Advancement in Science and Technology Research

Vol. 2(2), pp. 19-41, May 2015

ISSN: 2437-1319
Full Length Research Paper

The transport process in the catalytic dehydrogenation

of ethyl alcohol
Mohammed Abdulsalam Kassim
Ministry of Science and Technology, Iraq.
Accepted 17 March, 2015

ABSTRACT

The vapour phase dehydrogenation of ethyl alcohol to acetaldehyde has been studied in an integral flow
reactor in the temperature range of 300 to 425C at atmospheric pressure and W/F values ranges from 0.93
to 2.915 g cat./g mole feed/h. This study has been carried out by using the integral flow reactor of diameter
18 mm over ZnO-CuO/Al2O3 catalyst. The maximum conversion of ethyl alcohol, selectivity of acetaldehyde
yield was 48, 85.3 and 32% respectively and the concentration of by product hydrogen was 98%.

Keywords: Dehydrogenation, ethyl alcohol, acetaldehyde, catalyst, integral flow reactor.

E-mail: [email protected].

INTRODUCTION

Acetaldehyde is respected to be one of the most hydrogenation and dehydrogenation over silica supported
important intermediate aliphatic chemicals serving as the copper catalyst, under atmospheric pressure. The
raw material for the production of acetic acid, acetic dehydrogenation reaction temperature range was 300 to
anhydride, ethyl acetate, hexanol and many other 400C and hydrogenation temperature was between 200
products. and 250C. A kinetic model, based on a dual site catalyst
The study covers the dehydrogenation of ethyl alcohol was studied with variation of the operating parameters in
over copper catalysts supported on rice husk ash order to evaluate the controlling step. Surface reaction on
prepared by incipient wetness impregnation. The catalytic a dual site was postulated as rate-controlling step at all
activity by ethyl alcohol dehydrogenation at temperatures studied temperatures. Its effect was evaluated by
between 473 and 573 K has been examined. The activity optimizing the proposed model using the Quasi-Newton
of catalyst increases with an increase in reaction optimization technique, was chosen due to it is rapid
temperature (Chang et al., 2003). convergence over other techniques.
Dehydrogenation of ethyl alcohol over Cu/ZnO Frankarts et al. (1964) used a similar catalyst in a flow
catalysts prepared from various co-precipitated were reactor in the temperature 285C at pressure varying
more active than other precursors. Selectivity to ethyl between 1 and 10 atm and W/F values varying between
acetate over Cu/ZnO was higher than that over Cu/SiO 2 0.2 to 1.6 h/mol.
(Fujita et al., 2001). Different preparation methods have been examined to
The dehydrogenation of ethyl alcohol occurred over Cu, develop MgCrO catalysts for oxidative dehydrogenation
Cu/SiO2, Cu/ZrO2, Cu/Al2O3, Cu/MgO, and Cu/ZnO at of ethanol to acetaldehyde. The characterization results
temperature 380 to 420 K, giving acetaldehyde, ethyl reveal that a spinel highly organized, with a possible
acetate and C4-species (Iwasa and Takezawa, 1991). excess of oxygen at the surface, is obtained irrespective
Chhabra and Venkateswaralu (1988) studied the of preparation method. The initial crystallization
dehydrogenation of ethyl alcohol in a fixed bed reactor temperature of spinel phase is around 450C, lower than
over precipitated copper catalyst, in temperature of that required if the preparation is from oxides. The
300C and (weight of catalyst/ethyl alcohol flow rate) W/F samples calcined at 500C are active at 260 and 280C
values ranging from 0.6 to 6.9 gm cat./g mole feed per h. with selectivity to acetaldehyde higher than 75%. The
Wakao et al. (1988) studied the transporting energy for sample obtained by using citric acid leads to a relatively
 Adv Sci Technol Res 20

lower COX formation due likely to a lower oxygen excess consists of two sections, preheated section and reaction
at the surface (Castro et al., 2009). section. The preheating section filled with small glass
The aim of the investigation is to study the effect of the particles 0.3 cm diameter. The reaction section contains
operating parameters namely; time of reaction, reaction the catalyst bed and small glass particles with 0.6 cm
temperature, W/F, the ethyl alcohol concentration on the diameter in order to support the catalyst bed.
activity of the catalyst and the kinetic of ethyl alcohol Nitrogen was used in the thermal treatment of catalyst
dehydrogenation to estimate the controlling step. at 450C. The ethyl alcohol vapor reacted over the
catalyst bed at the specified temperature and W/F. The
vapor products were passed through the two consecutive
EXPERIMENTAL double-pipe condensers. The condensed liquid products
were acetaldehyde, un-reacted ethyl alcohol, acetone,
Catalysts ethyl acetate, acetic acid and water. Figure 1 shows the
schematically diagram of experimental rig.
Two types of commercial catalysts were used, which
were provided by (ICI-52.1 and BASF). The specifications
of these catalysts are shown in Table 1. Analysis by chromatography

The separation and analysis of the liquid products into

Experimental rig and procedure their components were carried out by gas-liquid
chromatography (shimadzu, GC-2010). A porapack Q
The dehydrogenation of ethyl alcohol was carried out in stainless steel column with an outside diameter of 1/8
the apparatus was constructed of integral flow reactor inch and length of 3 m was used. The GLC column was
that was constructed of Pyrex Glass, it has an inside connected to thermal conductivity detector (TCD). Table
diameter and length of 1.8 and 70 cm, respectively. It 2 shows the GLC optimum conditions.

RESULTS AND DISCUSSION

Effect of duration time of experiments on the activity of catalyst

Duration time was studied at constant temperature of 400C, W = 4 g and W/F = 1.6 (g catalyst/gmol/h) for catalyst (1).
The conversion of ethyl alcohol decreased with time till it reached a stable limit due to decline in catalyst activity. This
decline in activity might be attributed to coke deposition. The intermediate product, aldehyde, may itself be
dehydrogenation and condensed on the active sites of the catalyst, and finally converted to coke (Hughes, 1984).
Figure 2 shows the duration time on the conversion of ethyl alcohol and yield of acetaldehyde. Figure 3 shows the
relationship between the selectivity of acetaldehyde with duration time. It is seen the selectivity ascends till it reaches a
steady state at 1 h approximately. This behavior further advocates the increase in activity phenomenon (Hughes, 1984).
The reaction period where the catalyst showed stability is 1 h as shown in the two previously mentioned figures.
Nevertheless, because of the minor changes in conversion and yield, we selected 0.5 h to be more economically
feasible.

Effect of the temperature on the reaction

The relationships between reaction temperature versus ethyl alcohol conversion and acetaldehyde yield for catalyst (1)
are shown in Figure 4. These relationships show that the conversion and yield ascend to maximum value at temperature
of 350C, and then descend to be stable with further increase in temperature. This step-down behavior could be
explained on the following basis: sintering and coke deposition occurs on the catalyst with a rise in temperature leading
to a significant loss in the active area of the catalyst and consequently loss of activity (Hughes, 1984).
The selectivity of acetaldehyde versus temperature is shown in Figure 5, this behavior is similar to the conversion of
ethyl alcohol and acetaldehyde yield behaviors.

Effect of space time (W/F)

The ratio of weight of catalyst (in grams) to flow rate (in gmol/h) of ethyl alcohol (W/F) was studied at different
temperatures with fixed weight of catalyst (W of 4 and 5 g) using catalyst (1).
 Kassim 21

Table 1. Catalyst specification.

Particle density 2 Pore volume Form

Type Composition Surface area (m /g)
(m) 103
3 3
(kg/m ) (m /kg)
ZnO 53%
ZnO-CuO/Al2O3
Catalyst (1) CuO 32% 1592 70 3.2 104 5.4 3.6
(ICI-52.1)
Al2O3 15%

ZnO 40%
ZnO-CuO/Al2O3
Catalyst (2) CuO 40% 1887 100 3.5 104 5 5
(BASF)
Al2O3 20%

8 10
1
9
7
11

5 6
3
Vent

13 14

12
2

15

1 Ethanol cylinder 9 Reactor mantle

2 Nitrogen cylinder 10 Temp. inde. controller
3 Feed burette 11 Condenser
4 Needle pump 12 Cooling unit (Chiller)
5 Preheating section 13 Recevior
6 Insulation 14 Scrubbers
7 Catalyst bed 15 GC
8 Integral flow reactor

Figure 1. Schematic diagram of the experimental rig.

Table 2. The GLC optimum conditions.

Column temp. (C) TCD temp. (C) Initial temp. (C) Injection temp. (C) Rate (C/min)
250 200 175 200 5

Figures 6 and 7 show the relationships between the W/F (0.93, 1.6 and 2.33) (gmol/h) at (Wc = 4 g) versus ethyl
alcohol conversion, acetaldehyde yield and selectivity of acetaldehyde at a temperature of 325C. They show that the
ethyl alcohol conversion, acetaldehyde yield increase and the selectivity of acetaldehyde as expected decreases with
increasing W/F. These increases are attributed to the resulting increase in contact time of the reactant (Figures 8 and 9).
Figures 10 and 11 show similar behaviors to that noticed in Figures 6 and 7, for the studied temperatures 350 and
375C respectively.
Figures 12 to 19 show the effect of W/F (1.17, 1.94 and 2.915 gmol/h) at W = 5 g and temperature 300, 325, 350 and
 Fig.(2): Effect time on ethy alcohol conversion and
acetaldehyde yield for ZnO,CuO/Al2O3 catalyst (W=4gm, Adv Sci Technol Res 22
T=400C)(cat.1)

26

Ethyl alcohol Conversion % and 24

Acetaldehyde Yield %
22

conv. %
20
yield %

18

16

14
0.25 0.5 1 1.5 2
Time (hr)

Figure 2. Effect time on ethyl alcohol conversation and acetaldehyde yield for ZnO, CuO/Al2O3 catalyst (W =
4 g, T = 400C) Fig.(3):
(cat.1). Effect of Time on Acetaldehyde Selectivity for
ZnO,CuO/Al2O3 Catalyst (W=4gm,T=400C)(Cat. 1)

82

80

78
Selectivity %

76

74

72

70
0 0.5 1 1.5 2 2.5
Time (hr)

Figure 3. Effect of time on acetaldehyde selectivity for ZnO, CuO/Al2O3 catalyst (W = 4 g, T = 400C) (Cat. 1).

375C on the ethyl alcohol conversion, acetaldehyde yield and selectivity of acetaldehyde, this effect is similar to that in
Figures 6 to 11.

Effect of ethyl alcohol concentration on the reaction

From the previously studied parameters, the optimum conditions of temperature, W/F and W for catalyst (1), are 350C,
2.915 and 5 g respectively. The effect of alcohol concentrations 100, 95 and 90% at these optimum conditions was
studied.
Decreasing the alcohol concentration leads to different responses in conversion of ethyl alcohol, acetaldehyde yield,
selectivity of acetaldehyde and byproducts yield.
Figure 20 indicates that the conversion increases, and no changes in yield are noticed. The selectivity of the reaction
decreased as shown in Figure 21. As for the yield of byproducts; ethyl acetate decreased, acetone increased and acetic
 Kassim 23
Fig.(4): Effect of Temperature on Ethyl alcohol Conversion and
Acetaldehyde Yield for ZnO,CuO/Al2O3 Catalyst (W=4gm)(Cat. 1)

40

Ethyl alcohol Conversion % and

35

Acetaldehyde Yield %
30

25
Conversion %
20
Yield %
15

10

0
325 350 375 400 425
Temperature C

Figure 4. Effect of temperature on ethyl alcohol conversion and acetaldehyde yield for ZnO, CuO/Al 2 O3
catalyst (W = 4Fig.(5): Effect of Reaction Temperature on Acetaldehyde
g) (Cat. 1).
Selectivity for ZnO,CuO/Al2O3 Catalyst (W=4gm)(Cat. 1)

84

82

80
Selectivity %

78

76

74

72

70
1 2 3 4 5
Temperature C
Fig.(6): Effect of W/F on Ethyl alcohol Conversion % and
Figure Acetaldehyde
5. Effect of reaction temperature
yield on acetaldehyde selectivity
% for ZnO,CuO/Al2O3 Catalyst for ZnO, CuO/AlT=325
(W=4gm, 2O3 catalyst (W =
4 g) (Cat. 1).
C)(cat. 1)

35
Ethyl alcohol Conversion % and

30
Acetaldehyde Yield %

25
Conversion %
20
Yield %
15

10

0
0.93 1.6 2.33
W/F

Figure 6. Effect of W/F on ethyl alcohol conversion % and acetaldehyde yield % for ZnO, CuO/Al 2O3
catalyst (W = 4 g, T = 325C) (Cat. 1).
 Adv Sci Technol Res 24
Fig.(7): Effect of W/F on Acetaldehyde Selectivity for
ZnO,CuO/Al2O3 Catalyst (W=4gm, T=325 C) (Cat. 1)

79
78
77

Selectivity %
76
75
74
73
72
71
70
0.5 1 1.5 2 2.5
W/F
Fig.(8):
Figure 7. Effect ofEffect
W/F on of W/F on Ethyl
acetaldehyde alcohol
selectivity for ZnO, Conversion % (W
CuO/Al2O3 catalyst and
= 4 g, T
= 325C) (Cat. 1).
Acetaldehyde Yield % for ZnO,CuO/Al2O3 Catalyst (W=4gm,
T=350 C)(Cat. 1)

40
Ethyl alcohol Conversion % and

35
Acetaldehyde Yield %

30

25
Conversion %
20
Yield %
15

10

0
0.93 1.6 2.33
W/F

Figure 8. Effect of W/F on ethyl alcohol conversion % and acetaldehyde yield % for ZnO, CuO/Al 2 O3 catalyst
(W = 4 g, T = 350C)Fig.(9):
(Cat. 1). Effect of W/F on Acetaldehyde Selectivity for
ZnO,CuO/Al2O3 Catalyst (W=4gm, T=350 C)(Cat. 1)

82.5

82
Selectivity %

81.5

81

80.5

80

79.5
0.5 0.7 0.9 1.1 1.3 1.5 1.7 1.9 2.1 2.3 2.5
W/F

Figure 9. Effect of W/F on acetaldehyde selectivity for ZnO, CuO/Al2O3 catalyst (W = 4 g, T =

350C) (Cat. 1).
 Fig. (10): Effect of W/F on Ethyl alcohol Conversion % and
Acetaldehyde Yield % for ZnO,CuO/Al2O3 Catalyst (W=4gm, Kassim 25
T=375 C)(cat. 1)

30

Ethyl alcohol Conversion % and

25

Acetaldehyde Yield % 20
Conversion %
15
yield %
10

0
0.93 1.6 2.33
W/F

Figure 10. EffectFig.(11):

of W/F onEffect
ethyl alcohol conversion%
of W/F and acetaldehyde
on Acetaldehyde yield %for
Selectivity for ZnO, CuO/Al 2O3
catalyst (W = 4 g, T = 375C) (Cat. 1).
ZnO,CuO/Al2O3 Catalyst (W=4gm, T=375 C)(Cat. 1)

81

80

79
Selectivity %

78

77

76

75

74
0.5 0.7 0.9 1.1 1.3 1.5 1.7 1.9 2.1 2.3 2.5
W/F
Fig. (12): Effect of W/F on Ethyl alcohol Conversion % and
Figure 11. Acetaldehyde
Effect of W/F on acetaldehyde
Yield % forselectivity for ZnO, CuO/Al2O3
ZnO,CuO/Al2O3 Catalystcatalyst
(W=5gm,(W=4g, T=375C)
(Cat. 1).
T=300 C)(cat. 1)

40
Ethyl alcohol Conversion % and

35
Acetaldehyde Yield %

30
25
Conversion %
20
yield %
15
10

5
0
1.17 1.94 2.915
W/F

Figure 12. Effect of W/F on ethyl alcohol conversion % and acetaldehyde yield for ZnO, CuO/Al 2 O3
catalyst (W = 5 g, T = 300C).
 Adv Sci Technol Res 26
Fig.(13): Effect of W/F on Acetaldehyde Selectivity for
ZnO,CuO/Al2O3 Catalyst (W=5gm, T=300 C)(Cat. 1)

86
85
84
Selectivity %
83
82
81
80
79
78
77
0.5 1 1.5 2 2.5 3 3.5
Fig. (14): Effect of W/F on EthylW/F alcohol Conversion % and
Acetaldehyde Yield % for ZnO,CuO/Al2O3 Catalyst (W=5gm,
Figure 13. Effect of W/F on acetaldehyde selectivity for ZnO, CuO/Al2O3 catalyst (W = 5 g, T = 300C).
T=325 C)(cat. 1)

45
Ethyl alcohol Conversion % and

40
Acetaldehyde Yield %

35
30
25 Conversion %
20 yield %
15
10
5
0
1.17 1.94 2.915
W/F

Figure 14. Effect of W/F on ethyl alcohol conversion % and acetaldehyde yield % for ZnO, CuO/Al 2O3
catalyst (W = 5 g, Fig.(15):
T = 325C)Effect
(cat. 1).of W/F on Acetaldehyde Selectivity for
ZnO,CuO/Al2O3 Catalyst (W=5gm, T=325 C)(Cat. 1)

86
85
84
Selectivity %

83
82
81
80
79
78
77
0.5 1 1.5 2 2.5 3 3.5
W/F

Figure 15. Effect of W/F on acetaldehyde selectivity for ZnO, CuO/Al2O3 catalyst (W = 5 g, T =
325C) (Cat. 1).
 Fig. (16): Effect of W/F on Ethyl alcohol Conversion % and
Acetaldehyde Yield % for ZnO,CuO/Al2O3 Catalyst (W=5gm, Kassim 27
T=350 C)(cat. 1)

50

Ethyl alcohol Conversion % and

45
40

Acetaldehyde Yield %
35
30
Conversion %
25
yield %
20
15
10
5
0
1.17 1.94 2.915
W/F

Figure 16. Effect of W/F on ethyl alcohol conversion % and acetaldehyde yield % for ZnO, CuO/Al 2O3
catalyst (W = 5 g, T = 350C)
Fig.(17): (Cat. 1).
Effect of W/F on Acetaldehyde Selectivity for
ZnO,CuO/Al2O3 Catalyst (W=5gm, T=350 C)(Cat. 1)

83

82
81
Selectivity %

80

79
78
77

76

75
0.5 1 1.5 2 2.5 3 3.5

Fig. (18): Effect of W/F on EthylW/F alcohol Conversion % and

Acetaldehyde Yield % for ZnO,CuO/Al2O3 Catalyst
Figure 17. Effect of W/F on acetaldehyde selectivity for ZnO, CuO/Al (W=5gm,
2O3 catalyst (W = 5g, T = 350C).
T=375 C)(cat. 1)

35
Ethyl alcohol Conversion % and

30
Acetaldehyde Yield %

25

20 Conversion %

15 yield %

10

0
1.17 1.94 2.915
W/F

Figure 18. Effect of W/F on ethyl alcohol conversion % and acetaldehyde yield % for ZnO, CuO/Al 2O3
catalyst (W = 5 g, T = 375C) (cat. 1).
 Adv Sci Technol Res 28
Fig.(19): Effect of W/F on Acetaldehyde Selectivity for
ZnO,CuO/Al2O3 Catalyst (W=5gm, T=375 C)(Cat. 1)

79

78.5

78
Selectivity %

77.5

77

76.5

76
0.5 1 1.5 2 2.5 3 3.5
W/F
Fig. (20): Effect of Feed Concentration % on Ethyl alcohol
Figure 19. Effect of W/F on acetaldehyde selectivity for ZnO, CuO/Al2O3 catalyst (W = 5 g, T = 375C)
Conversion % and Acetaldehyde Yield % for ZnO,CuO/Al2O3
(Cat. 1).
Catalyst (W=5gm, T=350 C)(cat. 1)

50
Ethyl alcohol Conversion % and

45
Acetaldehyde Yield %

40
Conversion %
yield %
35

30

25
90 95 100
Concentration %

Figure 20. Effect of feed concentration % on ethyl alcohol conversion % and acetaldehyde yield % for
ZnO, CuO/Al2Fig.(21):
O3 catalyst Effect
(W = 5 g,ofT =Feed Concentration
350C) (cat. 1). % on Acetaldehyde
Selectivity for ZnO,CuO/Al2O3 Catalyst (W=5gm, T=350 C)(Cat. 1)

78

76
Selectivity %

74

72

70

68

66
85 87 89 91 93 95 97 99
Concentration %

Figure 21. Effect of feed concentration % on acetaldehyde selectivity for ZnO, CuO/Al 2O3 catalyst (W
= 5 g, T = 350C).
 Fig.(22): Effect of Feed Concentration % on By Product Yield Kassim 29
% for ZnO,CuO/Al2O3 Catalyst (W=5gm,T=350 C)(Cat. 1)

14

By Product Yield % 12

10
Aceton %
8 Ethyl acetate %

6 Acetic Acid %
Water %
4

0
90 95 100
Concentration %

Figure 22. Effect of feed concentration % on by-product yield % for ZnO, CuO/Al2O3 catalyst (W = 5 g, T =
350C) (Cat. 1).

acid was unaltered as shown in Figure 22. These behaviors are explained as follows: the existence of excess amounts
of water promotes the acetone production reaction on behalf of ethyl acetate reaction as mentioned by Nakajima et al.
(1989) that proposed the dehydrogenation reaction mechanism proceeds in the order
(ethanol acetaldehyde ethylacetate acetic acid acetone), over the
(ZnO-CaO) catalyst at various temperatures. The mechanism is shown as follows:

Catalyst (2) was studied under the same selected optimum conditions. Similar behaviors are noticed as shown in
Figures 23 to 25. Comparison between the two types of catalyst showed catalyst (1) to be more active. The conversion
reached 42% at 100% alcohol concentration for catalyst (1), while it was 22% for catalyst (2).
 Fig. (23): Effect of Feed Concentration % on Ethyl alcohol
Conversion % and Acetaldehyde Yield % for ZnO,CuO/Al2O3 Adv Sci Technol Res 30
Catalyst (W=5gm, T=350 C)(cat. 2)

50

Ethyl alcohol Conversion % and

45
40

Acetaldehyde Yield %
35
30
Conversion %
25
yield %
20
15
10
5
0
90 95 100
Concentration %

Figure 23. Effect of feed concentration % on ethyl alcohol conversion % and acetaldehyde yield % for ZnO,
Fig.(24): Effect of Feed Concentration % on Acetaldehyde
CuO/Al2O3 catalyst (W = 5 g, T = 350C) (Cat. 2).
Selectivity for ZnO,CuO/Al2O3 Catalyst (W=5gm, T=350 C)(Cat. 2)

80
78

76
Selectivity %

74

72

70

68
66
64
85 87 89 91 93 95 97 99
Concentration %

Figure 24. Effect of feed concentration % on acetaldehyde selectivity for ZnO, CuO/Al 2 O3 catalyst (W =
Fig.(25):
5 g, T = 350C) Effect of Feed Concentration % on By Product Yield
(Cat. 2).
% for ZnO,CuO/Al2O3 Catalyst (W=5gm,T=350 C)(Cat. 2)

14

12
By Product Yield %

10
Aceton %
8
Ethyl acetate %

6 Acetic Acid %
Water %
4

0
90 95 100
Concentration %

Figure 25. Effect of feed concentration % on by-product yield % for ZnO, CuO/Al2O3 catalyst (W = 5 g,
T = 350C) (Cat. 2).
 Fig.(26): ln(Ci/Co) vs. (1/LHSV) for Dehydrogenation of Ethyl Kassim 31
alcohol ,(W=5gm)(Cat.1), First Order Reaction

0.6

0.5

0.4
ln(Ci/Co)

T=325 C
0.3 T=350 C
T=300 C
0.2

0.1

0
0 0.0138 0.0231 0.0346
1/LHSV

Figure 26. In(Ci/Co) vs. (1/LHSV) for dehydrogenation of ethyl alcohol (W = 5 g) (Cat. 1), first order
reaction.

Kinetic for the dehydrogenation reaction

The kinetic of ethyl alcohol dehydrogenation reaction were studied for 5 g catalyst (1) at temperature of 300, 325 and
350C.

Rate constant for the dehydrogenation reaction

The dehydrogenation of ethyl alcohol rate constant at various temperatures was estimated by employing the first order
equation (Levenspiel, 1972; Ahmed, 1986) as follows:

ln Ci/Co k/LHSV (1)

Where: Ci Inlet ethyl alcohol concentration, Co Outlet ethyl alcohol concentration, k Reaction rate constant (h1),
LHSV Liquid hourly space velocity (h1).
The value of LHSV can be estimated by using the following equation (Fogler, 1974):

(2)

Where: vo Volumetric flow rate of ethyl alcohol (m /h), V Real Volume of catalyst (m ).
3 3

Plots of ln Ci/Co vs. 1/LHHSV at different temperatures for catalyst (1) are shown in Figure 26. The straight lines
obtained in these plots, according to equation (1), have slopes equal to the rate constant at different temperatures. The
rate constants were calculated from these slopes by using the least squares method. The values of rate constant (k) are
tabulated in Table 3.

Activation energy for the dehydrogenation reaction

The activation energy for dehydrogenation of ethyl alcohol over catalyst (1) was calculated using the Arrhenius equation.
This equation satisfies the relationship between rate constant and the reaction temperature (Froment and Bischoff,
1979):

k A exp (E/RT) (3)

 Adv Sci Technol Res 32

Table 3. The values of rate constant (k).

Flowrate of ethyl alcohol K

Temp. (K) 1/LHSV (h) Ln Ci/Co E (kJ/mol)
(h1) (s1)
3 3
m /h m /s
1 104 2.78 108 0.0346 0.4463
573 1.5 104 4.167 108 0.0231 0.3147 12.143 3.373 103
2.5 104 6.94 108 0.0138 0.1863

1 104 2.78 108 0.0346 0.49

598 1.5 104 4.167 108 0.0231 0.342 14.4502 4.014 103 16.711
2.5 104 6.94 108 0.0138 0.2107

1 104 2.78 108 0.0346 0.545

4 8
623 1.5 10 4.167 10 0.0231 0.371 16.0717 4.464 103
2.5 104Fig.(27): 108
6.94Activation Energy
0.0138 for Dehydrogenation
0.25 of Ethyl
alcohol,(W=5gm)(Cat.1), First Order Reaction

2.85
2.8
2.75
2.7
2.65
ln K

2.6
2.55
2.5
2.45
2.4
2.35
1.605 1.672 1.745
1/T (K^-1) x10^-3

Figure 27. Activation energy for dehydrogenation of ethyl alcohol (W=5g) (Cat. 1), first order reaction.

Where: A Pre-exponential factor, E Apparent activation energy, R Universal gas constant, T Reaction
temperature.
A plot of (ln k) vs. (1/T), as shown in Figure 27 gives a straight line with a slope equal to (E/R), from which the
activation energy was calculated. Values of E are given in Table 3.

Rate of dehydrogenation reaction

The rate of ethyl alcohol dehydrogenation reaction are various temperatures 300, 325 and 350C, for catalyst (1) is
estimated by employing the first order, reversible reaction, as follows:

k1
C2 H5 OH C2 H4 O + H2 and (4)
k2 (4)

(4) (5)
 Kassim 33

Where Rate of reaction (mole/gm.s), Concentration of ethyl alcohol,

Concentration of acetaldehyde, Concentration of hydrogen.

Effectiveness factor () is calculated according to the relation given by Levenspiel (1984):

(6)

Where: I1, Io Bessel function factor of Thiele modulus.

In order to calculate the effectiveness factor, we need to estimate the Thiele modulus (M T) or weisz modulus (MW ) as
follows (Levenspiel, 1984):

(7)

and

(8)

The Bessel function (I1, Io) of various values of Thiele modulus (MT) is estimated by using equations 9 and 10, as given
by Korn and Korn (1968).

(9)

and

(10)

Where x 2MT.
Effective diffusivity was estimated using Equation 11 as given by Froment and Bischoff (1979).

(11)

For estimating the effective diffusivity we must calculate the porosity (p) by using Equation 12, as given by Fogler
(1974). Porosity () was found to be equal to 0.514.

(12)

The tourtosity factor is taken, for cylindrical pores, to be equal to 3 as estimated by Satterfield (1980).
Knudsen diffusivity is estimated using the relation given by Satterfield (1980).

(13)
 Adv Sci Technol Res 34

Table 4.

Knudsen Effective Thiele Weisz Bessel Bessel

Temp. Effectiveness
diffusivity diffusivity modulus modulus function function
(K) 2 2 factor ()
(m /s) (m /s) (M T) (M W) factor (Io) factor (I1)
573 3.156 106 5.407 107 24.4700 24.2207 1.03 1020 1.022 1020 0.04045
3.224 106 5.524 107
15 15
598 19.6234 19.4988 7.08 10 7.0365 10 0.0506
623 3.29 106 5.637 107
Fig.(28):Thiele Modulus vs.
16.116 Effectivness
15.858 1012 for 6.92 1012
7.03Factor 0.06106
Dehydrogenation of Ethyl alcohol

0.07

0.06
Effectivness Factor

0.05

0.04

0.03

0.02

0.01

0
16.116 19.6234 24.47
Thiele Modulus ( Mt)

Figure 28. Thiele modulus vs. effectiveness factor for dehydrogenation of ethyl alcohol.

Where

(m) (14)

Where T Absolute temperature (K), M Molecular weight of diffusing species, S Surface area, Pellet density
3
(kg/m ).
From Equation 14, the value of pore radius (rp) was found to be equal to 9.2247 109 m and then, the Kundsen
diffusivity was calculated for various temperatures, their values are listed in Table 4. Furthermore, we estimated the
Thiele modulus (MT) and Weisz modulus (MW ). Their values are shown in Table 4. The Bessel function factors Io, I1 are
evaluated and are listed in Table 4.
The effectiveness factor () is plotted vs. Thiele modulus (M T) as shown in Figure 28. It is seen that a decrease in MT
results in an increase in .
Prior to the calculation of the rate of the reaction from Equation 5, the equilibrium constant for various temperatures
300, 325 and 350C, is estimated. Chhabra and Venkateswaralu (1988) reported that equilibrium constant at 300C is
equal to 6.2523. The Vanthoff equation (15) is used to estimate the values of K for temperatures 325 and 350C, as
given by Fogler (1986):

(15)

Where: HR Heat of reaction (J/mole), Cp Average heat capacity (J/mole.K).

In order to calculate the equilibrium constant, using Equation 15 the values of HR were estimated to be equal to
 Kassim 35

Table 5. Equilibrium conversion.

Temp. (K) Cp (J/mole K) H (J/mole) K Xe

573 3.9947 6.2523 0.9285
598 3.6086 68910 11.442 0.959
623 3.2206 19.935 0.976

Table 6. Dehydrogenation reaction rate.

Temp. (K) Flowrate (m3/s) Rate of reaction (rA) (mole/g.s)

2.78 108 1.4142 104
573 4.167 108 1.427 104
6.94 108 1.445 104

2.78 108 1.981 104

598 4.167 108 1.9917 104
6.94 108 2.0042 104

2.78 108 2.6837 104

623 4.167 108 2.693 104
6.94 108 2.702 104

(68910 J/mole). Values of Cp are estimated for various temperature (Table 5), as given by Smith and Van Ness (1987).
From the values in Tables 4 and 5, the dehydrogenation reaction rate was calculated for various temperatures and W/F.
These values are tabulated in Table 6.

Equilibrium conversion (Xe)

Equilibrium conversion is estimated by employing Equation 16, this equation is given by Chhabra and Venkateswaralu
(1988):

(16)

The values of equilibrium conversion (Xe) are given in Table 5.

Comparison between (W/F)expt. and (W/F)calcul.

For studying the comparison between (W/F)expt. And (W/F)calcul., we must find the integral rate equation for the first order
irreversible reaction, by deriving the design equation of the integral flow reactor as given by Froment and Bischoff,
(1979), as follows:

(17)

For first order irreversible reaction Chhabra and Venkateswaralu (1988):

rA k CA (18)
 Adv Sci Technol Res 36

Where:

(19)

The general equation for the reaction:

aA bB + cC (20)

(21)

Where: 1

(22)

From ideal gas law

(23)

(24)

By integrating of the equation:

(25)

Where: 1

(26)

The equation is rearranged in order to find the integral rate equation as follows:

(27)

Where: Pt Total pressure (atm), x Ethyl alcohol conversion.

By using the experimental data, (x 2ln (1 x)) is plotted vs. (W/F), at different temperatures 300, 325 and 350C. A
straight line passing through the origin is obtained. The values of (k) (reaction rate constant) at various temperatures are
found from the slope, these are shown in Figure 29 and listed in Table 7.
The effect of temperature on the reaction rate constant is determined by using Arrhenius equation. The Constants
obtained by a plot of (ln k) against (1/T) are shown in Figure 30. The values of (E) and (A) from such a plot are:

E 18.173 kJ/mole
A 387.157
 Fig.(29): W/F vs. -x-2ln(1-x) for Dehydrogenation of Ethyl Kassim 37
alcohol ,(W=5gm)(Cat.1), First Order Reaction

0.8

0.7

0.6

0.5
-x-2 ln(1-x)

T=325 C
0.4 T=350 C
T=300 C
0.3

0.2

0.1

0
0 0.0138 0.0231 0.0346
W/F

Figure 29. W/F vs. x-2ln(1-x) for dehydrogenation of ethyl alcohol (W = 5 g) (Cat. 1), first order reaction.

Table 7.

Temp. Flowrate F (W/F) Reaction rate constant 1/T E (W/F)

x2ln(1x) ln k
(K) (m 3/s) expt. K (s1) (K1)103 (KJ/mol) calcul.
2.78 108 2.915 0.5326 2.9341
573 4.167 108 1.94 0.3594 2.384 103 2.012 1.7452 1.9801
6.94 108 1.17 0.2026 1.12

2.78 108 2.915 0.587 2.88

598 4.167 108 1.94 0.395 2.748 103 2.292 1.672 18.173 1.9362
6.94 108 1.17 0.231 1.135

2.78 108 2.915 0.669 2.9524

623 4.167 108 1.94 0.432 3.242 103 2.457 1.605 1.906
6.94 108 Fig.(30):
1.17 Activation
0.277 Energy for Dehydrogenation of Ethyl 1.2213
alcohol,(W=5gm)(Cat.1), First Order Reaction

2.5
2.45
2.4
2.35
2.3
ln K

2.25
2.2
2.15
2.1
2.05
2
1.605 1.672 1.745
1/T (K^-1) x10^-3

Figure 30. Activation energy for dehydrogenation of ethyl alcohol (W = 5 g) (Cat.1), first order reaction.
 Fig.(31): (W/F)expt. vs. (W/F)calcd. forr DehydrogenationAdv
of Sci Technol Res 38
Ethyl alcohol , (W=5gm)(Cat.1), First Order Reaction

3.5

2.5
(W/F)calcd.

2 T=325 C
T=350 C
1.5 T=300 C

0.5

0
0.0138 0.0231 0.0346
(W/F)expt.

Figure 31. (W/F) expt. vs. (W/F) calcd for dehydrogenation of ethyl alcohol, (W= 5 g) (Cat. 1), first order
reaction.

Substituting the values of (E) and (A) in Equation 27, the following expression is obtained:

(28)

Using Equation 28, (W/F) values for different x values are obtained. These calculated values at a particular temperature
are compared with the experimental (W/F) values and are plotted in Figure 31. The closeness of these values expressed
as absolute average error is equal to 2.09%.
From comparing the two values obtained, it is clear that the method of Levenspiel is more accurate than the other
method presented by Chhabra and Venkateswaralu (1988). For the second method, the assumption that the reaction is
irreversible is not quite accurate according to Eric (1921), Church and Joshi (1951), Franckaerts and Froment (1964),
Froment and Bischoff (1979) and Wakao et al. (1988). Thus this deviation between the results is thought to be a
consequence of this assumption.

Rate equation based on reaction mechanism

In the present investigation, it is assumed that the kinetic data are not influenced by internal and external diffusions
(Chhabra and Venkateswaralu, 1988). Six possible mechanisms for this reaction are investigated. The corresponding
equations along with simplified forms for the six mechanisms tested for this reaction are expressed as follows:

Adsorption of ethyl alcohol controlling, single site

(29)

(30)
 Kassim 39

Simplified equation:

a + b x2 y (31)

Surface reaction controlling, single site

(32)

(33)

Simplified equation:

a + b x3 + c x2 y (34)

Desorption of acetaldehyde controlling, single site

(35)

(36)

Simplified equation:

a + b x3 + c (x3 / x2) y / x2 (37)

Adsorption of ethyl alcohol controlling, dual site

(38)

(39)

Simplified equation:

a + b x1 x2 + c x1 + d x2 y (40)
 Adv Sci Technol Res 40

Surface reaction controlling, dual site

(41)

(42)

Simplified equation:

a + b x3 + c x2 + d x1 (43)

Desorption of acetaldehyde controlling, dual site

(44)

(45)

Simplified equation is:

a + b x3 + c (x3/x1) + d x1 y/x1 (46)

Where:

x1 PS , x2 PR , x3 PA

The variables for different equations were estimated using the Quasi-Newton optimization technique, which gives
parameters estimation convergence rapidly. The computer-analyzed data show the coefficients of different rate-
controlling mechanisms at (300, 325 and 350C).
The parameters and standard deviation are tabulated in Table 8. From the results, we can conclude that dual site
surface reaction (serial No. 5) is the rate limiting. Results by Chhabra and Venkateswaralu (1988) further advocate our
conclusion.

CONCLUSIONS Refinery, has been used successfully in the present

investigation for the dehydrogenation of ethyl alcohol.
1. The new catalyst (ZnO-CuO/Al2O3) which is currently 2. The optimum operating conditions for a 0.5 h reaction
being used in the production of CO2 from CO in Baiji period were; reaction temperature (350C), W/F (2.915)
 Kassim 41

Table 8. Coefficient of reaction mechanism equations for ethyl alcohol.

Temp. Mechanism
Coefficients
(C) 1 2 3 4 5 6
a 1.8798 0.6855 0.025224 3.803 1.025 0.617
b 0.006313 0.6855 0.025224 4.014 1.025 0.012
c - 0.0022 1.921 1.9735 0.0057 1.255
300
d - - - 3.9207 0.6979 0.012
Standard deviation 6.932104 6.932104 2.60914 7.4255104 2.4084104 8.10323104
Correlation coeff. 0.64 0.643 0.986 0.845 0.79 0.628

a 1.3665 0.67 0.1359 1.472 26.3831 21.366

b 0.0041 0.67 0.1359 0.6076 26.3831 5.5
c - 1.6361 1.3374 0.1067 1.83724 11.745
325
d - - - 0.594 56.0202 5.5
Standard deviation 1.09395103 1.09395103 1.721 5.5877104 4.69403104 6.6582103
Correlation coeff. 0.526 0.04 0.992 0.58 0.88 0.99

a 1.0193 0.505 0.0687 1.3087 0.51358 221.34

b 0.001245 0.505 0.0687 1.2253 0.51358 57.18
c - 0.000651 1.000224 0.2997 0.001212 108.12
350
d - - - 1.1842 0.0186 57.18
Standard deviation 1.4401104 6.97227105 0.98524 1.4401104 8.2644105 2.0803103
Correlation coeff. 0.578 0.969 0.969 0.77 0.93 0.873

gmol/h, weight of catalyst (5 g), type of catalyst (No. 1) Church JM, Joshi HK, 1951. Acetaldehyde by dehydrogenation of ethyl
alcohol. Ind Eng Chem, 43(8):1804-1811.
and ethyl alcohol concentration (90%).
Eric KR, 1921. On the Catalytic Dehydrogenation of Alcohols. Proc Roy
3. Increasing the reaction temperature, consequently Soc, 99A, 153.
leads to an increase in the conversion and yield to a Fogler HS, 1974. The Elements of Chemical Kinetics and Reactor
maximum of (33 and 27%) respectively at temperature Calculations. Prentice-Hall Inc., New Jersey.
350C, then decrease till a stable limit of 22 and 17%. Fogler HS, 1986. Elements of Chemical Reaction Engineering.
Prentice-Hall, New Jersey.
This behavior occurs due to a probable sintering and Franckaerts J, Froment GF, 1964. Kinetic study of the
fouling of the catalyst. dehydrogenation of ethanol. Chem Eng Sci, 19:807-818.
4. The conversion and yield increase by increasing W/F, Froment GF, Bischoff KB, 1979. Chemical Reactor Analysis and
Design. John Wiley and Sons, New York.
the maximum value for conversion and yield are 42 and
Hughes R, 1984. Deactivation of Catalysts. Academic Press, London.
32%. This is attributed to an increase in contact time Iwasa N, Takezawa N, 1991. Removing ethanol-dehydrogenation to
between catalyst and ethyl alcohol. ethyl acetate and steam reforming to acetic acid over copper based
5. Decreasing the ethyl alcohol concentration resulted in catalyst. Bull Chem Soc Jap, 64:2619-2623.
a significant increase in the ethyl alcohol conversion Korn GA, Korn TM, 1968. Mathematical Hand Book for Scientists and
Engineers. McGraw-Hill, New York.
(maximum 48%). On the other hand, the acetaldehyde Levenspiel O, 1972. Chemical Reaction Engineering. John Wiley and
yield was unaltered indicating, a decrease in the Sons, London.
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6. The controlling step was found to be a dual-site Nakajima T, Tanabe K, Yamaguchi T, Matsuzaki I, Mishima S, 1989.
surface reaction. It was estimated using fast converging Conversion of ethanol to acetone over zinc oxide-calcium oxide
Quasi-Newton optimization technique. catalyst. Appl Catalysis, 52, 237.
Satterfield CN, 1980. Heterogeneous catalysis in practice. McGraw-
Hill, New York.
Smith JM, Van Ness HC, 1987. Introduction to Chemical Engineering
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