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CHAPTER NO.

Kinetics Of Wet Air


Oxidation Of MDEA

Kinetics Of Wet Air Oxidation Of MDEA

9. Kinetics of MDEA Wet Oxidation


9.1 Introduction
Since knowledge on reaction mechanism and kinetics is essential for the design and
operation of wastewater treatment units, a kinetic study appears desirable. This investigation
presents a study on the kinetics of the catalytic wet oxidation reaction of MDEA using Ru/TiO 2
catalyst. Kinetic data are being generated over a wide range in temperatures (100 200C), O 2
partial pressures (0.69 1.38 MPa), speed of agitation (300 1000 rpm) and catalyst loading
3

(0.05 0.15 kg/m ). A power-law kinetic model was used for representing TOC decay kinetics.
9.2 Experimental
9.2.1 Materials
MDEA (99% concentration) was purchased from S. D. Fine Chemicals Pvt. Ltd., Mumbai,
India. Materials are required to study reaction kinetics discussed in Section 8.2.1.
9.2.2 Experimental set up
3

All experiments were conducted in a 0.3 dm SS 316 Parr high pressure reactor (Parr
Instruments Company, USA). The setup was equipped with Parr 4842 controller, as described in
Section 4.2.2. The entire assembly was proven to have no leak. A schematic diagram of
experimental setup is shown in Figure 4.1.
9.2.3 Experimental procedure
3

A series of experiments was conducted using a 0.5 kg/m aqueous MDEA solution. In each
3

experiment, the reactor was charged with 0.15 dm of the solution and predetermined amount of
the catalyst. The remaining procedure was the same as that described in section 5.2.4 for the
catalytic wet oxidation of MDEA. The collected samples analysed for TOC contain on TOC
analyzer as explained in section 4.2.4.

9.3 Results and discussion


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Kinetics Of Wet Air Oxidation Of MDEA

Catalytic wet air oxidation is a typical gas-liquid-solid heterogeneous reaction system in


which reactants transport steps takes place as discussed in section 6.3.
9.3.1 Mass transfer considerations
Catalytic wet air oxidation is a heterogeneous gas-liquid-solid catalyzed reaction. The
diffusion of dissolved O2 from the bulk gas phase to a liquid phase and then to catalyst surface
occurs in series. The gas side resistance was deemed to be negligible due to low solubility of
oxygen in water and its high diffusivity in the gas phase. Use of pure O 2 eliminates the gas side
mass transfer limitation. The diffusional resistances associated with transfer of dissolved oxygen
from bulk liquid phase to catalyst surface can be eliminated by changing the extent of turbulence
in the liquid phase. In a slurry reactor, where the catalyst is kept in suspension, the impeller
speed controls the intensity of turbulence.
The effect of speed of agitation on the rate of TOC reduction was studied in the range of 300
rpm to 1000 rpm at an initial MDEA concentration of 500 mg/L ,200 C, 1.38 MPa O 2 partial
3

pressure and a catalyst loading of 0.05 kg/m . It was observed that the rate of TOC reduction
was independent of the speed of agitation above an impeller speed of 900 rpm, thereby
indicating the absence of resistances associated with transfer of O 2 from gas liquid interface to
bulk liquid phase and bulk liquid to solid surface. Fig. 9.1 exhibits the effect of speed of
agitation on TOC reduction. So, all further experiments were carried out at 1000 rpm. The
absence of the intra-particle diffusion resistance was ascertained by using the Weisz-Prater
2

criterion (Eq. 2.10). The parameter was estimated. The gas concentration at the catalyst
2

surface Cs was equal to the oxygen solubility in water. The value of the parameter was far
less than unity for both the reactants. Therefore, the pore diffusional resistance was negligible.
This was expected, due to the small catalyst particle size. Thus, it is seen from above discussion
that under the experimental conditions, all diffusional resistances were eliminated and the system
conformed to the kinetically controlled reaction regime.

9.3.2 Effect of process parameters


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Kinetics Of Wet Air Oxidation Of MDEA


Effect of temperature
Reaction temperature is the important process parameter to study. The effect of temperature was
studied from 100 C to 200 C, at 0.69 MPa oxygen partial pressure, using a catalyst loading of
3

0.05 kg/m . As expected, the TOC reduction rate increased with an increase in temperature. The
% TOC reduction was 46% at 100 C, which increased drastically to 77%. The TOC reduction
was enhanced with increased in temperature.
Effect of oxygen partial pressure
The effect of O2 partial pressure on MDEA wet oxidation was studied over the range of O 2
partial pressure 0.69 to 1.38 MPa at temperature of 200 C, using a catalyst loading of 0.05
3

kg/m . The results are shown in Table 9.1 and a plot of oxygen partial pressure on % TOC
reduction is shown in Figure 9.3. The results indicated that the rate of TOC reduction increased
with an increase in the oxygen partial pressure but at higher pressures the % TOC reduction
remained constant and starting reducing as it leads to formation of nitrate, hence at 0.69 MPa
maximum conversion of TOC was obtained as 77%.
Effect of catalyst concentration
3

Experiments were performed in the range of catalyst loading from 0.05 to 0.15 kg/m at 180 C
and 200C and O2 partial pressure of 0.69 MPa. It was observed that the rate varied linearly with
catalyst concentration. The results are shown in Table 9.2 and a plot of initial rates vs. catalyst
concentration is shown in Figure 9.4. All further experiments were conducted at a catalyst
concentration of 0.05 kg/m

9.4 Kinetics of catalytic wet air oxidation of MDEA


Power law model
The power law model, which expresses the dependence of the reaction rate on the reactant
concentrations, is a simplified model for describing intrinsic kinetics. It is commonly used by
engineers in process design. It is lumped parameter model and can be conveniently used to
ascertain the rate controlling step. In other words, the kinetic rate can be compared with the heat
and mass transfer rates and suitable reactor configuration can be selected (Ramachandran and
Chaudhari, 1993).

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A power-law kinetic model was used for representing oxidation kinetics. TOC removal rates
were represented by the following general correlation:

d (TOC)
dt

(TOC)m (CO2 )n (Catalyst) p

mn

mn

(TOC)m (HO2 PO2 )n (Catalyst) p

(9.1)

Where H O denotes the Henrys constant for O2. Eq. 1 was rewritten as follows:
2

d(TOC)
k
dt

(TOC)m (P )n

(9.2)

O2

Where the rate constant k is given by

kmn

(H
O2

)n ( catalyst )p

kmn = ko exp(-E/RgT)
The effect of catalyst

(9.3)
(9.4)

loading on TOC destruction rates were studied for

MDEA at 180 C, and it was found that, in the range of catalyst concentrations studied, 0.053

0.15 kg/m , the rate varied linearly with concentration (see Figure 9.4). Therefore, the
investigated reaction is of the first order with respect to the catalyst concentration, and the value
of p is unity. If the reaction is of the first order with respect to TOC concentration (m=1), at a
given temperature and O2 partial pressure, eq. 9.2 on integration yields the following correlation:

ln(

TOCi
)kt
TOC

(9.5)

Where the constant k is defined as

k k (P ) n
O

(9.6)

A plot of ln(TOCi /TOC) vs. t for MDEA at 100,120, 180, 200 and 200 C is shown in
Figure 9.5. The plots showed linear nature, at low temperature rate was found to be low which
increased significantly with increase in temperature. The values of k mn and n at various
temperatures and O2 partial pressures were estimated and are shown in Table 9.4. The values of
n vary with temperature, thereby suggesting that the system is complex. From the temperature
dependence kmn the activation energy was found to be 47.63 kJ/mol (see Figure 9.6).

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Kinetics Of Wet Air Oxidation Of MDEA


9.5 Conclusions
1. A power law kinetic model of MDEA wet oxidation was studied.
2. TOC reduction (77%) was obtained at 200 C, 0.69 MPa O2 pressure and
catalyst loading of 0.05 kg/m

3. In CWAO, after 2 h of reaction, the pH of the reaction reduced as the temperature and
catalyst concentration was increased, which ensures the degradation of MDEA into low
molecular weight acids.
The heterogeneous catalyst 5% Ru/TiO2 was found to be an effective catalyst for wet air
oxidation of aqueous MDEA.

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Kinetics Of Wet Air Oxidation Of MDEA


Table 9.1: Effect of O2 partial pressure on TOC reduction during CWO of
MDEA over Ru/TiO2 catalyst
Conditions:
Temperature

2000C
3

Catalyst loading

0.05 kg/m

Reaction time

120 min

Speed of agitation

1000 rpm

Time (min)
O2 partial pressure

%TOC
Reduction

0.69 MPa
0

1.03 MPa
0

1.38 MPa
0

10

20

21

21

20

48

45

44

30

62

60

59

60

66

65

61

90

72

70

65

120

76

74

69

Table 9.2: Effect of catalyst concentration on TOC reduction during CWO of MDEA
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over Ru/TiO2 catalyst
Conditions:
Operating Temperature

180, 200 C

O2 partial pressure

0.69 MPa

Reaction time

120 min

Speed of agitation

1000 rpm

Time (min)
Temperature
Catalyst Loading

% TOC reduction
200 C

0.05
3
kg/m
0

180 C
0.1
3
kg/m
0

0.15
3
kg/m
0

0.05
3
kg/m
0

0.1
3
kg/m
0

0.15
3
kg/m
0

10

16

17

20

20

23

25

20

37

36

38

48

50

52

30

50

54

44

62

64

65

60

62

59

57

66

68

70

90

68

64

66

72

70

74

120

71

69

72

77

75

75

Table 9.3. Values of the reaction rate constant kmn and n at 150, 180 and 200 C
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Temperature (C)

kmn x 10

150

21+0.6

0.672

180

32+1.4

0.762

200

48+2.1

0.831

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% TOC Reduction Vs Time


100
80

% TOC Reduction

60

300 rpm

40

1000 rpm

20
0
0 20 40 60 80 100120
Time (min)

Figure 9.1: Effect of speed of agitation on TOC reduction during CWO over Ru/TiO 2 catalyst,
3

O2 partial pressure 0.69 MPa (100 psi), catalyst loading 0.05 kg/m , reaction time 2 h.,
temperature 200 C)

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Kinetics Of Wet Air Oxidation Of MDEA

% TOC Reduction Vs Time


100
80
60
% TOC Reduction

0.69 MPa
1.03 MPa

40

1.38 MPa

20
0
0

20 40 60 80 100 120
Time (min)

Figure 9.2: Effect of O2 partial pressure on % TOC reduction, Temperature 200 C, speed of
3

agitation 1000 rpm, catalyst loading 0.05 kg/m , reaction time 2 h.)

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Kinetics Of Wet Air Oxidation Of MDEA

1
0.8
0.6
Initial Rate (kg/(m3min)) ( x 1000)

0.4
0.2
0
0

0.05 0.1 0.15 0.2

Catalyst Loading (kg/m3)

Figure 9.3: Effect of catalyst conc. on initial rate during CWO of MDEA over Ru/TiO2, reaction
time 2 h., speed of agitation 1000 rpm, temperature 200 C).

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Kinetics Of Wet Air Oxidation Of MDEA

ln (TOCi/TOC) Vs Time
2
1.5
ln (TOCi/TOC)

100C
150C

180C
200C

0.5
0
0

20

40

60

80

100

120

Time (min)

Figure 9.4: A plot of ln(TOCi /TOC) vs. t at various temperatures during CWO of MDEA in the
presence of Ru/TiO2 catalyst, reaction time 2 h., speed of agitation 1000 rpm, catalyst loading
3

0.05 kg/m , O2 partial pressure 0.69 MPa).

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Kinetics Of Wet Air Oxidation Of MDEA

4.5
4
f(x) = - 3244.13x + 10.69

3.5
3
2.5

lnkmn

2
1.5
1
0.5
0
0

1/T (K-1)

Figure 9.5: Arrhenius plot

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