Journal of Analytical and Applied Pyrolysis 125 (2017) 234–242

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Journal of Analytical and Applied Pyrolysis

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

Fixed-bed pyrolysis of walnut shell: Parameter effects on yields and

characterization of products
Korkut Açıkalın a,∗ , Fatma Karaca b
a
Yalova University, Energy Systems Eng. Department, 77200 Yalova, Turkey
b
Marmara University, Chemical Eng. Department, 34722 Göztepe, İstanbul, Turkey

a r t i c l e i n f o a b s t r a c t

Article history: Fixed-bed pyrolysis experiments of walnut shell have been conducted in a well-swept tubular reactor to
Received 15 February 2017 investigate the effects of various process parameters on product yields. For this purpose, pyrolysis tem-
Accepted 28 March 2017 perature, reaction time and sweeping gas (N2 ) flow rate were set in the ranges of 350–650 ◦ C, 10–50 min
Available online 30 March 2017
and 50–450 ml min−1 , respectively. The heating rate was fixed at 40 ◦ C min−1 . Maximum liquid yield was
obtained at 500 ◦ C, 30 min and 150 ml min−1 as 48.2%. The liquid product was characterized by FTIR and
Keywords:
GC–MS analyses, and shown to be a highly oxygenated complex mixture with 32 identified compounds
Biomass
whose carbon distribution was between C2 -C10 . In addition, the solid product was analyzed by means of
Walnut shell
Pyrolysis
FTIR, SEM and BET surface area which showed that solid product, as produced, was not appropriate for
Biofuel activated carbon applications. However, the higher heating value of solid product was higher than that
Product characterization of sub-bituminous coal, indicating a valuable solid fuel.
© 2017 Elsevier B.V. All rights reserved.

1. Introduction mately estimated as 96,732 t per year. Although it is known that

The renewable energy sources can mainly be classified as
biomass energy, hydro power, geothermal energy, solar energy and
wind energy. Among these sources, biomass is often believed to
have the highest potential to contribute to a future sustainable
energy supply since it is the only renewable energy source that
can be directly converted to solid, liquid and gaseous products, as
well as being environmentally clean and abundantly available.
Biomass can be defined as all of the non-fossil organic mate-
rials whose main components are carbohydrate compounds. The
principal biomass resources are agricultural crops and their waste
byproducts, animal wastes, aquatic organisms (alg, seaweed etc.),
forestry crops and residues, food processing wastes, low grade
plants, municipal wastes, wood and wood processing residues. One
kind of biomass waste material is walnut shell which mainly arises
from the need for use of its nut in confectionery, snack foods and
pastry industries. Turkey was the fourth largest walnut producer
in the world in 2014 with a production of 180,807 t [1]. Consid-
ering that the shell/walnut ratio is between 40 and 67% wt. with
respect to its variety [2–4], and taking the average of these values,
the potential amount of walnut shell in Turkey can be approxi-
∗ Corresponding author at: Yalova Üniversitesi Enerji Sistemleri Mühendisliği
Bölümü, Çınarcık yolu üzeri, Merkez Yerleşke, B Blok, 77200, Yalova, Turkey.
E-mail address: korkut.acikalin@gmail.com (K. Açıkalın).
the walnut shells can be used in cosmetic and medicine sectors [5],
they have no utilization except direct combustion in Turkey [6].
This way of evaluation is thought to be inefficient since the calorific
value of walnut shell is quite low. On the other hand, promising
results may be obtained by converting the walnut shells into more
convenient fuels and/or chemicals by applying thermochemical
conversion processes.
Pyrolysis is one of the thermochemical conversion processes in
which biomass is heated to moderate temperatures (400–600 ◦ C) in
an inert atmosphere to produce solid, liquid and gaseous products.
The yield and quality of products depend on feedstock properties
and process parameters. Typical feedstock properties are parti-
cle size, porosity, fixed carbon/volatile ratio, humidity, cellulose,
hemicellulose, lignin, ash and mineral content whereas pyrolysis
temperature, heating rate, reaction time, residence time, reactor
type, catalyst type and amount, sweeping gas type and flow rate are
process parameters. These parameters can be tuned to maximize
the yield of desired product. It is known that high solid product
yields can be obtained at lower pyrolysis temperatures and longer
vapor residence times. On the other hand, higher temperature and
longer residence time increase biomass conversion to gas, and mod-
erate temperatures with short vapor residence times are optimum
for producing liquids [7].
The present study focuses on two aspects of fixed-bed walnut
shell pyrolysis: (i) effect of pyrolysis conditions (pyrolysis tem-

http://dx.doi.org/10.1016/j.jaap.2017.03.018
0165-2370/© 2017 Elsevier B.V. All rights reserved.
 K. Açıkalın, F. Karaca / Journal of Analytical and Applied Pyrolysis 125 (2017) 234–242 235

Table 1
Proximate and ultimate analyses of walnut shell.

Proximate analysis (%) Ultimate analysis (%)

Ma VMb FCc Ash HHVd C H O N S

2.57 78.04 18.75 0.64 4265 48.34 6.16 44.78 0.69 0.03
a
Moisture.
b
Volatile matter.
c
Fixed carbon.
d
Higher heating value (kcal kg−1 ); VM, FC, Ash values are in dry basis; Oxygen amount is calculated by difference.

perature, reaction time and sweeping gas (N2 ) flow rate) on the
product yields; and (ii) characterization of solid and liquid products
by means of chromatographic and spectroscopic analyses.
2. Material and methods
2.1. Materials
The biomass waste material pyrolyzed in present study was wal-
nut shell. Walnuts were obtained from a local market of Edirne
province which is located in the far north-west of Turkey. The shells
were gently separated from the fruit. Shell samples were milled by
using an IKA 11 model analytic mill, and then sieved to obtain a
uniform material having an average particle size between 1 and
2 mm. The samples were dried under vacuum at 105 ◦ C, and were
kept in glass containers. The proximate and ultimate analyses data
for walnut shell are given in Table 1.
2.2. Pyrolysis experiments
Pyrolysis experiments were performed in a tubular reactor
(Fig. 1). The reactor was made up of quartz, and has a length of
102 cm and an inner diameter of 4 cm. The 45 cm length lying at
the center of the reactor was electrically heated. The temperature
of the heated section was measured by a thermocouple within an
accuracy of ±2 ◦ C, and maintained at the desired value by a PID
controller.
The schematic diagram of the pyrolysis process is given in Fig. 1.
For each run, 10 g of walnut shell sample was put in a sample holder
which has holes of 1 mm diameter on itself. Then, the sample holder
was placed at the center of the reactor. Two ice-water traps at ∼0 ◦ C
were positioned at the reactor exit to capture the liquid products.
After arranging the connections, nitrogen gas was passed through
the reactor to provide an air/oxygen free reaction medium. There-
after, the nitrogen flow rate was set to the requested value, and the
reactor was heated to the desired reaction temperature at a fixed
heating rate of 40 ◦ C min−1 . When the desired reaction time was
attained, heating was terminated, and the reactor was left for cool-
ing to room temperature. Following the cooling, the sample holder
was removed from the reactor, and solid amount was weighed
(QS1 ). Then, the traps and connections were carefully removed, and
liquid amount was weighed (QL1 ). The reactor containing some
liquid and solid products was also removed and weighed (QR1 ).
Next, the reactor was washed with tetrahydrofuran to separate the
liquid products, and reweighed after drying (QR2 ). The amount of
liquid product in the reactor (QL2 ) was determined from the dif-

Fig. 1. The schematics of pyrolysis reactor and pyrolysis process.

236 K. Açıkalın, F. Karaca / Journal of Analytical and Applied Pyrolysis 125 (2017) 234–242
Fig. 2. Effect of reaction temperature on pyrolysis product yields (30 min reaction
time, 250 ml min−1 N2 flow rate, 40 ◦ C min−1 heating rate).
ference of QR1 -QR2 ; whereas the solid product in the reactor (QS2 )
was calculated from the difference between QR2 and the weight
of empty reactor. The amount of total liquid (QL ) and total solid
(QS ) products were calculated as QL1 + QL2 and QS1 + QS2 , respec-
tively. These values were converted to yields by dividing them to
the original amount of biomass sample. The gaseous product yield
was calculated by difference.
2.3. Analyses
Infrared spectra of solid and liquid products were recorded
by using a Fourier transform infrared spectroscope (Perkin Elmer
Spectrum One). The solid products were finely powdered and
encapsulated with KBr at 1/100 sample/KBr weight ratio to pre-
pare translucent sample disks. The liquid products were analyzed
directly without any preparation.
The scanning electron micrographs of solid products were
obtained by using a Jeol JSM-6390LV model equipment. The sam-
ples were coated with platinum to prevent the accumulation of
static electric charge on the specimen during the analyses. The BET
surface area of solid products were determined with Costech Sorp-
tometer 1042 model equipment after a six hour degasing process
of samples in He atmosphere.
The low molecular mass content of liquid product was ana-
lyzed by a GC–MS system combining Agilent Technologies 6890N
GC and Agilent 5973 Inert Mass Selective Detector. The capillary
column used in analyses was DB-VRX (60 m × 0.25 mm; 1.40 ␮m
film thickness) whose allowable working temperature interval is
−10 ◦ C − 260 ◦ C. The temperature programme was 10 min at 45 ◦ C;
12 ◦ C min−1 to 190 ◦ C, 2 min at 190 ◦ C; 6 ◦ C min−1 to 225 ◦ C, 1 min
at 225 ◦ C; 3 ◦ C min−1 to 250 ◦ C and 5 min at 250 ◦ C. Helium was
used as a carrier gas at a flow rate of 10 ml min−1 . Liquid prod-
uct was injected to the system after mixing with methanol. The
chromatographic peaks were identified by using Wiley 7 library.
The higher heating values (HHV) of solid and liquid products
were measured by IKA C4000 model bomb calorimeter.
3. Results and discussion
3.1. Effect of parameters on pyrolysis product yields
3.1.1. Effect of pyrolysis temperature
Walnut shell was pyrolyzed at five different temperatures (350,
425, 500, 575 and 650 ◦ C) fixing the reaction time, N2 flow rate
and heating rate at 30 min, 250 ml min−1 and 40 ◦ C min−1 , respec-
tively. Fig. 2 shows the product yields as a function of pyrolysis
Fig. 3. Effect of reaction time on pyrolysis product yields (500 ◦ C reaction temper-
ature, 250 ml min−1 N2 flow rate, 40 ◦ C min−1 heating rate).
Fig. 4. Effect of nitrogen flow rate on pyrolysis product yields (500 ◦ C reaction tem-
perature, 30 min reaction time, 40 ◦ C min−1 heating rate).
temperature. It can be seen that all of the pyrolysis yields were
sensitive to temperature variations in the studied range. As it was
shown, the liquid product yield was 44.11% at 350 ◦ C, but this yield
increased with increasing pyrolysis temperature, and reached to its
maximum value (45.38%) at 425 ◦ C. However, further increment of
pyrolysis temperature resulted in a decrease, and the liquid product
yield was observed as 42.23% at 650 ◦ C. By considering the increase
in gaseous product yield and the decrease in solid product yield in
the 425–650 ◦ C interval, the decrease in liquid product yield was
attributed to the secondary reactions of pyrolysis vapors which
favor gas formation. The pyrolysis temperature had stronger influ-
ence on gaseous product yield compared to its influence on liquid
product yield. The gas yield was 21.96% at 350 ◦ C, and it showed a
continuous increase reaching 31.92% at 650 ◦ C. The increase in gas
yield between 350 and 425 ◦ C can be attributed to the degradation
of original biomass and the possible degradation of intermediate
solid product since only solid product yield decreased at the men-
tioned temperature interval. However, to explain the increase in gas
yield at 425–650 ◦ C interval, secondary reactions of volatiles should
also be added to the above explanations made for 350–425 ◦ C inter-
val. This is mainly due to the decrement of both liquid and solid
product yields in 425–650 ◦ C range. In contradiction to gaseous
product yield, solid product yield exhibited a continuous decrease
with increasing pyrolysis temperature. It was observed as 33.93%
and 25.85% at 350 ◦ C and 650 ◦ C, respectively. This was a prospec-
tive result since higher-molecular-weight components of walnut
shell and intermediate solid product underwent thermal degrada-
 K. Açıkalın, F. Karaca / Journal of Analytical and Applied Pyrolysis 125 (2017) 234–242 237

Fig. 5. SEM micrographs of solid products obtained at various pyrolysis temperatures (30 min reaction time, 250 ml min−1 N2 flow rate, 40 ◦ C min−1 heating rate).

tion at elevated pyrolysis temperatures. The tendency of the yields
with varying pyrolysis temperatures observed in present study was
consistent with the previously done pyrolysis studies of pine saw-
dust [8], fruit pulp [9], rapeseed stalk [10], waste wood, cardboard
and textile residues [11].
3.1.2. Effect of reaction time
Pyrolysis of walnut shell was carried out at 500 ◦ C under
250 ml min−1 N2 flow rate for five different reaction times (10, 20,
30, 40 and 50 min) in order to investigate the effects of reaction
time on product yields. As it can be seen from Fig. 3, the gaseous
and liquid product yields were slightly affected with varying reac-
tion times. The liquid product yield was 47.14% at 10 min reaction
time, and showed a very slight increase reaching to 47.39% as the
reaction time was increased to 20 min. Liquid yield exhibited a
decreasing trend with further increments, and it was obtained as
44.67% at 50 min reaction time. By considering the stableness of
solid yield and the increase in gas yield at 30–50 min reaction time
range, it would be righteous to say that the condensable pyrolysis
vapors were thermally cracked to lower-molecular-weight non-
condensable gaseous products at reaction times higher than 20 min.
This explanation was also prevailing for the continuous increase
observed for gas yield at 10–50 min reaction time interval. The
values of gas yield were 25.11% and 28.34% at 10 min and 50 min
reaction times, respectively. On the other hand, the solid product
yield was not affected by the varying reaction times, and was at
around ∼27%. In other words, 10 min reaction time was sufficient
to obtain the highest possible pyrolysis conversion at studied pyrol-
ysis temperature (500 ◦ C), and left a solid residue (or solid product)
of ∼27% by weight of original biomass. As stated in literature, high
cellulose content favors the pyrolysis rate [12], and thus lowers the
reaction time. This was also recognized in the present study since
238 K. Açıkalın, F. Karaca / Journal of Analytical and Applied Pyrolysis 125 (2017) 234–242
Fig. 6. FTIR spectra of (a) walnut shell (b) solid products obtained at different pyrolysis temperatures (30 min reaction time, 250 ml min−1 N2 flow rate, 40 ◦ C min−1 heating
rate).
a previous study [13] showed that walnut shell has a holocellulosic
content of ∼64% by weight. Paradela et al. [14] studied the pyrol-
ysis of forestry wastes, and reported that increasing reaction time
had caused a slight increase in gas yields. They observed the max-
imum liquid yield at 15 min reaction time, and marked a decrease
with higher reaction times. These results were consistent with the
present study.
3.1.3. Effect of nitrogen flow rate
Walnut shell was pyrolyzed under five different N2 flow rates
(50, 150, 250, 350 and 450 ml min−1 ) fixing the pyrolysis tem-
perature, reaction time and heating rate at 500 ◦ C, 30 min and
40 ◦ C min−1 , respectively. Fig. 4 shows the product distribution as
a function of N2 flow rate. Liquid product yield was considerably
affected by varying N2 flow rates. Increasing the N2 flow rate from
50 to 150 ml min−1 resulted a very slight increase, and liquid yield
increased from 48% to 48.2%. By further increments, a decreas-
ing trend was observed, and the liquid yield dropped to 43.52% at
450 ml min−1 . One of the most important events that occur during
pyrolysis is the interaction between the newly formed pyroly-
sis vapors and the decomposing solid. This interaction involves
exothermic reactions in which solid formation is favored. The N2
gas sweeping the reaction medium sets the residence time of vapors
in reactor, and thus providing the necessary flow rate can pre-
vent the concerned interactions and possible cracking of vapors
to gaseous products yielding higher amounts of liquid product. The
 K. Açıkalın, F. Karaca / Journal of Analytical and Applied Pyrolysis 125 (2017) 234–242
Fig. 7. FTIR spectra of liquid products obtained at different pyrolysis temperatures (30 min reaction time, 250 ml min−1 N2 flow rate, 40 ◦ C min−1 heating rate).
slight increase in liquid yield can be explained in such a way since
both solid and gas yields remained constant at 50–150 ml min−1
N2 flow rates. On the other hand, increasing the N2 flow rate
decreases the residence time of pyrolysis vapors in condenser.
Hence, high flow rates may restrain the condensation of vapors
yielding lower amounts of liquid product. The decrease in liquid
yield in 150–450 ml min−1 range was explained in such a man-
ner since solid yield remained constant at around 27%, and gas
yield increased from 24.58% to 29.95%. Moreover, by considering
the constant value of solid product yield for all studied N2 flow
rates and reaction time values (given in previous section), pyroly-
sis temperature can be assigned as the main determinative factor
in pyrolysis conversion. The product yields obtained from pyroly-
sis of empty fruit bunches [15] and corn stalk [16] have presented
similar behaviors with varying sweeping gas flow rates.
3.2. Analyses of solid and liquid products
3.2.1. SEM, BET surface area and heating value of solid products
SEM micrographs of solid products obtained at 350, 500 and
650 ◦ C pyrolysis temperatures were given in Fig. 5. It was clear
that surface morphology of solid products changed with varying
pyrolysis temperature. The product obtained at 350 ◦ C had a dishar-
monious surface, including scattered particles of various sizes on
itself. Pore forming was few, and hardly observed. The solid prod-
uct obtained at 500 ◦ C had a more harmonious surface compared to
that of the product obtained at 350 ◦ C. The surface was wavy with
observable pores, and contained some craters. These craters may
be thought like chimneys formed as the hot gases produced during
the pyrolysis escaped suddenly from the sample [17]. The surface
of the solid product obtained at 650 ◦ C contained many thin sheets
or layers. This may be due to the melting of high parts of waves,
and consequently falling over to the low parts of surface. The pores
on the surface of the layers were easily observed together with the
holes between the layers. So, in the studied temperature range, it
may be concluded that the porosity of the solid product increases
239
as the pyrolysis temperature increases since higher amounts of
volatiles are removed at higher temperatures.
The BET surface area of the solid products obtained at 350, 500
and 650 ◦ C were measured as 0.18, 1.01 and 4.00 m2 g−1 , respec-
tively. The increase in surface area can also be explained by the
release of higher amounts of volatiles from the structure as the
temperature increases. The surface area is an important property
of a material to be used as an activated carbon. The values given
above are very low compared to a typical activated carbon whose
surface area is depicted by hundreds of meter square per gram. For
this reason, the solid products cannot be used directly as activated
carbon.
The higher heating values (HHV) of solid products obtained
at 350, 500 and 650 ◦ C were measured as 6372, 6692 and
7070 kcal kg−1 , respectively. This increase can be attributed to the
increasing content of carbon and decreasing content of oxygen as
pyrolysis temperature increases. Comparing these values with the
HHV of original biomass (4265 kcal kg−1 ), a solid fuel with a higher
energy content having a calorific value between sub-bituminous
and bituminous coal was produced.
3.2.2. FTIR analyses of solid products
The FTIR spectrum of solid products obtained at 30 min reaction
time, 250 ml min−1 N2 flow rate and five different pyrolysis tem-
peratures (350, 425, 500, 575, 650 ◦ C) were given in Fig. 6-b. As it
can be seen from the figure, some of the peaks present for walnut
shell (Fig. 6-a) were not observed, or observed at lower intensi-
ties in solid product spectra since some of the functional groups
of walnut shell were removed (or partially removed) during the
pyrolysis processes applied at different pyrolysis temperatures. The
effect of pyrolysis temperature on the solid product characteris-
tics can be easily noticed from Fig. 6-b. For instance, the peak at
around 3410 cm−1 was less intensive for the products obtained at
high temperatures. Since this peak was ascribed to O H stretch-
ing vibrations in hydroxyl groups [18], and showed the presence of
alcohols, phenols or acids; it was said that the products obtained
240 K. Açıkalın, F. Karaca / Journal of Analytical and Applied Pyrolysis 125 (2017) 234–242

Table 2
GC–MS characterization of pyrolysis liquid product.a

Peak no. tR b (min) Tentative assignment Emprical formula Molecular weight Area (%) Q.c (%)

4 13.24 Acetaldehyde, hydroxy- C2 H4 O2 60.05 0.54 86

5 15.53 Acetic acid C2 H4 O2 60.05 9.72 91
6 18.63 2-Propanone, 1-hydroxy- C3 H6 O2 74.08 1.64 90
7 24.57 1-Hydroxy-2-butanone C4 H8 O2 88.11 0.90 78
8 29.37 2-Furancarboxaldehyde C5 H4 O2 96.08 1.16 93
9 30.35 2-Pentanone, 3-ethyl- C7 H14 O 114.19 0.25 59
10 30.81 2-Propanone, 1-(acetlyoxy)- C5 H8 O3 116.12 0.29 78
11 33.71 2(5H)-Furanone C4 H4 O2 84.07 0.71 90
12 35.79 4-oxo-5-methoxy-2-penten-5-olide C4 H5 N3 O 111.10 0.38 64
13 36.28 Phenol C6 H6 O 94.11 0.94 94
14 39.72 2-Cyclopenten-1-one, 2-hydroxy- C6 H8 O2 112.13 0.70 96
15 40.73 Phenol, 2-methyl- C7 H8 O 108.14 0.53 96
16 40.94 2-Pyrrolidinone, 1-methyl- C5 H9 NO 99.13 3.55 91
17 41.75 Phenol, 4-methyl- C7 H8 O 108.14 0.84 97
18 43.70 Phenol, 2-methoxy- C7 H8 O2 124.14 2.15 95
19 44.86 2-Cyclopenten-1-one, 3-ethyl-2-hydroxy- C7 H10 O2 126.15 0.33 93
20 45.91 Phenol, 2,4-dimethyl- C8 H10 O 122.16 0.32 97
21 47.34 1,2-Benzenediol C6 H6 O2 110.11 1.07 94
22 47.72 5-Hydroxymethyldihydrofuran-2-one C5 H8 O3 116.12 0.28 70
23 48.69 Phenol, 2-methoxy-4-methyl- C8 H10 O2 138.16 0.97 95
24 50.30 Hydroquinone C6 H6 O2 110.11 0.29 93
25 50.62 1,2-Benzenediol, 3-methyl- C7 H8 O2 124.14 0.48 93
26 51.95 1,2-Benzendiol, 3-methoxy- C7 H8 O3 140.14 0.79 95
27 52.76 Benzeneethanol, 2-methoxy- C9 H12 O2 152.19 0.98 93
28 56.18 Phenol, 2,6-dimethoxy- C8 H10 O3 154.16 3.88 93
29 56.53 Eugenol C10 H12 O2 164.20 0.47 95
30 57.00 Phenol, 2-methoxy-4-propyl- C10 H14 O2 166.22 0.23 74
31 58.71 Benzaldehyde, 4-hydroxy-3-methoxy- C8 H8 O3 152.15 0.31 91
32 60.24 3-Hydroxy-4-methoxybenzoic acid C8 H8 O4 168.15 1.69 64
33 60.63 1,6-Anhydro-beta-d-glucopyranose C6 H10 O5 162.14 1.34 59
34 62.24 Ethanone, 1-(4-hydroxy-3-methoxyphenyl)- C9 H10 O3 166.17 0.21 90
35 63.19 2,3,5-Trimethoxytoluene C10 H14 O3 182.21 1.49 90
Total Area (%): 39.43
a
Obtained at 500 ◦ C reaction temperature, 30 min reaction time and 250 ml min−1 N2 flow rate.
b
Retention time.
c
Quality; The peak area of methanol was 58.42%.

at high temperatures contained lesser amounts of the mentioned
chemical groups. Moreover, the peaks observed at around 2920
and 2850 cm−1 were respectively due to the methylene asymmetric
C H stretching and methylene symmetric stretching [19], and were
hardly observed for high temperature solid products. This indicated
that high temperature solid products contained lesser amounts of
aliphatic content compared to the solid products obtained at low
temperatures. A similar case was also reported for chars produced
from lignin [20]. The intensity of aromatic content related peaks
(C C vibrations at 1580–1560 cm−1 and C H out-of-plane bending
vibrations at 874, 808 and 744 cm−1 ) have also changed with vary-
ing pyrolysis temperature. For instance, for the products obtained
at up to 500 ◦ C, the 1580–1560 cm−1 peaks had almost the same
intensity but the intensity of 874, 808 and 744 cm-1 peaks increased
slightly. Thus, it might be said that aromaticity of solid products had
increased slightly as the pyrolysis temperature increased from 350
to 500 ◦ C. However, at higher pyrolysis temperatures the intensity
of both peak groups decreased, and pointed out a decrease in aro-
maticity of solid products. Finally, the spectrum of solid product
obtained at 650 ◦ C did only have a few very low intensity peaks.
Thus, it could be thought that unpyrolyzed material present in the
carbon matrix was very low, and the pyrolysis process was almost
completed.
3.2.3. FTIR analyses of liquid products
FTIR spectrums of liquid products obtained at 350, 425, 500,
575 and 650 ◦ C pyrolysis temperatures were given in Fig. 7. The
spectra were almost identical showing that the qualitative compo-
sition of liquid product was independent of pyrolysis temperature
but dependent on the composition of biomass meaning that the
qualitative composition of biomass was defined by its constituents
such as cellulose, hemicellulose, lignin etc. All of these constituents
were same during the pyrolysis studies of walnut shell regardless
of applied pyrolysis temperature. In addition, it is known that the
liquid product mainly consists of the condensed volatiles coming
from cellulose and hemicellulose which decompose almost com-
pletely at temperatures around 350 ◦ C. Hence, the spectra obtained
at different pyrolysis temperatures were similar as expected. The
same observation was also made in the pyrolysis study of almond
shells [21]. Another point observed was the resemblance between
the spectra of walnut shell (Fig. 6-a) and liquid products. It was seen
that many of the peaks observed for walnut shell were also present
in liquid product but at different intensities. In other words, many of
the chemical functional groups of walnut shell were also present in
its pyrolysis liquid product. As to analyze the spectra, the wide and
intensive peak at 3392 cm−1 was indicative of abundant presence of
oxygenated compounds since it was caused by the O H stretching
vibrations of hydroxyl groups present in water, alcohol, phenol or
carboxylic acids. The peak appeared at 2941 cm−1 was due to the
C H stretching vibrations of aliphatic CH3 and CH2 groups [22].
The weak peak at 2615 cm−1 may be due to S H stretching [23] or
O H vibrations of carboxylic acid [24]. The sharp peak at 1706 cm−1
was ascribed to C O stretching vibrations revealing the presence of
ketones or aldehydes. The peak at around 1640 cm−1 was possibly
caused by the C C stretching vibrations of alkenes and aromatics.
An aromatic related peak was also observed at 1515 cm−1 due to the
skeletal stretching. The peaks between 1450 and 1360 cm−1 trans-
mittance can be attributed to C H bending vibrations indicative
of alkane groups. The explicit peaks observed at 1300–1000 cm−1
band were due to C O stretching and O H deformation vibrations,
and showed the presence of alcohols, phenols, ethers and esters.
Moreover, the peaks at 884, 814 and 756 cm−1 were attributable
 K. Açıkalın, F. Karaca / Journal of Analytical and Applied Pyrolysis 125 (2017) 234–242
to single ring aromatic compounds and polycyclic aromatic com-
pounds [25].
3.2.4. GC–MS analysis of liquid product
The liquid product obtained at 500 ◦ C pyrolysis temperature,
30 min reaction time and 250 ml min−1 N2 flow rate was analyzed
with GC–MS in order to get an idea of its nature and the type of com-
pounds present in its structure. The tentative compounds, which
were listed as the possible compounds by MS search file (Wiley
7 library), are given in Table 2. As it can be seen from the table,
the liquid product was a complex mixture involving many types of
oxygenated and aromatic organics which was essentially confirmed
by the FTIR analyses. The main chemical groups present in the liq-
uid product can be listed as carboxylic acids, phenols, ketones and
aldehydes. The total number of identified compounds was 32. The
carbon distribution of these compounds was in the range of C2 –C10
whereas their molecular weight varied between 60 and 182. Some
of the compounds identified here were also observed in the liq-
uid products of different biomass pyrolysis processes. For instance,
the compounds having the peak numbers of 11, 13, 14, 15, 17, 18,
20, 21, 24, 25, 28, 29, 33 and 34 (Table 2) were also present in the
liquid pyrolysis product of wood industry residues [26]. This sim-
ilarity can be attributed to the common components of biomass
materials such as cellulose, hemicellulose and lignin. The acidic
content of the pyrolysis liquid product was quite remarkable con-
sidering the related peak area. The total peak area of acetic acid and
3-hydroxy-4-methoxybenzoic acid was approximately 11.4% indi-
cating the acidity of liquid product. Thus, the liquid product should
be count corrosive, and necessary design precautions should be
considered when storing or using as a fuel in boilers or furnaces. On
the other hand, high acetic acid content makes the liquid product
a potential raw material from which acetic acid can be produced.
High acetic acid content is a generally encountered occasion, and
was also observed in the liquid pyrolysis product of rice husk [27].
The amount of phenolic compounds in the present liquid pyroly-
sis product was also remarkable. Their peak area was almost 10%
approving that the liquid product can be utilized as a raw material
for producing phenol and its derivatives.
3.2.5. Higher heating value (HHV) of liquid product
The HHV of the liquid product obtained at 500 ◦ C pyrolysis tem-
perature, 30 min reaction time and 250 ml min−1 N2 flow rate was
measured as 4799 kcal kg−1 . This value was a little higher than the
HHV of the original walnut shell sample (4265 kcal kg−1 ), smaller
than the HHV of the solid product (6692 kcal kg−1 ) obtained at the
same conditions, and approximately half of the HHV of conven-
tional fuels such as heavy fuel oil or diesel oil. The low heating value
of the liquid product was assigned to the oxygenated compounds
and water content as specified from the FTIR and GC–MS analyses.
4. Conclusions
Walnut shell was pyrolyzed in a well-swept tubular fixed-bed
reactor to investigate the effects of pyrolysis temperature, reac-
tion time and N2 flow rate. Temperature was the most effective
parameter on product yields. Increasing temperature caused a con-
tinuous decrease in solid and increase in gas yields. The liquid
yield showed an increasing trend until 425–500 ◦ C but further
increments resulted in a decrease. Reaction time did not have an
influence on solid yield but it was observed that lower reaction
times should be chosen for higher liquid yields. Similarly, N2 flow
rate was not effective on solid yields. However, higher flow rate val-
ues featured higher gas yields. As a result, the highest liquid yield
was obtained as 48.2% at 500 ◦ C, 30 min and 150 ml min−1 pyrolysis
conditions.
241
The liquid product of pyrolysis process was a highly oxygenated
complex mixture mainly composed of carboxylic acids, phenols,
ketones and aldehydes. The total number of identified compounds
was 32 with a carbon distribution of C2 -C10 . The low calorific value
and highly oxygenated structure unveiled a need for upgrading of
liquid product if it is considered as a transportation fuel. However,
it may be thought as a low-grade fuel to be used in boilers or fur-
naces if their construction materials are provided to be corrosive
resistant since the liquid product had a considerable acidic content.
Additionally, the liquid product may be utilized as a raw material
for obtaining phenol and phenol derivatives due to its high phenolic
content.
The higher heating value of the solid product showed an increas-
ing trend with increasing pyrolysis temperature. The obtained
values were higher than that of sub-bituminous coal and close to
that of bituminous coal. Thus, the solid product may be thought as a
valuable fuel which can replace most of the conventional solid fossil
fuels. On the other hand, the solid product, as produced, was found
to be unsuitable for activated carbon applications even though
the surface area increased with increasing temperature since the
resulting values were very low.
Acknowledgements
Present study was conducted in Chemical Engineering Depart-
ment of Yıldız Technical University, and was supported by
YTÜBAPK (Project No. 25-07-01-04). The authors are grateful to
Işık Yavuz for her valuable help during the analyses.
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