Energy Sources, Part A: Recovery, Utilization, and

Environmental Effects

ISSN: 1556-7036 (Print) 1556-7230 (Online) Journal homepage: http://www.tandfonline.com/loi/ueso20

Pyrolysis of giant mullein (Verbascum thapsus

L.) in a fixed-bed reactor: Effects of pyrolysis
parameters on product yields and character

Tevfik Aysu & Halil Durak

To cite this article: Tevfik Aysu & Halil Durak (2016) Pyrolysis of giant mullein (Verbascum
thapsus L.) in a fixed-bed reactor: Effects of pyrolysis parameters on product yields and
character, Energy Sources, Part A: Recovery, Utilization, and Environmental Effects, 38:5,
661-669, DOI: 10.1080/15567036.2013.819049

To link to this article: http://dx.doi.org/10.1080/15567036.2013.819049

Published online: 11 Apr 2016.

Submit your article to this journal

Article views: 23

View related articles

View Crossmark data

Full Terms & Conditions of access and use can be found at

http://www.tandfonline.com/action/journalInformation?journalCode=ueso20

Download by: [University of Tennessee, Knoxville] Date: 30 May 2016, At: 17:16
 ENERGY SOURCES, PART A: RECOVERY, UTILIZATION, AND ENVIRONMENTAL EFFECTS
2016, VOL. 38, NO. 5, 661–669
http://dx.doi.org/10.1080/15567036.2013.819049

Pyrolysis of giant mullein (Verbascum thapsus L.) in a fixed-bed

reactor: Effects of pyrolysis parameters on product yields and
character
Tevfik Aysua and Halil Durakb
a
Educational Faculty, Yuzuncu Yil University, Van, Turkey; bVocational School of Health Services, Yuzuncu Yil
University, Van, Turkey
Downloaded by [University of Tennessee, Knoxville] at 17:16 30 May 2016

ABSTRACT KEYWORDS
Slow pyrolysis of giant mullein (Verbascum thapsus L.) stalks have been Biomass; bio-oil; energy;
carried out in a fixed-bed tubular reactor with (Al2O3, ZnO) and without giant mullein; pyrolysis;
catalyst at four different temperatures between 400 to 550°C with a con- Verbascum thapsus L.
stant heating rate of 50°C/min and with a constant sweeping gas (N2) flow
rate of 100 cm3/min. The amounts of bio-char, bio-oil, and gas produced
were calculated and the compositions of the obtained bio-oils were deter-
mined by gas chromatography-mass spectrometry. The effects of pyrolysis
parameters, such as temperature and catalyst, on the product yields were
investigated. The results show that both temperature and catalyst have
significant effects on the conversion of Verbascum thapsus L. into solid,
liquid, and gaseous products. The highest liquid yield of 40.43% by weight
including the aqeous phase was obtained with 10% zinc oxide catalyst at
500°C temperature. Sixty-seven different products were identified by gas
chromatography-mass spectrometry in the bio-oils obtained at 500°C
temperature.

1. Introduction
In recent years, the studies on alternative and renewable energy sources have been intensified due to
environmental concerns about global warming and air pollution since limited fuel costs were
increased drastically. Biomass is the primary canditate as a substitute for fossil fuels as it is the
only source of renewable fixed carbon required for the production of conventional transportation
fuels and value-added chemicals (Demiral and Şensöz, 2006; Efendi et al., 2008). Biomass, having
lignin and cellulose in its structure, is one of the most abundant and cheap sustainable sources of
carbon, which could be converted to renewable and environmentally friendly fuels and value added
chemicals (Huber et al., 2006; Zhang et al., 2011). The utilization of biomass as a renewable energy
resource has certain advantages, such as minimal environmental problems, high energy content, low
contamination of sulphur, and reduction of greenhouse gases emissions (Kim et al., 2010).
Production of energy from biomass by conversion could be achieved by using two main
processes: thermochemical and biochemical. Biochemical processes are used to produce mainly
bio-ethanol, biogas, and hydrogen (Özçimen and Ersoy-Meriçboyu, 2008). Thermochemical pro-
cesses include gasification, combustion, and pyrolysis (Mckendry, 2002). In the thermochemical
processes, pyrolysis has received much more attention than other processes in recent years. The
yields of pyrolysis products depend mainly on the composition of raw material, pyrolysis process
type, and pyrolysis parameters, such as temperature, heating rate, catalyst, residence time, and
sweeping gas flow rate (Nisar et al., 2011). Low temperature, high heating rate, and short residence

CONTACT Tevfik Aysu tevfikaysu@hotmail.com Department of Chemistry, Faculty of Education, Yuzuncu University, Van
65080, Turkey.
© 2016 Taylor & Francis Group, LLC
 662 T. AYSU AND H. DURAK

time pyrolysis process is used for obtaining the maximum amount of liquid product, while low
heating rate is required for a higher amount of charcol yield. For high fuel gas production, high
temperature, low heating rate, and long gas residence time process should be used (Demirbaş, 2002).
One of the methods used in pyrolysis to produce hydrocarbon fuels is catalytic pyrolysis; in
carbon-carbon bonds bio-oil compounds are ruptured in the presence of some shape selective
catalysts. Decarboxylation, dehydration, and decarbonylation of compounds are the cracking reac-
tions that produce aromatic hydrocarbons, carbon dioxide, and water. Using a catalyst in pyrolysis
processes produces a better quality of bio-oil at atmospheric pressure without using hydrogen gas,
which makes it cheaper than a hydrodeoxygenation process (Williams and Nugranad, 2000). It has
been reported in a limited number of micro-scale studies (Carlson et al., 2009; French and Czernik,
2010) that high aromatic carbon (30–40 wt%) yields have been achieved by direct catalytic pyrolysis
of lignocellulosic biomass or its constituent units of cellulose, hemicellulose, and lignin in recent
years (Thangalazhy-Gopakumar et al., 2012).
Downloaded by [University of Tennessee, Knoxville] at 17:16 30 May 2016

Biomass feedstocks, such as wood, agricultural and forest residues, energy plants, urban and solid
industrial wastes, lumber, and municipal wastes have attracted great attention as renewable energy
sources worldwide. Turkey has a high potential of agricultural renewable sources with diverse crops
production in 25 million hectares of arable land (Aysu et al., 2012; Aysu and Küçük, 2013).
Numerous types of plants grow in the lands of Turkey and they could be used as a source of
biomass for production of clean energy or chemicals (Aysu, 2012). One of them, commonly named
“giant mullein” (Verbascum thapsus L.), is a biennial forb native to Eurasia and Africa. Plants are
unbranched and can grow to more than 2 m tall. The genus Verbascum is represented by 232
species, 196 of which are endemic, in the flora of Turkey (Tatlı et al., 2008). The leaves and the
flowers of Verbascum species are reported to have expectorant, mucolytic, and demulcent properties,
which are used to treat respiratory problems, such as bronchitis, dry coughs, tuberculosis, and
asthma. The seeds of Verbascum species are used as a fish poison (piscicide) due to their saponin
contents. These species are also used externally for desiccating wounds, anal fistula, and pruritic
conditions in urogenital organs as well as internally for hemorrhoids. Oil made from the flowers is
used to help sooth earache, and can be applied externally for eczema and other types of inflamed
skin conditions. These species are used to treat rheumatic pain, superficial fungal infections, and
diarrhea. They are traditionally consumed as tea to relieve abdominal pains (Turker and Camper,
2002). Additionally, several Verbascum species are known as antiseptic, antimalarial, astringent,
demulcent, emollient, sedative, narcotic and for the treatment of tumors, inflammations, migraine,
asthma, and spasmodic coughs in Europe, Asia, and North America (Kozan et al., 2011). However,
there is no study of utilization of its stalks, which have no value in terms of industrial or medicinal
respect in the literature. Therefore, pyrolysis experiments have been carried out with its stalks with
(ZnO, Al2O3) and without catalysts, four different temperatures ranging from 400 to 550°C with the
aim of obtaining bio-oil or valuable chemicals production.

2. Materials and methods

2.1. Materials
Verbascum thapsus L. plants were collected in agricultural zones in Ordu, a province of Turkey. They
were harvested in May and the stems cleaned from leaves and tops and dried naturally in open air
and then were ground, milled, and screen-sieved. Samples of different particle sizes ranging between
0.425 and 0.850 mm were used in this study.
The chemical properties of the Verbascum thapsus L. were analyzed and the results are as follows:
lignin: 26.8%, cellulose: 54.5%, holocellulose: 68.3%, moisture: 4.7%, ash: 3.2%, and Soxhlet extrac-
tives: 0.9% as percent of dry feedstock. Chemical composition of Verbascum thapsus L. was
determined using Tappi test methods. Lignin and cellulose were determined according to Tappi
T222 and Tappi T202 methods, respectively. Hollocellulose content was determined using the
 ENERGY SOURCES, PART A: RECOVERY, UTILIZATION, AND ENVIRONMENTAL EFFECTS 663

chloride method. Ash and moisture contents were determined by Tappi T211 and Tappi T264,
respectively.

2.2. Experimental procedure

The slow pyrolysis experiments were performed in a fixed-bed reactor made of stainless steel with
dimensions of 70 mm inner diameter, 10 mm outer diameter, and 200 mm height equipped with a
connection for inert gas input. In each trial, 20 g of raw material were put inside the reactor and
closed tightly with connections for inert gas entry and a products output pipe connected to liquid
product collecting bottles. The reactor was heated externally by an electric furnace and the tem-
perature is controlled by a NiCr–Ni thermocouple placed inside the bed. The liquid collecting bottles
were cooled to –10°C using frozen salt-ethanol and water mixture and the temperature is kept
constant at –10°C until no more gas is evolved from the pyrolysis process. The gas product was
Downloaded by [University of Tennessee, Knoxville] at 17:16 30 May 2016

discharged into a chimney through a hose and a fan. During the whole pyrolysis process, nitrogen
gas is circulated in the reactor with 100 cm3/min constant flowing rate to provide the inert atmo-
sphere inside the reactor. By inputting the desired variables to the control unit in a heater, pyrolysis
experiments at different conditions have been performed.
The pyrolysis experiments were done in two series. In the first one, experiments without catalyst
at four different temperatures ranging from 400 to 550°C with a constant heating rate of 50°C/min
were carried out to investigate the effect of temperature. The condensed liquid products, which
contain an aqeous and oil phase, were collected in bottles. They were washed with dichloromethane,
put in a separating funnel, and separated from each other by decantation. Bio-oil is dried with
anhydrous sodium sulphate and recovered by evaporating the solvent in a rotary evaporator at a
temperature of 313 K and reduced pressure of 11 kPa and its yield was calculated. After cooling the
pyrolysis reactor, the amount of bio-char left behind was removed and weighed. The amount of gas
evolved was calculated by subtraction of the amount of bio-char and liquid product from 20, the
amount of initial raw material. In the second group of experiments, two different catalysts (ZnO and
Al2O3) with 10% by weight were added to the reactor and pyrolysis experiments at the same
temperatures used in non-catalytic runs with a constant heating rate of 50°C/min were carried out
to investigate the effect of catalyst on product yields. Upon completion of all experiments, the
product yields were calculated and expressed on dry and ash-free basis.

3. Results and discussion

3.1. Effect of temperature and catalyst on product yields
The conversion and distribution of products obtained by pyrolysis of Verbascum thapsus L. at
different temperatures with and without catalyst are shown in Table 1. The effect of temperature
and catalyst on conversion and product yields are given in Figures 1–4. The data given in Figures 1–
4 were obtained from the experimental runs (Table 1) at different temperatures ranging from 400 to
550°C with a heating rate of 50°C/min. Figures 1 and 4 indicate that temperature has a positive effect
on both conversion and gaseous product yields at all temperatures. As for the bio-oil yields,
temperature has increased the yields until 500°C and then decreased slightly at 550°C. As it is
seen from Table 1, when temperature is increased from 400 to 500°C, liquid product yield was
increased from 36.12 to 39.84%, but decreased to 37.61% at 550°C in the non-catalytic runs.
According to the literature, temperature is considered as the most important parameter on product
yields in pyrolysis of biomass (Pütün et al., 2002; Luo et al., 2004; Onay, 2007; Şensöz and Angın,
2008; Ertaş and Alma, 2010). The gasesous product yields were increased constantly with increasing
pyrolysis temperature. When temperature was increased from 400 to 550°C, the gaseous product
yields were increased from 30.70 to 38.71% in the non-catalytic runs. The reason for decreasing of
liquid product yield and increasing of gaseous product yield at higher pyrolysis temperatures is
 664 T. AYSU AND H. DURAK

Table 1. The conversiona and distribution of products obtained by pyrolysis of Verbascum thapsus L. at different temperatures with
and without catalyst.
Temperature, °C Conversion, % Bio-char, % Bio-oil, % Gas, %
No catalyst
400°C 66.82 33.18 36.12 30.70
450°C 71.52 28.48 38.07 33.45
500°C 74.14 25.86 39.84 34.30
550°C 76.32 23.68 37.61 38.71
Zinc oxide (10%)
400°C 68.42 31.58 37.85 30.57
450°C 73.24 26.76 38.77 34.47
500°C 76.52 23.48 40.43 36.09
550°C 77.96 22.04 38.67 39.29
Aluminium oxide (10%)
400°C 72.28 27.72 34.26 38.02
450°C 75.63 24.37 36.91 38.72
500°C 77.16 22.84 37.38 39.78
Downloaded by [University of Tennessee, Knoxville] at 17:16 30 May 2016

550°C 79.35 20.65 35.41 43.94

a
Mass fraction percentage of the dry and ash-free feedstock.

Figure 1. Effect of temperature and catalyst on conversion.

Figure 2. Effect of temperature and catalyst on bio-char yields.

 ENERGY SOURCES, PART A: RECOVERY, UTILIZATION, AND ENVIRONMENTAL EFFECTS 665
Downloaded by [University of Tennessee, Knoxville] at 17:16 30 May 2016

Figure 3. Effect of temperature and catalyst on bio-oil yields.

Figure 4. Effect of temperature and catalyst on gas yields.

thought to be the formation of secondary cracking reactions of the pyrolysis vapors. On the other
hand, secondary decomposition of the bio-char could produce non-condensable gaseous substances
at higher temperatures contributing to an increase in gaseous products (Demiral and Şensöz, 2006;
Keleş et al., 2011). Bio-char yields were always decreased with increasing the pyrolysis temperature,
because of greater primary decomposition of the biomass or secondary decomposition of the char
residue, leading the higher conversions with increasing temperature. As pyrolysis temperature
increases from 400 to 550°C, bio-char yields decrease from 33.18 to 23.68% in the non-catalytic
runs. The higher heating rate of 50°C/min used in this study causes the solid material to lead to a fast
depolymerization to primary volatiles; on the other hand, the lower heating rates lead to a very slow
and limited dehydration to more stable anhydrocellulose (Zanzi et al., 2002; Demirbaş, 2004).
Pyrolysis experiments with catalysts were also carried out at a constant heating rate of 50°C/min
at the same temperatures used in non-catalytic runs to determine the effect of catalysts (ZnO and
Al2O3) on the product yields. As seen from Figures 1–4, catalysts affected the product yields
differently. Both catalysts have increased the conversion with increasing temperature with non-
catalytic runs. Among them, aluminium oxide is more effective than zinc oxide in terms of
conversion. The highest conversion of 79.35% was obtained with aluminum oxide in the catalytic
 666 T. AYSU AND H. DURAK

runs at 550°C temperature. On the other hand, effects of catalysts on liquid product yields were
different from each other. In the experiments performed with zinc oxide, the liquid product yields
have increased steadily at the temperatures of 400, 450, and 500°C but have decreased at 550°C. On
the other hand, when using aluminium oxide, which had more positive effect on conversion than
zinc oxide, the liquid product yields were less than the ones obtained without catalyst at all pyrolysis
temperatures. The liquid product yield, which was 39.84% without catalyst, reached the maximum
value of 37.38% with aluminium oxide catalyst at 550°C. The gaseous product yields for both
catalysts have increased in comparison with non-catalytic runs. For example, the gas product yield
of 38.02% at 400°C has increased to 43.94% at 550°C in the catalytic run with 10% aluminium oxide.
In recent years, numerous studies were performed investigating the effect of catalysts on product
yields of biomass samples. The use of a catalyst can make significant changes on the properties and
yields of pyrolysis products. Using a catalyst had different effects on the liquid yields, which has
increased the yields in some studies, while in others, it had a negative effect and decreased the liquid
Downloaded by [University of Tennessee, Knoxville] at 17:16 30 May 2016

yields. Similar results were obtained for bio-char and gaseous product yields, which were either
increased or decreased by using catalysts. The liquid product obtained in pyrolysis contains an
aqueous phase and bio-oil or oil phase, which is generally named as pyrolytic liquid. It is a black
liquid containing highly oxygenated compounds and is used as boiler fuel in power stations for heat
production. If it is intended to be used as transportation fuels, they should be upgraded first by
hydrodeoxygenation to produce aromatics or hydrocarbons, or catalytic cracking by using zeolite to
produce aromatic light alkanes. Having acidic sites on it, aluminium oxide can speed up the
dehydration, decarbonylation, and hydrogenation reactions, which occur during pyrolysis.

3.2. Characterization of bio-oils by gas chromatography-mass spectrometry analysis

The liquid products (bio-oils) obtained at optimum conditions (500°C) were analyzed and char-
acterized by gas chromatography-mass spectrometry (GC-MS). The GC-MS analysis was performed
at the scientific and technological research center in Malatya Inonu University on an Agilent GC-MS
7890A/5975C series. The column (HP–INNOWAX; length: 60 m, I.D.: 0,250 mm, film: 0,25 μm,
temperature limits: from 40 to 260°C) and injector temperatures were the same as those for GC.
Chemical constituents were identified by comparison of their retention indices with literature values
(Adams, 2007) and their mass spectral data with those from the Wiley7n.1, ADAMS.1, and NIST05a.
L mass spectral databases.
The list of the compounds identified by GC-MS is given in Table 2. There are many types of
compounds with different molecular structures and molecular weights in the bio-oils produced by
the thermal degradation of hemicellulose, cellulose, and lignin of raw material.
The compounds identified by GC-MS consist of complex mixtures of organic compounds, which
could be classified into four different classes. These are monoaromatics and derivatives, aliphatics,
oxygenated compounds, and nitrogenated compounds. Monoaromatics include benzene and deri-
vatives, furans, and phenols and derivatives. Aliphatics are mainly composed of alkanes, alkenes, and
their derivatives while oxygenated compounds contain aldehydes, ketones, esters, and carboxylic
acids. Amines and amides, such as methanamine, benzenamine, and N,N-dimethyl acetamide, are
classified as nitrogenated compounds.
Many of the compounds identified in bio-oils are phenolics and its derivatives, which are formed by
degradation of lignin in the raw material. They consist of phenols, methoxy phenols, alkyl phenols, and
eugenol. As bio-oils obtained by pyrolysis can be used not only as a fuel in engines or boilers, but also as
valuable organic chemicals, phenols could be considered as one of them for its commercial value.

4. Conclusion
In this study, pyrolysis of Verbascum thapsus L. was carried out to obtain solid (bio-char) and liquid
(bio-oil) products under different temperatures ranging from 400 to 550°C with and without catalyst.
 ENERGY SOURCES, PART A: RECOVERY, UTILIZATION, AND ENVIRONMENTAL EFFECTS 667

Table 2. Main chemical compounds present in the bio-oils obtained with and without catalyst at 500°C.
Area, % Area, % Area, %
Number Compound (No catalyst) (Al2O3) (ZnO)
1 Hexane 0.67 0.48 1.08
2 Propanal — 28.18
3 Dimethylamine-borane 64.14 — —
4 N,N-Dimethylacetamide 0.36 — —
5 3-Penten-2-one, 4-methyl- 0.74 — —
6 Propanenitrile, 3-(ethylamino)- 0.28 — —
7 AZETIDINE-D1 — 66.63 36.41
8 Caspan — 1.07 —
9 1H-Pyrazole, 3-methyl — 0.57 —
10 Pentane, 3-methyl — 0.56 —
11 Hydrazine, 1,1-dimethyl- — 7.95 —
12 Furfural — 1.46 1.00
13 2,5-dimethyl-1,4-hexadiene — 7.67 —
14 1-Hydroxy-2-pentanone — 0.42 —
Downloaded by [University of Tennessee, Knoxville] at 17:16 30 May 2016

15 2-Cyclopenten-1-one, 3-methyl- — 0.54 0.67

16 Propanoic acid — 0.94 1.58
17 2-Furancarboxaldehyde, 5-methyl- — 0.35 0.32
18 2H-Pyran — 0.50 —
19 2-Furanmethanol — 1.53 1.08
20 3,4-Dihydropyran 0.20 0.49 —
21 1H-Imidazole-2-methanol — 0.61 —
22 Guaicol acetate 0.78 1.49 1.85
23 o-Cresol 1.25 1.03 —
24 Phenol 1.86 1.76 2.43
25 1H-Inden-1-one, 2,3-dihydro- 0.40 0.50 0.53
26 Phenol, 2,5-dimethyl- 0.36 0.25 —
27 Phenol, 2,4-dimethyl- 0.40 0.31 —
28 p-Cresol 0.92 0.67 1.92
29 m-Cresol — 1.30 1.31
30 3-Heptanone — 1.82 —
31 Phenol, 3,5-dimethyl- — 1.01 —
32 Phenol, 3-ethyl- 0.71 0.66 1.55
33 Phenol, 2-ethyl- 1.37 — —
34 4-Vinylguaiacol — 0.34 0.39
35 Phenol, 2,6-dimethoxy- 4.25 3.17 —
36 1-Methyl-5-iodouracil — 0.52 —
37 1,4-Benzodioxin, 2,3-dihydro- 1.46 0.67 —
38 2-Undecanone — — 0.27
39 Acrylic acid methyl ester — — 0.40
40 Acetic acid 0.99 — 4.82
41 Ethanone, 1-(2-furanyl)- — — 0.34
42 1-Penten-3-ol, 2-methyl- — — 0.59
43 4-Octyne — — 0.48
44 Tetrahydro-2-furanone — — 0.62
45 2 (3H)-Furanone 0.23 — 0.41
46 2-Cyclopenten-1-one, 2-hydroxy- — — 0.29
47 2 (1H)-Pyrimidinone — — 0.74
48 Naphthalene, 1-methyl- — — 0.26
49 o-Cresol — — 1.50
50 4-Hydroxy-3-methoxy ethyl benzene — — 0.18
51 Phenol, 2,6-dimethyl- 0.35 — 3.24
52 6,8-Dioxabicyclo[3.2.1] octane — — 1.73
53 Pyrazine, 2,3,5-trimethyl- — — 0.44
54 1-Ethyl-3-hydroxybenzene — — 0.63
55 3,4-Xylenol — — 0.31
56 2,4-Xylenol 0.42 — —
57 3,5-Dimethoxybenzyl alcohol — — 0.58
58 2-Methoxypyrazine — — 0.75
59 Isoferulic acid — — 0.49
60 Pyrazine, 1,4-dioxide 0.39 — —
61 3-Pentanone, 2,2-dimethyl- 1.60 — —
62 m-Difluorotetrachlorobenzene 0.16 — —
(Continued )
 668 T. AYSU AND H. DURAK

Table 2. (Continued).
Area, % Area, % Area, %
Number Compound (No catalyst) (Al2O3) (ZnO)
63 Benzeneamine, 2-methoxy-5-nitro- 0.50 — —
64 2-Pentenoic acid, 2-methyl- 0.49 — —
65 2-Octene 7.89 — —
66 Phthalic anhydride 4.52 — —
67 2-Tridecanone 0.53 — —

It was found that the optimum condition for bio-oil formation is at 500°C both in catalytic and non-
catalytic runs. The effects of different catalysts on degradation of Verbascum thapsus L. were also
investigated and zinc oxide catalyst was found to be more effective than aluminium oxide in terms of
bio-oil formation. The composition of the bio-oil products was characterized by GC-MS. In con-
Downloaded by [University of Tennessee, Knoxville] at 17:16 30 May 2016

clusion, Verbascum thapsus L. is a good candidate for producing bio-chars and bio-oils with higher
heating values or value-added chemicals by pyrolysis process.

References
Adams, R. P. 2007. Identification of Essential Oil Components by Gas Chromatograph/Quadrupole Mass Spectroscopy,
4th Ed. Carol Stream IL: Allured Publishing Corporation.
Aysu, T. 2012. Supercritical fluid extraction of reed canary grass (Phalaris arundinacea). Biomass Bioenergy 41:139–
144.
Aysu, T., and Küçük, M. M. 2013. Liquefaction of giant reed (Arundo donax L.) by supercritical fluid extraction. Fuel
103:758–763.
Aysu, T., Turhan, M., and Küçük, M. M. 2012. Liquefaction of Typha latifolia by supercritical fluid extraction.
Bioresour. Technol. 107:464–470.
Carlson, T. R., Tompsett, G. A., Conner, W. C., and Huber, G. W. 2009. Aromatic production from catalytic fast
pyrolysis of biomass-derived feedstocks. Top. Catal. 52:241–252.
Demiral, İ., and Şensöz, S. 2006. Fixed-bed pyrolysis of hazelnut (Corylus Avellana L.) bagasse: Influence of pyrolysis
parameters on product yields. Energy Sources Part A 28:1149–1158.
Demirbaş, A. 2002. An overview of biomass pyrolysis. Energy Sources 24:471–482.
Demirbaş, A. 2004. Determination of calorific values of bio-chars and pyro-oils from pyrolysis of beech trunkbarks. J.
Anal. Appl. Pyrolysis 72:215–219.
Efendi, A., Gerhauser, H., and Bridgwater, A. V. 2008. Production of renewable phenolic resins by thermochemical
conversion of biomass. Renewable Sustainable Energy Rev. 12:2092–2116.
Ertaş, M., and Alma, M. H. 2010. Pyrolysis of laurel (Laurus nobilis L.) extraction residues in a fixed-bed reactor:
Characterization of bio-oil and bio-char. J. Anal. Appl. Pyrolysis 88:22–29.
French, R., and Czernik, S. 2010. Catalytic pyrolysis of biomass for biofuels production. Fuel Process. Technol. 91:25–32.
Huber, G. W., Iborra, S., and Corma, A. 2006. Synthesis of transportation fuels from biomass: Chemistry, catalysts,
and engineering. Chem. Rev. 106:4044–4098.
Keleş, S., Kaygusuz, K., and Akgün, M. 2011. Pyrolysis of woody biomass for sustainable bio-oil. Energy Sources Part A
33:879–889.
Kim, J., Lingaraju, B. P., Rheaume, R., Lee, J. Y., and Siddiqui, K. F. 2010. Removal of ammonia from wastewater
effluent by Chlorella vulgaris. Tsinghua Sci. Technol. 15:391–396.
Kozan, E., Çankaya, I. T., Kahraman, Ç., Akkol, E. K., and Akdemir, Z. 2011. The in vivo anthelmintic efficacy of some
Verbascum species growing in Turkey. Exper. Parasitol. 129:211–214.
Luo, Z., Wang, S., Liao, Y., Zhou, J., Gu, Y., and Cen, K. 2004. Research on biomass fast pyrolysis for liquid fuel.
Biomass Bioenergy 26:455–462.
Mckendry, P. 2002. Energy production from biomass (part 1): Overview of biomass. Bioresour. Technol. 83:37–46.
Nisar, J., Ali, M., and Awan, I. A. 2011. Catalytic thermal decomposition of polyethylene by pyrolysis gas chromato-
graphy. Chil. Chem. Soc. 56:653–655.
Onay, Ö. 2007. Influence of pyrolysis temperature and heating rate on the production of bio-oil and char from
safflower seed by pyrolysis, using a well-swept fixed-bed reactor. Fuel Process. Technol. 88:523–531.
Özçimen, D., and Ersoy-Meriçboyu, A. 2008. A study on the carbonization of grapeseed and chestnut shell. Fuel
Process. Technol. 89:1041–1046.
Pütün, A. E., Apaydın, E., and Pütün, E. 2002. Bio-oil production from pyrolysis and steam pyrolysis of soybean cake:
Product yields and compositon. Energy 27:703–713.
 ENERGY SOURCES, PART A: RECOVERY, UTILIZATION, AND ENVIRONMENTAL EFFECTS 669

Şensöz, S., and Angın, D. 2008. Pyrolysis of safflower (Charthamus tinctorius L.) seed pres cake: Part 1. The effects of
pyrolysis parameters on the product yields. Bioresour. Technol. 99:5492–5497.
Tatlı, I., Erdogan, T. F., Kahraman, C., Kıvcak, B., and Akdemir, Z. S. 2008. Brine shrimp lethality bioassay of some
Verbascum species growing ın Turkey. J. Pharm. Sci. 33:193–198.
Thangalazhy-Gopakumar, S., Adhikari, S., Chattanathan, S. A., and Gupta, R. B. 2012. Catalytic pyrolysis of green
algae for hydrocarbon production using H+ZSM-5 catalyst. Bioresour. Technol. 118:150–157.
Turker, A., and Camper, N. D. 2002. Biological activity of common mullein, a medicinal plant. J. Ethnopharm. 82:117–
125.
Williams, P. T., and Nugranad, N. 2000. Comparison of products from the pyrolysis and catalytic pyrolysis of rice
husks. Energy 25:493–513.
Zanzi, R., Sjöström, K., and Björnbom, E. 2002. Rapid pyrolysis of agricultural residues at high temperatures. Biomass
Bioenergy 23:357–366.
Zhang, H., Xiao, R., Wang, D., He, G., Shao, S., Zhang, J., and Zhong, Z. 2011. Biomass fast pyrolysis in a fluidized bed
reactor under N2, CO2, CO, CH4 and H2 atmospheres. Bioresour. Technol. 102:4258–4264.
Downloaded by [University of Tennessee, Knoxville] at 17:16 30 May 2016