Article

pubs.acs.org/EF

Tar Reforming under a Microwave Plasma Torch

Rodrigo Monteiro Eliott,† Manoel F. M. Nogueira,*,‡ Argemiro S. Silva Sobrinho,† Bruno A. P. Couto,‡
Homero S. Maciel,§ and Pedro T. Lacava†
†
Technological Institute of Aeronautics, Praça Mal. Eduardo Gomes 50, Vila das Acácias, 12.228-900 São José dos Campos-SP, Brazil
‡
Federal University of Pará, Av. Augusto Corrêa 1, LABEM, 66075-110 Belém-PA, Brazil
§
Paraiba Valley University, Av. Shishima Hifumi 2911, São José dos Campos-SP, Brazil

ABSTRACT: Because of the scarcity of nonrenewable natural resources, such as petroleum and natural gas, the use of biofuel is
needed. Gasification is a major process used to obtain renewable fuels from biomass; however, the gas cleaning system is a
constraint for its broad utilization. During the pyrolysis process, a mixture of organic compounds in the gas phase is produced
and must be removed from the gases before it is used in the most practical applications. In order to remove such organic
compounds, which are known as tar, large, sophisticated, problematic, and expensive gas cleaning systems are added to the
gasifier gas exit. Previous papers have shown that the plasma torch has the potential to destroy produced tar, being a simpler and
less-expensive system than traditional gas cleaners. This work presents a qualitative and quantitative evaluation of a microwave
plasma system running on tar destruction and its reforming. In order to evaluate a 1 kW microwave plasma system performance,
an apparatus was developed and installed at ITA Laboratory of Plasmas and Processes (LPP-ITA). The system runs at
atmospheric pressure with nitrogen and argon as carrier gas under a large range of flow rates. Experiments were performed using
a gas mixture of N2, H2O, ethanol, and tar at controlled concentration in order to simulate the gases produced by a gasifier. The
injected tar was obtained from pine pyrolysis and characterized for energy purposes. In order to reduce tar viscosity, it was
diluted in commercial ethanol (92.5% ethanol and 7.5% water) and its concentration varied from 0.8 gtar/Nmgas3 to 4.2 gtar/
Nmgas3. Species formed in the microwave plasma torch were identified using an optical spectrometer. The reactor exit gases had
their composition evaluated on tar content as well as for noncondensable gases. As a result, this paper shows that no tar content
was detected at the reactor outlet, indicating that all supplied tar was destroyed in the plasma reactor. The main detected
products were CO and solid carbon (C(s)). Furthermore, neither NO nor CO2 were detected, and an indication of H2 formation
was obtained. This paper concludes that the microwave plasma system is capable of destroying and reforming tar efficiently and
produces mainly H2, CO, O2, and C(s) as byproducts.

1. INTRODUCTION mixtures) in the presence of a gaseous mixture (90% of N2

The pyrolysis process of vegetable biomass produces many
condensable volatiles that are collectively called tar. This
organic molecule mixture (tar) is recognized as carcinogenic,
harmful for human health and environment, a hazard for
mechanical equipment, and a poison to synthesis gas (CO, H2,
and CH4). Because of these problems, gasifier gas cannot be
used directly in engines or on second-generation fuel
production processes, such as Fischer−Tropsch. For such
applications, tar must be previously removed and regular
techniques are costly and complex cleaning systems that
generally produce byproducts, which will need further treat-
ment. Furthermore, tar is a hydrocarbon species mixture and
the consequence of its removal is a reduction on the gas heating
value. An alternative technique for tar removal (destruction) is
the use of microwave plasma torches. The benefit of this
technique is a reduction in size and a simple cleaning operation,
as well as the elimination of hazardous byproducts, thereby
reducing environmental impacts and keeping the gross gas
heating value at a high level.
Successful hydrocarbon destruction with plasma sources was
reported.1 In this case, a microwave plasma torch reformed
methane, obtaining H2 and solid carbon (C(s)) as products.1 In
another work,2 corona discharge was applied for the breakdown
of naphthalene molecules (species present in many tar
and 10% of CO2). Two other works3,4 tested and analyzed a
microwave plasma torch at atmospheric pressure, using argon
as the gas carrier. References 5−7 show proposed reaction
pathways for tar conversion into smaller species. Water steam
was disintegrated using a microwave plasma torch.8 All the
above works indicate that it is possible to destroy vegetable tar
in aqueous solution, using a microwave plasma torch at ambient
pressure, but it has not been done so far.
This work describes an apparatus and experimental results
that led to complete pine tar destruction, using a microwave
plasma torch at ambient pressure with concentrations up to 4.2
gtar/Nmgas3 without hazardous byproduct production. This
technique proved to be capable of converting an undesired
element (tar) into smaller and noncondensable species.
2. APPARATUS DESCRIPTION
The apparatus basic concept consists of microwave plasma
torch acting on a known inlet gas mixture flow concentration
(argon, nitrogen, water, ethanol, and tar) and to measure tar
and species concentration after the plasma reactor. The plasma
Received: August 25, 2012
Revised: December 16, 2012
Published: December 17, 2012

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Energy & Fuels
Figure 1. Apparatus scheme adopted in this work for the tar reforming with a microwave plasma torch.
torch was started up only with argon flowing through it. The
reactor then was supplied with a known mixture of argon,
nitrogen, and tar solution (ethanol + water + pine tar). The
reason for the presence of argon upon ignition and afterward
was to provide stability to the torch (and avoid subsequent
torch extinction), because of the fact that argon is easier
ionized, when compared to other gases. The reason for using
nitrogen instead of argon was to simulate gasifier exhaust gases,
which are mostly comprised of nitrogen.
2.1. Doping and Evaporation. Figure 1 illustrates the
experimental apparatus. Nitrogen and argon go through flow
meters, where they have their flow rates individually registered
and controlled with valves. After passing through flow meters,
gases mix themselves and go to a 1/4-in. copper pipe coil
located inside a tube furnace thermally heated with 3500 W
electrical resistances. In order to avoid heat losses, this furnace
was insulated with rock wool and glass wool covered with
aluminum foil. Standard operation procedure keeps the gas
temperature at the furnace exit heated to temperatures over 300
°C. After passing through the first tube furnace, argon−
nitrogen mixture receives tar solution from a syringe pump
(manufactured by KDS Scientific, Model KDS100, with an
error of 1%). This 10-mL syringe pump dopes the carrier gas
with tar solution comprised of 63.49% ethanol (mass fraction),
which is responsible for tar dilution; 6.51% water (oxygen and
hydrogen donor); and 30% pine tar.
The heated mixture of argon and nitrogen drags and
evaporates the tar solution injected by the syringe pump while
it flows in the second furnace. The second tube furnace
increases the doped gas temperature up to ∼350 °C. It is
responsible for completing the tar evaporation process, seeking
to avoid droplet presence in the plasma torch. The second tube
furnace was constructed similarly to the first one.
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After passing through the second tube furnace, the gas
mixture was driven to the microwave plasma reactor. In the
entrance of the microwave plasma reactor, there is a Type K
thermocouple connected to a digital display, which measures
doped gas temperature at the reactor entrance.
In order to avoid tar condensation and subsequent
obstruction in the pipe feeding, tar solution was injected
when the gas temperature at the reactor inlet was equal to or
higher than 250 °C. This temperature value was chosen after
experimental evaluation for tar solution boiling temperature.
The doped gas mixture then enters in the microwave plasma
reactor, where tar breakdown was expected to occur, as well as
new chemical species formation.
2.2. Microwave Plasma Reactor. The microwave plasma
reactor utilized in this work, with a maximum power of 3000 W
and source voltage of 5500 V, is illustrated in Figure 1. Its
magnetron converts the electrical current into microwave. A
circulator is located downstream from the magnetron source, to
prevent the electromagnetic current from returning and damage
the magnetron. The circulator has a system to measure incident
and reflected power, which is intended to evaluate the
microwave application efficiency into the gas passing through
the reactor. Downstream from the circulator, the microwaves
are conducted through a waveguide to a quartz tube, 10 mm
ID, where they were absorbed by the gas coming from the
feeding system, on swirl way, ionizing a fraction of molecules in
this gas, thereby generating the plasma torch. In order to
maximize tar breakdown and facilitate plasma generation, the
impedance of the plasma region is important to approach the
impedance from the microwave generator (magnetron). This is
accomplished by using a movable piston and stubs.
The microwave plasma reactor ignition system consists of a
tungsten rod inside the quartz tube in the plasma region
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Energy & Fuels
Figure 2. Apparatus scheme for the tar measurement system applied in this work.
(shown in Figure 1). The purpose of such a tungsten rod is to
concentrate the electromagnetic waves and start the plasma
torch. Upon ignition, maximum power is imposed to the flow
(3000 W) during a short period of time (on the order of
milliseconds). After this period, the system reduces its power to
the chosen prerequested level and holds it constant and steady
(1000 W). The power can be modified later, without
interruptions, during the microwave plasma reactor operation.
2.3. Tar Measurement System. Downstream from the
microwave plasma reactor is the tar concentration measure-
ment system. The applied tar measurement system, shown in
Figure 2, with a lower detection limit of 0.01gtar/mgas3, was
based on the procedure9,10 and successfully utilized.11
The exhaust gases from the plasma torch were fed into the
tar filtration system at a specific mass flow rate. Such flow was
controlled through a valve, and flow surplus was sent to the
alternative output. The gas sample then flows through a tar
borosilicate filter (1 μm mesh filter with efficiency above 99%).
Its external wall is electrically heated at 200 °C, using a 120-W
electrical-resistance-type collar, thereby preventing tar from
condensing on the filter holder walls. In this filter, mainly
primary tars were trapped and removed from the hot gas.
The next step was trapping the remaining tar content
through one or up to six gas washing flasks (Schout, 500 mL
with 100 mL of isopropanol in each flask). The quantity of gas
washing flasks depends upon the tar concentration in the gas.
The flasks with isopropanol retain the remaining tars that will
be quantified through weight measuring. The last flask of 500
mL contains silica gel and works as tar presence warning,
indicating need to add new washing flasks and avoid tar
presence in the vacuum pump. The gas washing flasks were
kept at temperatures of approximately −5 °C with an 18-L
ethylene glycol cooler system, cooling the gas and facilitating
tar condensation.
The cooled gas, which is now free from tar, passes through a
vacuum pump (with a maximum flow of 120 L/min). After
passing through such vacuum pump, the gas flows through a
meter with a Type K thermocouple connected to a temperature
display and a manometer (pressure gauge minihelic II model
with a measurement range of pressure between 0 and 100 mm
of H2O). Subsequently, the gas without tar was driven to a gas
analyzer (greenline GL8000) with detection ranges from 20
ppm up to 8000 ppm for CO and from 250 ppm up to 250 000
ppm for O2) or released to the atmosphere.
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The retained tar quantification was performed as follows:
before being used, the gas washing flask was individually
weighed with 100 mL of isopropanol. After using these bottles,
the mixture of tar and isopropanol contained in each individual
bottle was weighed again, and the difference in flask weight
before and after experiment is the amount of tar mass trapped.
It is important to keep in mind that the reactor eluded gas has
no water in its composition.
The borosilicate filter was dried in a drying oven for 1 h
(time provided by the manufacturer) before being used in the
tar measurement system. After passing through the laboratory
drying oven, the borosilicate filters were weighed. After the
experiment, the borosilicate filter was weighed again and the
difference between these weights was added to the tar mass
trapped in the washing flasks, thereby providing the total mass
of retained tar.
The volume shown in the gas meter after the test is
subtracted from the amount shown before the test was
performed. The difference between such volumes is the gas
volume analyzed by the tar measurement system. Using the
values obtained from the manometer and the thermocouple at
the gas meter, the volume of the analyzed gas was converted
from mgas3 to Nmgas3. The total amount of retained tar in the tar
measurement system was divided by the gas volume (gtar/
Nmgas3), as shown in eq 1.
m
C tar = tar
Vgas (1)
2.4. Optical Spectroscopy and Tar Characterization.
During the species ionization process present in the plasma
torch, these species have their electrons excited. The excited
electrons return to the standard state, thereby emitting
photons. The color and tone of the photons are characteristics
of each chemical species of the plasma torch present, allowing
species identification through optical emission spectroscopy.
The optical spectroscopy utilized in this experiment was an
optical emission spectrometer (Model UV−vis, Ocean Optics
USB4000) with a resolution of 1.5 nm and operating range in
the ultraviolet (UV) and visible (Vis). The spectrum was
obtained by an OOIBase32 program.
Chromatographic analysis was performed in the sample tar
solution aiming to identify organic species in the tar. The
chromatograph used was a Model GCT-Premier system
manufactured by Waters, and its main parameters are given
as follows: column, HP-5 (5% phenylmethylsiloxane) MS 30 m
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of long × 0.25 mm ID; initial temperature, 40 °C; column
temperature, 280 °C; injector temperature, 270 °C; detector
temperature, 280 °C; helium flow, 1 mL/min; constant
pressure, 80 kPa; and library peak identification used, NIST
(National Institutes for Standards and Technology).
In order to qualify the atomic composition present in the
used tar, an ultimate analysis was conducted. The apparatus
used for such analysis was an Ultimate Analyzer 2400 Series II
CHNS/O system and an analytical balance of six decimal
figures (Model AD-6), both manufactured by Perkin−Elmer.
The EBMA laboratory also provided measurement for used the
gross heating value (GHV) of the used tar. The apparatus used
for such analysis was a calorimeter manufactured by Ika Werke
(Model C 2000).
3. EXPERIMENTAL METHODOLOGY
Before the microwave plasma reactor starts, a 10-mL syringe is filled
with tar solution and assembled into the syringe pump; its needle is
inserted into the pipeline of the feeding system, as described above,
and already set up at the desired injection flow rate. Once the gas flow
reaches the desired temperature, the syringe pump was turned on and
the tar solution was added to the feeding system. During the plasma
reactor operation, the tar solution flow rate can be modified without
interrupting the experiment.
Initially, the reactor cooler system was turned on and only the argon
valve was opened and adjusted at a flow rate of 16 L/min. The
movable piston then was positioned at 125 mm (the movable piston is
shown in Figure 1) and the magnetron electrical power system is set
on the control panel, thereby igniting the microwave plasma torch.
Finally, the movable piston is moved up or down aiming at the
minimization of the reflected microwave (the values for the reflected
power are registered).
Once the feeding gas temperature after the second tube furnace was
equal to or greater than 250 °C, the syringe pump was turned on,
thereby injecting tar solution into the feeding system. After a few
minutes of operation, the plasma torch color was changed to green.
The tar solution saturation time in the feeding system depends on the
tar solution concentration. After the green color from the plasma torch
was obtained, the movable piston is moved again, seeking the
minimization of the reflected microwave. After the reflected micro-
waves were minimized, the nitrogen gas entrance flow was opened and
its flow rate was adjusted to 1 L/min. The plasma torch color changed
again from green to purple. The movable piston was moved again, in
order to maximize the microwave power absorbed by gases in the
microwave reactor.
After the plasma torch was in steady operation, the argon flow rate
was reduced to 3.8 L/min and the nitrogen flow rate was increased to
8.8 L/min. During the flow rates changes, the movable piston was
moved again, in order to minimize the reflected microwave power.
During plasma torch operation, which destroys and reforms tar, a
fraction of the tar carbon content that was not able to recombine with
oxygen turns out to be solid carbon and adheres on the quartz tube
internal wall, with its amount increasing with time. This effect was also
observed1 when methane gas was destroyed, utilizing a microwave
plasma torch. Such carbon deposit absorbs a fraction of the incident
microwaves in an amount directly proportional to the carbon
concentration on the quartz tube surface, reducing the amount of
energy delivered by the microwaves to the gas flow, leading to
instability and posterior torch extinction. During all experiments, the
adopted measurement system did not identify tar presence in the
reactor eluded gases. It was noticed that, when working with tar
concentrations at or above 4.974 gtar/Nmgas3, tar was not vaporized
completely into both tube furnaces; therefore, the tar concentration
reaction was not performed downstream. After carrying out the tar
destruction and reform tests, the best conditions obtained are shown
in Table 1.
In these experiments, the temperatures of both tube furnaces were
maintained between 330 °C and 350 °C, and the inlet gas temperature
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Table 1. Main Operational Parameters Adopted during the
Experiments
tar solution (mL/h) tar concentration (gtar/Nmgas3)
6 1.7
9 2.5
12 3.3
15 4.2
of the plasma reactor was ∼250 °C. Nitrogen and argon flow in all
experiments were kept constant at 8.8 and 3.8 L/min, respectively.
Throughout the operation, the power reflected and not absorbed by
the plasma torch did not exceed 0.5% of the power supplied by the
microwave plasma reactor.
4. RESULTS AND DISCUSSION
Figure 3 shows the chromatographic gaseous mass spectrom-
etry analysis (CG/MS) and Table 2 shows the ultimate
analysis, as well as the gross heating values (GHV) results for
pine tar applied.
4.1. Spectroscopy. In order to identify the species formed
just after tar destruction (without overlapping with emissions
from water and ethanol destruction), experiments were initially
performed only with water and ethanol solution doping into
the feeding system, and the result is shown in Figure 4.
Then, and under the same conditions, tar was added and the
optical spectrum obtained is shown in Figure 5. The integration
time used in the acquisition of both optical spectra was the
same. In order to identify the peaks present in these spectra, the
works on the subject12−14 were consulted.
Comparing the wavelength of 247.83 nm in both spectra, an
increase on the peak intensity can be seen as an increase on
carbon-neutral formation. Possibly, it is the carbon retained on
the wall of the quartz tube. Carbon-ionized formation is seen in
Figure 5 at 430.76 nm. The ionized carbon can form CO
molecules, reacting with ionized free oxygen. The presence of
ionized oxygen can be confirmed by peaks observed at 467.71,
469.15 and 558.11 nm.
The wavelength at 436.47 nm (Figure 5) indicates that the
formation of ionized sulfur, along with ionized oxygen atoms,
can produce sulfur dioxide. As shown in the ultimate analysis,
the sulfur is originated from tar, which is confirmed by the
absence of sulfur in Figure 4.
Figure 5 shows a peak in the wavelength range of 600 nm
that does not exist in Figure 4. This peak is an indication of
hydrogen gas (H2) formation. This comparison shows the
possible formation of H2 during the tar reforming. Another
important fact, which may reinforce the hypothesis of H2
formation, refers to the wavelength range of 549−563 nm in
both spectra. Peaks at such wavelengths are more intensified in
Figure 5 than in Figure 4. This fact suggests H2 formation as a
product of tar reforming.
Despite the fact that the ultimate analysis indicates nitrogen
atoms in tar composition, the emission of a nitrogen species
apparently was not found in the optical spectrum. A possible
explanation for this is the lack of resolution in the optical
spectroscopy used, which does not have enough resolution to
separate and show nitrogen species peaks.
Figure 6 shows the spectrum of the water molecules
destruction and reforming via microwave action. After analyzing
the spectrum shown in Figure 6, the formation of various free
radicals (Hα, Hβ, and O+) was observed. The presence of these
free radicals is important to avoid tar broken molecules to
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Energy & Fuels Article

Figure 3. Result from chromatographic gaseous mass spectrometry analysis (CG/MS) of the tar solution used in this experiment.

Table 2. Results from Tar Ultimate Analysis (Mass Fraction)

and Gross Heating Value (GHV)
parameter value
ultimate analysis (mass fraction)
C 51.05
H 5.1
N 6.85
S 6.68
O 30.32
gross heating value, GHV (kJ/kg) 6769

recombine into larger molecules. It indicates a major role that

water plays on tar reforming via plasma torch. The carbon that
exists in the high-temperature plasma torch can react with the
water, providing CO and H2 products.15
4.2. Gas Composition Downstream from the Plasma
Reactor. Results obtained from the gas analyzer are shown in
Figure 7, and they were averaged from 120 measured values
obtained during the experiments. Each experiment refers to a
specific flow of tar solution injected into the feeding system.
The operation conditions are shown in Table 1. Figure 7 shows
that CO increases and O2 concentrations decrease as the tar
solution flow rate increases. Figure 4. Result from optical emission spectroscopy for inlet gas
without tar.
It is important to highlight that no oxygen gas was supplied
to the reactor. All oxygen atoms in the detected CO and O2
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Figure 5. Results from optical emission spectroscopy for inlet gas with
tar.
Figure 6. Results from optical spectrum formed after the destruction
of water molecules (only).
came from ethanol, water, and tar. Furthermore, the approach
adopted in this work keeps the inlet C/O and C/H ratios
constant and independent of the tar solution flow rate applied
(C/O = 1.3 and C/H = 4.6). Therefore, an increase in the tar
solution flow rate implies only a reduction in reactant residence
time in the plasma reactor.
The initially expected result for Figure 7, once tar mixture
rate increases, is an increase on CO and O2 mass fraction as
well; but this was not the result that was obtained. Possibly, it is
consequence of the reactant residence time: Long residence
time favors O2 formation and low residence time favors CO
formation.
This experiment was conducted with lack of oxygen to
produce CO (C/O = 1.68, after ultimate analysis);
consequently, free carbon turned solid and was deposited on
the quartz tube. In addition, above a certain tar solution flow
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rate, the quartz tube wall saturates so fast that it quenches the
plasma. The beginning of instabilization is shown in Figure 7
(CO curve after tar solution of 12 mL/h).
The presence of hydrocarbons (CxHy) was not detected in
the exhaust gases, thereby reinforcing the hypothesis that tar,
after being reformed in a plasma torch microwave, results in
small chain species (diatomic or triatomic). The presence of
SO2 concentration (max average concentration of 212.48 ppm)
was measured, and the presence of either NO or CO2 was not
verified.
4.3. Inlet−Exit Species Mass Balance. In order to
validate the data obtained, an investigation on the absence of
NO and CO2, and possible formation of H2 molecules, a mass
balance was conducted. Table 3 shows the inlet mass flow rates
for all listed species, and Table 4 contains the exit mass flow
rates only for the species listed. Here, only the tar solution
atom population was considered, after argon and nitrogen were
determined to play an inert role. In Table 4, the solid carbon
flow rate was obtained by the difference between the carbon
flow rate from tar solution and that from the eluded CO
measured. In the same table, the adsorbed oxygen flow rate was
obtained using the difference between the oxygen flow rates
from tar solution and that from the eluded CO, SO2, and O2
measured.
As written above, the approach adopted in this work was to
keep the mass ratio between atoms constant and independent
of the tar solution flow rate. This can be inferred from the last
five columns in Table 3. In Table 4, the last three columns on
the right show the atoms mass flow rate evaluated only with the
measured species downstream from the reactor (CO, SO2, O2,
and C(s)). One can see that an increase in tar solution flow
increases the CO formation, but this growth is not linear,
indicating excess of free carbon available for reaction and
having, as a consequence, an increased solid carbon formation.
The relationships between C and O for each tar solution flow
gap in Table 3 show an inlet C/O ratio that is constant and
independent of the tar solution flow rate applied (C/O = 1.3).
Therefore, the reactant residence time in the plasma region
influences the formation of CO and O2. An increase in the tar
solution flow rate implies a reduction of reactant residence time
in the plasma reactor, decreasing the O2 formation and
increasing the CO formation. Another observation that occurs
with the increase of the tar mixture flow, thereby reducing the
residence time in the reactor, is SO2 formation. It seems to go
through a maximum of 9 mL/h.
Observing the oxygen atom flow adsorbed by carbon
contained in the quartz tube, which is shown in Table 4 (O-
adsorbed), there is a very low flow, which is null at low tar
solution flows, meaning that all the oxygen present in the tar
solution reacts with carbon and the remainder, with sulfur and
oxygen, forming SO2 and O2, respectively. This fact can explain
the absence of both CO2 and NO downstream from the
reactor. Another important fact is that little oxygen is available
to react with atomic hydrogen in order to form H2O molecules.
Moreover, as shown in this paper, there was no unburned
hydrocarbon presence downstream from the reactor; therefore,
hydrogen atoms do not react with available carbon. Therefore,
the hydrogen atoms may have reacted with each other in order
to form hydrogen molecules (H2), instead of reacting with
either oxygen or carbon atoms. Because of a lack of availability
of equipment in the laboratory during this work, hydrogen gas
was not quantified. The main products measured were C(s), O2,
CO, SO2, and possibly H2. With the exception of SO2
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Figure 7. Concentrations of CO and O2 (mole fraction) measured downstream from the microwave plasma reactor, relative to the inlet tar flow rate.

Table 3. Inlet Mass Flow Rates for Species and Atoms

Inlet Tar Solution Atom Flow Rate (g/min)
tar solution flow
unity (mL/h) total N2 argon H2O ethanol tar C O S N H
ḿ (g/min) 6 22.27 14.5 7.669 0.0053 0.0648 0.0300 0.04833 0.03711 0.00200 0.00206 0.01050
Y (%) 6 100 65.12 34.43 0.0292 0.2851 0.1347 0.04833 0.03711 0.00200 0.00206 0.01050

ḿ (g/min) 9 22.319 14.5 7.669 0.0079 0.0971 0.0450 0.07249 0.05567 0.00301 0.00308 0.01575
Y (%) 9 100 64.97 34.35 0.0437 0.4266 0.2016 0.07249 0.05567 0.00301 0.00308 0.01575

ḿ (g/min) 12 22.369 14.5 7.669 0.0105 0.1295 0.0600 0.09666 0.07422 0.00401 0.00411 0.02100
Y (%) 12 100 64.83 34.28 0.0582 0.5676 0.2682 0.09666 0.07422 0.00401 0.00411 0.02100

ḿ (g/min) 15 22.419 14.5 7.669 0.0131 0.1618 0.0750 0.12082 0.09278 0.00501 0.00514 0.02625
Y (%) 15 100 64.68 34.20 0.0726 0.7079 0.3345 0.12082 0.09278 0.00501 0.00514 0.02625

Table 4. Exit Mass Flow Rates for Species and Atoms

Atom Flow Rate Obtained from
Measures CO, SO2, and O2
Exit (g/min)
unity tar solution flow (mL/h) total CO SO2 O2 C-solid O-ads orbed C O S
ḿ (g/min) 6 0.09041 0.02741 0.00397 0.02249 0.03655 0.00000 0.01178 0.04010 0.00199
X (ppm) 6 1419.20 90.00 1019.00

ḿ (g/min) 9 0.13719 0.06634 0.00938 0.01750 0.04397 0.00000 0.02853 0.06000 0.00469
X (ppm) 9 3435.50 212.48 792.96

ḿ (g/min) 12 0.17455 0.07530 0.00733 0.01562 0.06428 0.01201 0.03238 0.06221 0.00367
X (ppm) 12 3899.50 166.13 707.83

ḿ (g/min) 15 0.21678 0.07752 0.00636 0.01473 0.08749 0.03068 0.03333 0.06210 0.00318
X (ppm) 15 4014.50 144.00 667.65

molecules, these products are the same that are obtained when
destroying and reforming carbon particles through the use of a
microwave plasma torch.15,16
4.4. Energy Consumption. During the experiment, the gas
temperature was regularly measured immediately upstream
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from the plasma reactor, but not immediately downstream. The
reactor exit was coupled to the tar sampling line, but
occasionally the reactor exit gas temperature was obtained
(∼340 °C) when the reactor-sampling line coupling was
disassembled. Without a regular measurement of gas temper-
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Energy & Fuels
ature immediately after the plasma reactor, the energy balance
was not performed. Instead, the specific energy consumption
was evaluated through the ratio between the inlet electric
power and the mass of tar destroyed. Despite experimental
observations indicating that tar was destroyed through a
microwave effect, further experiments must validate such a
conclusion against a thermal effect.
The specific energy consumption for a plasma torch can be
defined as the ratio between incident power and the destroyed
tar mass flow rate (J/kg). Under the best operating conditions
during all experiments in this work, 15 mL/h of tar solution
(4.5 g/h of tar) was destroyed with 995 W of microwave power
consumed, meaning 796 kJ/gtar. This work did not try to reduce
power; therefore, it is possible to obtain lower specific energy
consumption.
5. CONCLUSIONS
Considering the results obtained with Greenline GL8000 (the
absence of unburned hydrocarbons) and keeping in mind that
the tar measurement system has a lower limit of detection for
tar concentration of 0.01 gtar/Nmgas3 and a tar concentration up
to 4.2 gtar/Nmgas3 was imposed with no tar concentration
detected in the gas downstream from the reactor, the
conclusion is that a microwave plasma torch operating at
ambient pressure can break all tar molecules into smaller
species.
Results from the optical spectrum, as well as those from a gas
analyzer and calculated in mass balance, drive one to the
conclusion that the destroyed tar was converted mainly to CO,
O2, solid carbon (C(s)), and probably into H2 formation.
Hydrogen gas formation was inferred by comparison between
the results provided from the gas analyzer and the mass
balance, along with the results shown by optical spectroscopy.
Reactant resident time in the plasma region influences the
product formation: low residence time favors CO formation
and high residence time favors O2. The results shown in this
paper can validate the proposed reaction pathways for the tar
conversion into proposed smaller species,6 i.e., the microwave
plasma source, at atmospheric pressure, is capable of reducing
tar to smaller species, such as CO, H2, and C(s).
The major drawback of these experiments was the fact that it
was not possible to integrally replace the argon by nitrogen.
The maximum nitrogen−argon (N/Ar) mass ratio obtained
was 1.9. Above this ratio, the torch became unstable and
quenching was inevitable. Another drawback was the
accumulation of carbon inside the torch reactor quartz tube,
preventing the microwave from reaching the gas molecules and
also leading to quenching. Perhaps both problems can be
solved by increasing water concentration in the gas upstream
from the reactor. Such an increase in water doping can be
achieved by raising the liquid water content in the tar solution
or injecting water steam. It is interesting to remember that the
water concentration in this experiment was far below the typical
water concentration in the gasifier-eluded gases.
■
AUTHOR INFORMATION
Corresponding Author
*Tel.: (+55 91) 3201 8343. Fax: (+55 91) 3223 9534. E-mail:
mfmn@ufpa.br.
Notes
The authors declare no competing financial interest.
1181
■
Article
ACKNOWLEDGMENTS
Authors wish to thanks the Aeronautical Institute of
Technology (ITA), the Federal University of Para (UFPA),
the University of Campinas (UNICAMP), Federal Agency for
Support and Evaluation of Graduated Education (CAPES-
Procad NF), the Polaris, and the National Council for Scientific
and Technological Development (CNPq-Project No. 578106/
2008-6) for allowed grants and support given, as well as
doctorate and master fellowships for R.M.E. and B.A.P.C.
■
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