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Energy Sources, Part A: Recovery,

Utilization, and Environmental Effects
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An Analysis of Wood Pyrolysis Tar from

High Temperature Thermal Cracking
Process
a a c a c
T. Wongchang , S. Patumsawad & B. Fungtammasan
a
Department of Mechanical Engineering, Faculty of Engineering,
King Mongkut's , University of Technology North Bangkok , Bangsue ,
Bangkok , Thailand
b
The Joint Graduate School of Energy and Environment, King
Mongkut's University of Technology Thonburi , Tungkru , Bangkok ,
Thailand
c
S&T Postgraduate Education and Research Development Office ,
Bangkok , Thailand
Published online: 08 Apr 2013.

To cite this article: T. Wongchang , S. Patumsawad & B. Fungtammasan (2013) An Analysis of Wood
Pyrolysis Tar from High Temperature Thermal Cracking Process, Energy Sources, Part A: Recovery,
Utilization, and Environmental Effects, 35:10, 926-935, DOI: 10.1080/15567036.2012.707748

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 Energy Sources, Part A, 35:926–935, 2013
Copyright © Taylor & Francis Group, LLC
ISSN: 1556-7036 print/1556-7230 online
DOI: 10.1080/15567036.2012.707748

An Analysis of Wood Pyrolysis Tar from High

Temperature Thermal Cracking Process

T. Wongchang,1 S. Patumsawad,1;3 and B. Fungtammasan2;3

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1
Department of Mechanical Engineering, Faculty of Engineering, King Mongkut’s
University of Technology North Bangkok, Bangsue, Bangkok, Thailand
2
The Joint Graduate School of Energy and Environment, King Mongkut’s University of
Technology Thonburi, Tungkru, Bangkok, Thailand
3
S&T Postgraduate Education and Research Development Office, Bangkok, Thailand

The objective of this study is to investigate and analyze the tar yields and structural changes of tar
formed during a high temperature thermal cracking process. Experiments were conducted in order
to study the effect of temperature on the yield and characteristic chemicals of tar. All experiments
were carried out with parawood under steady-state conditions. The temperature of the pyrolyzer was
controlled at 600ıC and pyrolysis gases were carried to the reformer by nitrogen. The thermal cracking
tests were performed at six different temperatures: 700, 800, 900, 1,000, 1,100, and 1,200ıC. The
samples of tar were analyzed by gravimetric analysis, gas chromatography-flame ionization detector,
and gel permeation chromatography techniques in order to get information and an understanding
about the tar, such as tar yield, compositions, and average molecular weight. From the experimental
results and quantity analysis, the amount of tar decreased continually to 90% reduction as temperature
increased from 600 to 1,200ıC resulting from thermal cracking of tar into the lighter products.
In chemical analysis, at a low temperature range, the aromatic compounds were dominant in tar
compositions. Meanwhile, these phenomena were adverse at higher temperatures and polycyclic
aromatic hydrocarbons dominated. These resulted in higher than the average molecular weight as
the temperature increased.

Keywords: biomass, high temperature, pyrolysis, tar, thermal cracking

RATIONALE

The major issue for biomass pyrolysis/gasification is to deal with the tar formation during the
process. Tar can be defined as all organic contaminants production under thermal or partial-
oxidation regimes of any organic material and assumed to be largely aromatic with a molecular
weight start and larger than benzene. Tar has a complex mixture of condensable hydrocarbons,
which includes single ring to 5-ring aromatic compounds along with other oxygen-containing
hydrocarbons and complex polycyclic aromatic hydrocarbons (PAHs) (Li and Suzuki, 2009; Milne
and Evans, 1998). Tar could be condensed at low temperatures, lead to blocking and fouling

Address correspondence to Dr. Suthum Patumsawad, Department of Mechanical Engineering, King Mongkut’s
University of Technology North Bangkok, 1518 Pibulsongkram Rd., Bangsue, Bangkok 10800, Thailand. E-mail:
stt@kmutnb.ac.th

926
 ANALYSIS OF WOOD PYROLYSIS TAR 927

process equipment (i.e., engines and turbines). The amount and chemical structure of tar depends
on the fuel types (biomass properties) and the process conditions, such as pressure, temperature,
etc. (Elliott, 1988). The gas production can contain significant amounts of tars, which can be
eliminated by thermal cracking (Bridgwater, 1995). For the thermal cracking method, the gases
derived from pyrolysis are heated to a high temperature, where tar molecules can be cracked
into lighter gases. Researchers have investigated the thermal cracking process by heating the raw
gases derived from gasification or pyrolysis processes to a high temperature and found that tar
molecules could be cracked into lighter gases (Phuphuakrat et al., 2010; Gilbert et al., 2009;
Houben et al., 2005; Morf et al., 2002; Fagbemi et al., 2001; Brandt and Henrikson, 2000).
However, the tar problems are still a major challenge in the research field of biomass thermal
decomposition. Therefore, a better understanding of the tar formation mechanism would be helpful
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for investigating the solution of tar reduction.

The authors have previously studied the effect of reaction temperature on the amount of tar but
not on tar compositions (Wongchang, 2010). Therefore, in the study, the objective is to investigate
and analyze the structural changes of tar formed during the high temperature thermal cracking
process.

EXPERIMENTAL SETUP AND METHODOLOGIES

Experimental Apparatus
The experimental apparatus employed in this study mainly consist of: (1) pyrolyzer, (2) reformer,
(3) steam generator, (4) gas analysis train, and (5) auxiliary units, as shown in Figure 1. Ex-

FIGURE 1 Schematic diagram of experimental apparatus.

 928 T. WONGCHANG ET AL.

periments were carried out at an atmospheric pressure. The free fall type pyrolyzer is made of
stainless steel with a 30-mm-diameter 400-mm-length tube, surrounded by an electric heater in
which the reactor temperature can be adjusted. Biomass was fed on the top and controlled by a
quantitative feeding device. Nitrogen was used as the carrier gas. Biomass was pyrolyzed into
gas, tar as gaseous form, and residue char. The residue char was collected and removed at the
bottom part of the pyrolyzer, while the gas and tars were introduced into the reformer. At this
stage, the temperature was increased and controlled at each desired condition to study the effect
of thermal cracking to tar quantity and quality.

Biomass Preparation
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Sawdust from the parawood (Hevea brasiliensis) industry was used as a feed material and its
proximate and ultimate analysis are shown in Table 1. Sawdust was ground into a size less than
425 microns and dried in the oven.

Tar Sampling
The tar sampling system was modified and set up from the guidelines following the tar sampling
method (CEN BT/TF 143, 2005; Hasler and Nussbaumer, 2000; Pekka et al., 1998). The schematic
diagram of the tar sampling system is also shown in Figure 1. The sampling points were located
at two points: A and B (inlet and outlet of the reformer). The sampling gas was drawn through
the tar sampling system by a vacuum pump. This gas was sent to a series of impinger trains
that were immersed in two baths of ice-water solvent 0ı C and dry ice-isopropanol solvent
20ı C, where the tar was absorbed in isopropanol solvent. Each impinge bottle was filled with
200 ml isopropanol. The gas sampling flow rate was controlled at 2 l/min at standard normal
pressure by adjusting the mixed-gas flow meter control valve and the by-pass valve over the
diaphragm pump. Time duration for sampling was determined by a sufficient amount of tar for
the gravimetric determination (approximately 20 min). For each sample, about 40 liters of gas
were used.

Tar Analysis
Quantitative Analysis
For each sample, the amount of tar was dissolved by isopropanol contained in a series of
impinge bottles. To eliminate any errors, tar deposited on glassware and inside the sampling
lines was also recovered by rinsing with isopropanol and acetone. After the sampling, the tar
was finely filtered by vacuum filter and stored in a sealed translucent container (glass bottle with

TABLE 1
Proximate and Ultimate Analysis of Sawdust

Ultimate Analysis, wt%,

Dry Ash Free Basis Proximate Analysis, wt%

C H O N S Volatile Matter Fixed Carbon Ash

50.9 6.1 42.6 0.3 nd 83.94 15.12 0.94

nd: not detected.

 ANALYSIS OF WOOD PYROLYSIS TAR 929

brown color) to avoid the light. To determine the tar yield, the isopropanol was removed by a
rotary evaporator (BUCHI R-205/V800/B-490). The evaporation residual (tar) was then weighed.
As the total weight of tar was based on the 40 liters of the dry synthesis gas sampled, the values
were converted into grams or milligrams of tar per Nm3 of pyrolysis gas.

Chemical Analysis
The gel permeation chromatography (GPC) technique by HPLC-UV detector (SPD20A, Shi-
madzu, Columbia, MD) was used to analyze the molecular weight of tar. The column for detecting
molecular weight for this research is a Shodex column (code: GPC KF-803; column size: 8.0 mm
inside diameter  300 mm each; gel lot number: 040107; Showa Denko America, New York).
The analysis conditions for this column are listed as follows: eluent (the carrier that moves the
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chemicals through the column)—Tetrahydrofuran (THF); flow rate—1.0 ml/min; detector—UV

(254 nm); temperature—ambient (25ıC); sample size—20 l; pressure—1.4 MPa. The column
can be detected linearly by the molecular weight (MW) of a substance between 20,000 down
to 100 with elution volume between 6 to 12 ml, respectively. To identify the MW of tars, the
standard MW substances were conducted in advance. The five standard substances have a MW of
162, 545, 1,300, 2,960, and 13,800. The result of peak time and amplitude is shown in Figure 2.
The equation of curve fitting is Œlog MW D 13:7184 C 1:8345t 0:0496t 2, where t D peak time
(from HPLC) and MW = molecular weight (sample). Overall results of five standards show that
the maximum MW gets minimum peak time.
In this study, the components of a tar sample were analyzed using a gas chromatograph (model
Clarus 500, Perkin-Elmer, Waltham, MA) coupled with a flame ionization detector. The column
used in GC was an Rxi-1MS capillary column (60 m  0.25 mm, 0.25 m film thickness;
RESTEK Corporation, Bellefonte, PA). A small volume of sample (1 l) was injected into the
capillary column in GC-FID for identifying the tar components. The peak times of 10 selected
standard tars were used to compare the compositions of the tar sample. The 10 standard tars were
diluted in iso-propanol before analysis by GC-FID.

FIGURE 2 Peak time of five standard molecular weight samples. (color figure available online)
 930 T. WONGCHANG ET AL.

Experimental Procedure
All experiments were carried out under steady-state conditions. Parawood sawdust was fed via
a screw feeder at the rate of 0.536 g/min. To get independence from the effect of pyrolysis
temperature to product concentration, the temperature of the pyrolyzer was controlled at 600ıC.
The composition of pyrolysis gas can be divided into two groups: the amount of tar and the
concentration of non-condensable gas. The amount of tar is 38.63 g/Nm3 . The concentration of
these gases can be considered in three groups: the most quantity group (e.g., CO accounted to
47.80%), the moderate amount group (e.g., H2 , CH4 , and CO2 accounted to 18.57, 16.92, and
13.50%, respectively), and the least amount group (e.g., C2 H4 and C2 H6 accounted to 1.66 and
1.55%). The product gas from the pyrolysis process was carried to the reformer by nitrogen. The
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flow rate of the carrier gas (nitrogen) was adjustable resulting in constant retention time in the
reformer. The thermal cracking tests were performed at six different temperatures: 700, 800, 900,
1,000, 1,100, and 1,200ı C.

RESULTS AND DISCUSSION

Quantitative Analysis
The quantitative analysis of tar using gravimetric measurement, shown as a function of tempera-
ture, is illustrated in Figure 3. The amount of tar decreased continually as temperature increased
from 600 to 1,200ı C. In this temperature range, the amount of tar was depleted to 90% at the
temperature of 1,200ıC, compared to that of 600ıC. It can be seen clearly that the temperature
enhances tar cracking into the lighter products and reduces the amount of tar. Many researchers
(Qin et al., 2007; Li et al., 2004) agree that the quantity of tar was decreased with increasing
temperatures.

Chemical Analysis
The analysis of chemicals of tar was done in terms of average molecular weight and composition
of tar.

FIGURE 3 Effect of temperature on percentage of tar reduction. (color figure available online)
 ANALYSIS OF WOOD PYROLYSIS TAR 931

Average Molecular Weight

Figure 4 shows the average molecular weight of tar at different thermal cracking temperatures.
From experimental results and analyses, the effect of temperature on the average molecular weight
into two temperature ranges could be considered, namely, low temperature range (600–800ıC)
and high temperature range (800–1,200ıC), and also the average molecular weight, namely, low
and high molecular weight groups. At the low temperature range, tar samples showed indifferent
the average molecular weight (MW of 160–170). In the case of the high temperature range, two
peaks of the average molecular weight were observed as low and high average molecular groups,
as shown in Figure 4. The average molecular weights started to form two peaks at the temperature
of 800ıC. This evidence might be the effect of temperature causing tar decomposition. At the
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low average molecular weight group, they are about MW of 190–200, but at the high average
molecular weight group, they are in the range of 410–480.

Tar Compositions
This article is focused on ten standard tars as shown in Table 2. The ten standard tars can be
classified into three main groups as follows:

Group 1: Aromatic compounds: benzene, toluene, xylene, styrene, and indene;

Group 2: Phenol;
Group 3: Polycyclic aromatic hydrocarbons (PAHs): naphthalene, phenanthrene, anthracene,
and pyrene.

Figure 5 illustrates tar compositions from thermal cracking of pyrolysis gas at temperatures of
600, 800, 1,000, and 1,200ı C. From the chromatograph of GC-FID, the effect of temperature on
tar compositions can be obviously seen. The higher the temperature of thermal cracking processes
were, the higher PAHs were formed and the less aromatic compounds and phenol were formed.
At a temperature of 600ıC, the maximum of aromatic compounds (benzene, toluene, xylene, and
indene) were found except for styrene. Phenol and PAHs (especially naphthalene) formations were

FIGURE 4 Average molecular weight of tar at different temperatures. (color figure available online)
 932 T. WONGCHANG ET AL.

TABLE 2
Peak Times of 10 Standard Tars Detected by GC-FID

Chemical Peak Time, Molecular

No. Standard Formula sec Weight Structural

1 Iso-Propanol (CH3 )2 CHOH Before 5 60.09

2 Benzene C6 H6 5.802 78.11

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3 Toluene C7 H8 8.627 92.14

4 Xylene C8 H10 12.115 106.16

5 Styrene C8 H8 13.574 104.15

6 Phenol C6 H5 OH 19.6 94.11

7 Indene C9 H8 22.014 116.16

8 Naphthalene C10 H8 24.187 128.16

9 Phenanthrene C14 H10 40.1 178.23

10 Anthracene C14 H10 40.3 178.23

11 Pyrene C16 H10 47.5 202.25

 ANALYSIS OF WOOD PYROLYSIS TAR 933
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FIGURE 5 Tar composition from GC-FID analyses at elevated temperature.

 934 T. WONGCHANG ET AL.

also noticed. At a higher temperature (800ıC), the aromatic compounds were formed with the
maximum of styrene content. The peaks of phenol and naphthalene occurred at this temperature.
At a temperature of 1,000ı C, the chromatogram of phenol could not be observed. PAHs formation
were obviously seen at a high temperature range (1,000–1,200ıC), meanwhile the lower level of
aromatic compounds were also found. These tar composition phenomena were consistent with the
average molecular weight results. As temperatures increased, PAHs tended to form resulting in
higher molecular weight.

CONCLUSIONS
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In this study, experiments were conducted in order to study the effect of temperature on tar
yields and compositions. The samples of tar were analyzed by gravimetric analysis, GC-FID,
and GPC techniques in order to get information and an understanding about the tar, such as tar
yield, compositions, and average molecular weight. From the experimental results and analysis,
the amount of tar decreased continually to 90% reduction as the temperature increased from 600
to 1,200ıC resulting from thermal cracking of tar into the lighter products. At a low temperature
range, the aromatic compounds were dominant in tar compositions. Meanwhile, these phenomena
were adverse at higher temperatures and PAHs dominated. These resulted in a higher average
molecular weight as the temperature increased.

ACKNOWLEDGMENTS

This research was funded by The Joint Graduate School of Energy and Environment (JGSEE) and
The Royal Golden Jubilee Ph.D. Program (RGJ). The authors appreciate this financial support.

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