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(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.
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.
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
d (TOC)
dt
mn
mn
(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
kmn
(H
O2
)n ( catalyst )p
kmn = ko exp(-E/RgT)
The effect of catalyst
(9.3)
(9.4)
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)
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).
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.
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
Studies In Advanced Oxidation ProcessesPage 87
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
Studies In Advanced Oxidation ProcessesPage 88
Temperature (C)
kmn x 10
150
21+0.6
0.672
180
32+1.4
0.762
200
48+2.1
0.831
% 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)
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.)
1
0.8
0.6
Initial Rate (kg/(m3min)) ( x 1000)
0.4
0.2
0
0
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).
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
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)