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gliding arc plasma processing for decomposition of

chloroform

antonius indarto��, jae-wook choi, hwaung lee and hyung keun song
korea institute of science & technology, clean technology research center,
p.o. box 131, cheongryang, seoul 130-650, korea

abstract- an innovative treatment process using gliding arc plasma has been shown
to be an effective way for the destruction of chloroform (chcl3), one of stable
chlorinated volatile organic compounds (cvocs). the result data of experiments
regarding the performance of gliding arc discharge were presented in this paper.
different values of initial concentration of chloroform, total gas flow rate, and
input power frequency refers to power consumption have been used as the
experimental variables and studied to investigate the effect of these to the
amount and distribution of the products. experiment results indicated that the
maximum conversion of chloroform was about 97% at the total gas feed 180 nl/hr,
containing 1% v/v of chloroform. under atmospheric air as the carrier gas,
decomposition of chloroform would produce the main gas products ccl4, co2, co, and
cl2. small amount of hcl and cocl2 have been detected. liquid product was also
produced instead of gas product. the conversion of chloroform was increased with
the increasing applied voltage and decreasing total gas flow rate.
keywords: plasma, gliding arc plasma, chloroform, decomposition

1. introduction

emission of various chloromethane compounds, such as chloroform (chcl3), are


categorized as toxic species that become an important task to be removed from
indoor or outdoor ambient gas [1]. chloroform is used as a solvent, in production
of other chemicals, and in some imported pesticide formulations. however,
chloroform has high thermal stability [2] and global warming potential (gwp) [3].
to eliminate this pollutant, usually two approaches were taken: thermal oxidation
and catalytic oxidation. although several thermal oxidation technologies have been
developed, there were still required high temperature (between 760 to 980oc) and
longer residence time to complete oxidation reaction [4]. trying to solve these
problems, many researchers have examined to apply catalytic oxidation technology.
this technology can reduce the resident time, but removal efficiency was lower
than thermal oxidation. at low temperature, catalyst's lifetime was very short [4]
and also required different type of catalyst if the target voc is mixed [5].
nowadays, plasma-assisted technology (thermal and non-thermal) has been proposed
to overcome these kinds of problem. most of them, to eliminate these hindrances,
gliding arc discharge have a bright prospect to be applied, especially in
industrial scale. gliding arc discharge was the subject of renewed interest in
applications to a varied of chemical reactions. therefore, the main innovative
aspect of utilizing gliding arc discharge was the powerful electrical discharges
under thermally non-equilibrium conditions [6], very short resident time, and high
both gas flow rate and concentration capacity.
previous study about kinetic destruction of chloroform using photosensitized
oxidation [7], thermal oxidation [8], photocatalytic [9], uv lamp [10] have been
done but no detail report explanation about pathway reaction under direct plasma
condition such as gliding arc discharge. in the present work, the decomposition of
chloroform diluted with (atmospheric compressed) air has been done to study the
reaction mechanism of chloroform destruction under gliding arc discharge. the main
gas products, such as: co, co2, cl2, and ccl4, have been used as the object of
analysis. to ensure the explanation, a model simulation based on kinetic reaction
term, has been made and compared to the experimental result.

2. experiment setup
the schematic diagram of experimental setup is shown in figure 1. chloroform and
compressed air have been used as source of gas. details of each part of the system
are described in the next section.

2.1. plasma reactor and applied power system

the reactor was made from a quartz-glass tube of inner diameter 45 mm and length
300 mm. the upper part and bottom of the reactor supplied with a teflon seal
comprised two electrodes made of stainless steel. the length of the electrodes was
100 mm. the separation of the electrodes in the narrowest section was 1.5 mm. the
gas mixture was introduced between the electrodes through a capillary of inner
diameter 0.8 mm. a thermocouple, located 10cm above the electrode, has been
provided to measure the outlet gas temperature. a high frequency ac power supply
(auto electric, a1831) was connected to the gliding arc electrode to generate
plasma. figure 2 shows typical waveforms of voltage and discharge current used in
this experiment.

2.2. input gas

chloroform (chcl3) that was used as the starting material was purchased from
junsei chemical co., inc. it has purity of ~99.0% and concentration has been
varied to 1, 3, 5, 8% volume of total gas flow rate. atmospheric air was used as
the carrier gas and controlled by a mass flow controller (tylan, fc-280s) and the
air flow rate were 180, 240, and 300 nl/hr. air entering the reactor was first
passed through a scrubber and mixed with chloroform. chloroform was introduced by
passing a portion of air through a diffusion tube (bubbling vapor-pressure
method), which was located in a water bath. concentration of chloroform was
controlled by controlling both temperature of water bath and injected gas flow
rate to diffusion tube. isolating tape was attached surrounding the line stream to
maintain the input line temperature. the mixture composition of the outlet reactor
was analyzed before and after the plasma operation.

2.3. measurement system

the outlet gas composition was examined by quadrapole mass spectroscopy (balzers,
qms 200) with quadstar 421 software. this software was used for the qualitative
and quantitative analysis of the reactants and products. two gcs have been used to
analyze the quantitative amount of products. the contents of ccl4 in the gas
mixture before and after the reaction were determined by gc-fid (younglin m600d,
column: bentone). and for determination of co and co2 in the outlet gas mixture, a
gc-tcd (younglin m600d, column: sk carbon) was used. chlorine gas (cl2) was
determined by bubbling the reacted gas through 0.05 m aqueous ki during measured-
experiment time and followed by iodometric titration 0.05 m na2so3.
the evaluation of system performance, selectivity and conversion, were formulated
as:
(1)
(2)
(3)
these parameters were used to study the effect of initial chloroform
concentration, total gas flow rate, and input power frequency (respect to power
consumption). the amount of power supplied was shown in term of voltage and
current which was captured by oscilloscope (agilent 54641a) and calculated to
power term by following equation:
(4)
in this study, each data of experiment was taken after 30 minutes from the start
of gliding plasma operation refers to the stability of bulk gas outlet
temperature, which has been measured by thermocouple.

3. results and discussion

the destruction of chloroform (chcl3) produced main products of ccl4, co2, co,
cl2. another products such as: hcl, cocl2 were also detected by mass spectrometer,
but the concentration was very low. the selectivity of co and cl2 was much higher
than co2 and ccl4. generally, concentration of co2 was 3-5 times lower than
concentration of co in the gas product. ccl4 production has selectivity range
between 8-15%. furthermore, the destruction performance was studied deeply as
function of initial chloroform concentration, injected total gas flow rate, and
input frequency and the gas product would be focused on co, co2 and cl2 because
these compounds became the target material of chloroform decomposition.

3.1. effect of initial concentration.

fig. 3a shows the effect of various initial concentration of chloroform on its


conversion at input power frequency 20 khz. the maximum conversion could reach 97%
at the lowest concentration of chloroform 1% v/v and total air flow rate 180
nl/hr. conversion efficiency gradually decreased when the initial concentration of
chloroform increased. the decreasing rate of conversion reached 2.5% per 1% of
increasing initial chloroform concentration in the gas stream. using figure 3a,
the chloroform removal decreased from 97% to 90% when initial concentration of
chloroform increased from 1% to 8% at total gas flow rate 180 nl/hr. the same
phenomenon was found also at total gas flow rate 240 and 300 nl/hr. the increment
concentration of chloroform in the feed gas mixture would decrease the ratio of
reactive species, such as: oxygen radical and electron, to chloroform during
plasma reaction. figure 3b shows the power consumption decreased when the initial
concentration of chloroform increased. decreasing power that was supplied to the
plasma system would reduce the number of reactive species. it brought the chance
of chloroform to collide with reactive species became smaller and gave lower
chloroform conversion. the role of radical species, such as oxygen and oxygen
radical that came from air, to hold the decomposition process has been studied
[11]. calculation of qms spectra on o2 concentration resulted that when plasma
turned on, the concentration of o2 in product stream after plasma reaction was
decreased between 10-15% compare to input stream before plasma reaction.
small increment of bulk gas temperature due do increasing initial chloroform
concentration has been measured. output gas temperature could reach 250oc and
increased ~2-3oc per 1% increment of initial chloroform. this was caused mainly by
plasma reaction disposed to be oxidation reaction. the reaction would produce co,
co2 and cl2 gas. increasing initial concentration of chloroform would produce more
oxidation reaction and supply more heat to environment.
the selectivity of gas products, (co+co2) and cl2, is shown in figure 3c-d. no
significant different value of (co+co2) selectivity when the different value of
initial concentration of chloroform was applied. the maximum selectivity of
(co+co2) was ~50%. it could be suspected that almost half of reaction went to
oxidation reaction to produce co or co2. in case of cl2, the selectivity slightly
increased with increasing chloroform concentration.

3.2. effect of total gas flow rate

the effect of total gas flow rate, related to the residence time of chloroform in
the reactor, was examined. fig. 4a shows the chloroform conversion according to
the various total gas flow rates at initial chloroform concentration of 1, 3, 5%
and power supply frequency 20 khz. the conversion of chloroform decreased with the
increase of total flow rate. the increasing of total gas flow rate reduced the
residence time of chloroform in the reactor. it means reducing the chance and time
of the molecule to collide with electrons and other high-energy state species,
which had enough energy to destroy the carbon-hydrogen-chloride bond. the power
supply also has contribution to the decreasing chloroform conversion. generally,
as shown in figure 4b, increasing total gas flow rate would reduce the supply
power to the plasma system.
increasing total gas flow rate gave the different tendency to the curve trend of
(co+co2) selectivity and cl2 selectivity. figure 4b shows the (co+co2) selectivity
increased with the increasing of total gas flow rate. in the reverse site, figure
4c, the selectivity of cl2 disposed to decrease. in term of total gas flow rate
and power supply variation, the shorter residence time and lower supply power
would increase the (co+co2) selectivity and decrease the cl2 selectivity.
dealing with partial and complete oxidation reaction of chloroform,
(5)
(6)
the ratio of cl2 to co or co2 must be 1.5 in the product gas composition. compared
to the reaction under gliding arc plasma system, this ratio could be fulfilled
when it was done at lower gas flow rate.

3.3. effect of applied frequency

fig. 5a shows the effect of applied frequency of input power on the chcl3
conversion at 1% of ccl4. the conversion of chcl3 slightly increased from 92% to
97% when the frequency was increased from 15 to 20 khz at 180 nl/min. the same
increment trend was found, started from 42% to 60% at 300 nl/hr. this could be
suggested that increasing frequency would increase the total supply power to
plasma system respectively (fig. 5b). higher input power provided more energy for
ionization of gas molecules and increased the effective collision among the
reactants. in case of (co+co2) selectivity, as shown in figure 5c, increasing
value of power supply frequency also gave significant effect on decreasing
selectivity of products to (co+co2). lower frequency and power value would
decrease the plasma reaction to produce co and co2. figure 5d shows the
selectivity of cl2.

3.4. qms spectra

a qms spectrum of chloroform decomposition is shown in figure 6. fig. 6a shows the


components in the 240 nl/hr feed stream containing compressed air mixed with 1% of
chloroform. the baseline spectra of chloroform were 82/84/86 (). co2 has spectra
at 44 () but it was collided with major n2o spectra (), which has possibility to
exist in the gas product. co was at 29 () but it was also collided with minor n2
spectra 29 (). it made difficult to distinguish them using qms. in this
experiment, co and co2 were analyzed by gas chromatography. when the plasma was
applied, fig. 6b, the peak intensity of 83/84/86 got decreased and produced some
new peaks: 63/65, which is known as cocl2 (), 69/71 as cl2 (), 117 as ccl4 ().

4. conclusions

the performance of chloroform conversion in gliding arc plasma at atmospheric


pressure, related with initial concentration of chloroform, total gas flow rate,
and input power frequency, was studied. gliding plasma could generate effective
electrons enough to fragment chloroform molecules. the maximum conversion of
chloroform was 97% for feed gas stream containing 1% of v/v and total air flow
rate 180 nl/hr. co, co2, ccl4 and cl2 were the major products.
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figure 1. schematic diagram of experimental set up

figure 2. voltage and current profile

figure 3. effect of initial chloroform concentration on (a) chloroform conversion,

(b) power consumption, (c) (co + co2) selectivity, and (d) cl2 selectivity.

figure 4. effect of total gas flow rate on (a) chloroform conversion,


(b) power consumption, (c) (co + co2) selectivity, and (d) cl2 selectivity.

figure 5. effect of applied power frequency on (a) chloroform conversion,


(b) power consumption, (c) (co + co2) selectivity, and (d) cl2 selectivity.

figure 6. qms spectra of chloroform decomposition (taken at applied frequency


20khz,
1% of chcl3, total gas flow rate 240 nl/h); (a) before (b) after gliding plasma on

�� corresponding author: e-mail:indarto_antonius@yahoo.com, tel:+82-19-352-1981