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Box − Behnken experimental design

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

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

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

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.

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

2.1. 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).

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).

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

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].

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

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

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

166

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

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

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

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).

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 :

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

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

P-values b 0.05 were considered to be signicant.

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

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.

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.

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

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

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

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

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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