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Department of Chemical Engineering, Tarbiat Modares University, P.O. Box 14115-143, Tehran, Iran
Gas Research Division, Research Institute of Petroleum Industry, P.O. Box 14665-1998, Tehran, Iran
a r t i c l e
i n f o
Article history:
Received 13 March 2012
Received in revised form 26 August 2012
Accepted 26 October 2012
Available online 30 November 2012
Keywords:
H2S catalytic oxidation
SiC nanoparticles
BoxBehnken experimental design
a b s t r a c t
Catalysts of sodium silicate and cadmium oxide supported on silicon carbide nanopowders were synthesized and
used in catalytic oxidation of H2S to elemental sulfur. The effect of temperature (from 150 to 250 C); gas hour
space velocity (from 2000 to 4000 h1) and sodium:cadmium weight ratio (from 1 to 5), on the conversion of
H2S were studied by a BoxBehnken experimental design method. A quadratic regression equation was developed to describe relationship between the operating conditions and the response. The signicance of main factors and their quadratic interactions on the conversion of H2S in catalytic oxidation were examined by means of
the analysis of variance (ANOVA). The results showed that temperature had the most signicant effect on H2S
conversion compared with other two variables. F value of 29.46, coefcient of determination (R2) of 0.9779,
adjusted-R2 of 0.9447, absolute average deviation (AAD) of 0.29% and, coefcient of variation (CV) of 0.59%, implied the satisfactory adjustment of the quadratic model. The results indicated that up to 100% H2S conversion
was obtained at the optimum conditions.
2012 Elsevier B.V. All rights reserved.
1. Introduction
Hydrogen sulde, existing in the acid gases generated by oil reneries or natural gas plants, must be recovered before releasing to the
atmosphere due to the high toxicity and corrosive effect [1]. Nowadays conversion of H2S to elemental sulfur is the most effective method to eliminate the sulfur pollutant from natural gas [2]. This process
is conventionally treated by the popular Claus process to produce
elemental sulfur. According to thermodynamics limitations, the used
catalysts and the number of reactors in plants, the maximum efciency could not exceed 97% [3,4]. A typical tail gas of the Claus unit may
contain 6000 ppm SO2 and 12,000 ppm H2S [4]. Thus, it's necessary to
embed a tail gas treatment unit (TGT) at the end of the Claus unit, to
remove the residual hydrogen sulde [5]. The typical TGTs are wet
processes. These processes use liquid to reduce the residual H2S in
the tail gas, but the drawback of these methods is that they are
quite expensive [6]. Currently, dry catalytic processes based on selective catalytic oxidation of H2S to elemental sulfur are being developed
[7]. Comprimo's Super-Claus process and Mobil's direct-oxidation
process are two examples of dry processes that use catalyst (-alumina
supported iron oxide/chromium oxide and TiO2-based catalyst
respectively) to catalyze the oxidation of H2S to sulfur [3,6,8].
Many of researchers have investigated the operating conditions to obtain
the maximum efciency of H2S removal from gaseous streams [911].
Corresponding author.
E-mail address: TOWFIGHI@modares.ac.ir (J.T. Daryan).
0378-3820/$ see front matter 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.fuproc.2012.10.013
164
xi
Xhigh Xlow
2
Xhigh Xlow
2
Xi
y 0
3
X
i1
i xi
3
X
i1
ii xi
3 X
3
X
ij xi xj
i1 i<j
where y is predicted response of H2S conversion, x1, x2, and x3 are the
coded independent variables, 0 is the intercept, i is the linear coefcient, ij is the interaction quadratic coefcient, ii is the squared coefcient, i and j are the index numbers for variables and is the
random error which shows the different sources of variability.
Least squares method is used to solve this set of equations [27].
165
Table 1
Factors and levels for the BBD design.
Factors
A
B
C
Level
Reaction temperature
Space velocity
Na/Cd
+1
150
2000
1
200
3000
3
250
4000
5
Fig. 1. XRD patterns of the nanocatalysts before H2S oxidation (a) silicon carbide nanopowder, (b) sodium silicate supported on SiC, (c) catalyst with Na:Cd = 1:1, and (d)
cadmium oxide supported on SiC.
with cadmium and sodium oxides, the BET surface area has decreased
in the modied SiC catalyst.
3.2. Statistical analysis of experiments
The actual design of experiments, the conversion and concentration of outlet H2S are tabulated, as given in Table 3. The conversion
of H2S to elemental sulfur was calculated through Eq. (4):
Conversion%
H2 Sin H2 Sout
100
H2 Sin
where [H2S]in and [H2S]out are the concentration of H2S in inlet and
out let streams in ppmv, respectively.
The results were analyzed using the analysis of variance (ANOVA),
a regression model, coefcient of determination (R 2), adjusted
R-square, coefcient of variation (CV), absolute average deviation
(AAD), statisticaldiagnostic and response plots.
The analysis of variance (ANOVA) test is a robust and usual statistical method in the different elds. The ANOVA provides a statistical procedure that determines whether the means of several groups are equal
or not. The Fisher's variance ratio, F-value, is used to test the signicance
of the model, individual variables and their interactions [22,29]. Mean
square (MSS) is the sum of squares divided by the degrees of freedom,
of variable
for each source. The F-value is dened as: MSS
, and shows the relMSS of residual
ative contribution of the sample variance to the residual variance. If the
ratio deviates more and more from 1, the samples are not from the same
population, with more condence.
The analysis of variance (ANOVA) based on data from experiments
are shown in Table 4.
We can compare the F-value of calculations with F-value obtained
from F-distribution table with and e degrees of freedom and the
166
Fig. 2. (a) SEM and (b) TEM of the silicon carbide nanopowder.
SSModel
SS
1 error :
SSTotal
SSTotal
SiC nanopowder
Catalyst with 10 wt.% Na
Na:Cd = 5:1
Na:Cd = 3:1
Na:Cd = 1:1
Catalyst with 10 wt.% Cd
90
86.4
86.5
86.8
87.0
87.1
Table 3
The design matrix and experimental data of the out let H2S concentration and H2S conversion from the BBD design.
Run
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
Independent
variables
Response
200
200
150
250
150
250
200
200
200
200
150
250
200
150
250
200
200
200
200
200
3000
2000
2000
2000
3000
3000
4000
2000
3000
4000
3000
4000
3000
4000
3000
3000
3000
3000
3000
3000
3
5
3
3
5
1
1
1
3
5
1
3
3
3
5
3
Na
Cd
SiC
110
12
380
20
201
10
325
15
95
85
522
8
102
620
1
86
1
92
2006
2335
98.62
99.85
95.25
99.75
97.45
99.87
95.94
99.81
98.81
98.94
93.47
99.90
98.72
92.25
99.99
98.92
99.99
98.95
74.20
70.81
167
Table 4
Analysis of variance (ANOVA) of the response surface model for the prediction of conversion of H2S in catalytic oxidation.
Source
Model
AT
B-GHSV
CNa:Cd
AB
AC
BC
A2
B2
C2
Residual
Total
Statistics coefcient
2.63
0.95
0.90
0.79
0.98
0.74
1.46
0.53
0.39
Sum of square
Mean square
F-value
Remark
87.78
55.39
7.29
6.41
2.48
3.80
2.19
8.48
1.12
0.61
1.99
89.76
9
1
1
1
1
1
1
1
1
1
6
15
9.75
55.39
7.29
6.41
2.48
3.80
2.19
8.48
1.12
0.61
0.33
29.46
167.31
22.03
19.37
7.49
11.49
6.63
25.62
3.37
1.84
4.099
5.987
5.987
5.987
5.987
5.987
5.987
5.987
5.987
5.987
0.0003
b0.0001
0.0033
0.0046
0.0339
0.0147
0.0421
0.0023
0.1161
0.2234
Signicant
Signicant
Signicant
Signicant
Signicant
Signicant
Signicant
Signicant
13
where yi,pre is the predicted and yi,real is the real result, respectively,
and k is the number of experimental tests. As mentioned above, the
high values of R 2 and adj-R 2 indicated that the quadratic equation
can predict the response under the experimental data domain. Calculating the R 2 and AAD values together should be better to check the
accuracy of the model. The value of AAD in this case is 0.29%. So this
amount of R 2 and AAD shows that the model equation denes the
true behavior of the system. The result shows that this regression
model can be used for interpolation in the experimental domain.
The normal probability plot (NPP) determines the normal distribution and the homogenization of the data. In this case, the normal
probability of residuals plot (Fig. 4) is straight that implies a satisfactory normal distribution and the independence of the residuals.
The optimal level of key factors and their interaction effects on H2S
conversion were further investigated by the BoxBehnken design of
RSM.
3.4. Effects of the model components and their interactions on H2S conversion
From Fig. 5, H2S conversion was increased by increasing the reaction temperature and NaCd ratio and decreased by increasing space
velocity. According to Table 4, temperature is the most effective individual factor in H2S conversion (F = 167.31, p b 0.0001). The average
conversion of 98.77% is observed at temperature between 150 and
250 C (GHSV = 3000 h 1, Na:Cd = 3). But in non-catalytic thermal
test (T = 200 C), the maximum conversion reached 70.81%
(Table 3). It implies that one catalytic step without initial thermal
step is able to signicantly enhance the conversion of H2S. Besides
the thermal reaction at temperatures above 200 C leads to produce
SO2 in efuent gas. The conversion of 74.20% is observed in SiC test.
The test was done only with the support, without adding salts. This
conversion is close to the conversion of reaction with no catalyst
(70.81%), so the support is inertness in all reactions.
The conversion in the reaction of sodium silicate catalyst reached
to 99.99% and it reached to 98.95% in cadmium oxide catalyst. The relative basic strength of sodium silicate is more than cadmium oxide
and reducing in H2S concentration is related to the basic strength.
Fig. 6 shows interaction behavior of each two variables. As seen in
this gure, the effect of GHSV was negligible when temperature was
Table 5
Observed responses and predicted values with residuals.
Run
Temp
GHSV
Na:
Cd
Observed
(Cppmo)
Predicted
(Cppmp)
Residuals
(Cppmo Cppmp)
Error (%)
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
200
200
150
250
150
250
200
200
200
200
150
250
200
150
250
200
3000
2000
2000
2000
3000
3000
4000
2000
3000
4000
3000
4000
3000
4000
3000
3000
3
5
3
3
5
1
1
1
3
5
1
3
3
3
5
3
98.62
99.85
95.25
99.75
97.45
99.87
95.94
99.81
98.81
98.94
93.47
99.90
98.72
92.25
99.99
98.92
98.77289
99.74475
95.89919
99.58719
96.94607
100.4185
96.04477
99.43538
98.77289
99.31664
93.20545
99.25283
98.77289
92.41483
100.2591
98.77289
0.15289
0.10525
0.64919
0.162808
0.50393
0.54845
0.10477
0.374618
0.037114
0.37664
0.26455
0.64717
0.05289
0.16483
0.26907
0.147114
0.15503
0.105408
0.68157
0.163216
0.517116
0.54916
0.1092
0.375331
0.037561
0.38068
0.283032
0.647818
0.05357
0.17868
0.2691
0.14872
168
set at the high level. A sharp decrease in H2S conversion, from 95.9%
to 92.4% was found for GHSV as temperature was kept at the low
level. This phenomenon happens because of temperature and GHSV
interaction. Similarly, these synergistic effects on the H2S conversion
can be seen for the T and (NaCd) and GHSV and (NaCd) interactions in Fig. 6.
Fig. 5. Main effects of reaction temperature (A), GHSV (B), and Na:Cd (C) on the conversion of H2S.
T250 C
xGHSV3000 h1 0, and x(Na : Cd = 5) = 1. The predicted H2S conversion, in mentioned coordinate, is equal to 100, too. This point is specied in Fig. 8ac. Besides, two more points between optimization
intervals have been selected to compare the result of model with experimental ones. The rst test was carried out in operating condition
of T = 225 C, GHSV = 3000 h 1 and Na:Cd = 4. The conversion of
this run was 99.95%. The second test was performed at T = 200 C,
GHSV = 3000 h 1 and Na:Cd = 5 which leads to the conversion of
99.78%. The prediction of model for both of these points is 100% and
169
Fig. 7. Contour and response surface plots for H2S conversion as a function of temperature vs. GHSV (a, b), temperature vs. Na:Cd (c, d) and GHSV vs. Na:Cd (e, f).
as it is obvious the results are very close to the calculated one. By entering the results in AAD calculations it still remains very low (0.28%).
4. Conclusion
For formulate and obtain the optimal condition of H2S conversion
in a catalytic oxidation reaction, response surface methodology and
170
Fig. 8. (a) Response surface, (b) contour and (c) cube plots of H2S conversion at T= 250 C, GHSV = 3000 h1, and Na:Cd = 5.
interaction with a positive effect on conversion. The values of coefcient of determination (0.9779), adjusted-R 2 (0.9447), absolute average deviation (0.29%), coefcient of variation (0.59%) and F value of
29.46 illustrate a suitable adaption of experimental data with derived
equation. There were wide ranges of optimum conditions that H2S
conversion reaches to maximum level. There is a plane of 100% conversion of H2S in temperatureGHSVNa:Cd coordinate.
Acknowledgments
Financial support of the Research Institute of Petroleum Industry
(RIPI) is appreciated.
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