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Fuel Processing Technology 109 (2013) 163171

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Fuel Processing Technology


journal homepage: www.elsevier.com/locate/fuproc

Response surface modeling of H2S conversion by catalytic oxidation reaction over


catalysts based on SiC nanoparticles using Box Behnken experimental design
Momene Moradi a, Jafar Towghi Daryan a,, Ali Mohamadalizadeh b
a
b

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

Optimization is a method used in diverse processes with the aim of


obtaining the highest yields in the shortest period of time with the
lowest cost [12].
Response surface methodology (RMS) is a famous and up-to-date approach for modeling and optimizing experimental observations [1318].
Optimizing the surface response and determining the relationship between input variables and response of tests are considered in RSM
technique.
RSM applications have been performed for optimization of different
process. Ismail et al. [19] developed an empirical model by using RSM
and determined the optimal conditions for maximizing butylgalactoside
concentration in an enzymatic synthesis. Manohar et al. [20] used
PlackettBurman, BoxBehnken and central composite designs and
response surface method in lipase catalyzed esterication reactions.
Guo and coworkers [13] optimized the culture condition for Hydrogen
production by Ethanoligenens harbinense B49 by RSM. Can [15] employed
a 23 full-factorial central composite design and response surface methodology to optimize the removal efciency of Ni(II) from cone biomass
of Pinus sylvestris. Some authors [12] presented a quadratic model for
Pb(II) removal from aqueous solution by Pistacia vera using response
surface modeling and BoxBehnken experimental design. elik [21]
synthesized phenylacetaldehyde by oxidation of 2-phenylethanol
through biotransformation. The effects of biotransformation time, initial
substrate concentration, agitation speed and fed-batch number on the
phenylacetaldehyde production was investigated and optimized by
the response surface methodology. Keyvanloo et al. [22] investigated
the effects of temperature, steam-to-naphtha ratio, residence time and
the interactions between them in naphtha steam cracking process.

164

M. Moradi et al. / Fuel Processing Technology 109 (2013) 163171

They provided a model and nd the optimized operating condition for


the study. Habibi and coworkers [9] studied on H2S adsorption from synthesized natural gas. They selected the sorbent morphology, GHSV and
H2S feed concentration to be used as effective parameters on adsorption
of hydrogen sulde by central composite design and a mathematical
model was offered to obtain the H2S concentration in the range of operating conditions of variables [9]. Catalytic oxidation of isopropyl mercaptan on tungsten oxide nanoparticle catalysts supported on multiwall
carbon nanotubes (MWNTs) has been investigated by Farahzadi et al.
[23]. They optimized the operating conditions, such as temperature, catalyst loading, gas hour space velocity and oxygen-to-IPM molar ratio, by
means of RSM method. The quadratic and cubic interactions were investigated by use of central composite design (CCD). Temperature and nano
tungsten oxide loading revealed the most effects on mercaptan content
of outlet stream.
This study is devoted to use response surface methodology to identify the inuence of parameters such as temperature, sodiumcadmium
ratio and GHSV on conversion of H2S from gas stream in a catalytic oxidation reaction. Also the optimum operating conditions are determined. A quadratic model is proposed based on the BoxBehnken
design (BBD) including the effect of the process variables over the H2S
catalytic oxidation conversion.

2.3. H2S catalytic oxidation set-up


Catalytic tests were carried out isothermally under atmospheric
pressure. The reaction between hydrogen sulde and oxygen was carried out in a tubular reactor. The apparatus used for the H2S catalytic
oxidation has been described in previous publications [9,24,25].
The reactant mixture contained H2S (8000 ppmv), O2 (16,000 ppmv),
steam (20 vol.%) and balance helium, which are typically the industrial
working concentrations [4,26]. The ow rates of gas streams were controlled by a mass ow controller (Bronkhorst mass ow meters linked
to a JUMO (dTRON 304) electronic control units). Water vapor was introduced to the reactant streams using a steam evaporator.
The gaseous feed stream was 130150 cm3/min and the amount of
catalyst was assigned by desired space velocity. The tests were done
for 360 min.
The efuent gas from the reactor was passed through a trap
containing a concentrated NaOH solution and vented out to a hood. For
sampling, the efuent gas was conducted to a 20%-KOH solution and
then analyzed by a potential metric titration instrument (METTLER DL
40GP (memotitrator), with an accuracy of 1% of 1 mL) equipped
with an AgAg2S electrode (DM 141-SC). By using this method the concentration of H2S in outlet and feed streams were achieved.
2.4. BoxBehnken experimental design and optimization by RSM

2. Materials and methods


2.1. Catalyst preparation
Silicon carbide nanopowders (>99% purity) with 90 m2/g surface
area and particle size of 50 nm, used as a catalyst support, were supplied
from Neutrino Company. Catalysts with 10 wt.% of sodiumcadmium
were provided (different mass ratio of sodium/cadmium in each catalyst). The catalysts of Na/Cd (0:1, 1:1, 3:1, 5:1, and 1:0) were synthesized.
Catalysts were prepared by impregnation method. Sodium methylate
(CH3ONa) was used to load sodium silicate while cadmium acetate
((CH3COO)2Cd2H2O) was used to load cadmium oxide particles on
silicon carbide nanopowders support. To prepare the catalysts, the prenominate salts were dissolved in distilled water and the solution was
poured on SiC nanopowders. The wet solid was dried by rotary evaporator at 70 C to penetrate the salts in pores and then was dried in oven at
120 C for 2 h. The mixture was then calcinated in air from room temperature to 600 C with a slope of 5 C/min in order to transform the
salt precursors into their corresponding oxide and silicate. The prepared
calcinated nanocatalysts were pelletized and meshed between 20 and
30 m, then loaded in the reactor to be tested according to determined
experiments by DoE (Design of Experiments).

2.2. Characterization techniques


Different characterization methods involving XRD, ASAP, TEM and
SEM were used to identify prepared catalysts. The structural characterization studies of the solids were carried out by X-ray diffraction.
XRD measurements were carried out with a Philips diffractometer,
(CoK Radiation, =1.78896, step size=0.02/s at 40 kV and
20 mA). The specic surface area (SBET) was calculated by the
BrunauerEmmettTeller (BET) method. The surface area and pore size
measurements were performed on a micrometrics ASAP 2010 instrument using N2 adsorption at 77 K. Before nitrogen physical adsorption,
the samples were degassed at 300 C for 5 h. Scanning electron microscopy (SEM) images were obtained with a Philips, XL30 device. Gold was
used as the conductive material for sample coating. TEM images were
obtained with a Philips, CM 200 device. Gold was used as the conductive
material for sample coating. The presence and location of the different
species in the samples were conrmed by EDS with an EDAM3 X-ray
analyzer (diameter of the probe: ~3 nm).

The optimum conditions for maximizing the conversion of H2S and


investigation of the effect of quadratic interactions as well as main
effects in H2S catalytic oxidation were determined by means of a three
factor, BoxBehnken design combined with response surface modeling
and quadratic programming. This experimental methodology uses
regression design to model the response as a mathematical function of
factors with unbiased and minimum variance. Thus the graphical outlook of the mathematical model describes the shape of the response
surface, being investigated [27]. For this study, the effects of three process variables of A: reaction temperature (C), B: space velocity (h1)
and C: sodiumcadmium weight ratio, on the conversion of H2S was
investigated.
The parameters should be normalized before analyzing the regression. The natural variables are coded as +1, 1 and 0 for high, low
and central point, respectively. So the units of the parameters are not
important. The actual variables (Xi) are coded by linear transformation
as follow:

xi

Xhigh Xlow
2
Xhigh Xlow
2

Xi

where xi is the dimensionless coded value of ith factor, Xi is the uncoded


value of the ith independent variable (natural factor), Xhigh and Xlow are
the uncoded factor value at high and low level, respectively. The three
examined levels and experimental ranges of each independent variable
are given in Table 1.
The behavior of the system is explained by the following quadratic
polynomial equation as a function of independent variables involving
their quadratic interactions and squared terms.

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].

M. Moradi et al. / Fuel Processing Technology 109 (2013) 163171

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

In statistics, BoxBehnken designs (BBD) are typical experimental


design for response surface methodology. BBD is a class of rotatable or
nearly rotatable second-order designs based on three-level incomplete factorial designs. Each design can be thought of as a combination of a two-level (full or fractional) factorial design with an
incomplete block design. In each block, a certain number of factors
are put through all combinations for the factorial design, while the
other factors are kept at the central values. The BoxBehnken design
is a good design for this methodology because:
1. It permits estimation of the parameters of the quadratic model.
2. There are no runs where all factors are at either the + 1 or 1
levels.
3. They are all spherical designs and require factors to be run at only
three levels.
4. Use of blocks.
The number of experiments (N) required for the development of
BBD is dened as follow:
N 2k k1 Co

where k is number of factors and Co is the number of central points.


Based on Eq. (3), with 3 main factors and 4 times replication in
center point to reduce the magnitude of error, (k = 3 and Co = 4),
the runs will be limited to 16. Four tests for catalysts with only sodium silicate supported on SiC, cadmium oxide supported on SiC, pure
SiC and the one without catalyst have been done. By applying this
method 20 runs should be performed.
3. Results and discussion
3.1. Nano catalysts characterization
The XRD patterns of catalysts and metal phase located on silicon carbide nanoparticles before the H2S oxidation is exhibited in Fig. 1. As is
evident from these patterns (Fig. 1a), the crystalline phases detected
in the fresh support could be indexed to the -SiC structure and have
peaks at 2 = 85.88, 71.0, 48.5 and 41.6. Exposing the catalysts to
air stream, for calcination, as shown in (Fig. 1b and d) new peaks
appeared corresponding to sodium silicate and cadmium oxide, respectively. Catalysts contain sodium silicate (Fig. 1b) have peaks at 2 =
54.58, 51.92, 48.4, 39.1, 35.3, 31.3, and 20.86. The XRD of catalysts
contain cadmium oxide is shown in Fig. 1d, and has peaks at 2= 78.3,
65.2, 44.4, and 38.5. Catalyst with Na:Ca = 1:1 is displayed in Fig. 1c.
In catalysts of sodium oxide and Na:Cd = 1:1 there is a peak at the angle
of 25.2 that is attributed to silica. Considering that, Na2O is one of the
few materials that react with SiC, so during calcination, reaction of sodium methylate with silicon carbide produces SiO2 and sodium silicate
[28].
SEM and TEM images of SiC nanoparticles are presented in Fig. 2a
and b. The SEM image shows the uniform surface morphology of SiC
nanoparticles (Fig. 2a). The SiC nano particles are exactly clear in Fig. 2b.
The diameter of SiC nanoparticles are in the range of 4090 nm (Fig. 2b).
The BET results are shown in Table 2. Surface areas of catalysts with
total loading of 10 wt.% of sodium and cadmium, decreased from
90 m 2/g belongs to SiC nanopowders. Because SiC pores are lled up

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

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M. Moradi et al. / Fuel Processing Technology 109 (2013) 163171

Fig. 2. (a) SEM and (b) TEM of the silicon carbide nanopowder.

level of (signicance level) to discern the signicance and adequacy


of the model [17]. An effect is statistically signicant, if the calculated
F-value for the effect is greater than the F-value extracted from the
table in desirable probability level.
Based on calculated p-value, all three factors, temperature, GHSV
and Na/Cd and their interaction effects and also the temperature
squared term were found to be signicant (Table 4).
The regression equation obtained after variance analysis gives the
level of H2S conversion. It includes a linear relationship between all
the main effects and response, a quadratic relationship with temperature and, the product of temperature and GHSV, temperature and
Na:Cd, and GHSV and Na:Cd. The nal quadratic polynomial equations in terms of coded and natural variables are presented as follows:
ConversionH2 S 98:77 2:63A0:95B 0:90C 0:79AB0:98AC
5
2
2
2
0:74BC1:46A 0:53B 0:39C

3.3. Statistical evaluation


The coefcient of determination, R 2, indicates the overall predictive capability of the model. It shows how well a regression approximates experimental data and can be dened as:
2

SSModel
SS
1 error :
SSTotal
SSTotal

The R 2 value of the model has been determined as 0.9779. Therefore,


it can be assumed that 97.79% of the total variations in the response
could be explained by the model. However, this large amount of R 2
does not necessarily imply that the regression model is a suitable one.
Adjusted R-square is dened to correct the R 2. In this case,
adjusted-R2 value is 0.9447. As it can be seen adj-R2 is very close to
R2, emphasizes the high signicance of the model. Another way to describe the variation of a model is calculating the coefcient of variation
(CV).

ConversionH2 S 69:52656 0:26763T2:04687  10 GHSV


0:70078Na : Cd 1:575  105 T  GHSV9:75
6
103 T  Na : Cd 3:70313  104 GHSV
Na : Cd5:825  104 T2 5:28125  107 GHSV2
2
0:097656Na : Cd :

As seen in Table 4 the Fisher's F-value and a very low probability


value of the regression model are found to be 29.46 and 0.0003, respectively. This implies that the terms in the model have a signicant effect
on the response. The tabular F-value with model = 9 and error = 6 as
degrees of freedom of model and error, respectively, at the signicance
level of 0.05 (F0.05,(9,6) = 4.0990) is much lower than the calculated
model
F-value F0:05;9;6 MSS
MSSerror 29:46 , represents that most of the variation in the response can be explained by the regression equation.
Table 2
The BET results of catalysts.
Samples

Surface area (m2/g)

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

Out let H2S concentration (ppm)

H2S conversion (%)

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

M. Moradi et al. / Fuel Processing Technology 109 (2013) 163171

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

F-value from table (p = 0.005)

P-value (prob > F)

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

indicates the degree of freedom.


P-values b 0.05 were considered to be signicant.

The low value of the coefcient of variation (0.59%) in this model


shows a very high degree of accuracy and condence of tests.
Table 5 shows the observed and predicted response values with
residuals and percent error of responses for the runs. This is also described in Fig. 3. It shows the experimental results of H2S conversion
versus model results. The point collections around the diagonal line
illustrate that deviation between the experimental and predicted
values was less and good t of the model is obtained. Moreover calculating the absolute average deviation (AAD) is a direct method for
explaining the deviations. The AAD is dened as:
1
0
1
0

k
yi;real yi;pre 
X
@
A
C
B
B
C
yi;real
B i1
C
B
AAD B
 100C
C
k
B
C
@
A

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

Fig. 3. The experimental results of H2S conversion versus model results.

168

M. Moradi et al. / Fuel Processing Technology 109 (2013) 163171

Fig. 4. The normal probability plot of the raw residuals.

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.

3.5. Graphical description of the model equation and determination of


optimal operating conditions
Response surface plots and contour plots are useful for the model
equation image and perceiving the nature of response surface. They
are presented in Fig. 7af, which depicts the interaction of each two
variables by keeping the other at its central level for H2S conversion.
Eq. (6) is used to draw the curves.
The dependence of the degree of enhancement of H2S conversion
on the mutual interaction between T and GHSV can be best
interpreted from the response surface contour diagram (Fig. 7a),
which indicates that H2S conversion is inversely related to GHSV
and directly related to temperature. The residence time increases by
decrease of GHSV and, the rate of reaction accelerates by increase of
temperature so, hydrogen sulde converting can be enhanced. At
temperatures higher than 225 C and low GHSV, increasing in temperature reduces the H2S conversion. That occurs, because with longer residence of reactants and products in reactor at high
temperatures backward Claus reaction accelerates. The contour plot
displays elliptical lines. The maximum conversion of H2S occurs at
temperature between 225 and 250 C and GHSV between 2500 and
3000 h 1 at Na/Cd: 3 in the area conned in the smallest ellipse.
This interaction implies that maximum H2S conversion is reached to
about 100%.

Fig. 5. Main effects of reaction temperature (A), GHSV (B), and Na:Cd (C) on the conversion of H2S.

Analysis of the contour plots revealed that signicant interactions


occurred between temperature and Na:Cd ratio, as is shown by the
hyperbolic nature of the contours in Fig. 7c. According to the F and
p-value in Table 4 interaction between temperature and Na:Cd (F =
11.49 and p = 0.0147) has the greatest interaction inuence in changing the concentration of H2S. In this case, there is a stationary point
(like a saddle point) that is neither a maximum nor a minimum
point. In constant Na:Cd, rising temperature increases H2S conversion
to its highest level, then conversion will decrease again. This reduction in conversion occurs at high temperatures which backward reactions can be performed. In the range of 2.53.5 of Na:Cd there is no
area that H2S conversion reaches 100%. At temperatures below
225 C, increasing the amount of Na to Cd has a positive effect on increasing the H2S conversion. This means that sodium silicate is more
active than cadmium oxide at low temperatures. At temperatures
higher than 225 C, rising Na:Cd ratio decreased the conversion to
its minimum level then, it increased again. In the range of 12.5 and
3.55 of Na:Cd, H2S conversion reaches nearly 100%, but in 3.5 b Na:
Cd there is wider area of full conversion.
As it is shown in Fig. 7e, GHSV and Na:Cd ratio have the least signicant interaction effect (F = 6.63, P = 0.0421). Obviously, in GHSV
range of 20003000 h 1 and Na:Cd ratio of 5 (maximum) the minimum concentration of H2S occurs. Basic strength of sodium silicate
is greater than cadmium oxide.
The aim of this work was to maximize the H2S conversion in catalytic oxidation. The optimal values of key factors (temperature, GHSV
and Na:Cd) were obtained by solving the regression in Eq. (6). As it
can be seen in Fig. 7af, there are wide ranges of optimum conditions
that H2S conversion reaches to maximum level. Because of strong interactions between experimental parameters we could not pick out a
single point for maximum conversion. There are many combinations
of T, GHSV and Na:Cd that could give the maximum conversion of
H2S. In this work we have a plane of 100% conversion of H2S in
temperatureGHSVNa:Cd coordinate. The point of T = 250 C,
GHSV = 3000 h 1 and Na:Cd = 5 in experimental design is one of
the points with 100% conversion. The coded values obtained by
 1,
substituting the respective values of Xi in Eq. (5) are: x

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

Fig. 6. Interaction effects of A B, A C and B C on the conversion of H2S: where (+)


and () indicate the high and low levels of these factors, respectively.

M. Moradi et al. / Fuel Processing Technology 109 (2013) 163171

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

BoxBehnken experimental design were adopted Based on analysis


of experimental data all three parameters of temperature, GHSV and
sodium: cadmium weight ratio were effective in H2S conversion,
meanwhile, temperature had the most signicant effect of independent variables. Main effect of each parameter was more signicant
than respective quadratic effect; it implies the direct effect of variables on H2S conversion. TNa:Cd combination was the most effective

170

M. Moradi et al. / Fuel Processing Technology 109 (2013) 163171

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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