CCl4 Decomposition by Gliding Arc Plasma:

Role of C2 compounds on products distribution

Antonius Indarto†, Jae-Wook Choi, Hwaung Lee, and Hyung Keun Song

Clean Technology Research Center, Korea Institute of Science & Technology

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

†
Correspondence address: e-mail: indarto_antonius@[Link], [Link]

1
Abstract- The goal of this work is to investigate the role of existing C2 compounds in

the plasma reactions of carbon tetrachloride (CCl4) decomposition. Decomposition of

CCl4 was experimentally done using gliding arc plasma. The decomposition products

were dominated by CO, CO2, and Cl2. The conversion of CCl4 into Cl2 and (CO+CO2)

reaches ~50% and ~40%, respectively. Other chlorinated compounds are suspected to be

produced, such as COCl, COCl2, and C2 compounds. In order to prove the existence of

those compounds, such us chlorinated C2 compounds, a kinetic simulation was

performed and crossed check with the experimental results to satisfy the reactions

mechanism.

Keywords: Plasma; Gliding Arc; CCl4 decomposition; Reaction mechanism.

2
INTRODUCTION

Emissions of chlorinated volatile organic compounds (CVOCs) from various industries,

such as carbon tetrachloride (CCl4), create environmental problems (Butler, 2000; Shah

and Singh, 1988). Chemical degradation of CVOCs in our atmosphere will produce

toxic chloride compounds, e.g. HCl, and HCl is classified as the main component of

acid rain (Sanhueza 2001). Some studies report that CCl4 will produce very-active

chlorine radicals by solar radiation reaction. These species will react and destruct ozone

molecules in the stratosphere (Butler, 2000; US-EPA, 2002). Moreover, the most severe

problem of the emission of CCl4 is caused by the high toxicity as well as the

carcinogenic of those to the human health (IARC, 1987). Those can be the reason for

increasing demand to find effective methods in reducing the emission of CVOC.

The most widely adopted technique for the treatment of CVOCs was thermal

combustion or incineration (Lou and Chang, 1997). The decomposition process is done

by direct thermal reaction with oxidant, e.g. air. Although this method is simple, it

requires high temperature conditions which usually in the range of 800 to 1,100 ℃ to

achieve the optimum decomposition percentage. Taylor’s paper reports that incomplete

combustion condition will make the reaction tend to produce a large amount of complex

chlorinated products (Taylor and Dellinger, 1988).

To overcome these problems, many studies are carried out on the application of new

technologies. Plasma-assisted technology is one of the promising technologies to

decompose CVOCs. Low thermal plasma processes, such as RF plasma (Lee et al.,

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

3
(Tonkyn et al., 1996), pulsed discharge reactor (Yamamoto et al., 1992), and capillary-

tube type discharge reactor (Kohno et al., 1998) have been investigated and developed.

In this study, gliding arc plasma was used to decompose the carbon tetrachloride.

Compared to the previous plasmas, gliding arc plasma has great chance to be utilized

for industrial chemical reactions because of some advantages (Fridman et al., 1999).

Gliding arc plasma can achieve higher flame temperature and power which are very

useful to destruct the chemical bond of toxic compounds than other plasmas, such as

corona, DBD, etc. In addition, gliding arc can be applied in higher input flow rate.

Kinetic reaction models of CCl4 decomposition in dry air using electron beam have been

investigated (Penetrante et al., 1995; Koch et al., 1995; Nichipor et al., 2000). The

models suggest that the main products will be dominated by chlorinated C1 compounds,

such as: COCl2, CO, CO2, ClNO3, ClO3, and Cl2. Fragmentation of CCl4 will be

occurred by two mechanisms (Penetrante et al., 1995). In the oxygen-rich condition, the

dissociated species of oxygen, such as ground state of atomic oxygen O( 3P) and excited

atomic oxygen O(1D) have enough energy level to destruct the bonds of CCl4.

O( 3 P ) + CCl 4 ⇒ ClO + CCl 3 (1)

O( 1D) + CCl 4 ⇒ CCl 3 + ClO2 (2)

The second mechanism is via secondary electron reaction. Secondary electrons will

dissociate CCl4 into CCl3 and negative chlorine ion (Cl‾),

e + CCl 4 ⇒ CCl 3 + Cl − (3)

Radical ClO and CCl3 are suspected to be the most important intermediate species in

4
determination of the final products of the CCl4 decomposition. The concentration of O

and Cl in the system can also influence the radical reactions, both initiation and

termination reactions.

Nichipor’s (2000) investigation shows that CO, Cl2 and CO2 are formed by dissociation

process between electron and COCl2:

e + COCl 2 ⇒ CO + Cl 2 k = 10-7 cm3/mol (4)

and CO will be oxidized by ClO to produce CO2:

CO + ClO ⇒ CO 2 + Cl (5)

However, less paper discussed about the importance of chlorinated C2 in the

decomposition reaction of CCl4. In this study, we are investigating the role of

chlorinated C2 compounds on the reactions mechanism and products selectivity,

especially CO, CO2, and Cl2. Two different schemes of reaction mechanisms have been

used and compared with experimental results. Some reaction mechanisms taken from

microwave plasma and combustion process were used to approach the real system of

gliding arc plasma. The simulation results were compared to the experimental ones to

satisfy the kinetic models.

EXPERIMENTAL SETUP

Figure 1

5
The schematic diagram of experimental setup is shown in Figure 1. Carbon tetrachloride

and air were used as the source gases. Details of each parts of the system are described

below.

The reactor was made from a quartz tube with inner diameter of 45 mm and length of

300 mm. The upper and bottom part of the reactor were sealed with teflon and two

electrodes was set up inside the reactor. The electrode made from stainless steel has a

triangular form with the height of 100 mm. The shortest gap between two electrodes

was only 1.5 mm. The gas was introduced between the electrodes through a capillary

tube with inner diameter of 0.8 mm. A thermocouple, located 10 cm above the

electrode, was installed to measure the outlet gas temperature.

A high frequency AC power supply (Auto electric A1831, Korea) was connected to the

gliding arc electrodes to generate plasmas. Figure 2 shows the typical waveform of

voltage and current.

Figure 2

Liquid carbon tetrachloride (CCl4) was purchased from Kanto Chemical Co., Inc. The

purity was more than 99.5%. The concentration of CCl4 in the input gas was varied

followed 1, 3, 5, 8 vol% of total flow rate. Atmospheric pressure air was used as a

carrier gas and controlled by a Mass Flow Controller (Tylan FC-280S, U.S.). The flow

rates of air were 180, 240, and 300 L/hr. CCl4 was introduced to the reactor by passing a

portion of air through a bubbling tube of liquid CCl 4, which was immersed in a water

bath. Concentration of CCl4 was adjusted by controlling both temperature of water bath

6
and injected gas flow rate to the bubbling tube. The feed line stream was covered by

heating band to avoid the condensation of CCl4 vapor.

Mass spectroscopy and two Gas Chromatographers (GCs) were used for the qualitative

and quantitative analysis of the reactants and products. The concentrations of CCl4 in

the gas mixture before and after the reaction was determined by GC-FID (YoungLin

M600D, Column: Bentone, Korea) and the concentrations of CO and CO2 were

measured by GC-TCD (YoungLin M600D, Column: SK Carbon, Korea). Analysis of

species of the decomposition products was done by quadruple mass spectroscopy

(Balzers QMS 200, U.S.) with Quadstar 421 software. Chlorine gas (Cl2) was

determined by bubbling the output gas through 0.05 M of aqueous KI during measured-

experiment time and followed by iodometric titration 0.05 M of Na 2SO3 (Skoog et al.,

2000).

Selectivity of products and conversion of CCl4 were defined as:

moles of Cl 2 formed
Selectivity of Cl 2 = × 100% (6)
2 × moles of CCl 4 converted

moles of CO formed
Selectivity of CO = × 100%
moles of CCl 4 converted (7)

moles of CO2 formed

Selectivity of CO2 = × 100% (8)
moles of CCl 4 converted

moles of CCl 4 consumed

Conversion of CCl 4 = × 100% (9)
moles of CCl 4 introduced

moles of Cl 2 formed
Cl 2 / (CO + CO2 ) ratio = (10)
moles of CO formed + moles of CO2 formed

7
The consumed power for the process was calculated as the products of voltage and

current waveform captured by oscilloscope (Agilent 54641A, U.S.). In this experiment,

we limit the consumed power from 286 to 304 Watt. Sample data was taken after 30

minutes operation referring to the stable temperature condition of output line measured

by thermocouple.

KINETIC STUDY AND MODEL

Figure 3

Table 1

To investigate the reactions mechanism, a chemical kinetic reaction model of CCl4

decomposition has been constructed. The gas-phase reaction model consists of the 21

elementary reactions which are proposed by literatures as the most significant pathway

of reactions (Lou and Chang, 1997; Chang and Senkan, 1989; NASA, 1994; Penetrante

et al., 1995, Koch et al., 1995, Nichipor et al., 2000). The rate constant of each reactions

is expressed in a modified Arrhenius form,

βj  Ej 
k j = A jT exp − 
(11)
 RT 

The simulation was focused on the reactions of Cl2, CO, CO2 and chlorinated C1

production. Other products, such as chlorinated C2, were considered as intermediate

species caused the concentrations of those components in the product line was small.

8
Table 1 shows list of elementary chemical reactions of CCl4 decomposition.

The model was coded in MATLAB program and numerically solved using shooting

method (Walas, 1991; Chapra and Canale, 1990). The algorithm of the program is

shown in Figure 3a. MATLAB modules of ode23s and fmins were utilized to solve the

15 sets (15 species) of differential equation (shown in formula 12 and 13) and minimize

the absolute error, respectively (MathWorks, 1992).

= ∑ f j ( k j , xi (t ),..., x n (t ) )
dxi m

dt j =1
(12)

xi (t 0 ) = xiinput ; xi (t ) = xiproduct (13)

The concentration of Cl2 in the products was used as the basis of calculation (boundary

condition) to calculate the concentration ratio of Cl2 to (CO+CO2) and converted CCl4.

To check the validity of model, the simulation and experimental results were compared

for each points and the absolute error was calculated as:

{ (
∆ ε = abs xClsim2 − xClproduct
2
)
+ abs x (sim ( ) (
CO + CO2 ) − x ( CO + CO2 ) + abs x CCl 4 − xCCl 4
product sim product
)} 2
(14)

The model stiffness was checked by varying input guess. Figure 3b shows that the

model produces an almost similar absolute error although the input guess is varied from

3.9 to 6.5.

RESULTS AND DISCUSSION

9
CCl4 conversion

Figure 4

Figure 4a shows the effect of initial concentration of CCl4 on the conversion at

frequency of 20 kHz. Conversion decreases gradually when the initial concentration of

CCl4 is increased. The maximum conversion reaches 80% at the concentration of 1

vol% and flow rate of 180 L/hr. Increasing concentration of CCl 4 will decrease the ratio

of the high-energy energetic species (e.g. electron and radical atoms/molecules) to CCl4.

At the same flow rate and supplied energy, the amount of high-energy energetic species,

both quality and quantity, can be assumed to be same. This will reduce the chance of

CCl4 to collide with those species which able to destruct the C-Cl molecule bonds.

However, although the collision probabilities are lower, the effectiveness of absolute

collision at higher initial concentration of CCl4 is higher that that at lower concentration

of CCl4. For example, at 1% and 3 % of CCl4 concentration, it can be calculated as 1

(percentage) x 80 (% of conversion) and 3 x 73, respectively. This will lead to the ratio

of 80:219 which shows that the process at 3% of CCl 4 concentration produces 219/80

times more effective in destructing CCl4 molecules than that at 1% of CCl4

concentration.

Analysis of QMS spectrum (Figure 8) shows that the main gaseous products are CO,

CO2, and Cl2. It also shows that the concentration of other chlorinated compounds is

relatively small.

10
CO+CO2 selectivity

Increasing initial concentration of CCl4 will affect on reducing the selectivity of

CO+CO2. As shown in Figure 4b, the selectivity of CO+CO2 decreases around 2 %

when the concentration of CCl4 is increased from 1% to 8%. Our kinetic simulation

calculates that higher initial concentration of CCl4 produces higher amounts of single

chlorine species (Cl) in the reactor by (Chang 1989):

CCl 4 = CCl 3 + Cl (15)

CCl 3 + O = COCl 2 + Cl (16)

This species will compete with oxygen (O) to have reactions with carbon (C). Higher

concentration of Cl makes the probability of C and O reaction to produce CO becomes

smaller.

Kinetic reaction studies of CO, CO2, and Cl2 formation in thermal oxidation show the

similar reaction mechanisms as proposed by literatures (Chang and Senkan, 1989; Lou

and Chang, 1997). The major pathways responsible for the formation of CO2 are:

COCl + Cl = CO + Cl 2 (17)

COCl + M = CO + Cl + M (18)

CO2 is mainly generated from the reaction of CO and ClO:

11
CO + ClO = CO2 + Cl (19)

where ClO was formed via:

CCl 4 + O = CCl 3 + ClO (20)

CCl 3 + O2 = COCl 2 + ClO (21)

Koch et al. (1995) also reported the similar radical mechanism, as mentioned above, in

the electron beam system for CCl4 decomposition when the O2 was existed.

However, formula 19 is not counted as the main mechanism for Cl production because

the concentration of CO2 in the product stream was relatively low. The concentration of

CO2 was 5-10 times lower than CO in all of experimental ranges.

The importance of oxygen atom (O) and oxygen radical (O⋅) in the reaction kinetic has

been rigorously investigated (Davidson et al., 1978). Both O and O⋅ can be produced

from dissociation reactions (Penetrante et al., 1995):

e + O 2 ⇒ e + O( 3 P ) + O ( 3 P ) (22)

e +O 2 ⇒ e + O ( 3 P ) + O ( 1 D ) (23)

In our experiments, the concentration of oxygen in the reactor was around ~20% as we

used atmospheric air as the dilution gas for CCl 4. QMS spectrum analysis shows that in

plasma condition, the peak intensity of O2 in product stream was slightly lower than that

in feed stream. The magnitude of decreasing peak intensity caused by plasma was not

12
change when the initial concentration of CCl4 was varied. It means the concentration of

excited oxygen species can be assumed same at the same power and flow rate. And

following the above statement, increasing CCl4 in the feed stream will increase the

intermediate species Cl which can be a competitor for O to collide with C. This can be

the reason why the selectivity of (CO+CO2) decreases when the initial concentration of

CCl4 is increased.

Cl2 selectivity

Opposite with the trend of (CO+CO2) selectivity, the selectivity of Cl2 shows increased

when the initial concentration of CCl4 is increased (Figure 4c). Intermediate Cl species

has an important role in the termination reactions to produce Cl 2 as the final product of

the decomposition reactions.

The major pathways of Cl2 formation can be:

COCl 2 + Cl = COCl + Cl 2 (24)

COCl + Cl = CO + Cl 2 (25)

Higher initial CCl4 concentration will give a tendency to produce more Cl species in the

plasma reactor. However, above reaction mechanisms only show the chlorinated C1

compounds as the main intermediate species in the production of CO, CO2, and Cl2.

13
Simulation of Cl2, CO, and CO2

Figure 6

Figure 7

To investigate the role of chlorinated C2 compounds in the decomposition reaction

CCl4, especially in CO, CO2, and Cl2 production, we constructed two types of kinetic

reactions from table 1. The first scenario considers the formula (17) – (19) and (24) –

(25) as the main reaction pathways to produce CO, CO 2, and Cl2 and neglects the

production of those compounds from chlorinated C2 compounds, such as C2H4, C2H5,

and C2H6 (Figure 4a). This reaction pathway is chose to examine the dependence of Cl2,

CO, and CO2 production on the literature proposed formulas, e.g. formula (17) - (19)

and (24) – (25). The second scenario will calculate the existence and the contribution of

higher carbon-chloride compounds in the decomposition reactions (Figure 4b).

Figure 6 shows the comparison between simulation and experimental results. The

second scenario shows the result of simulation closer to the experiment result compared

to the first scenario. The first scenario of the model results a high different value

compared with experimental results which is around 8-50%. It is higher than the second

one which is only 2-10%. In our model calculation, neglecting the existence of

chlorinated C2 compounds in the reactions mechanism of CO, CO2, and Cl2 production

will produce lower selectivity of chlorine gas (Cl2) and higher selectivity of CO and

CO2 than the experimental results.

14
Direct conversion of chlorinated C2 compounds to Cl2 could be counted as a significant

pathway of Cl2 production. Lou and Chang (1997) also identified the production of Cl 2

from chlorinated C2 compounds, e.g. C2Cl5.

C 2 Cl 5 + Cl = CCl 3 + CCl 3 (26)

On the other hand, the existence of chlorinated C2 compounds will reduce the

selectivity of CO and CO2. Instead of oxidation reaction, intermediate species, e.g. CCl3,

has a chance to have a couple-reaction to form chlorinated C2 compounds

CCl 3 + CCl 3 = C 2 Cl 6 (27)

CCl 3 + CCl 3 = C 2 Cl 4 + Cl 2 (28)

Although the first scenario does not match exactly with experimental results, but still, it

can summarized that formula (17) – (19) have an important role on the production of

CO, and CO2 and formula (24) – (25) on Cl2 production. Calculation of first scenario

model shows that formula (17) – (19) and (24) - (25) can enhance more than 50% of the

production of CO, CO2, and Cl2, respectively. The existence of COCl2 which is obtained

using our QMS, shown in figure 8b, can be the evidence for this case. COCl 2 is one of

the most important intermediate species in Cl2 production (formula 24). Figure 7 shows

the main routes of Cl2, CO, and CO2 formation from CCl4 decomposition by gliding arc

plasma.

QMS spectra

15
 Figure 8

QMS spectra of CCl4 decomposition diluted in atmospheric arc by gliding arc plasma

are shown in Figure 8. Figure 8a shows the compounds spectrum of 1 vol% of CCl4

diluted in 180 L/hr of atmospheric air. The main spectrums of CCl4 are m/z 83/85 (

CCl 2+ ) and m/z 117 ( CCl 3+ ). CO2 has its molecular ion at 44 ( CO2+ ). CO molecular ion

+ +
spectrum is colliding with minor N2 at m/z 29 ( CO / N 2 ). The main N2 is at m/z 28 (
N 2+ ). However, due to small concentration of CO in the atmospheric air, CO compound

can be neglected in this spectrum line.

The spectrum of the products of CCl4 decomposition is shown in Figure 8b. The peak

intensity of m/z 83/85 is decreased as well as intensity of m/z 117 and a new spectrum
+
of Cl2 is appeared at m/z 71 ( Cl 2 ). Intensity of CO2 increases but the difference

between before and after plasma condition is slightly small. High magnification of

spectrum intensity is occurred at m/z 29 of N2 and CO. Because N2 is classified as a

stable compound and no available source of nitrogen (N) in this system to produce N2, it

can be sure that the increment intensity of m/z 29 is caused by production of CO. At

high initial concentration of CCl4, spectrogram of products produces a new spectrum at

+
m/z 63 ( CClO ). Based on QMS library, it can be suspected to be COCl or COCl 2.

Good evidence that COCl and COCl2 which have a significant role especially to the

16
production of CO, CO2, and Cl2 existed in the reaction mechanisms. Another

intermediate species that possibly exists is CCl2 at m/z 84 (CCl+).

CONCLUSION

The decomposition of CCl4 in gliding arc plasma as well as kinetic study was

experimentally investigated. The maximum conversion of CCl4 is 80% at 1 vol% of

CCl4 and total flow rate of 180 L/hr. CO, CO2, and Cl2 are identified as the main

products of the decomposition process. CCl3, COCl2, and COCl play an important role

as intermediate species on CO, CO2 and Cl2 production. The existence of chlorinated C2

compounds should be counted also as the source of Cl 2 production in the final products.

However, formation of chlorinated C2 compounds can reduce the selectivity of CO and

CO2 caused by coupling reactions of intermediate species, e.g. CCl3.

ACKNOWLEDGEMENTS

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

Minister of Science and Technology.

17
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 air under the influence of an electron beam.” Rad. -Phys. Chem., 57, 519-525.
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19
 v e n t to
a tm o s p h e r e

F ID G C
B e n to n e

MFC- 1
TC D G C
S K C a rb o n

C o m p re s s e d Q u a d ra p o le
a ir M ass
S p e c t ro m e te r

MFC- 2

C C l4
w a t e rb a th
K I s o l u t io n

P la s m a
R e a c to r

Figure 1. Schematic diagram of experimental set up

20
 6000

4000

2000
Voltage (V)
0

-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

Cycle of time (s)

Figure 2. Voltage and current profile

21
 S ta r t

G uess:
C l 2 s e le c t i v i t y

S e t c o n s ta n t:
r e a c t io n f o r m u la

new guess
C a lc u la t e :
C C l4 c o n v e r s io n ,
( C O + C O 2 ) s e le c t i v i t y

s o lv e t h e c o u le d O D E s
A b s o lu t e E r r o r :
( C l2 ) e x p . - ( C l2 ) s im .
( C O + C O 2 ) e x p . - ( C O + C O 2 ) s im .
( C C l4 ) e x p . - ( C C l4 ) s im .

u n s a tis f a c to ry
R e s u lt :
( C C l4 ) s im .
( C O + C O 2 ) s im .

End

1.8

3.9
1.6
4.55
1.4
4.55
1.2 5.85
6.5
1
rε

0.8

0.6

0.4

0.2

0
0 5 10 15 20 25 30 35 40

Number of iteration steps

Figure 3. (a) The algorithm of simulation;

22
(b) Error sensitivity of model as function of input guesses variation

23
 r5
CCl4 r 8,r9 CCl3
r1
r3
r9 r4
r13

r14
ClO COCl2 r5
Cl2
r10 r14 r11

CO2 r 10 CO r11 ,r12 ,r13 COCl

(a)

r1 r7
r17
r5
C C l4 r 8,r9 C C l3 r6 C 2C l6 r 20 ,r 21 C 2 C l5
r3 r19 r19
r9 r4 r21 r18 r16
r13 r1
r18
r14
C lO C O C l2 r5
C l2 C 2 C l4
r2
r10 r14 r11 r15

CO 2 r10 CO r11,r12,r 13 CO Cl r2
r2
C C l2
(b)

Figure 4. Model scenario of CCl4 decomposition;

(a) first scenario (b) second scenario

24
 100

90

80

70
Conversion (%)

60

50

40

30

20 180 L/min
240 L/min
10
300 L/min

0
0 1 2 3 4 5 6 7 8 9

CCl4 concentration (%)

(a)

100

90 180 N/min (exp.)

240 L/min (exp.)
80
300 L/min (exp.)
(CO+CO2) selectivity (%)

70 simulation

60

50

40

30

20

10

0
0 1 2 3 4 5 6 7 8 9

CCl4 concentration (%)

(b)

25
 100

90

80

70
Cl2 selectivity (%)

60

50

40

30
180 L/min (exp.)
20 240 L/min (exp.)
300 L/min (exp.)
10
simulation

0
0 1 2 3 4 5 6 7 8 9

CCl4 concentration (%)

(c)

Figure 5. Effects of initial CCl4 concentration on (a) CCl4 conversion,

(b) (CO + CO2) selectivity and (c) Cl2 selectivity

26
 100

Simulation Cl2, CO,CO2 selectivity (%)

80

60

40

180 Nl/hr1
180 Nl/hr2
20 240 Nl/hr1
240 Nl/hr2
300 Nl/hr1
300 Nl/hr2

0
0 20 40 60 80 100
Experimental Cl2, CO, CO2 selectivity (%)

Note: 1first model scenario, 2second scenario

Figure 6. Parity plot of products selectivity comparison between calculation and

experimental results.

27
 C C l4 e
C C l3

O O

C C l3 Cl C O C l2

O 2
Cl
C lO
Cl CO Cl
CO CO
CO 2 C l2

Figure 7. Main routes of CO, CO2 and Cl2 production from CCl4 decomposition

28
 1.4e-9 (a) 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 (b) after

1.2e-9
CO and N2 COCl, COCl2
1.0e-9
Intensity

8.0e-10
0 20 40 60 80 100 120

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)

Note: - obtained at 1 vol% of CCl4 and total gas flow rate of 180 L/h

Figure 8. QMS spectra of CCl4 decomposition; (a) input stream (b) products stream

29
Table 1. Chemical kinetic for decomposition of CCl4

reaction1 log A n E ∆Hr(298 K)

1. CCl 2 + Cl 2 = CCl 3 + Cl 12.70 0 3.0 -7.8

2. CCl 2 + O2 = ClO + COCl 13.00 0 1.0 -37.1

3. CCl 3 + O = COCl 2 + Cl (*) 14.00 0 0 -102.8

4. CCl 3 + O2 = COCl 2 + ClO (*) 13.00 0 28.0 -47.7

5. CCl 3 + Cl 2 = CCl 4 + Cl 12.40 0 6.0 -11.4

6. CCl 3 + CCl 3 = C 2 Cl 6 36.15 -7.48 6.7 -67.5

7. CCl 3 + CCl 3 = C 2 Cl 4 + Cl 2 26.35 -4.43 9.0 -40.7

8. CCl 4 = CCl 3 + Cl (*) 35.87 -6.52 75.4 70.8

9. CCl 4 + O = CCl 3 + ClO (*) 10.40 0 2.3 5.0

10. CO + ClO = CO2 + Cl 11.78 0 7.4 -62.2

30
 11. COCl + Cl = CO + Cl 2 (*) 13.10 0.5 0.5 -52.4

12. COCl + M = CO + Cl + M (*)

14.30 0 6.5 7.1

13. COCl + O = CO + ClO 14.00 0 0 -58.7

14. COCl 2 + Cl = COCl + Cl 2 (*) 13.50 0.5 20 18.5

15. C 2 Cl 4 + O = COCl 2 + CCl 2 13.00 0 5.0 -54.3

16. C 2 Cl 4 + Cl = C 2 Cl 5 35.42 -7.71 5.3 -17.8

17. C 2 Cl 5 + Cl = CCl 3 + CCl 3 27.23 -4.01 12.1 -1.0

18. C 2 Cl 5 + Cl = C 2 Cl 4 + Cl 2 27.10 -4.73 8.9 -41.7

19. C 2 Cl 6 = Cl 2 + C 2 Cl 4 35.21 -6.53 63.2 26.8

20. C 2 Cl 6 = Cl + C 2 Cl 5 36.13 -6.48 74.4 68.5

21. C 2 Cl 6 + Cl = Cl 2 + C 2 Cl 5 13.80 0 18.3 9.0

Note: 1 k = AT n exp(− E / RT ) , in cm, kcal, s, and mole units.

(*)
most significant reactions in this experiment.

31