PARAMETERS AFFECTING THE

REMOVAL OF NAPHTHALENE OVER A

FIXED BIOMASS CHAR BED

Ziad Abu El-Ruba, Gerrit Bremb, Eddy Bramerb

a
Department of Pharmaceutical and Chemical Engineering, German
Jordanian University, P. O. Box 35247, 11180 Amman, Jordan
b
Laboratory of Thermal Engineering, University of Twente , P. O. Box 217,
7500 AE Enschede, The Netherlands

ABSTRACT: Biomass gasification is an emerging thermochemical technology hindered by

the removal of the tar byproducts. This study focused on investigating some parameters
that influence the catalytic performance of biomass char in naphthalene removal. The
following parameters were tested; bed temperature, inlet naphthalene concentration, feed
gas composition, and char precursor. Experiments were carried out at 750 to 900 oC, 1.2 s
gas residence times, and 500 to 630 μm particle sizes. It was found that a bed
temperature of 800-850 °C seemed to be optimal for high naphthalene conversion, which
was found to be kinetically limited. The naphthalene conversion was independent of its
initial feed concentration. Whereas, the CO2-N2 gas mixture gave the highest naphthalene
conversion. Finally, the presence of metals like iron and alkalis in the char enhanced the
naphthalene removal.

KEYWORDS: biomass char, catalyst, tar, naphthalene, fixed bed, gasification

1. INTRODUCTION

The world is in a dire need to develop renewable energy sources that compensate the
decrease in fossil fuels reserves and mitigate their negative environmental effects. Biomass is
one of the renewable energy solutions due to its availability and being CO2-neutral. Biomass
gasification is a thermochemical technology that can be used to convert biomass into
combustible gasses and chemicals. However, it produces tars that reduce the technical
efficiency of the process. These tars consist mainly of organic compounds heavier than
benzene. They can be removed physically, thermally, or catalytically. The latter is considered
the most economical one.
It was found that the char can be removed the hydrogen atom from the tar species to form a
free radical (Greensfelder et al., 1949). The latter undergoes polymerization reactions that
form products deposited as coke on the surface of the char (Nestler et al., 2016 and Fuentes-
Cano et al. 2013). The severity of coke formation can be related to the number of aromatic
rings in the tar species (Messenbok et al. 1999, Tesner et al. 1997, Menon 1990, and Hosokai

Proceedings Venice2016, Sixth International Symposium on Energy from Biomass and Waste,
14 - 17 November 2016
Great School of St. John the Evangelist, Venice, Italy
© 2016 by CISA Publisher, Italy
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Sixth International Symposium on Energy from Biomass and Waste

et al. 2008). It was reported that Naphthalene has the highest tendency for coke formation
(Tesner et al. 1997).
The objective of this study was to investigate the elimination of naphthalene as a model tar
component using a fixed bed of biomass char. This was done by studying some parameters
that affect naphthalene elimination, such as char bed temperature, inlet naphthalene
concentration, feed gas composition, and char precursor.

2. EXPERIMENTAL

A fixed bed setup was used for these experiments as shown in Figure 1. A gas mixing station
was used to compose a feed gas consisting of CO2, CO, H2, N2, H2O and/or naphthalene. The
gas was fed to the heated fixed bed reactor. The biomass char is placed in the fixed bed
reactor. The naphthalene conversion was measured by sampling the in- and outgoing gas with
the solid phase adsorption (SPA) method [5] and analyzing the samples in a gas
chromatograph-mass spectrometer (GC-MS).

Figure 1. Fixed bed experimental setup

2.1 Char properties

The biomass char was sourced out from a commercial supplier and pre-treated by heating up
to 850 ℃ and soaking for 30 minutes. The chemical and physical properties of the treated
biomass char are given in Table 1.
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Table 1. Chemical and physical properties of treated biomass char

Proximate analysis of biomass char Mass fraction
Water 0.20%
Ash 9.55%
Volatiles 2.01%
Fixed carbon 88.24%
Ultimate analysis of biomass char Mass fraction
C 89.03%
N 0.24%
H 0.12%
S <0.01%
Cl 0.02%
Br < 0.01%
F 0.40%
O 10.00%
Ash analysis Mass fraction
Na 1.09%
K 0.48%
Mg 12.40%
Ca 29.90%
Al 2.21%
Ti 0.81%
Fe 9.10%
Si 0.66%
C 0.17%
Physical properties of biomass char
BET-surface area 353 m2·g-1
Total pore volume 0.19 cm3·g-1
Adsorption average pore width 29 Å

2.2 Reference Conditions

The following experimental conditions were mostly applied in the so-called reference
conditions (see Table 2). In the shown results, only the varying parameter was presented,
unless otherwise mentioned, the rest of experimental conditions were kept constant.
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Table 2. Process conditions of the reference conditions

Parameter Symbol Value
Pressure P (Pa) 1.01·105
Tar C10H8 Naphthalene
Bed Temperature T (°C) 900
Gas space time τ (s) 1.2
Char particle size dp (µm) 500-630
Time on stream t (min) 15
Average gas mixture composition Volume fraction
CO 6.0%
CO2 10.0%
H2 O 7.0%
H2 4.0%
CH4 2.4%
N2 Balance
Naphthalene 10-20 g·Nm-3

3. RESULTS AND DISCUSSION

3.1 Effect of char bed temperature

Figure 2 shows the resulted naphthalene reduction at temperatures lower than the reference
temperature (900 oC). In addition, a larger particle size and a shorter gas residence time was
applied compared to the reference experiment. Despite these changes, the naphthalene
reduction in mass fraction at 900 °C was 100%. At lower temperatures, the naphthalene
reduction decreased to about 90% at 750 °C. Below this temperature, the naphthalene
reduction decreased sharply to 70% at 700 °C. Based on these data, a first order kinetic model
for naphthalene reduction was applied to calculate the kinetic constants as published in a
previous work [8]. The apparent activation energy (Eapp) and the pre-exponential factor (kapp)
were found to be 61 kJ·mol-1 and 1·104 s-1 respectively.
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Figure 1. Naphthalene conversion as function of char bed temperature, τ= 0.3 s; dp= 500-800 μm. The
dashed curve represents the naphthalene conversion calculated using a kinetic model from a previous
work (Abu El-Rub et al., 2008).

3.2 Effect of the inlet naphthalene concentration

It was found that the naphthalene conversion was almost constant (89%-91%) for inlet
naphthalene concentrations in the range from 6 to 18 g·Nm-3 at a gas residence time of 0.15 s,
a temperature of 900 oC, and a particle size of 1400-1700 µm. This showed that the
naphthalene-char reaction was first order as it is independent of the initial naphthalene
concentration at these process conditions. For longer gas residence times and lower
temperatures, the deposition of coke may influence the activity of the char, and the higher the
initial naphthalene concentration, the more coke may be formed and this might influence the
naphthalene reduction.

3.3 Effect of gas composition

Naphthalene was consumed by the steam and dry reforming reactions. The effect of the H2O
and CO2 concentration in the producer gas was studied. For each component, two volume
fractions were tested, 10% and 20%, as they were considered common concentrations in a
producer gas.
The experimental results given in Table 3 show that naphthalene was not only converted by
the steam (H2O) reforming reaction but can also be converted by the dry reforming reaction
(CO2). It was found that the gas composition affected the naphthalene conversion and that the
CO2-N2 mixture gave the highest naphthalene conversion whereas the steam-N2, the steam-
CO2-N2, and the standard gas mixtures gave a comparable but lower naphthalene conversion.
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Table 3. Effect of the ambient gas components on naphthalene conversion, T=750 oC; gas balance is
N2
Gas composition (volume fraction) Naphthalene mass conversion
H2 O CO2 H2 CO CH4
10% - - - - 93%
- 10% - - - 97%
10% 10% - - - 93%
7% 10% 4% 6% 2.4 5 93%*
*
average value for 4 experiments

The (10% volume fraction CO2, balance N2) gas mixture showed a higher naphthalene
conversion than the other gas mixtures. This could mean that CO2 created more active sites
on the char surface for naphthalene adsorption and reaction than the steam and the other gas
components.
The presence of the other components in the producer gas (H2, CO, CH4) shown in Table 3
caused a lower naphthalene conversion. Because CO, and to a less extent H2, do not
participate in the conversion reactions with the adsorbed naphthalene, their presence in the
gas may cause occupation of the char surface and thus caused an inhibitory effect for the
naphthalene conversion. Because of the water gas shift reaction, the inhibiting H2 can be
produced out of the other components (H2O + CO H2 + CO2). More CO2 produced less H2
and allowed a higher naphthalene conversion and more H2O produced more H2 resulting in
a lower naphthalene conversion. The experiment where no H2 could be formed (10% CO2, N2)
had the highest naphthalene conversion.

3.3 Effect of char source

At temperatures usually used for catalytic tar conversion, the metal content of the char
catalyzes the gasification reactions. To investigate these effects, experiments with char from
different sources were carried out. The sources used for the production of the char were
pinewood biomass, rietspruyt coal, and brown coal. The char particle size was ranging from
100 to 500 µm. The ultimate analysis of the char produced from the three sources is given in
Table 5.

Table 5 Ultimate analysis and mineral content of pinewood char and commercial coal chars
Mass fractions Pinewood char Rietspruyt coal char Brown coal char
C 87.90% 82.3 89.60%
N 0.30% 2 0.80%
H 0.60% 0.4 1.10%
Ash 4.70% 15.3 7.80%
O (by difference) 6.50% 0 0.70%
MgO 0.20% 0.29% 0.09%
Al2O3 - 4.70% 0.32%
K2 O 0.85% 0.06% 0.01%
CaO 1.81% 0.79% 2.35%
Fe2O3 0.11% 0.28% 0.85%
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It was found that the chars from coal (rietspruyt and brown coal) gave higher naphthalene
conversion than the char from biomass (Table 6). This can mainly be attributed to the high
content of ash (metals) in the coal char. Among the investigated types of chars, the brown coal
had the highest iron content and it gave the highest naphthalene conversion (Table 6).
Therefore, not only alkali content in the char was important but also the iron content.

Table 6 Effect of char source type on char BET surface area and naphthalene conversion
Char source BET Naphthalene Conversion
Pinewood 330 97.80%
Rietspruyt coal 25.3 99.40%
Brown coal 210 99.80%
1 o o
Char production temperature: 900 C ; heating rate: 10 C/min, τ= 0.25 s; dp= 100-500 µm

5. CONCLUSIONS

Biomass char was found to be a highly active catalyst. A temperature in the range of 800-
850 °C seems to be optimal for high tar conversion. The naphthalene conversion was
independent of its in feed concentration. However, the higher the feed concentration the lower
the stability of the catalytic activity of the biomass char due to the coke deposition. The feed
gas composition affected the naphthalene conversion. The CO2-N2 gas mixture gave the
highest naphthalene conversion. Whereas, H2 (and CO) had an inhibitory effect that reduced
the naphthalene conversion. Finally, the presence of metals like iron and alkalis in the ash had
an apparent influence on the naphthalene removal.

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