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CHARACTERIZATION OF THE PYROLYSIS PRODUCTS OF RDF

Conference Paper · July 2013

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 3rd International Exergy, Life Cycle Assessment, and Sustainability Workshop & Symposium (ELCAS3)
07 -09 July, 2013, NISYROS - GREECE

CHARACTERIZATION OF THE PYROLYSIS PRODUCTS OF RDF

A. Ozkan, M. Banar, Z. Cokaygil, O. Tezer, A. Mergen,

G. Kucukacil, G. Gokce, O. Ceren

Anadolu University, Faculty of Engineering, Department of Environmental Engineering

Iki Eylül Campus
26555, Eskisehir, Turkey
Email: aysunozkan@anadolu.edu.tr; mbanar@anadolu.edu.tr; zcokaygil@anadolu.edu.tr; 
otezer@anadolu.edu.tr; amergen@anadolu.edu.tr; ngzede@hotmail.com;
gulsevingokce@hotmail.com;oytuncrn@windowslive.com

Abstract
A sustainable and integrated waste management system primarily depends on the local and
national waste management policies. On the European Union (EU) directives related to waste, it is
stated that member/candidate countries must generate minimal waste and tended to integrated
solutions in terms of the sustainability of natural resources. According to this situation, in Turkey,
many new legislation arrangements have been made for the harmonization. In the Landfill
Regulation (2010) it is focused on the waste volume reduction that to be landfilled with physical,
thermal, chemical, or biological processes which purposes increase the recovery of waste. In this
content, wastes remaining after recycling processes should be recovered by producing a
homogenous material which is called Refuse Derived Fuel (RDF) with high calorific value (20-23
MJ/kg) via cracking, mixing and pressing processes.
In this study, evaluation of industrial origin RDF by pyrolysis is discussed. Firstly, RDF was
characterized in terms of elemental analysis (C, H, N, S), moisture, ash, volatile matter. Then,
pyrolysis experiments were carried out on a fixed bed pyrolysis reactor at 400, 500, 600 and 700°C
with a heating rate of 35 °C/min. Density, pH, moisture, ash content, volatile matter, fixed carbon,
calorific value, C, H, N, S were determined for the solid product obtained by pyrolysis.
Additionally, elemental analysis, calorific value analysis, GC-MS, FT-IR and H-NMR analysis were
performed on the pyrolysis liquid product. As a result of the pyrolysis studies, the highest liquid
product yield (11.03%) and the highest solid product yield (58.16%) were obtained at 500 °C and
400 °C, respectively.
Keywords: RDF; Pyrolysis; Industrial Wastes

1. Introduction
It is the important point that, there has been a problem to disposal municipal and industrial
wastes. Technological improvements are increasing rapidly and as a result of this
situation, treatment costs increase also. There are several techniques to treat wastes
such as incineration, gasification etc. These techniques have several disadvantages such
as air pollution, soil pollution. To prevent the disadvantages of these techniques, wastes
could be converted to refuse derived fuel (RDF) which has high calorific value to obtain
energy.

Industrial wastes have a very good calorific value which makes it a good source of energy.
Waste power plants which are also called waste to energy plants are designed to dispose
of MSW and to produce electricity as a byproduct in an incinerator. RDF from industrial
solid waste can be an alternative form of energy to replace fossil fuels [1].
With an increasing emphasis on waste volume reduction related with EU Directives, there
are many new legislation arrangements have been made in Turkey. As a result of this,

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physical, thermal, chemical or biological technologies must be applied to reduce waste

volume and increase the recovery of waste. One of the best technologies for preventing
the destruction of these materials in favour of their reuse is the use of these solid wastes
as a supplementary fuel in cement kilns; hence, there are the simultaneous benefits of
destroying these wastes while generating energy from them. Also, one of these alternative
technologies is pyrolysis. The pyrolysis of RDF has been investigated by several research
groups [2, 3, 4, 5]. In this study, RDF was characterized in terms of elemental analysis
(C, H, N, S), moisture, ash and volatile matter. Pyrolysis experiments were carried out on
a fixed bed pyrolysis reactor at 400, 500, 600 and 700°C with a heating rate of 35 °C/min.
Density, pH, moisture, ash content, volatile matter, fixed carbon, calorific value, C, H, N,
S, were determined for the solid product obtained by pyrolysis. Additionally, elemental
analysis, calorific value analysis, GC-MS, FT-IR and H-NMR analysis were performed on
the pyrolysis liquid product.

2. Experimental Methodology
The flow chart of the study and methodology are given in Fig. 1. Methods of the analysis
were mentioned in their own sections.

RDF Analysis
Section 2.1
 Elemental composition
 Moisture, ash, volatiles, fixed carbon content
 Higher heating value (HHV)

RDF Pyrolysis
Section 2.2

Characterization of Pyrolytic Solid Products Characterization of Pyrolytic Liquid Products

Section 2.3 Section 2.4
 Density, pH, moisture, ash, volatile matter,  Elemental composition
fixed carbon  HHV
 HHV  GC-MS
 Elemental composition  FT-IR
 H-NMR

Fig. 1: Flowchart of the Study

2.1. RDF Analysis

Refuse-derived fuel (RDF) samples were supplied from a RDF plant in Turkey, shredded
to get them homogeneous size. The moisture, ash, volatiles and fixed carbon content of
the RDF samples were determined according to ASTM D-3173-85, ASTM D-3174-12,
ASTM D-3172-73 and ASTM D-3175-82, respectively. The elemental composition and

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 3rd International Exergy, Life Cycle Assessment, and Sustainability Workshop & Symposium (ELCAS3)
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Higher Heating Value (HHV) of the RDF samples were determined using a LECO CHN
and S and IKA C200 calorimeter (ASTM D-5865), respectively. All of these main
characteristics of the RDF samples are given in Table 1.

Table 1: Characterization of RDF

Ultimate analysis (%) Proximate analysis (%) HHV (MJ kg-1)

C 54.18 Moisture 0.74 31.60

H 8.18 Ash 22.72
N <0.01 Volatiles 72.18
S 0.52 Fixed Carbon 4.36

2.2. RDF Pyrolysis

Pyrolysis experiments were carried out under atmospheric pressure at different

temperatures of 400, 500, 600 and 700 °C in a fixed bed stainless steel 240 cm3 reactor.
The pyrolysis system was shown is Figure 2. In a typical run, a 10 g sample was placed
into the reactor which was sealed. The system was heated at the rate of 35 °C/min to the
desired pyrolysis temperature, and maintained there for one hour. The liquid phase was
collected in a cold trap maintained at about 0 °C. The aqueous and oil fractions of liquid
phase were separated and weighted. Solid and liquid product yields were determined in
each experiment by weighting. The gas yields were determined by the mass difference.
All the yields were expressed on a dry basis and the average yields of at least three
experiments were used.

Fig. 2: Pyrolysis system

2.5. Characterization of Pyrolytic Solid Products

Density and pH values of the solid products were determined according to ASTM 1512
and ASTM 1513. The moisture, ash, volatiles and fixed carbon content of solid products
were carried out according to ASTM D-3173-85, ASTM D-3174-12, ASTM D-3172-73 and

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 3rd International Exergy, Life Cycle Assessment, and Sustainability Workshop & Symposium (ELCAS3)
07 -09 July, 2013, NISYROS - GREECE

ASTM D-3175-82, respectively. The elemental composition and Higher Heating Value
(HHV) of the RDF samples were determined using a LECO CHN and S and IKA C200
calorimeter (ASTM D-5865), respectively.

2.6. Characterization of Pyrolytic Liquid Products

The elemental composition and HHV of the pyrolytic liquid products were determined
using a LECO CHN and S and IKA C200 calorimeter (ASTM D-5865), respectively. The
compositional functional group analysis of the pyrolytic liquids was carried out between
the wavelengths of 4000-400 cm-1 by using a Perkin Elmer Spectrum 100 FT-IR which has
data processing and spectral library search facilities. A small amount of the pyrolytic liquid
product was mounted on a KBr disk which had been previously scanned as a background
and the infra-red spectra of the sample were taken. 1H-NMR spectrums of the pyrolytic
liquid products were obtained at a Bruker 500 MHz Ultra Shield. The samples were
dissolved in chloroform-d.

The liquid products were fractionated using liquid column chromatography. The pyrolytic
liquid products were separated into two fractions as n-pentane soluble and insoluble
compounds (asphaltenes). The n-pentane soluble fraction was further separated on
activated silica- gel (70–230 mesh) that was pretreated at 105 °C for 2 h prior to introduce
in a 50 x 1 cm i.d. column. The column was eluted successively with n-pentane, benzene,
ethyl acetate and methanol to produce aliphatic, aromatic, hetero-atom and polar
fractions, respectively. Each fraction was dried and weighed. After then n-pentane
fractions were analyzed by a Shimadzu GC-MSQP2010 Plus (30 m x 0.25 mm i.d.; 0.25
mm film thickness, TRB-5MS column). Helium was used as carrier gas at a constant flow
of 1.2 ml/min. The GC oven temperature was programmed for alkanes in n-pentane
fraction to 100 °C and held for 5 min. then from 100 °C to 280 °C at 7 °C min-1 and held at
280 °C for 2 min. When the temperature reached 320 °C at 20 °C min-1 it was held at 320
°C for 10 min. Typical operating conditions for MS were: ionization energy 70 eV; ion
source temperature 200 °C; mass range between m/z 40 and 400. The concentrations of
alkanes were calculated according to calibration curves prepared by certified reference
materials (Dr. Ehrenstorfer Alkanes Mix 10 Lot no: 90703TO).

3. Results and Discussion

3.1. Pyrolysis Products Yields

Solid, liquid and gas products yield obtained at different pyrolysis temperatures were
given in Table 2. This table shows that the highest solid product yield (58.16%) was
obtained at 400 °C. The highest liquid product yield (11.03%) was obtained at 500 °C.

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 3rd International Exergy, Life Cycle Assessment, and Sustainability Workshop & Symposium (ELCAS3)
07 -09 July, 2013, NISYROS - GREECE

Table 2: Yield of pyrolysis products for different pyrolysis temperatures

Product Yields (%)

Temperature (°C)
Solid product Liquid product Gas product
400 58.16 5.71 36.13
500 40.37 11.03 48.60
600 28.76 8.59 62.64
700 36.46 3.94 59.60

3.2. Characterization of Pyrolytic Solid Products

Density, pH, proximate analysis (moisture, ash, volatile matter, fixed carbon), HHV and
elemental analysis (C, H, N, S) results of pyrolysis solid products were given in Table 3 for
different pyrolysis temperatures. According to table, C content of solid products were
obtained at low values while ash contents were obtained at high values.

Table 3: Pyrolysis solid product properties for different pyrolysis temperatures

Analyses Temperatures (°C)
400 500 600 700
Density (gr cm-3) 0.920 1.055 0.855 0.980
pH 9.17 9.20 9.06 8.90
Proximate analysis (%)
Moisture 1.32 1.05 1.61 1.45
Ash 82.90 83.74 84.36 84.87
Volatile matter 13.75 9.74 9.51 9.75
Fixed Carbon 2.03 5.48 4.52 3.90
HHV (MJ kg-1) 8.40 5.54 5.36 9.26
Elemental analysis (%)
C 17.17 13.27 12.11 16.45
H <0.01 <0.01 <0.01 <0.01
N <0.01 <0.01 <0.01 <0.01
S 0.15 0.14 0.13 0.10

3.3. Characterization of Pyrolytic Liquid Products

HHV and elemental analysis (C, H, N, S) results of pyrolysis liquids products were given in
Table 4 for different pyrolysis temperatures. According to this table, the highest HHV and
C content were obtained at 600 °C.

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 3rd International Exergy, Life Cycle Assessment, and Sustainability Workshop & Symposium (ELCAS3)
07 -09 July, 2013, NISYROS - GREECE

Table 4: Pyrolysis liquid product properties for different pyrolysis temperatures

Analyses Temperatures (°C)
400 500 600 700
HHV (MJ kg-1) 38.46 41.23 40.37 40.94
Elemental analysis (%)
C 76.47 80.47 81.51 79.63
H 8.52 10.08 10.96 9.95
N <0.01 <0.01 <0.01 <0.01
S 1.08 1.19 0.96 1.11

Figure 3 shows the FT-IR spectrums of the liquid products. The C-H stretching vibrations
between 2800 and 3000 cm-1 and C-H deformation vibrations between 1350 and 1475 cm-
1
indicate the presence of alkanes. The C=O stretching vibrations with absorbance
between 1650 and 1750 cm-1 indicate the presence of ketones or aldehydes. The
absorbance peaks between 1575 and 1675 cm-1 represent C=C stretching vibrations
indicative of alkenes and aromatics.  
 

Fig.4: FT-IR Spectrums of Pyrolytic Liquid Products

Figure 5 shows the 1H-NMR spectrum and hydrogen distributions of the liquid products
obtained from pyrolysis experiments at different pyrolysis temperatures.

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 3rd International Exergy, Life Cycle Assessment, and Sustainability Workshop & Symposium (ELCAS3)
07 -09 July, 2013, NISYROS - GREECE

a  b 

 
c  d 

Fig. 5: H-NMR Spectrums and Hydrogen Distributions of the Liquid Products (a) 400 °C (b) 500 °C
(c) 600 °C (d) 700 °C
1
H-NMR results of the pyrolytic liquid products are given in Table 5. Table 5 indicates that
the main structure of the liquid products seems to be aliphatic bounded to aliphatic only
(0.4–1.8 ppm chemical sift range) and there is no existence of aliphatic carbon that is
bound to oxygen (peaks in 3.5–4.5 ppm chemical shift range).

Table 4: 1H-NMR results of the pyrolytic liquid products

Type of hydrogen Chemical % of total hydrogen (mol %)

shift 400 (°C) 500 (°C) 600 (°C) 700 (°C)
(ppm)
Aromatic 6.5-9.0 6.29 4.61 5.16 4.30
Phenolic (OH) or olefinic proton 4.5-6.5 2.86 2.82 3.45 3.23
Aliphatic adjacent to oxygen/hydroxyl group 3.3-4.5 - - - -

Aliphatic adjacent to aromatic/alkene group 1.8-3.3 7.58 6.30 6.91 3.96

Other aliphatic (bonded to aliphatic only) 0.4-1.8 83.28 86.27 84.48 88.52

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 3rd International Exergy, Life Cycle Assessment, and Sustainability Workshop & Symposium (ELCAS3)
07 -09 July, 2013, NISYROS - GREECE

For a detailed analysis, the liquid product was separated into two fractions, n-pentane
soluble and insoluble compounds by using n-pentane. The n-pentane soluble material
was further separated by column chromatography (Table 6).

Table 6: Chemical class fractionation of pyrolysis liquid products

Temperatures n-pentane Pentane Benzene Ethyl Methanol

(°C) solubles subfraction subfraction acetate subfraction
(wt. %) (wt. %) (wt. %) subfraction (wt. %)
(wt. %)
400 69.53 68.88 12.50 11.44 7.18
500 35.10 71.35 11.39 9.39 7.48
600 82.63 67.07 15.07 10.59 6.97
700 50.68 69.54 12.14 11.77 6.67

Table 7: Concentration of alkanes in pyrolysis liquid products in relation to pyrolysis temperature

(ppb)

Pyrolysis Temperature (°C)

Compound
400 500 600 700
n-Decane 29.03 1180 996 88.1
n-Undecane 143.97 8.65 17.2 416.8
n-Dodecane 219.65 16.75 26.75 740.35
n-Tridecane 165.91 19.2 28.65 792.65
n-Tetradecane 101.93 21.15 31.25 599.25
n-Pentadecane 58.79 21.65 30.5 331.25
n-hexadecane 27.42 14.95 28.35 153.55
n-Heptadecane 36.93 15.95 24.25 76.8
n-Octadecane 30.56 14.2 20.9 33.25
n-Nonadecane 14.4 11.35 19.85 -
n-Eicosane - 10.7 19.2 -
n-Henicosane 4.68 9.05 17.35 -
n-Docosane - 7.8 17 -
n-Tricosane - 7.45 15.9 -
n-Tetracosane - 7.55 16.8 -
n-Pentacosane 81.31 8.1 18.1 -
n-Hexacosane - 8.35 20.6 -
n-Heptacosane 8.04 11.65 29.55 -
n-Octacosane 434.63 11.65 28.85 -
n-Nonacosane 244.3 15.25 39.55 -
n-Triacontane 3137.98 16.05 30.15 -
n-Hentriacontane 354.34 17.7 34.25 -
n-Dotriacontane 1300.38 7.6 15.7 -
n-Tritriacontane 245.76 10.4 20.75 -
n-Tetratriacontane 104.2 971 10.25 -
n-Pentatriacontane 1645.73 837 8.5 -

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 3rd International Exergy, Life Cycle Assessment, and Sustainability Workshop & Symposium (ELCAS3)
07 -09 July, 2013, NISYROS - GREECE

The GC-MS analyses were conducted on the n-pentane fractions to confirm alkanes
(Table 7). GC-MS analysis show that the liquid product contained mainly aliphatic
compounds such as n-undecane, n-dodecane, n-tridecane, n-tetradecane, n-
pentadecane, n-hexadecane, n-heptadecane and some other high molecular weight
alkanes.

4. Conclusion
In this study, RDF pyrolysis was studied and pyrolysis solid and liquid products properties
were investigated. The highest solid product yield (58.16%) was obtained at 400 °C and
the highest liquid product yield (11.03%) was obtained at 500 °C. C content of solid
products were obtained at low values while ash contents were obtained at high values.
For liquid product, the highest HHV and C content were obtained at 600 °C. The average
HHV value of RDF pyrolysis liquid product (40.25 MJ kg-1) is close to that of diesel (45.5
MJ kg-1) and gasoline (43.9 MJ kg-1) [6]. As a conclusion, it was observed that pyrolysis is
an useful thermal method to obtain a liquid product with high hydrocarbon content from
RDF and it would be possible to utilize this product as a fuel.

References
[1]. Dinesh S.& Romeela M., Power Generatıon from Refuse Derıved Fuel, 2nd International
Conference on Environmental Engineering and ApplicationsIPCBEE vol.17 (2011)
[2]. Kyari, M., Cunliffe, A. & Williams, P.T., Energy & Fuels, 19 (2005) 1165 – 1173.
[3]. Lin, K.S., Wang, H.P., Liu, S.H., Chang, N.B., Huang, Y.J. & Wang H.C., Fuel Processing
Technology, 2 (1999) 103 – 110.
[4]. Miskolczi, N, Borsodi, N., Buyong, F., Angyal, A. & Williams, P.T., Fuel Processing
Technology, 92 (2011) 925 -932.
[5]. Miskolczi, N, Buyong, F., Angyal, A., Williams, P.T. & Barthaa, L., Bioresource Technology,
101 (2010) 8881 – 8890.

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