Unit Operations

47
CHAPTER 3

LOW COVERAGE ADSORPTION OF
LINEAR ALKANES ON ZSM-5 ZEOLITE

The influence of the composition and synthesis method on the low coverage adsorption
properties of C
5
-C
9
n-alkanes on ZSM-5 zeolites is studied using the pulse chromatographic
technique, at temperatures between 200 and 400C. Experiments are performed with
materials having Si/Al ratios between 12-400, synthesized with and without using an organic
template. For all ZSM-5 samples, with increasing carbon number, an exponential increase of
the Henry adsorption constants, an exponential decrease of the pre-exponential factors and a
linear increase of the adsorption enthalpy is found. Henry constants and adsorption
enthalpies decrease with increasing Si/Al ratio pointing at the dependence of the alkane
adsorption on the zeolite composition. Also the relationship between enthalpy and entropy is
different when the samples are synthesized without template.
Chapter 3: Low coverage adsorption of linear alkanes on ZSM-5 zeolite
48
3.1. Introduction

Among all zeolites, ZSM-5 is one of the most frequently studied, investigated in numerous
catalytic, adsorption and diffusion studies and too often- considered a model adsorbent. Its
properties are however dependent on the synthesis method as will be shown here.

Molecules hosted in the narrow pores of ZSM-5 have a strong interaction with the force field
exerted by the zeolite pore walls leading to pronounced differences in the adsorption of
molecules with different size, polarity, shape etc. Obviously, a good knowledge of these
adsorption properties will help to understand zeolite catalysis, explaining the efforts put into
the determination of adsorption equilibria on ZSM-5 zeolites. Particularly, the adsorption of
n-alkanes on ZSM-5 has been studied extensively by a range of experimental techniques
(Table 3.1; references in Table 3.2).

Generally, a linear increase of the adsorption enthalpy with the alkane carbon number was
observed (Titiloye et al., 1991; Hufton et al., 1993; Savitz et al., 1998; Zhu et al., 1998;
Abdul-Rehman et al., 1990; Richards et al., 1987; Stach et al. 1993; Eder et al. 1997;
Narbeshuber et al. 1995; Maginn et al. 1994; Sun et al. 1996; Smit, 1995). The linear
relationship between adsorption enthalpy and carbon number is explained by the additive
character of the dispersive forces invoked upon adsorption of alkanes (Stach et al. 1986;
Richards et al. 1987, Eder et al. 1997; Calero et al. 2001). Eder et al. (Eder et al. 1997) claim
that at low coverages, hydrocarbons are adsorbed via hydrogen bonds to the Brnsted acid
sites of the zeolites. Beside dispersive interactions, this hydrogen bonding contributes to a
limited extent to the total adsorption enthalpy. The strength of hydrogen bonding slightly
increases with increasing size of the adsorbed alkanes, caused by an increase of the mean
polarizability of the alkanes with chain length.

A large experimental dataset on the low coverage adsorption of alkanes is available. In Table
3.1, published data on adsorption enthalpies of n-alkanes (C
1
-C
10
) on ZSM-5 and silicalite-1
zeolites are summarized and shown in Figure 3.1 as a function of the carbon number.
Strikingly, a very large scatter in the experimental data is observed, showing differences up to
32 kJ/mol between the lowest and highest reported value for one particular n-alkane (Table
3.1). With respect to the increase of the adsorption enthalpy with carbon number, also
different values are reported: 9.81 kJ/mol per added CH
2
group (Stach et al. 1993), 9.96
kJ/mol (Hufton et al. 1993), 10.08 kJ/mol (Abdul-Rehman et al. 1990), 10.2 kJ/mol (Savitz et
49
al. 1998), 11.0 kJ/mol (Denayer et al. 1998), 11.3 kJ/mol (Zhu et al. 1998) and 12 kJ/mol
(Eder et al. 1997). Linear regression of data for pentane to decane on silicalite-1 obtained by
Sun et al. (Sun et al. 1996) result in an increase of 14.7 kJ/mol per added CH
2
group. It
should be mentioned that Suns data show a deviation from linear behaviour for hexane and
heptane, which is attributed to unique manner in which these molecules occupy the channels
of silicalite-1. Richards and Rees (Richards and Rees, 1987) found a slope of 10 kJ/mol from
ethane to butane, and only 5 kJ/mol from butane to hexane. Finally, using the values for
propane to hexane by Narbeshuber et al. (Narbeshuber et al., 1995) an increase of 15.9
kJ/mol per CH
2
group was calculated. Configurational-bias Monte Carlo simulations by
Smit (Smit, 1995) result in an increase of 11 kJ/mol for short alkanes (C
4
-C
8
) and 13 kJ/mol
for long alkanes (C
8
-C
12
). The more pronounced increase for long alkanes is explained by the
preferential sitting of the long-chain alkanes in the linear channels of silicalite-1. Molecular
simulations by Maginn et al. (Maginn et al., 1994) contrarily lead to a value of 10.5 kJ/mol
for the C
4
-C
28
n-alkane series.

This distribution of experimental and theoretical data for such a commonly used catalyst as
ZSM-5 is remarkable. Factors that could influence the experimental data are first of all the
experimental methodology and technique, but other factors such as synthesis method,
composition (Si/Al ratio), pre-treatment procedure (calcination/activation/drying) are, among
others, often crucial in the experimental determination of adsorption enthalpies.

In the present work, we have determined low coverage adsorption properties of C
5
-C
9
n-
alkanes using the chromatographic technique on a series of ZSM-5 zeolites from different
suppliers and with a different Si/Al ratio, in order to verify if there exists a relationship
between the measured adsorption properties and the nature of the ZSM-5 sample, which
could be a potential cause for the experimental scatter observed in literature.

50
Table 3.1. Adsorption enthalpies of C
1
-C
10
n-alkanes on ZSM-5/silicalite-1 from the literature
-H
0
Technique Zeolite Ref. -H
0
Technique Zeolite Ref. H
0
Technique Zeolite Ref. -H
0
Technique Zeolite Ref.
(kJ/mol) (kJ/mol) (kJ/mol) (kJ/mol)
CH
4
29.8 Ch Silicalite-1 5 52* Ch NaZSM-5 (24) 21 100.5 S HZSM-5 2
26.5 Cal NaZSM-5 (30) 1 29 Cal Silicalite-1 12,17 51* Ch HZSM-5 (24) 21 68.8 Ch ZSM-5(137) 24
23.7 S HZSM-5 2 32* Cal Silicalite-1 18 51* Ch NaZSM-5 (44) 21 69* Cal Silicalite-1 12
21 Cal ZSM-5 (30) 3 32.78 V Linde S115 10 50 G Silicalite-1 (132) 14 70.3 Cal Silicalite-1 17
25.5 S ZSM-5 (30) 3 31.1 Cal Silicalite-1 1 53 TEOM Silicalite-1(>3000) 8 70.5 G Silicalite-1 25
19 Ch HZSM-5 (31.1) 4 36.5 S Silicalite-1 2 53* Cal Silicalite-1 12 83.8 S Silicalite-1 2
21.2 Ch NaZSM-5 (31.1) 4 30* S Silicalite-1 11 51 Cal Silicalite-1 17 70* S Silicalite-1 11
20.5 Ch Silicalite-1 5 C
3
H
8
50.2 Ch Silicalite-1 5 65* S Silicalite-1 22
20 Ch Linde S115 (189
+
) 6 46 G, Cal HMFI (35) 19 53* Cal Silicalite-1 18 70.2 S Silicalite-1 23
20.9 Cal, V Linde S115 (300) 7 43 G, Cal HZSM-5 (35) 20 48.27 V Linde S115 10 C
7
H
16

18.4 Ch Silicalite-1 (>1000) 4 42.8 G HZSM-5 (17) 13 63.4 S Silicalite-1 2 83.4 G Silicalite-1 25
18.6 TEOM Silicalite-1 (>3000) 8 44 G HZSM-5 (65) 13 50* S Silicalite-1 11 79.6 Ch ZSM-5(137) 24
18.6 V SilicaliteS115(282
+
) 9 40 G Silicalite-1 (132) 14 45* S Silicalite-1 22 101.2 S Silicalite-1 2
20.9 Cal Silicalite-1 1 37* FR,SU NaZSM-5 (135) 15 48.3 S Silicalite-1 23 101.8 S HZSM-5 2
20.39 V Linde S115 10 34 Ch LindeS115(189
+
) 6 47 Ch LindeS115(189
+
) 6 80* S Silicalite-1 11
22.7 S Silicalite-1 2 41.4 Cal, V Linde S115 (300) 7 49* Ch Silicalite-1 21 C
8
H
18

20* S Silicalite-1 11 40*

FR,SU Silicalite-1 (1230) 15 C
5
H
12
92.1 G Silicalite-1 25
C
2
H
6
40.9 TEOM Silicalite-1 (>3000) 8 70 G, Cal HMFI (35) 19 90.7 Ch ZSM-5(137) 24
38 Cal NaZSM-5 (30) 1 40.5 Ch Silicalite-1 5 74 G, Cal HZSM-5 (35) 20 118.5 S Silicalite-1 2
33.3 Cal HZSM-5 (30) 1 39.85 V Linde S115 10 54 G HZSM-5 (17) 13 130.8 S HZSM-5 2
37.5

Cal ZSM-5 (23) 12 35* Iso Silicalite-1 16 92.2 S HZSM-5 2 90* S Silicalite-1 11
37.5 G HZSM-5 (17) 13 50.6 S Silicalite-1 2 57.7 Ch ZSM-5 (137) 24 C
9
H
20

28 Ch HZSM-5 (31.1) 4 66.9 S HZSM-5 2 63.5 Cal Silicalite-1 17 107.7 G Silicalite-1 25
30 Ch NaZSM-5 (31.1) 4 40* S Silicalite-1 11 41.8 G Silicalite-1 25 103* S Silicalite-1 11
41.7 S HZSM-5 2 C
4
H
10
78.6 S Silicalite-1 2 C
10
H
22

42.7 G HZSM-5 (65) 13 58 G, Cal HMFI (35) 19 60* S Silicalite-1 11 109* Iso Silicalite-1 12
30 G Silicalite-1 (132) 14 62 G, Cal HZSM-5 (35) 20 C
6
H
14
120.5 G Silicalite-1 25
31.1 Cal, V Linde S115 (300) 7 47 G HZSM-5 (17) 13 82 G, Cal HMFI (35) 19 115* Cal Silicalite-1 17
28.3 Ch Silicalite-1 (>1000) 4 65* Cal ZSM-5 (23) 12 65.1 Cal ZSM-5 (35) 26 113* S Silicalite-1 11
30*

FR,SU Silicalite-1 (1230) 15 77.4 S HZSM-5 2 92 G, Cal HZSM-5 (35) 20 110* S Silicalite-1 22
30.7 TEOM Silicalite-1(>3000) 8 56* Ch NaZSM-5 (10) 21 60 G Silicalite-1 (132) 14
30* Iso Silicalite-1 16 54* Ch HZSM-5 (10) 21 72* FR,SU NaZSM-5 (135) 15
+ Si/Al ratios were calculated based on composition; * Adsorption enthalpies data were read from the graph. Cal: Calorimetry; Ch: Chromatography; FR, SU:
Frequency response and sorption uptake; G: Gravimetry; Iso: Isosteric measurements; S: Simulation; TEOM: Tapered element oscillating microbalance; V:
Volumetry; See Table 3.2 for references.

51
Table 3.2. References of Table 3.1

1: Dunne et al., 1996
2: Titiloye et al., 1991
3: Yang et al., 2001
4: Choudhary et al., 1993
5: Hufton et al., 1993
6: Chiang et al., 1984
7: Savitz et al., 1998
8: Zhu et al., 1998
9: Golden et al., 1994
10: Abdul-Rehman et al., 1990
11: Vlugt et al., 1999
12: Stach et al., 1986
13: Doelle et al., 1981
14: Richards et al., 1987
15: Blow et al., 1986
16: Hampson et al., 1991
17: Stach et al., 1993
18: Thamm, 1987
19: Eder et al., 1997
20: Narbeshuber et al., 1995
21: Lechert et al., 1984
22: Maginn et al., 1994
23: June et al., 1992
24: Denayer et al., 1998
25: Sun et al., 1996
26: Derouane et al., 1988

Figure 3.1. Adsorption enthalpy of n-alkanes on ZSM-5 and silicalite-1. The open shapes and x
symbols are from the literature.

0
20
40
60
80
100
120
140
0 2 4 6 8 10 12
Carbon Number
H

(
k
J
/
m
o
l
)
Si/Al 35
Si/Al>35
<
52
3.2. Experimental Results

In addition to Table 2.2 where the characteristics of ZSM-5 zeolite can be found, extra
properties of the zeolites and experimental conditions can be seen on Table 3.3.

Table 3.3. Properties of ZSM-5 zeolites and experimental conditions
Zeolite SM27 CBV3024 SM55 CBV5524 SH300 CBV30014 Silikalit
Supplier Z1 Z2 Z1 Z2 Z1 Z2 Z1
Mol Al/kg
zeolite
1.28 1.04 0.67 0.64 0.11 0.11 0.04
Mol unit cells/kg
zeolite
0.173 0.173 0.173 0.173 0.173 0.173 0.173
Mol straight
channels/kg
zeolite
0.69 0.69 0.69 0.69 0.69 0.69 0.69
Mol zigzag
channels/kg
zeolite
0.69 0.69 0.69 0.69 0.69 0.69 0.69
Mol
intersections/kg
zeolite
0.69 0.69 0.69 0.69 0.69 0.69 0.69
Exp. temperature
range (C)
200-350 200-325 200-400 200-325 200-375 200-325 200-400
Pressure range
(bar)
1.27-1.37 1.41-1.51 1.36-1.53 1.36-1.46 1.66-1.87 1.98-2.32 2.52-3.40
macr
+
ext
0.68 0.70 0.61 0.70 0.59 0.51 0.58
Z1: Alsi-Penta, Z2: Zeolyst

To discriminate between the zeolites from the two suppliers, the zeolite series will be denoted
as Z1 for supplier Alsi-Penta and Z2 for supplier Zeolyst.

According to the suppliers, samples Z1 (Si/Al= 150), Z1 (Si/Al= 400), Z2 (Si/Al= 15), Z2
(Si/Al= 25), Z2 (Si/Al= 150) were synthesized using an organic template, while the two other
samples Z1 (Si/Al= 12) and Z1 (Si/Al= 24) were synthesized without organic template.

The measurements were performed between 200 and 400C. Data points were taken at
temperature intervals of 10, 15 or 25 C depending on the zeolite, in order to obtain between
5 and 10 data points per component.

To verify if the experiments were performed at low coverage, namely in the Henry region,
volumes of 0.01 l, 0.02 l and 0.1 l were injected (see Figure 3.2). From 0.02 l on, no
change in the retention time was observed. Experiments with different injection volumes
were repeated at different temperatures, to check the effect on the adsorption enthalpy,
calculated according to the vant Hoff equation (Equation 2.3).
53

Figure 3.2. Response curves obtained with different amounts of pentane injected into the zeolite
column on ZSM-5 (Z2), Si/Al=15 at 200C.

For the adsorption of pentane on the zeolite CBV3024, an adsorption enthalpy of 59.4 kJ/mol
was obtained for 0.1 l, 60.0 kJ/mol for 0.02 l and 59.9 for 0.01 l. On zeolite SH-300, the
adsorption enthalpy was 78.1 kJ/mol for 0.1 l and 78.2 kJ/mol for 0.01 l for heptane and
89.0 kJ/mol for 0.1 l and 89.2 for 0.01 l for n-octane. These examples demonstrate the
repeatability of the experiments and prove that the data were obtained in the linear part of the
adsorption isotherm.

3.2.1. Adsorption Equilibrium: Henry constants

The Henry adsorption constants are shown as a function of the carbon number in Figure 3.3
for the Z1 ZSM-5 series. As expected, the Henry adsorption constants increase exponentially
with the carbon number.

Both in Z1 and Z2 series, the Henry constants decrease with increasing Si/Al ratio (see Table
3.4), the difference becoming larger at higher chain lengths. For nonane, a difference of about
one order of magnitude in Henry constant between Z1 with Si/Al= 12 and Z1 with Si/Al=
400 is observed (Table 3.4).

0 2 4 6 8
t(min)
S

(
a
.
u
.
)
0.1 l; = 2.96 min
0.02 l; = 3.10 min
0.01 l; = 3.04 min
54
Figure 3.3. Henry constants of linear alkanes on ZSM-5 (Z1) with various Si/Al ratios at 300C.

Table 3.4. Henry constants on ZSM-5 zeolites for n-alkanes at 300C
K (mol/(kg Pa))
Z1
Carbon number Si/Al = 12 Si/Al = 24 Si/Al = 150 Si/Al = 400
5 1.19 10
-5
6.78 10
-6
3.94 10
-6
2.99 10
-6

6 2.87 10
-5
1.60 10
-5
8.00 10
-6
5.93 10
-6

7 7.19 10
-5
3.78 10
-5
1.67 10
-5
1.22 10
-5

8 1.85 10
-4
8.88 10
-5
3.38 10
-5
2.49 10
-5

9 4.38 10
-4
1.94 10
-4
6.41 10
-5
4.73 10
-5

Z2
Si/Al = 15 Si/Al = 25 Si/Al = 150
5 7.30 10
-6
6.50 10
-6
3.99 10
-6

6 1.61 10
-5
1.39 10
-5
7.93 10
-6

7 3.68 10
-5
3.09 10
-5
1.61 10
-5

8 8.28 10
-5
6.78 10
-5
3.32 10
-5

9 1.39 10
-4
6.42 10
-5

In Figure 3.4, the Henry constants are depicted as a function of the zeolite aluminum content.
It is noticed that all the Henry constants of heptane obtained on the samples synthesized with
organic template fall on a line, while the Henry constants obtained with the samples
synthesized without template are higher.
4 5 6 7 8 9 10
Carbon number
K
'

(
m
o
l
/
(
k
g

.

P
a
)
)
Z1, Si/Al=12
Z1,Si/Al=24
Z1,Si/Al=150
Z1,Si/Al=400
1 10
-5
1 10
-4
1 10
-6
1 10
-3
55

Figure 3.4. Comparison of Henry constants of n-heptane on ZSM-5 (Z1) and (Z2) at 300C.

3.2.2. Adsorption Enthalpy

The temperature dependence of the Henry constants is shown in Figure 3.5 for the adsorption
of pentane to nonane on ZSM-5 (Z2) with a Si/Al ratio of 150. For all vant Hoff plots,
correlation factors larger than 0.999 were obtained.
Figure 3.5. Vant Hoff plot for n-alkane adsorption on ZSM-5 (Z2) (Si/Al=150).

0 0.2 0.4 0.6 0.8 1 1.2 1.4
mol Al/kg zeolite
K
'

(
m
o
l
/
(
k
g

.

P
a
)
)
n-heptane,Z2
n-heptane,Z1
8 10
-5
7 10
-5
6 10
-5
5 10
-5
4 10
-5
3 10
-5
2 10
-5
1 10
-5
0
no template
-14
-13
-12
-11
-10
-9
-8
-7
1/T (1/K)
l
n
(
K
'
(
m
o
l
/
(
k
g

.

P
a
)
)
)
n-pentane n-hexane
n-heptane n-octane
n-nonane
1.6 10
-3
1.7 10
-3
1.8 10
-3
1.9 10
-3
2 10
-3
2.1 10
-3 2.2 10
-3
56
Figure 3.6 shows the zero coverage adsorption enthalpies on the zeolites synthesized with
organic template. The data are also given in Table 3.5. The adsorption enthalpy appears to be
dependent on the Si/Al ratio.
Figure 3.6. Adsorption enthalpy against carbon number at zero coverage on zeolites synthesized with
organic template.

This is clearly demonstrated in Figure 3.7, where the adsorption enthalpy is plotted as a
function of the Al content for both zeolite series. For nonane, a difference of 10 kJ/mol is
observed between Z1 with Si/Al= 12 and Z1 with Si/Al= 400.

Figure 3.7. Adsorption enthalpy as a function of the zeolite Al content. Open shapes and x symbols:
Z1 series; solid shapes and + symbols: Z2 series.
50
60
70
80
90
100
110
4 5 6 7 8 9 10
Carbon number
H
0

(
k
J
/
m
o
l
)
Z2,Si/Al=15
Z2,Si/Al=25
Z2,Si/Al=150
Z1,Si/Al=400
40
50
60
70
80
90
100
110
120
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 1.1 1.2 1.3 1.4
mol Al/kg zeolite
-
H
0

(
k
J
/
m
o
l
)
n-pentane n-hexane
n-heptane n-octane
n-nonane
165 82 54 41 27 32 23 17 20 16 14 13 12
11
Si/Al ratio
57
As is generally observed, there exists a linear relationship between the carbon number and the
adsorption enthalpy:

+ = CN H
0
3.1

The factor, representing the increase of adsorption enthalpy with carbon number, is given
in Table 3.5. The increase of -H
0
with carbon number depends on the zeolite composition,
and is different for the two ZSM-5 series. For the Z1 series, an increase of 10.7 kJ/mol per
CH
2
group is observed for a Si/Al ratio of 12, while the enthalpy increases less strongly with
carbon number (10.1 kJ/mol per CH
2
group) for a Si/Al ratio equal to 400. Although there
seems to be a tendency to lower factors at low Al contents, the Z1 sample with Si/Al= 150
deviates from this tendency, with a sudden increase to 10.8 kJ/mol per added CH
2
group.

Table 3.5. Experimental adsorption enthalpies of n-alkanes
-H
0
(kJ/mol)
Z1
5 62.9 0.6 62.2 0.4 56.3 0.5 55.7 0.7
6 75.7 0.5 73.3 0.2 67.6 0.5 66.0 0.7
7 85.9 0.7 82.9 0.3 78.2 0.3 76.7 0.4
8 95.7 0.9 94.3 0.4 89.2 0.5 86.6 0.4
9 106.4 2.9 104.2 0.5 99.6 1.2 96.1 0.4

(kJ/mol) 10.7 0.3 10.5 0.1 10.8 0.1 10.1 0.1

Correlation factor (H
0
versus CN) 0.9977 0.9995 0.9999 0.9994
Z2
Si/Al = 15 Si/Al = 25 Si/Al = 150
5 59.9 0.3 59.2 0.4 56.2 0.5
6 72.4 0.1 70.1 0.7 67.2 0.3
7 83.9 0.2 81.9 0.2 78.4 0.2
8 96.4 0.2 93.9 0.2 89.2 0.2
9 105.0 0.6 99.1 0.5

(kJ/mol) 12.1 0.1 11.5 0.2 10.8 0.1

Correlation factor (H
0
versus CN) 0.9997 0.9997 0.9995

58
For the Z2 series, an increase of 12.1 kJ/mol is observed for a Si/Al ratio of 15, which is
significantly higher than the value found for Z1, with Si/Al = 12. Also for the Z2 zeolite with
Si/Al= 25, a higher value (11.5 kJ/mol) is found than with the Z1 ZSM-5 zeolite (10.5
kJ/mol) with a comparable Si/Al ratio of 24. Remarkably, both the Z1 and Z2 samples with
Si/Al= 150 have approximately the same adsorption enthalpy, and show exactly the same
increase in adsorption enthalpy with carbon number (10.8 kJ/mol). When only the ZSM-5
samples synthesized with organic template are considered (Z2 (Si/Al= 15), Z2 (Si/Al= 25),
Z2 (Si/Al= 150), Z1 (Si/Al= 150), Z1 (Si/Al= 400)), a continuous evolution of with the
composition is found (see Table 3.7). The samples synthesized without organic template
behave differently.

3.2.3. Adsorption entropy: Preexponential factors

The pre-exponential factors of the vant Hoff equation are given in Table 3.6, and plotted in
Figure 3.8 for the Z1 ZSM-5 series as a function of the carbon number. K
0
decreases
exponentially with the carbon number.

Figure 3.8: Pre-exponential factors of the vant Hoff equation against carbon number (ZSM-5 Z1
series).

The pre-exponential factor K
0
is related to the entropy of adsorption
local
S
, 0
and the number
of adsorption sites n
T
as it was also indicated in equation 2.4:
22
24
26
28
30
32
4 5 6 7 8 9 10
Carbon number
-
l
n

(
K
o
'
(
m
o
l
/
(
k
g

.

P
a
)
)
)
Z1,Si/Al=12
Z1,Si/Al=24
Z1,Si/Al=150
Z1,Si/Al=400
59

(
(
|
|
.
|
\
|
+
p
n
R
S
K
T local
2
ln exp
, 0
0

3.2

where
p is the standard pressure (1 atm). The subscript 0 refers to the zero coverage limit.
An exponential decrease of K
0
thus corresponds to a linear relationship between the
adsorption entropy and the carbon number, which has been observed for various other
adsorption systems (Eder et al., 1997; Lechert et al., 1984):

= +
0 local
S CN
,
3.3

The contribution to the adsorption entropy per carbon atom (given by the parameter)
depends on the ZSM-5 composition, and varies between 11.2 and 14.4 J/mol/K (Table 3.6).
Although the increase of the adsorption entropy with CN depends in a subtle way on the
zeolite composition, K
0
is not proportional to the Al content (Figure 3.9).

Table 3.6. Pre-exponential factors of the vant Hoff equation
K
0
'(mol/(kg Pa))
Z1
5 (2.23 0.32) 10
-11
(1.47 0.12) 10
-11
(2.98 0.34) 10
-11
(2.64 0.42) 10
-11

6 (3.58 0.44) 10
-12
(3.37 0.12) 10
-12
(5.69 0.58) 10
-12
(6.07 0.87) 10
-12

7 (1.06 0.16) 10
-12
(1.06 0.08) 10
-12
(1.28 0.09) 10
-12
(1.29 0.12) 10
-12

8 (3.47 0.69) 10
-13
(2.29 0.20) 10
-13
(2.55 0.24) 10
-13
(3.25 0.29) 10
-13

9 (8.39 5.28) 10
-14
(6.21 0.67) 10
-14
(5.50 1.34) 10
-14
(8.41 0.71) 10
-14

(J/(mol K)) 11.23 11.32 13.05 11.99
Z2
Si/Al = 15 Si/Al = 25 Si/Al = 150
5 (2.55 0.18) 10
-11
(2.61 0.22) 10
-11
(2.94 0.30) 10
-11

6 (4.10 0.09) 10
-12
(5.90 0.99) 10
-12
(5.90 0.42) 10
-12

7 (8.38 0.35) 10
-13
(1.07 0.04) 10
-12
(1.15 0.04) 10
-12

8 (1.36 0.06) 10
-13
(1.86 0.08) 10
-13
(2.47 0.12) 10
-13

9 (3.76 0.46) 10
-14
(5.96 0.69) 10
-14

(J/(mol K)) 14.38 13.76 12.95
s
60
Figure 3.9. Pre-exponential factors of the vant Hoff equation as a function of the Al content. Open
shapes and x symbols: Z1 series; solid shapes and + symbols: Z2 series.

3.2.4. Correlation for Henry constants

Equations 3.1 and 3.3 can be combined into the vant Hoff equation (eq. 2.3) to obtain a
general correlation for the Henry constants as a function of the carbon number:

ln ' ln K
RT R
CN
n
p
RT R
T
=
|
\
|
.
| +
|
\
|
.
|
|
+
(
(

2

3.4

By non-linear regression of this equation to the Henry constants, the and parameters can
be obtained directly, without prior calculation of the adsorption enthalpies and pre-
exponential factors as is done usually. The experimental data fit nicely on a plane, as is
shown in Figure 3.10 for the adsorption of C
5
-C
9
on the Z1 ZSM-5 sample with Si/Al = 12.
The parameters calculated using eq. 3.4 are compared to those obtained from linear
regression of the adsorption enthalpy and pre-exponential factors as a function of the carbon
number in Table 3.7. Only slight differences are found, the relative tendencies being the
same.
22
23
24
25
26
27
28
29
30
31
32
0 0.2 0.4 0.6 0.8 1 1.2 1.4
mol Al/kg zeolite
-
l
n
(
K
o
'
(
m
o
l
/
(
k
g

.

P
a
)
)
)
n-pentane n-hexane
n-heptane n-octane
n-nonane
61
-14
-12
-10
-8
-6
-4
-2
0.0016
0.0017
0.0018
0.0019
0.0020
0.0021
5.0
5.5
6.0
6.5
7.0
7.5
8.0
8.5
l
n
(
K
'

(
m
o
l
/
(
k
g

.

P
a
)
)
)
1
/
T

(
1
/
K
)
C
a
rb
o
n
n
u
m
b
e
r

Figure 3.10. Temperature and carbon number dependence of Henry constant of n-alkanes on ZSM-5
(Z1) (Si/Al=12).

Table 3.7. Coefficients , , of equation 3.4 between the Henry constants, carbon number and
temperature for linear alkanes
Organic template
(kJ/mol) (kJ/mol) (J/(mol K))
Supplier Si/Al ratio Method 1 Method 2 Method 1 Method 2 Method 1 Method 2
Z2 15 12.10 11.86 -0.47 0.85 14.38 13.98
Z2 25 11.54 11.81 1.22 -0.47 13.76 14.23
Z2 150 10.76 11.20 2.69 0.004 12.95 13.71
Z1 150 10.82 11.00 2.47 1.32 13.05 13.35
Z1 400 10.14 10.43 5.23 3.44 11.99 12.45
No template
Z1 12 10.71 10.96 10.31 8.88 11.23 11.63
Z1 24 10.49 10.48 9.96 9.86 11.32 11.30
Method 1: Linear regression of H
0
and K
0
data from Tables 3.4 and 3.5 as a function of
CN. Method 2: Nonlinear regression of experimental Henry constants using Eq. 3.4.

62
3.3. Discussion

The data of this work show a clear influence of the ZSM-5 composition and synthesis route
on the adsorption properties. The Henry constants decrease with decreasing Al content, but in
a different way for the two synthesis methods (Figure 3.4).

No significant effect of the Si/Al ratio on K
0
was observed for the ZSM-5 zeolites (Figure
3.9), whereas a pronounced effect of the Al content with e.g. faujasite zeolites was
encountered before (Denayer et al., 1998). For the faujasites, it was demonstrated that the
alkane molecules preferentially adsorb on the Brnsted acid sites or the cations of the zeolite
(Eder et al., 1997). As the number of Brnsted acid sites or cations equals the number of
tetrahedral Al atoms in the framework, K
0
decreases with increasing Si/Al (see Eq. 3.2). No
such simple relationship between Al content and K
0
is observed for ZSM-5: at a Si/Al ratio
of 12, the number of Brnsted acid sites equals 1.28 mol/kg, while at a Si/Al ratio of 400,
only 0.04 mol/kg Brnsted acid sites are present. It could be expected that this difference of a
factor 32 between the two extremes would also be reflected in the pre-exponential factors for
both zeolites, which is clearly not the case (Figure 3.9, Table 3.6).

With respect to the number of adsorption sites in ZSM-5, its pore structure needs some
consideration. Sinusoidal channels and linear channels intersect, to form free cavities with an
intersection diameter of 9 (June et al. 1992, Ottaviani et al., 2001). The length of the
sinusoidal channels (between two intersections) equals 6.7 (Ottaviani et al., 2001), while
the linear channels have a length of 4.5 . Without elaborating on which type of channel is
preferred by the alkane molecules, it is clear that the channels of ZSM-5 can very well
accommodate the alkane molecules, and that depending on the length of the molecule, each
intersection, linear or sinusoidal channel segment or even combinations of them can behave
as an adsorption site. According to this hypothesis, the number of adsorption sites is the same
for all ZSM-5 samples.

In Figures 3.11 and 3.12, the pre-exponential factors of the vant Hoff equation are shown as
a function of the adsorption enthalpy on the ZSM-5 series synthesized with and without
template respectively. The parameters of relationship between the pre-exponential factors and
the adsorption enthalpy, obtained by linear regression of the experimental data, are given in
Table 3.8.

63
Figure 3.11. Relationship between pre-
exponential factors and adsorption enthalpies at
zero coverage on the ZSM-5 samples synthesized
using organic template.
Figure 3.12. Relationship between pre-
exponential factors and enthalpies at zero
coverage on the ZSM-5 samples synthesized
without organic template.

Table 3.8. The parameters of the relationship between the pre-exponential factors and the adsorption
enthalpy ( B H A K + =
0 0
. ln )
Organic template
Supplier Si/Al ratio A (mol/kJ) B
Z2
15 0.143 15.8
Z2
25 0.143 15.9
Z2
150 0.145 16.1
Z1
150 0.145 16.1
Z1
400 0.143 16.4
No template
Z1
12 0.126 16.7
Z1
24 0.130 16.9

Strikingly, for all ZSM-5 samples prepared using an organic template (Z1: Si/Al = 150 and
400; Z2: Si/Al = 15, 25 and 150), exactly the same increase of K
0
with -H
0
is obtained
(Table 3.8), which means that the relationship between adsorption entropy and enthalpy is
independent on the ZSM-5 composition for these materials. The Z1 samples synthesized
without organic template (Si/Al = 12 and 24) also show a comparable behavior, but with a
lower increase of K
0
with H
0
. Hence, the shift of the lines on the -lnK
0
versus -H
0
plot
22
24
26
28
30
32
34
50 70 90 110 130
-H
0
(kJ/mol)
-
l
n
(
K
o
'
(
m
o
l
/
(
k
g

.

P
a
)
)
)
Z2,Si/Al=15
Z2,Si/Al=25
Z2,Si/Al=150
Z1,Si/Al=150
Z1,Si/Al=400
22
24
26
28
30
32
50 70 90 110
-H
0
(kJ/mol)
-
l
n
(
K
o
'
(
m
o
l
/
(
k
g

.

P
a
)
)
)
Z1,Si/Al=12
Z1,Si/Al=24
64
with Si/Al ratio can be attributed to differences in the number of adsorption sites. Based on
the correlations given in Table 3.8, together with eq. 3.2, it is calculated that the Z2 sample
with Si/Al = 15 has approximately 1.7 times more adsorption sites than the Z1 sample with
Si/Al = 400. This value is certainly much lower than the ratio of Brnsted acid site
concentrations on these materials, which is equal to 26 as calculated from the aluminum
content (see Table 3.3). It should be remarked that practically no difference in the number of
adsorption sites between the Z2 samples with Si/Al = 15 and 25 is observed (Figure 3.11).
Contrarily, for the two Z1 samples with Si/Al ratios of 12 and 24, a difference in number of
adsorption sites of about 1.6 is found, which is quite close to the ratio of Al contents of both
zeolites (1.9).

One possible explanation for the small difference in number of adsorption sites found with
the samples synthesized using an organic template is that at the highest Al content, the
preferred adsorption sites are the Brnsted acid sites, while at lower Al contents, the channel
segments and intersections serve as preferred adsorption site at low coverage. For the Z2
(Si/Al = 15) sample, the Al content equals 1.04 mol/kg, while the number of linear channels
equals 0.69 mol/kg, which gives us a ratio of 1.5, close the value of 1.7, found
experimentally. Alternatively, it could be argued that at high Al contents alkanes are
adsorbed in all channel types, while at low Al contents, only one of the two channel types is
used, which gives a difference of a factor 2 in n
T
(see Table 3.3). Obviously, these
suggestions are open for discussion, and other explanations might exist.

The adsorption enthalpy decreases with decreasing Al content (Figure 3.7, Table 3.5). Also
Stach et al. (Stach et al., 1986) found a difference of 9 kJ/mol for the adsorption of ethane on
ZSM-5 (Si/Al = 23) and silicalite-1 (Si/Al very large). As shown by IR measurements,
alkanes are adsorbed on Brnsted acid sites via hydrogen bonding (Eder et al. 1997).
Gravimetric/calorimetric measurements showed that this hydrogen bonding induces a polarity
in the alkane chain, leading to an additional interaction of 10 kJ/mol compared to non-
localized adsorption in the zeolite pores (Eder et al., 1997). The chain length dependence of
this induced polarization is negligible compared to the total interaction energy. Hence an
additional contribution of 10 kJ/mol for all studied alkanes is added to the dispersive
interaction between the molecule and the zeolite framework when the alkane is adsorbed on a
Brnsted acid site. When the Si/Al ratio of the zeolite increases, the Brnsted acid site
density decreases. At high Si/Al ratios, it is more probable that a molecule is adsorbed in a
65
non-localized way in the zeolite pores than on a Brnsted acid site, as was explained before.
The Z2 (Si/Al = 15) sample, synthesized with organic template contains 6.0 Brnsted acid
sites per unit cell, while the Z1 (Si/Al = 400) sample, also synthesized with organic template
contains only 0.23 Brnsted acid sites per unit cell. For octane, a difference in adsorption
enthalpy of 9.8 kJ/mol is found between these two zeolites, which corresponds quite well
with the contribution of 10 kJ/mol of the Brnsted acid site to the total adsorption enthalpy.
As the Henry adsorption constants increase exponentially with carbon number, the
probability to adsorb in a non-selective way rather than on a Brnsted acid site increases with
chain length, explaining the dependence of the factor (see Table 3.5) on the zeolite
composition.

A discrepancy is again observed for the two Z1 samples, synthesized without organic
template (Si/Al = 12 and 24). Compared to the other high alumina samples, these materials
show a lower increase of adsorption enthalpy with carbon number. According to the supplier
of the Z1 series, the samples with Si/Al = 12 and 24 are produced by direct, template-free
synthesis while the other two samples (Si/Al = 150 and 400) were produced using a synthesis
template. Compared to the samples synthesized with template, the Z1 (Si/Al = 12) and Z1
(Si/Al = 24) samples have smaller crystal sizes (0.5-5 m compared to > 10 m), a more
homogeneous distribution of Al across the crystals and contain more defects (silanol nests)
due to the removal of the organics via calcination. The samples synthesized with template are
enriched in aluminum on the outer crystal-zones (Tiler et al., 1988). Moreover, the samples
synthesized without template contain, besides Brnsted acid sites, a relatively large number
of Lewis acid sites (Wallau et al., 1993). The presence of defects and Lewis acid sites in the
structure of the samples synthesized without template and the different Al distribution
obviously influence the adsorption properties. The interaction between an alkane and a
Brnsted acid site is certainly different from that between an alkane and a Lewis acid site. A
profound characterization of the investigated samples would certainly contribute to the
understanding of the observed effects, but falls out of the scope of this work.

To conclude, it can be stated that, depending on the synthesis method, a different adsorption
behavior is observed. This is shown clearly in Figure 3.13, where the -parameter (giving the
increase of adsorption entropy with CN) is shown as a function of the -parameter (giving
the increase of adsorption enthalpy with CN). The parameters of the ZSM-5 samples
66
synthesized using organic template lie on a unique line, for which higher contributions to the
adsorption enthalpy are correlated with higher contributions to the adsorption entropy (per
CH
2
group). The samples synthesized without organic template first of all have a lower
increase of adsorption entropy with enthalpy, indicating that adsorption in these samples
occurs in a less constrained manner. Secondly, with these two zeolites, it appears that the
increase of entropy with CN is much less affected by the increase of enthalpy with CN.

Figure 3.13. Increase of adsorption entropy per CN versus increase of adsorption enthalpy per CN.

The present measurements show a clear dependency of the adsorption constants on the zeolite
source and composition, explaining at least a part of the distribution of reported adsorption
parameters in literature. A simple statistical analysis shows that 77 % of the experimental
data points from literature on adsorption enthalpy are inside the area between the two curves
giving the minimal and maximal adsorption enthalpies found in this work (Figure 3.14).
Experimental data from 26 publications were inside the same distribution, while experimental
data from 10 other publications were still outside.

10
10.5
11
11.5
12
12.5
13
13.5
14
14.5
15
10 10.5 11 11.5 12 12.5
(kJ/mol)

(
J
/
(
m
o
l

.

K
)
)
Z1, Si/Al=24,
template free
Z1, Si/Al=12,
template free
Z1, Si/Al=400,
template
Z1, Si/Al=150,
template
Z2, Si/Al=150,
template
Z2, Si/Al=25,
template
Z2, Si/Al=15,
template
67
3.4. Conclusions

Using the chromatographic technique, the influence of the zeolite composition and synthesis
method on the adsorption of n-alkanes has been investigated. For all investigated ZSM-5
samples, the commonly observed tendencies are found: with the increase of carbon number,
an exponential increase of the Henry constant, an exponential decrease of the pre-exponential
factors and a linear increase of the adsorption enthalpy is found.

Figure 3.14. Adsorption enthalpy of n-alkanes on ZSM-5 and silicalite-1. The open shapes and x
symbols are from the literature. The solid shapes are experimental values of this study.

The adsorption of n-alkanes on ZSM-5 zeolites depends strongly on the composition of the
material. Henry adsorption constants and adsorption enthalpies decrease with increasing
Si/Al ratio, and thus with decreasing Al content. This is probably due to the interaction
between the alkanes and the Brnsted acid sites for high Al samples. All ZSM-5 samples
synthesized using an organic template show the same relationship between adsorption
entropy and enthalpy. For the materials synthesized without organic template, the adsorption
entropy increases less strongly with the adsorption enthalpy, which should be caused by the
presence of Lewis acid sites and defects and the difference Al distribution in the structure.
y = 10.13x + 4.77
y = 10.70x + 10.92
0
20
40
60
80
100
120
140
0 2 4 6 8 10 12
Carbon Number
-
H
0

(
k
J
/
m
o
l
)
Si/Al 35
Si/Al>35
Si/Al=12,Z1,experimental
Si/Al=400,Z1,experimental
<

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