulphurb 0.6 – 0.3 0.1
Oxygenb,c 48.1 25.6 49.3 34.3
2.4. Characterization of bio-oil L.H.V. (MJ/kg) 15.3 23.4 15.7 20.5
Results expressed as a percentage of dry matter.
Elemental analysis of the bio-oil was performed according to b
Results expressed as a percentage of dry matter free of ashes.
ASTM D-5373. The heating value was determined according to c
Calculated by difference.
144 M.E. Sánchez et al. / J. Anal. Appl. Pyrolysis 85 (2009) 142–144

containing hydrogen at a low ratio and trace amounts of nitrogen Table 3

Elemental analysis (%) and heating value (MJ/kg) of bio-oil.
and sulphur. The volatile matter content is quite high, rape
contains 78.7% volatile matter, and 14.0% fixed carbon and 7.3% Ca Ha Na Sa Oa,b H.V. Residue
ash. The lower heating value is 15.3 MJ/kg. Sunflower contains
78.4 9.3 2.4 0.4 8.5 37.2 Rape
74.5% volatile matter, 17.2% fixed carbon and 8.3% ash. The lower 74.7 9.3 5.9 0.3 9 36.6 Sunflower
heating value is 15.7 MJ/kg. a
Results expressed as a percentage of dry matter.
Calculated by difference.
3.2. Pyrolysis product yields

Under the process conditions fixed the yields were 34% bio-oil, hydrogen content, probably due to the great proportion of
25% bio-char and 41% gas for rape and 30% bio-oil, 36% bio-char hydrogen compounds in the volatile matter. There was a
and 34% gas for sunflower. concentration of sulphur in the solid fraction, which caused
emissions of sulphur dioxide compound during combustion being
3.3. Characterization of the gases necessary a gas cleaning treatment for the combustion gases. The
heating value of the pyrolysed residue was similar in comparison
CO, CO2, hydrocarbons and hydrogen are the main products of with that of other fuels [14], higher even than that of the biomass
devolatilisation of the two biomasses (Table 2). In the pyrolysis before pyrolysis, the low ash content (22–29%) and low oxygen
process the heavier hydrocarbons are cracked, giving rise to lighter content are the reasons that explain the high heating value of the
ones, methane and hydrogen, those of greatest interest are the char. Other ways it may be employed include use as a source of C
light hydrocarbons as their heating values are higher than the and N. During the conversion of biomass to biochar the original
other gas components. Hydrogen was the main gas produced in the carbon is retained in the biochar, which offers a significant
experiment carried out with rape residue, being CO and CH4 the opportunity for creating a carbon sink. The long persistence of
second most important components of the gases; a 78% of biochar in soil makes it a prime candidate for the mitigation of
biosyngas (H2 + CO) is reached. The net calorific value that could climate change as a potential sink for atmospheric carbon dioxide
be theoretically be recovered through stoichiometric combustion [10]. The success of effective reduction of greenhouse gases
of the evolved pyrolytic volatiles at 550 8C is calculated accounting depends on the associated net emission reductions through
for the amounts of measured combustible volatiles at 550 8C and biochar sequestration. All organic matter added to soil signifi-
using the corresponding heat of combustion for each volatile. cantly improves soil functions, not the least the retention of
Heating value was similar at those recorded in studies by other several nutrients that are essential to plant growth. The biochar
authors also performed in electric ovens (13–14 MJ/m3) [11]. from rape contains 0.76% N, 0.36% P2O5 and 4.40% K2O and for
sunflower the contents: 1.19% N, 0.44% P2O5 and 7.26% K2O. The
3.4. Characterization of the bio-oil biochar persistence in soil is also important related with any
other form of organic matter applied to the land.
Bio-oil is one of the desirable products of pyrolysis. They are What is special about biochar is that it is much more effective in
usually mixed with condensed water. Bio-oil is a carbon-rich oxy- retaining most nutrients and keeping them available to plants than
fuel containing a small proportion of nitrogen and trace amounts of other organic matter for example compost or manures. It is
sulphur (Table 3). Bio-oil can be an alternative for heating fuel. The undisputed that biochar is much more persistent in soil than any
low sulphur content of bio-oil is a very important advantage [1]. other form of organic matter that is commonly applied to the land
[15]. Therefore, all associated benefits with respect to nutrient
3.5. Characterization of the bio-char retention and soil fertility are longer lasting than with alternative
Table 1 shows a chemical analysis of carbonized residues from
pyrolysis of rape and sunflower. As a consequence of the process
of pyrolysis, the carbon content of the carbonized residue
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Propane 0.07 0.22
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