Decomposition of CCl4 and CHCl3 on Gliding Arc Plasma

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- Decomposition of chlorinated hydrocarbons, CCl4 and CHCl3, in gliding

plasma was examined. The effects of initial concentrations, total gas flow rates, and

power consumption have been investigated. The conversion was relatively high. It could

reach 80% for CCl4 and 97% for CHCl3. Under atmospheric air as the carrier gas, the

reaction was occurred at exothermic reaction and the main products were CO2, CO, and

Cl2. Transformation into CCl4 was also detected for CHCl3 decomposition reaction. The

conversion of these compounds was increased with the increasing applied frequency

and decreasing total gas flow rate.

Key words: Plasma, Gliding Arc, CCl4, CHCl3, decomposition reaction

1. Introduction

Chlorinated volatile organic compounds (CVOCs) are released to the atmosphere in flue

gases from a variety of industrial processes. Chlorinated hydrocarbons have been

†
Correspondence addressed. E-mail:indarto_antonius@yahoo.com, Tel:+82-19-352-1981
widespread accepted as solvents and chemical intermediates in the manufacture of

herbicides and plastics [1]. Unfortunately, emissions of these compounds are harmful to

the environment and toxic [2-4]. Much effort was made to reduce it.

The current technology for elimination them is high temperature (> 800 oC) incineration

[5]. This method allows influent of CVOCs directly combusted with air. Although this

method is very simple, some problems have been reported. While the combustion was

not perfect (incomplete combustion), the reaction tend to yield a large amount of

complex chlorinated products. [6]

Catalytic oxidation which is employing metal and metal oxide catalyst has been

investigated also [7]. It has been reported that using this method, the conversion and the

product selectivity were very good, but the catalyst become easily deactivated by

impurities and solid product. Also, this method requires temperature heater to achieve

the activated catalyst temperature and reaction rate. Other limitation to use this method

in industrial plant is the input flow rate which was very small.

Due to overcome such those problems, many studies are carried out on the application

of new technologies. Plasma-assisted technology is one of the emerging and effective

technologies for destroying CVOCs. Plasma-assisted technology, such as Electron

Beam [8], RF plasma [9], surface discharge reactors [10], dielectric barrier discharge

reactors [11], pulsed discharge reactors [12], and capillary-tube type discharge reactors

[13], have been studied and develop. In this study, gliding arc plasma was used, to

decompose chloroform (CHCl3), and carbon tetrachloride (CCl4). Compare to the

previous plasma methods, gliding arc plasma has great chance to be utilized for

industrial chemical applications. It achieved higher flame temperature and power to

destruct the toxic input material [14]. One favor of this method was this method can

handle very high input flow rate.

2. Experiment setup

Figure 1

The schematic diagram of experimental setup is shown in figure 1. CCl4, CHCl3 and

atmospheric air have been used as source 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 150 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 10 cm above the electrode, has been provided to measure the

outlet gas temperature. A high frequency AC power supply (Auto electric, A1831) with

a maximum voltage 10 kV and a maximum ampere 100 mA was connected to the

gliding arc electrode to generate plasma. Figure 2 shows typical waveforms of voltage
and discharge current used in this experiment.

Figure 2

2.2. Input gas

Chlorinated hydrocarbons that were used as the starting material are:

a. Chloroform: CHCl3, molecular weight 119.38, purity 99.0%, purchased from Junsei

Chemical Co., Ltd., concentration 1, 3, 5, 8% v/v

b. Carbon tetrachloride: CCl4, molecular weight 153.82, purity 99.5%, purchased from

Kanto Chemical Co., Inc., concentration 1, 3, 5, 8% v/v.

Atmospheric air was used as the carrier gas and controlled by a Mass Flow Controller

(Tylan, FC-280S). The total mixed gas (air + chlorinated compounds) flow rate was

180, 240, and 300 Nl/hr. The composition of the outlet mixture 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 and CHCl3 in the gas mixture

before and after the reaction ware 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 (Cl 2) 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.

To evaluate the performance of system, selectivity and conversion were used and

formulated as:

for decomposition of CCl4:

moles of Cl 2 formed
Selectivity of Cl 2 = × 100% (1)
2 × moles of CCl 4 converted

moles of CO formed
Selectivity of CO = × 100%
moles of CCl 4 converted (2)

moles of CO2 formed

Selectivity of CO2 = × 100% (3)
moles of CCl 4 converted

moles of CCl 4 consumed

Conversion of CCl 4 = × 100% (4)
moles of CCl 4 introduced

for decomposition of CHCl3:

2 × moles of Cl 2 formed
Selectivity of Cl 2 = × 100% (5)
3 × moles of CHCl 3 converted

moles of CO formed
Selectivity of CO = × 100% (6)
moles of CHCl 3 converted

moles of CO2 formed

Selectivity of CO2 = × 100% (7)
moles of CHCl 3 converted
 moles of CCl 4 formed
Selectivity of CCl 4 = × 100% (8)
moles of CHCl 3 converted

moles of CHCl 3 consumed

Conversion of CHCl 3 = × 100% (9)
moles of CHCl 3 introduced

Those parameters were used to study the effect of initial chloromethane concentration,

total gas flow rates, and power frequency. The discharge power was calculated as a

product of voltage and current by oscilloscope (Agilent 54641A), defined as:

Discharge power = ∫ (V (t ) × I (t ) ) dt × frequency Watt (10)

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

measured by thermocouple.

3. Result and Discussion

3.1. Effect of initial concentration and total gas flow rate.

Figure 3

Figure 3a shows the trend of chlorinated hydrocarbons in various values of initial

concentration and total gas flow rate. Conversion gradually decreased when the initial
concentration increased. The conversion also decreased with increasing total gas flow

rate. The maximum conversion of CCl4 could reach 80% at the concentration 1% and

total air flow rate 180 Nl/hr. At same condition, CHCl3 conversion could reach higher

value, 97%. Although the conversion decreased, the removal efficiency has increased

with increasing initial concentration. It was proposed that Cl◦ initiated and gave positive

effect on decomposition process.

Table 1

Beside the conversion, different type of compounds, initial concentration, and total gas

flow rate also produced different value of consuming discharge power. Stability of

compounds under plasma treatment has the important role in destruction reaction. Table

1 shows that to destruct CCl4, it spent more energy compared to CHCl3. The chemical

bond and structure stability of CCl4 was stronger than CHCl3 [1]. Stronger form of

compound spent more energy to initiate the arc plasma. It also produced lower value of

conversion (comparison between CCl4 and CHCl3 conversion in figure 1). This

phenomenon has the same tendency when chlorinated hydrocarbons were treated by

oxidation combustion reaction [15].

Total gas flow rate was also has significant effect on power discharged. With the

increasing total gas flow rate, the total power was decreased. Physical study about this

phenomenon has been established in term of Paschen’s law [16].

Based on QMS spectra result and GC analysis, the gas product was dominated by CO,

CO2, and Cl2. The number of other C-Cl compounds was relatively small. In case of

CCl4, the selectivity of final product went to Cl2 gas was high. It could reach 42% up to

78.9%. Although not as high as CCl4, product probability of Cl2 on CHCl3

decomposition was also high, 33% up to 50.5%. Increasing CCl4 initial concentration

has decreased the product selectivity and it means the product distribution would be

varied. This phenomenon was not occurred in case of CHCl3. The selectivity of Cl2 gas

was relatively constant.

In case of CO and CO2 production, the selectivity has the same trend as Cl2 especially

for CCl4 decomposition. It could be proposed as kind of C vacancy due to lose Cl

species. When CCl4 was destructed into Cl2, it will remain C radical as an intermediate

species. It opened chance for C radical (C vacancy) to collide with another compounds.

Higher possibility to collide with oxygen to produce CO or CO2 compared to other kind

of composition. CO and CO2 have the stable structure and the concentration of oxygen

gas in the air-carrier stream was high (~20%). Based on calculation of QMS spectra of

oxygen (O2) produced that the concentration of oxygen (O2) in the product stream (after

plasma process) was 5-10% lower than concentration in inlet stream (before plasma

process). One possible reason was the losing oxygen was reacted and consumed into

CO and CO2. Comparison of produced CO2 to CO at the final product stream was

around 1/10 up to 1/5.

Decomposition of CHCl3 was also produced CCl4. The selectivity was not exceeded

more than 12%. During the experiment, another trace compounds were also detected,

such as COCl2 and HCl. Liquid product was also produced and might be counted as the

remaining C and Cl species.

3.2. Effect of frequency

As mentioned above, supplied discharge power to the plasma system has important role

on the decomposition reaction. This factor was also important to govern the product

distribution. In this experiment, there were three variables that gave influence on its

value. Among these variables, only power frequency that could be adjusted manually.

Voltage and current were automatic fixed into specific value after initial breakdown of

gliding arc.

Figure 4

Figure 5

Figure 6

The effect of power frequency is presented in figure 4. The maximum power frequency

was 20 kHz. As shown in figure 4, the conversion was increased with the increasing

frequency. For CCl4, the rate of conversion reached 4% higher per 1 kHz increment of

frequency and slightly lower for CHCl3. Increasing frequency leads to increase the

supplied discharge power. Figure 5 shows the increasing discharge power due to

increasing power frequency. Increasing frequency would give effect on AC wave form.

Higher frequency produced more number of peaks per cycle and supplied more energy

to the system. The change of patter of power wave form due different applied power

frequency is shown in figure 6.

Figure 7

Figure 7 shows the different value of frequency or power discharge also gives different
value of Cl2 gas production although the initial concentration and flow rate were same.

It means that power frequency or power discharge has the importance to be a factor to

decide the way of reaction. With the increasing power frequency, the selectivity of Cl2

was getting increased also. It could be proposed that in the higher energy field, the

plasma reaction tent to produce Cl2 gas as the final product.

3.3. QMS Spectroscopy

Figure 8

A QMS spectroscopy of the conversion of CCl4 is shown in figure 8. Figure 8a

describes the condition of components in the 180 Nl/hr feed stream containing
+
atmospheric air with 1% of CCl4. The baseline spectra of CCl4 were 83/85 ( CCl 2 ), and

+ +
117 ( CCl 3 ). CO2 has spectra at 44 ( CO2 ) and CO spectra was collide with minor N2

+ + +
spectra at 29 ( CO / N 2 ). Major N2 spectra, it self, was located at 28 ( N 2 ). But,

because the concentration of CO in the air was quite small, CO compound could be

negligible in this spectroscopy. When the plasma was applied, figure 8b, the peak

intensity of 83/85 got disappeared together with decreasing intensity of spectra 117 and
+
produced a new peak, 71, which is known as Cl 2 ( Cl 2 ). Intensity of CO2 was increased
also but the difference was very small. High increment has been occurred on spectra 28.

Because N2 was relatively stable gas and no source of N compound to produce N2, it

could be said that the increasing intensity of spectra 28 due to production of CO by

plasma.

Figure 9

The mass spectroscopy of CHCl3 before and after plasma reaction is presented in figure

9. Figure 9a shows the components in the 240 Nl/hr feed stream containing compressed
+
air mixed with 1% of CHCl3. The baseline spectra of CHCl3 were 82/84/86 ( CCl 2 ).

+ +
CO2 has spectra at 44 ( CO2 ) but it was collided with major N2O spectra ( N 2 O ),

+
which has possibility to exist in the gas product. CO was at 29 ( CO ) but it was also
+
collided with minor N2 spectra 29 ( N 2 ). It made difficult to distinguish them using

QMS. In this experiment, CO and CO2 were analyzed by gas chromatography. When the

plasma was applied, figure 9b, the peak intensity of 83/84/86 got decreased and

+
produced some new peaks: 63/65, which is known as COCl2 ( COCl ), 69/71 as Cl2 (

Cl 2+ ), 117 as CCl4 ( CCl 3+ ).

3.4. Reaction Pathway

The kinetic reaction of CO, CO2, and Cl2 formation which were produced from

chlorinated hydrocarbons has been studied and presented [8, 17-22]. The major

pathways responsible for the formation of Cl2 were:

COCl 2 + Cl = COCl + Cl 2 (11)

CHCl 3 + Cl = CHCl 2 + Cl 2 (12)

COCl + Cl = CO + Cl 2 (13)

However, the third reaction (formula 13) was also one of the primary reaction paths for

the formation of CO. Other one was:

COCl + M = CO + Cl + M (14)

It was seen that CO formation was initially through COCl2. The major reaction path for

the formation of CO2 was come from CO:

CO + ClO = CO2 + Cl (15)

CO + O + M = CO2 + M (16)

in which ClO forms via:

CCl 4 + O = CCl 3 + ClO (17)

CCl 3 + O2 = COCl 2 + ClO (18)

It means oxygen and oxygen radical have significantly contribution to held the reaction.

The production of O radical came from dissociation reaction [Penetrante, et. al, 1995]:

e + O 2 = e + O( 3 P ) + O ( 3 P ) (19)

e +O 2 = e + O ( 3 P ) + O ( 1D ) (20)

Cl radical in this formula can be produced from:

CCl 4 = CCl 3 + Cl (21)

CCl 3 + O = COCl 2 + Cl (22)

CCl 3 + Cl 2 = CCl 4 + Cl (23)

Reverse reaction could be happened on formula 21 as the main path way to produce

CCl4 in decomposition of CHCl3,

CCl 3 + Cl = CCl 4

4. Conclusion

The performance of CCl4 and CHCl3 decomposition on gliding arc plasma at

atmospheric pressure, related with initial concentration, total gas flow rate, and input

power frequency, was studied. Gliding plasma could generate effective electrons and
ions enough to fragment the molecules. The maximum conversion of CCl4 was 80% and

CHCl3 was 97% for feed gas stream containing 1% of v/v and total air flow rate 180

Nl/hr. The major final products were CO, CO2, and Cl2. Cl2 selectivity was relatively

high and reached up to 78.9% for CCl4 and 50.5% for CHCl3. Conversion into CCl4 was

found in case of CHCl3 decomposition, but not exceed than 12%. COCl2 has an

important role as intermediate species to produce Cl2 and CO. Mostly CO2 was

produced from CO reaction. From these result, it could be concluded that the gliding arc

plasma system was very useful for decomposition of CCl4 and CHCl3. Development

was needed to remove some traces unwanted compounds, such as: COCl2 in the final

product.

Acknowledgements

This study was supported by National Research Laboratory Program of Korea Minister

of Science and Technology.

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3rd edition, New York, pp. 668-713

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[10]. T. Oda, T. Takahahshi, and K. Ya,aji, IEEE Transactions on Industry Applications,

38(3), 873 (2002).

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S. Honda, IEEE Transactions on Industry Applications, 34(5), 953 (1998).

[14]. A. Czernichowski, Pure & Appl. Chem., 66 (6), 1301 (1994).

[15]. P. H. Taylor and B. Dellinger, Environ. Sci. Technol., 22 (4), 438 (1988).

[16]. J. D. Cobine, Gaseous Conductor Theory and Engineering Application (Dover

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 v e n t to
a tm o s p h e r e

F ID G C
B e n to n e

TC D G C
C o m p re s s e d S K C a rb o n
a ir
Q u a d ra p o le
M ass
S p e c t ro m e t e r
C h lo r in a te d
h y d ro c a rb o n

K I s o lu t i o n

P la s m a
R e a c to r

Figure 1. Schematic diagram of experimental set up

 6000

4000

2000
Voltage (V)

-2000

-4000

-6000

0.4

0.2
Current (A)

0.0

-0.2

-0.4

-0.6
-2e-5 -1e-5 0 1e-5 2e-5

Time (s)

Figure 2. Voltage and current profile

 100
CCl4
CCl4 conversion (%)

80

60

40

0 2 4 6 8 10

initial CCl4 concentration (% v/v)

CHCl3
100
CHCl3 conversion (%)

80

60

40

0 2 4 6 8 10

Initial CHCl3 concentration (% v/v)

Figure 3. Influence of initial concentration of injected chlorinated hydrocarbons and

total gas flow rate on its conversion. (■ 180 Nl/min; ● 240 Nl/min; ▲ 300 Nl/min)
 concentration flowrate power selectivity
(% v/ v) (Nl/ hr) (Watt) CO+CO2 Cl2
1 180 242.6 48.7 78.9
3 180 240.5 32.4 73.0
5 180 239.3 28.9 68.0
8 180 229.6 25.4 65.0
1 240 236.8 48.0 63.3
3 240 234.2 49.0 55.1
5 240 229.4 41.0 48.4
8 240 219.6 41.7 45.6
1 300 227.7 26.7 51.6
3 300 225.6 25.2 48.0
5 300 218.2 18.2 42.0

(a)

concentration flowrate power selectivity

(% v/ v) (Nl/ hr) (Watt) CO+CO2 CCl4 Cl2
1 180 234.5 31.1 6.4 33.0
3 180 232.1 40.3 9.7 34.9
5 180 226.8 42.5 10.9 33.8
8 180 212.8 48.6 11.8
1 240 222.1 31.1 9.4 42.7
3 240 216.6 34.4 10.0 38.8
5 240 205.1 41.0 10.2 48.3
8 240 175.0 43.8 11.8 47.4
1 300 220.0 22.2 5.3 50.5
3 300 212.6 27.4 7.9 43.3
5 300 197.4 24.6 10.0 47.5

(b)

Table 1. Effect of initial concentration and total gas flow rate on product distribution of

(a) CCl4 and (b) CHCl3 decomposition

 100
CCl4

80
CCl4 conversion (%)

60

40

20

14 16 18 20 22

Power frequency (kHz)

100
CHCl3

80
CHCl3 conversion (%)

60

40

20

14 16 18 20 22

Power frequency (kHz)

Figure 4. Effect of applied input power frequency on CCl4 and CHCl3 conversion (■ 

180 Nl/min;  ●  240 Nl/min;  ▲  300 Nl/min). Data was taken at 1% v/v of CCl4 and 1%
v/v of CHCl3.
 350

300
Discharge power (Watt)

250

200

150 CCl4; 180 Nl/hr

CCl4; 240 Nl/hr
CHCl3; 180 Nl/hr
100
CHCl3; 240 Nl/hr

14 16 18 20 22

Power frequency (kHz)

Figure 5. Effect of applied different power frequency on consumed discharge power. Data

was taken at 1% v/v of CCl4 and 1% v/v of CHCl3.

 1000

15 kHz
16.25 kHz
800 17.5 kHz
18.75 kHz
20 kHz
600
Power (Watt)

400

200

-200
-2e-5 -1e-5 0 1e-5 2e-5

Time (sec)

Figure 6. Effect of applied different power frequency on power-profile wave form. Data

was taken at 5% of CHCl3 and total gas flow rate 180 Nl/min
 CCl4; 180 Nl/hr
80
CCl4; 240 Nl/hr
CHCl3; 180 Nl/hr
CHCl3; 240 Nl/hr
60
Selectrivity (%)

40

20

0
14 16 18 20 22

Power frequency (kHz)

Figure 7. Effect of applied different power frequency on Cl2 gas production selectivity.

Data was taken at 1% v/v of CCl4 and 1% v/v of CHCl3.

 1.4e-9 before

1.2e-9

1.0e-9
CO and N2
Intensity

8.0e-10

6.0e-10

4.0e-10

Cl2
CCl4
2.0e-10 CO2
CCl4

0.0
1.4e-9 after

1.2e-9
CO and N2
1.0e-9
Intensity

8.0e-10

6.0e-10

4.0e-10

CO2
2.0e-10
Cl2 CCl4

0.0
0 20 40 60 80 100 120 140 160 180 200

AMU (m/z)

Figure 8. QMS spectrogram of CCl4 decomposition (taken at applied frequency 20kHz,

1% of CCl4, total gas flow rate 180 Nl/h); (a) before (b) after gliding plasma on
 1.2e-9 (a) before

1.0e-9

8.0e-10
intensity

6.0e-10

4.0e-10

2.0e-10 CHCl3

1.2e-9
(b) after

1.0e-9

8.0e-10
intensity

6.0e-10

4.0e-10

2.0e-10 COCl2
CHCl3
Cl2 CCl4

0 20 40 60 80 100 120 140 160 180 200

AMU (m/z)

Figure 9. QMS spectrogram of CHCl3 decomposition (taken at applied frequency

20kHz, 1% of CHCl3, total gas flow rate 180 Nl/h); (a) before (b) after gliding plasma

on