Treatment of Dichloromethane Using Gliding Arc Plasma

Antonius Indarto

Clean Technology Research Center, Korea Institute of Science & Technology

P.O. Box 131, Cheongryang, Seoul 130-650, Korea
Phone number: 02-958-6558
email: indarto@korea.com
Corresponding Author

Jae-Wook Choi

Clean Technology Research Center, Korea Institute of Science & Technology

P.O. Box 131, Cheongryang, Seoul 130-650, Korea

Hwaung Lee

Clean Technology Research Center, Korea Institute of Science & Technology

P.O. Box 131, Cheongryang, Seoul 130-650, Korea

Hyung Keun Song

Clean Technology Research Center, Korea Institute of Science & Technology

P.O. Box 131, Cheongryang, Seoul 130-650, Korea

Total counted words: 5253 (including: 1 table and 8 figures)

1
Abstract- Decomposition of dichloromethane (CH2Cl2) using a gliding plasma was examined

and reported in this paper. The effects of initial concentrations of CH 2Cl2, total gas flow rates,

and input frequency have been studied to evaluate the performance of gliding arc on CH2Cl2

decomposition. Using atmospheric pressure air as the carrier gas, experimental results

indicate that the maximum conversion of CH2Cl2 was 95.1% at a total gas flow rate of 180

L/hr containing 1% by volume of CH2Cl2. The reaction occurred at an exothermic condition

and gaseous products are dominated by CO, CHCl3, and Cl2. CO2 and CCl4 are also detected

in the product stream in small amounts. The conversion of CH2Cl2 increases with the

increasing applied voltage and decreasing total gas flow rate.

Key words: Plasma, Gliding Arc, CH2Cl2 decomposition

2
Introduction

Nowadays, gaseous wastes release to the atmosphere is growing in both amount and

complexity following the growth of industry and improvement of our living status. Various

Chlorine-based compounds which are used in the widespread industrial sectors have a high

potential to emit some chlorinated volatile organics compounds (CVOC), such as

dichloromethane (CH2Cl2). The Environmental Protection Agency (EPA) Toxic Release

Inventory reports that U.S. industrial discharges of dichloromethane amounted to 29,000

metric tons in 1994 (Keene et al. 1999). This compound has an atmospheric half-life of

several months. Radical-chlorine atoms from CVOC will initiate and participate in ozone-

depleting reactions in the stratosphere (Sanhueza 2001; US EPA 1999; Khalil and Rasmussen

1999). It will create a big environmental problem when the compound is released without any

treatments (Shah and Singh 1988). This situation shows that the rising of released

concentration of CVOC into the environment, together with its suspected toxicity and

carcinogenic, has increased the demand for finding effective methods to reduce it.

The most widely adopted technique for the treatment of chlorinated VOC effluents is thermal

combustion or incineration (Lou and Chang 1997). This method will process influent of

CVOC by direct oxidation reaction with air at high temperature range which is between 800-

1,100oC. The main problem is relating to the incomplete combustion reaction. The reaction

will produce numerous amounts of another complex chlorinated compound (Taylor and

Dellinger 1988).

Catalytic oxidation is a well-known process for treating chloromethane. Unfortunately, the

most active catalyst for the oxidation usually comes from noble and expensive metals, such as

Platinum and Ruthenium, supported by alumina. High temperature process is also required to

3
increase the reaction rate and to overcome chloride poisoning (Alberici and Jardim 1997).

Other limitation of plasma-assisted process is small flow rate of emission input process.

In recent years, many studies have been carried out on the application of new technologies to

destruct the emission of CVOC. Plasma-assisted technology, such as RF plasma (Lee et al.

1996), surface discharge reactors (Oda et al. 2002), dielectric barrier discharge reactors

(Tonkyn et al. 1996), pulsed discharge reactors (Yamamoto et al. 1992), and capillary-tube

type discharge reactors (Kohno et al. 1998), have been developed. Among non-thermal

plasmas, gliding arc plasma has a good energy efficiency conversion. This reason makes

gliding arc plasma a bright prospect to be utilized for industrial chemical reactions (Fridmann

et al. 1999). In this study, gliding arc plasma was used, as an attractive method due to better

production of radical species, higher flow rates, and higher concentration of input material, to

destruct dichloromethane (CH2Cl2). However, destruction of chloromethane, carbon

tetrachloride (CCl4) and chloroform (CHCl3), in gliding arc plasma has been studied

previously (Krawczyk and Ulejczyk 2003a; 2003b). The author reports that high destruction

efficiency can be achieved using this method.

Experimental Setup

Input Gas

Figure 1

A schematic diagram of experimental setup is shown in Figure 1. Liquid CH2Cl2 which was

used as the input material has a 99.0% purity (purchased from the Junsei Chemical Co.). The

carrier gas was atmospheric air and the flow rates were controlled with a Mass Flow

4
Controller (Tylan, FC-280S). The initial gas CH2Cl2 concentration was set as 1, 2, 3, and 4%

by volume. The flow rate of air to the plasma reactor was varied by 180, 240, and 300 L/hr.

Before entering the reactor, atmospheric air first passed through a scrubber and mixed with

CH2Cl2. Liquid CH2Cl2 was introduced by a syringe pump (KD Scientific, Model 100) and a

heater tape rolled covering the input line to vaporize the liquid CH2Cl2 into gas phase before it

was mixed with air. The composition of the outlet stream was analyzed before and after

plasma operation.

Plasma reactor and applied power system

The reactor was made from a quartz-glass tube of an inner diameter of 45 mm and a length of

300 mm. Top and bottom of the reactor are equipped with teflon seals, the lower comprising

two electrodes made of stainless steel, the length of the electrodes being 150 mm. The

distance of the electrodes in the narrowest section is only 1.5 mm. The gas mixture is fed

between the electrodes with a capillary of inner diameter 0.8 mm. A thermocouple, located 10

cm above the electrode, is provided to measure the outlet gas temperature. A high frequency

AC power supply (Auto electric, A1831) is connected to the gliding arc electrode to generate

the plasma. Figure 2 shows the typical waveform of voltage and discharge current used in

these experiments.

Figure 2

Measurement system

The outlet gas composition is examined by an electron-impact ionization quadrupole mass

spectrometer (Balzers, QMS 200) with software Quadstar 421. This software is used for both

5
qualitative and quantitative analysis of the inputs and products. Two GCs are used to analyze

the quantitative amount of products; CH2Cl2, also CHCl3 and CCl4, in the gas mixture before

and after the reaction are determined by GC-FID (YoungLin M600D, Column: Bentone), for

CO and CO2 by GC-TCD (YoungLin M600D, Column: Carbon Sieve).

Chlorine gas (Cl2) is determined by bubbling the reaction gas through 0.05 M aqueous KI for

a given time, followed by iodometric titration with 0.05 M Na2SO3 (Skoog et al. 2000).

To evaluate the performance of system, selectivity and conversion, is used and defined as:

moles of CH 2 Cl 2 consumed
Conversion of CH 2 Cl 2 = × 100% (1)
moles of CH 2 Cl 2 introduced

moles of CO formed
Selectivity of CO = × 100% (2)
moles of CH 2 Cl 2 converted

moles of CO2 formed

Selectivity of CO2 = × 100% (3)
moles of CH 2 Cl 2 converted

moles of CHCl 3 formed

Selectivity of CHCl 3 = × 100% (4)
moles of CH 2 Cl 2 converted

moles of CCl 4 formed

Selectivity of CCl 4 = × 100% (5)
moles of CH 2 Cl 2 converted

moles of Cl 2 formed
Selectivity of Cl 2 = × 100% (6)
moles of CH 2 Cl 2 converted

moles of CO formed + moles of CO2 formed + moles of CHCl 3 formed

Carbon balance =
moles of CH 2 Cl 2 converted

(7)

The supplied power was calculated as a product of voltage and current by oscilloscope

(Agilent 54641A).

6
Results and Discussion

Effect of concentration

Figure 3

CH2Cl2 was carried out at concentration range between 1% and 4% by volume and diluted in

atmospheric pressure air. In this study the experimental data was obtained 30 minutes after the

initiation of the plasma of gliding arc referred to the stable temperature of the bulk gas

measured by thermocouple. Figure 3 shows the effect of CH2Cl2 initial concentrations

variation on its conversion at a fixed power frequency of 20 kHz. Conversion efficiency

gradually decreases when the initial concentration of CH2Cl2 increases. The maximum

conversion reaches 95.1% at 1% of CH2Cl2 concentration and total air flow rate of 180 L/hr.

Based on QMS spectra result (figure 8), the gaseous products are dominated by CO, CHCl3

and Cl2. Small amount of CO2 and CCl4 are also detected. CO2 is detectable when the initial

concentration of CH2Cl2 is higher than 3%. Compared to the yields of CO, the yields of CO 2

was 4-7 times lower than CO yields in the products. In this study, mass balance analysis of C

(carbon) component is calculated based on the total concentration of CO, CO2 and CHCl3.

Table 1

Table 1 shows that more than half of reacted CH2Cl2 is converted into CO and CO2 as the

products of the plasma reaction. High production of CO and CO2 reflects that oxygen, which

exists in the air at concentration of 20%, has a significant role in the decomposition process.

Less than 15% of reacted CH2Cl2 is transformed into other chloromethane products, such as

CHCl3 and CCl4. As shown in table 1, when the initial concentration of CH2Cl2 is increased

7
from 2% to 4%, the reaction selectivity of CO gradually decreases from 58.2% to 50.5% at

total gas flow rate of 180 L/hr and 50.2% to 48% at 240 L/hr. This result indicates that higher

concentration of CH2Cl2 in the plasma reaction reduces the possibility of product to form CO.

However, at lower concentration of CH2Cl2, high-active state oxygen e.g. O (3P and 1D) or O2

(a1∆) enhances reaction with CH2Cl2 and other chlorine-contained compounds rather than at

higher concentration of CH2Cl2. In the presence of atomic oxygen, CH2Cl2 can be removed by

reaction (Fitzsimmons et al. 2000)

O + CH2Cl2  CHCl2 + OH (8)

The production of OH in the system can help the destruction process by

OH + CH2Cl2  CHCl2 + H2O (9)

CO is produced via oxidation of CH2Cl2 (Fitzsimmons et al. 2000; Hosson and Smith 1999;

Ho et al. 1992; Thuner et al. 1999; Bilde et al. 1999).

CH2Cl2  CH2Cl + Cl (10)

CH2Cl + O2  CH2ClO2 (11)

CH2ClO2 + CH2ClO2  2 CH2ClO + O2 (12)

CH2ClO + O2  HCOCl + HO2 (13)

CH2ClO  HCOCl + H (14)

O, Cl + HCOCl  CO + ClO, Cl (15)

Other CO production pathways via secondary OH reaction and third body species are also

proposed (Lou and Chang 1997; Fitzsimmons et al. 2000; Ho et al. 1992).

HCOCl + Cl  COCl + HCl (16)

OH + HCOCl  COCl + H2O (17)

8
COCl  Cl + CO (18)

A different phenomenon is found in chloroform (CHCl3) production. CH2Cl2 transformation

into CHCl3 is higher when initial concentration of CH2Cl2 is increased. Following references

(Hosson and Smith 1999; Ho et al. 1992; Thuner et al. 1999; Bilde et al. 1999), CHCl 3

production is dependent on the presence amount of Cl and CHCl2.

CHCl2 + Cl  CHCl3 (19)

Mostly, the source of Cl is obtained from unimolecular dissociation of CH2Cl2

CH2Cl2  CH2Cl + Cl (20)

Increasing the initial CH2Cl2 concentration in the input stream will produce higher amount of

atomic Cl. Cl will easily collide with intermediate species CHCl2, produced by reaction 8 and

9, to form stable gases such as CHCl3.

The ratio between total C (carbon) atom from gaseous products e.g. CO, CO 2, CHCl3, CCl4

and total C atom from reacted CH2Cl2 has a range between 0.5 and 0.75. It suggests that the

major end products of plasma processing of CH2Cl2 diluted in atmospheric air will be CO,

CO2, CHCl3, and CCl4. The remaining C possibly goes to the solid (shoot) or liquid

production which is also produced during experiment.

However, in term of energy consumption, higher initial concentration of CH2Cl2 increases the

energy consumption of plasma process, around 5-10 Watt for every 1% increase in the

concentration of CH2Cl2. Increasing amount of CH2Cl2 has a significant effect on alteration of

voltage and current waveform which effects on power consumption. In the presence of

CH2Cl2 molecule, gliding plasma spends more energy to destruct or break the chemical bond

of CH2Cl2 to achieve a plasma state. Increasing concentration of CH2Cl2 also has a significant

influence on the increment of gas temperature. A stable temperature is achieved after the

9
gliding plasma system is on for 30 min. Compared with a pure-air gliding arc, the gas

temperature increases by 5-25oC when the inlet stream contains CH2Cl2. It shows that the

destruction of CH2Cl2 is an exothermic reaction that releases heat to the surrounding

environment. The rising amount of destructed CH2Cl2 will produce more heat from the

destruction reaction.

Effect of total gas flow rate

Figure 4

The effect of total gas flow rate, which is related to the residence time of CH2Cl2 in the

reactor, was also examined. Figure 4 shows the CH2Cl2 conversion vs. total gas flow rates at

frequency of 20 kHz. The conversion of CH2Cl2 decreases when the total gas flow rate is

increased. Increasing total gas flow rate reduces the residence time of CH2Cl2 in the reactor

and hence the chance and time of CH2Cl2 to collide with electrons or other high-energy state

atoms or molecules.

Figure 5

Figure 5 clearly shows that the selectivity CO and CO 2 decreases with the increasing value of

total gas flow rate. Following above explanation, increasing total gas flow rate reduces the

chance of collision reaction between of CH2Cl2 and high-energy state species as well as

oxygen (atom or molecule). However, the carbon balance is also decreased with increasing

total gas flow rate.

10
Effect of applied frequency

Figure 6

Figure 7

Figure 6 shows the effect of various applied frequency of input power on the CH 2Cl2

destruction at 2% of CH2Cl2 concentration and the total gas flow rate of 180 L/min. The

removal efficiency decreases from 90% to 55% when the applied frequency is decreased from

20 kHz to 15 kHz. Decreasing applied frequency decreases the supplied energy to the reactor,

i.e., the energy source used to dissociate the molecule of CH2Cl2. Figure 7 shows that reaction

selectivity of CO relatively increased when the applied frequency was also increased. On the

other hand, the selectivity of CHCl3 is decreased. Increasing frequency linearly correlates with

increasing numbers of radical and high-active oxygen that come out from atmospheric air, and

tends to produce CO and CO2 as the gaseous end-product. This is the possible reason why the

selectivity of CO and CO2 increases with the applied frequency.

QMS spectra

Figure 8

QMS spectrum of the conversion of CH2Cl2 is shown in figure 8. Figure 8 (top) shows the

peak components in the input stream. The baseline spectra of CH2Cl2 are m/z 83(CCl2+) and

85(CH2Cl2+) and this spectra was also owned by CHCl3. To distinguish between CH2Cl2 and

CHCl3, we used a FID-GC as the analysis method. When the plasma is on, as shown in Figure

8 (bottom), peak intensity of m/z 83 and 85 are decreased and some new peaks appear, e.g.

m/z 61(COCl+), 71(Cl2+), and 118(CHCl3+). It is evident that COCl exists in the product

11
stream because COCl has an important role in CO production as an intermediate species.

Conclusion

The performance of CH2Cl2 conversion in gliding arc plasma at atmospheric pressure was

studied. Gliding plasma shows a good performance on the destruction of CH2Cl2 molecules.

The maximum conversion of CH2Cl2 was 95.1% for feed gas stream containing 1% of CH2Cl2

and air flow rate of 180 L/hr. The effect of the initial concentrations of CH2Cl2, gas flow rates,

and input power frequencies were also experimentally investigated. Destruction of CH2Cl2 in

gliding plasma environment occurred in an exothermic reaction. CO, CO2, Cl2 and CHCl3 are

the major product with small amount of CCl4. CO and CO2 selectivity achieved ~50% in all

range of experimental condition. Transformation into other chloromethane compounds

included a maximum of 15% for CHCl3 and 7% for CCl4. It is concluded that gliding arc

plasma is adequate for CH2Cl2 reduction.

Acknowledgements

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

Minister of Science and Technology.

References

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titanium dioxide, Appl. Catal. B: Environ., 14: 55.
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12
 Dichloromethane Destruction in Atmospheric-Pressure Gas Streams by a Dielectric Packed-Bed
Plasma Reactor. J. Phys. Chem. A, 104: 6032.
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(HClC=CCl2), and Tetrachloroethene (Cl2C=CCl2). J. Phys. Chem. A, 103: 2031.
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decomposition of 1,1-C2H2Cl2 contained gas in an RF plasma reactor. J. Hazardous Mat., 48: 51.
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Ramacher, B. 1999. Atmospheric Chemistry of Tetrachloroethene (Cl2C=CCl2): Products of
Chlorine Atom Initiated Oxidation. J. Phys. Chem. A, 103: 8657.
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13
U.S. Environmental Protection Agency (EPA). 1999. Greenhouse gases and global warming potential
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v e n t to
a tm o s p h e re

F ID G C TCD GC M ass
C o lu m n : C o lu m n : S p e c tro -
B e n to n S ie v e m e te r
C arb o n

M FC P la s m a
S cru b b e r R e a c to r
A t m o s p h e r ic
a ir

H e a te r ta p e
S y r in g p u m p

Figure 1. Schematic of experimental set up.

14
 6000

4000

2000
Voltage (V)

-2000

-4000

-6000

0.4 -2e-5 -1e-5 0 1e-5 2e-5

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 of the applied electric power input.

15
 100

90

80
Conversion (%)

70

60

180 L/hr
50 240 L/hr
300 L/hr

40
0.5 1 1.5 2 2.5 3 3.5 4 4.5

CH2Cl2 concentration (%)

Figure 3. Effect of initial CH2Cl2 concentration on CH2Cl2 conversion

(obtained at frequency of 20 kHz).

16
concentration flowrate selectivity (%)
(% v/ v) (L/ hr) CO+CO2 CHCl3 CCl4 HCl Cl2
2 180 58.23 4.45 2.17 2.55 12.84
3 180 55.82 11.02 0.00 6.94 12.15
4 180 50.52 14.92 6.66 11.43 15.68
2 240 50.20 3.95 2.76 1.04 12.51
3 240 56.67 6.24 4.82 3.68 8.24
4 240 48.01 8.39 1.35 7.73 10.76

Table 1. Effect of initial CH2Cl2 concentration on product selectivity

17
 100

90

80
Conversion (%)

70

60

1%
2%
50
3%
4%
40
150 170 190 210 230 250 270 290 310

Total Gas Flow Rate (L/hr)

Figure 4. Effect of total gas flow rate on CH2Cl2 conversion

(obtained at frequency of 20 kHz).

18
 CO and CO2 selectivity

60
Selectivity (%)

45

30

2%
3%
4%
15

0
Carbon balance

0.75
Carbon balance

0.60

0.45

2%
3%
0.30 4%

0.00
160 180 200 220 240 260 280 300 320

Total gas flow rate (L/hr)

Figure 5. Effect of total gas flow rate on CO2 and carbon balance.

19
 100

80

60
Conversion (%)

40

20

0
14 15 16 17 18 19 20 21

Frequency (kHz)

Figure 6. Effect of applied input power frequency on CH2Cl2 conversion

(obtained at the initial CH2Cl2 concentration of 2% and the total gas flow rate of 180 L/hr).

20
 (CO+CO2) and CHCl3 selectivity 70
20

(CO+CO2) selectivity (%)

60
CHCl3 selectivity (%)

15 50

40
10
30

CHCl3 selectivity
5 (CO+CO2) selectivity 20

0 0
0.8
Carbon balance

0.6
Carbon balance

0.4

0.2

0.0
0 14 15 16 17 18 19 20 21
Frequency (kHz)

Figure 7. Effect of applied input power frequency on (CO+CO2) and CHCl3 selectivity and

carbon balance.

21
 5e-10
before

4e-10

3e-10
Intensity

2e-10

1e-10

CH2Cl2, CHCl3

5e-10 after

4e-10
Intensity

3e-10

2e-10

1e-10
CO2
Cl2
CCl4
0
0 10 20 30 40 50 60 70 80 90 100 110 120 130 140 150

AMU (m/z)

Fig 8. QMS spectra of CH2Cl2 decomposition

(obtained at the initial CH2Cl2 concentration of 2% and the total gas flow rate of 180 L/hr)

22