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the absence of secondary olefin aromatization process. Protolytic cracking of the C - H bond,
Three H-ZSM-5 zeolites with SIO2/A1203 ratios (R) of 34,
240, arid 280 (samples defined as Z-34, Z-240, and Z-280, I'CH = kcHPc,[Z];
respectively) were used. Details of the catalyst prepara-
tion and catalytic measurements are reported elsewhere Protolytic cracking of the C-C bond,
(14).
rcc = kcc(n)Pc,[Z];
25
4. Olefin oligomerization and cracking,
ri= ~ uisrs 1 - - i - < 16,
s=l
k~(n,m)
+ CruZ. " CT+mZ
ko (n,ra)
where r; is the rate of transformation of the ith compo-
2<-n,m<-8,4<-n - 10.
+ m < nent, vis is the stoichiometric coefficient of the ith compo-
nent in the sth reaction step, and rs is the rate of the sth
5. Olefin adsorption and desorption, reaction step. Steady-state concentration of vacant cata-
lytic sites is calculated using the following equation:
Ka
C-~+Z. 'C~Z 2 - < n - < 10.
Rate Constants Note. Rate constant value for C - H bond cracking step has been
taken as unity (absolute value of this rate constant is 12.6 mmol
In order to define the effect of the aluminum content on g-lh-I).
HZSM-5 activity in the steps of protolytic cracking of the
C - H and C - C bonds in the n-hexane molecule and in the steps of hydrogen transfer between n-hexane and light
olefins, we compared the values of the rate constants of
these steps determined at 500C for Z-34, Z-240, and Z-
N 0.3 280 zeolites. The comparison has shown that zeolite ac-
0.2 tivity in all the above reaction steps is strictly propor-
tional to the zeolite aluminum content. Such a
i 0.1 H2 dependence was reported previously (16) for the steps of
O _ _ . _ _ . _ _ . - - - . - - ---C olefin oligomerization and cracking. These results further
o
0 0.02 0.04 0.06 support the conclusion, made in a number of papers (3, 4,
Contoct time, h 14, 17, 18), that HZSM-5 of different SiOJA1203 ratios,
i.6 when prepared in the absence of water vapor, contains
catalytic sites of only one type: bridging hydroxyl groups
g o J J
~ 0.8 associated with framework aluminum atoms.
L. Table 1 demonstrates the values of the rate constants
for protolytic cracking of n-hexane over Z-240 zeolite.
g o
0 0.02 0.04 0.06 The presented data indicate that the most probable event
Contoct time, h is the cracking of C - C bonds with formation of C2 and C3
paraffins and C4 and C3 olefins, respectively. The rela-
tively high probability of hydrogen formation in the C - H
4 bond cracking step should be also noted.
Rate constant values presented in Table 2 show that
the rate of hydrogen transfer between n-hexane and ole-
2
fins increases sharply from ethene to butenes and does
g
~J
o
0 0.02 O.Oq 0.06 TABLE 2
Contoct time, h
Activation Energy and Relative Values of the Rate Constants of
3
Hydrogen Transfer Steps on Z-240 Zeolite at 500C
2 Relative rate
Reaction step constant value Ea, kJ/mol
i
C6 + CTZ ~ C6Z + C,. 1 8.9
C6 + CTZ ~ C6Z + C3 48.3 7.4
o C6 + C~Z---~ C~Z + C4 73.3 4.1
0.02 0.04 0.06
Contoct time, h C6 + C-'~Z--* C~Z + C~ 73.3 4.1
FIG. 1. Cracking of hexane over Z-240 zeolite at 500C. Experimen- Note. Rate constant value for the step of n-hexane interaction with
tal data (points) and simulated curves for the concentrations of reaction adsorbed ethene has been taken as unity (absolute value of this rate
products as function of contact time. constant is 8.8 mmol g-lh-t).
90 LUKYANOV. SHTRAL, AND KHADZHIEV
Contribution of Hydrogen Transfer to Hexane Cracking acter of the reaction (see Fig. 3). In agreement with the
aforementioned data, the magnitude of the autocatalytic
In order to estimate quantitatively the contribution of effect decreases sharply with increasing temperatureL
hydrogen transfer steps in the overall hexane conversion,
we used the results of mathematical modeling performed a-Activity
in the following manner. At first, the hexane cracking
The reaction of n-hexane cracking has been used (1-4)
reaction was simulated using the rate constant values
as a test reaction (a-test) for the catalytic activity of zeo-
corresponding to the real catalyst (Z-240). In that way the
lite catalysts. In the modified a-test (3, 4), catalytic activ-
simulated dependence of the reaction rate r~ on hexane
ity was evaluated by determining the first-order rate con-
conversion was obtained. After that, the rate constants of
stant of cracking n-hexane at 538C and initial n-hexane
hydrogen transfer steps were equated with 0, and the
concentration of 13 tool%.
simulated dependence of the reaction rate r2 on hexane
The results of the previous (6, 12-15) and present stud-
conversion was obtained. The contribution of hydrogen
ies demonstrate that n-hexane cracking proceeds via two
transfer steps Cnx (%) was defined as the ratio 100(r~ -
reaction mechanisms. A question arises as to the nature
r2)/rl, using the values of rl and 1"2corresponding to the
of the catalytic activity measured in the a-test: it could be
same hexane conversion.
activity in protolytic cracking steps, or activity in hydro-
Figure 2 indicates that with increasing initial hexane
concentration and conversion level, and with decreasing
temperature, the contribution of hydrogen transfer steps TABLE 3
in the overall hexane conversion increases appreciably. Contribution of Hydrogen Transfer Steps to n-Hexane Cracking
Table 3 shows that the quantitative estimates obtained on over H-ZSM-5 at 450C (conversion 10%)
the basis of the proposed kinetic model are in reasonable
agreement with the estimates obtained previously by Initial hexane concentration, mol% 10 20 100
Haag and Dessau (6).
Cwr, % (data from Ref. (6)) 21 40 78
The contribution of hydrogen transfer steps in hexane CHr, % (data of this work) 15 24 54
transformation manifests itself in the autocatalytic char-
HEXANE CRACKING OVER H-ZSM-5 91
'7 0.0
~=
i
J
"~, -0.2 ~ , , , , , ~
g 400"C
z 240
i i
o:: q 8 12
x Z-240( o
Conversion, %
Z-240(1)
7 32
-0.6 , , ,
i 2 3 4
~ 20 i i
10 20 30
Conversion, % the catalyst sample weight and the feed molar rate. Fig-
ure 4 shows that the n-hexane cracking reaction, which
FIG. 3. Effect of n-hexane conversion on the rate of the reaction
over Z240 zeolite at 400 and 500C: Experimental data (points) and
proceeds via two mechanisms, can be described (under
simulated curves. the chosen conditions) by first-order kinetics, as has been
already reported previously (4). From Figure 4 it follows
that for Z-240 catalyst the first-order rate constant k~ is
gen transfer steps, or a combination of these two activi- equal to 135 mmol g-~h -I. This value coincides practi-
ties. cally with the sum of the rate constants of protolytic
In order to solve this question we performed mathe- cracking steps over this catalyst (at 538C this sum is
matical modeling of the n-hexane cracking reaction over equal to 133 mmol g-th-t).
real Z-240 catalyst and two hypothetical Z-240(1) and Z- Table 4 compares the first-order rate constants corre-
240(2) catalysts (activities of these catalysts are charac- sponding to Z-240, Z-240(1), and Z-240(2) catalysts with
terized by the data shown in Table 4). Simulations were the rate constants of different reaction steps over these
carried out under the conditions of the a-test, and the catalysts. From the presented data it is clear that a-activ-
dependence of n-hexane conversion on contact time ity is governed by the activity in protolytic cracking
(WHSV -t) was obtained for the three mentioned cata- steps, and slightly depends on the activity in hydrogen
lysts. After that simulated data were plotted in coordi- transfer steps. This finding, as well as the correctness of
nates of the first-order kinetic equation (see Fig. 4), the first-order kinetics for n-hexane cracking under the
where contact time was determined as the ratio between conditions of the a-test, can be explained by the low
contribution of hydrogen transfer steps to overall hexane
conversion under such reaction conditions (high temper-
TABLE 4
ature and low n-hexane concentration in the feed).
Relative Values of the Rate C o n s t a n t s of Proto-
lytic C r a c k i n g Steps a n d Hydrogen Transfer REFERENCES
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(198O).
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(1984).
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been taken as unity. Catal. 93, 30 (1985).
92 LUKYANOV, SHTRAL, AND KHADZHIEV
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