JOURNAL OF CATALYSIS 127, 51--66 (1991)

Relation between Properties and Performance of Zeolites

in Paraffin Cracking
A. F. H. WIELERS,M. VAARKAMP, AND M. F. M. POST
Koninklijke/Shell-Laboratorium Amsterdam (Shell Research B.V.), Badhuisweg 3,
1031 CM Amsterdam, The Netherlands

Received February 19, 1990; revised August 10, 1990

The effects of zeolite structure, acid site density, and reaction temperature on the mode of n-
hexane cracking have been studied. The results can be consistently explained in terms of the
occurrence of two different cracking routes, viz. the classical fl-scission route and the monomolecu-
lar protolytic pathway. The relative contribution of each of the two cracking routes is expressed by
the "cracking mechanism ratio" (CMR): a high value of this index points to a relatively high
contribution of the protolytic cracking route, whereas a low value indicates that the classical fl-
scission route is the main cracking pathway. With increasing temperature, decreasing aluminium
content, and decreasing pore dimensions the relative contribution of the (monomolecular) protolytic
cracking route increases as compared to the (bimolecular) classical route. On the basis of these
results the variation of the constraint index (i.e., the ratio of the first-order rate constants for
conversion of n-hexane and 3-methylpentane) with aluminium content and reaction temperature
can be easily rationalized. Furthermore, the present results also provide an explanation for the
change in the activation energy of n-hexane cracking with aluminium content in zeolite ZSM-5
(MFI). Finally, it is tentatively concluded that the classical cracking route is favoured by the
presence of two adjacent acid sites and by low reaction temperatures. Consequently, the relation
between the reaction rate constant and the lattice aluminium content changes with the reaction
temperature; whereas at 811 K the cracking constant varies linearly with the aluminium content,
at 623 K the order in the aluminium content increases to about 2. © 1991AcademicPress.Inc.

INTRODUCTION of the classical fl-scission route are propene

and isobutane, the typical products of the
In catalytic cracking solid acid materials protolytic cracking route are methane, eth-
are used as catalysts to convert vacuum dis- ene, ethane, and hydrogen.
tillates and residues into high-octane gaso- Haag and Dessau (4) and Corma et al. (5)
lines, diesel oil, and olefinic gases. Further- have suggested that protolytic cracking with
more, catalytic cracking of paraffins is zeolites proceeds via pentacoordinated car-
frequently used as a test reaction to assess bonium ions formed upon protonation of a
the acidic properties of the acid catalyst. paraffin, analogously to reactions occurring
With regard to the nature of the acid-cata- in liquid superacids (7, 8). However, as the
lysed cracking reaction it is generally ac- typical products of the protolytic cracking
cepted that cracking proceeds via a bimolec- route are methane, ethene, and hydrogen,
ular carbenium-ion chain mechanism Corma (9, 10) suggested that this reaction
involving a hydride-transfer step, followed proceeds via a radical cracking mechanism
by fl-scission (1-3). However, recently vari- catalysed by nonframework aluminium ions
ous authors have found evidence that crack- present in the zeolite. Regardless of the ex-
ing may also proceed via another route, act mechanism of the protolytic cracking
which has been called in the literature the route, it is important to identify the proper-
monomolecular protolytic cracking route ties of the zeolite and the reaction conditions
(4-6). Whereas the characteristic products affecting the relative contribution of this al-
51
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Copyright© 1991by AcademicPress, Inc.
All rightsof reproductionin any formreserved.
52 WlELERS, VAARKAMP, AND POST

ternative cracking pathway. Haag and Des- ingful comparison of selectivities can only
sau (4) found that the protolytic cracking be made at similar conversion levels, which
route is more favoured with the medium- condition was achieved by carefully adjust-
pore zeolite ZSM-5 (MFI) than with the ing the space velocity. Occasionally, n-H
large-pore zeolite FAU(Y) and amorphous cracking was studied at lower pressures (to-
silica-alumina material. Furthermore, they tal pressure 0.1 MPa; He/n-H = 4/1 mol/
showed that protolytic cracking becomes mol). Measurements of the constraint index
more prominent with increasing tempera- (CI) were normally carried out at standard
tures and decreasing reactant concentra- conditions as outlined in the Mobil publica-
tions. Gianetto et al. (11) concluded that tions (total pressure 0.1 MPa; He/(n-H + 3-
protolytic cracking is more pronounced with MP) = 4/1 mol/mol) (13, 14). The CI is
a silicon-rich FAU(Y) (Si/AI -- 35 mol/mol) the ratio of the first-order rate constants for
than with an aluminium-rich sample (Si/AI conversion of n-hexane and 3-methylpen-
= 3 mol/mol). Mirodatos and Barthomeuf tane. When isomerisation within the feed
(12) suggested that protolytic cracking is fa- was suspected, the experiments were per-
voured with small-pore zeolites and/or zeo- formed using pure hexane isomers as feed-
lites with a high tortuosity. stocks (vide infra).
From the survey of the literature it thus Two series of ZSM-5 zeolites (MFI) with
appears that several factors determine the Si/AI molar ratios between 8 and 400 were
relative contributions of the two acid-cata- prepared according to Mobil patents using
lysed cracking routes. In this work we have either tetrapropylammonium bromide
investigated in more detail the role of acid (TPABr) or hydroxide (TPAOH) as templat-
site density, the influence of zeolite struc- ing agent (15). The crystallinity of the MFI
ture and the effect of reaction temperature samples tested was I00%, except for the
on the relative contributions of the two sample with Si/AI = 8 mol/mol, which con-
cracking routes. In order to facilitate the tained traces of analcime. Zeolite ferrierite
interpretation of the results we used well- (FER) (Si/AI = 8 mol/mol) was synthesized
defined zeolite catalysts. The effect of zeo- according to an in-house developed proce-
lite structure has been investigated with a dure. Zeolite mordenite (MOR) (Si/AI = 8.5
series of four structurally different zeolites mol/mol) was obtained from Union Carbide
containing similar amounts of aluminium. and ultrastable faujasite (Y, FAU) (Si/AI =
The role of acid site density has been studied 10 mol/mol) from Grace Davison. Relevant
with a series of MFI samples differing in characteristics of the various zeolites are
lattice aluminium content, n-Hexane (n-H) given in Table 1. The calcined (773 K for
and 3-methylpentane (3-MP) cracking were 16 h in air) zeolite samples were exchanged
used as test reactions. with a large excess ofNH4NO 3 at 363 K for
16 h, washed and dried at 393 K. Prior to
the cracking experiments the catalysts were
EXPERIMENTAL
treated in the reactor with a stream of dried
The cracking experiments were per- helium at 773 K for 2 h.
formed in a small microflow reactor, n-Hex- 27A1 solid-state NMR showed that in the
ane cracking experiments, performed to elu- silicon-rich MFI samples (Si/AI > 10 mol/
cidate the effects of zeolite structure and mol) all aluminium ions are present in tetra-
acid site density on product selectivity, hedral positions. Owing to the presence of
were carried out at 723 K and a pressure of some amorphous material in aluminium-rich
0.5 MPa using diluted n-hexane as feed (He/ MFI sample (Si/AI = 8 mol/mol) this partic-
n-H = 4/1 mol/mol). Since the selectivity is ular sample contains a small amount of non-
a function of the conversion level, a mean- framework aluminium. Whereas in the fresh
 PROPERTIES AND PERFORMANCE OF ZEOLITES IN PARAFFIN CRACKING 53

TABLE 1

Relevant Characteristics of the Zeolites used in the Various E x p e r i m e n t s

Zeolite Si/A1 Crystallite size Source/

(mol/mol) diameter (tzm) preparation route

F A U (Y) 10.5 ~1 Grace D a v i s o n

MOR 8.5 0.5-1 Union Carbide
FER 8 0.5-1 Homemade
MFI 8 0.5-1.5 Via T P A B r route (15)
MFI 21 0.5-1.5 Do.
MFI 40 -- Do.
MFI 75 -- Do.
MFI 200 1-2 Do.
MFI 400 1-2 Do.
MFI 20 <0.1 Via T P A O H route (15)
MFI 25 2 Do.
MFI 30 <0.1 Do.
MFI 38 <0.2 Do.
MFI 45 -- Do.
MF1 65 0.13 Do.
MFI 100 I Do.
MFI 130 0.2 Do.

MOR and F E R samples all aluminium ions space velocity in a single run, and check-
are located in tetrahedral flame-work posi- backs at initial operating conditions were
tions, there is also a small amount of non- frequently carried out to verify that the zeo-
tetrahedrally coordinated aluminium pres- lite had not suffered from aging during the
ent in FAU(Y).
-In (l-x)
RESULTS
CONDITIONS: / 400°C
Activity in n-Hexane Cracking ptot = 0.1 MPa ,,~
It is known (16) that at high temperatures
(811 K, 538°C) the cracking rate is first order
in n-hexane. From the results shown in Fig.
1 it can be concluded that also at lower reac-
2
tion temperatures (673-573 K, 400-300°C)
340°C
the cracking rate is first order in n-hexane.
Thus, the apparent rate constant (k) can be
calculated via the well-known formula k =
- W H S V × In (1 - x), in which x is the 1
300°C
conversion level.
Table 2 shows the conversion levels of
four structurally different zeolites contain-
ing similar concentrations of aluminium
0
(with all four zeolites the Si/A1 molar ratio 1
is between 8 and 10). The very high stability WHSV-~(g,h.g "~)

of zeolite MFI for n-H cracking allowed us FIG. 1. Effect of space velocity on cracking rate of
to study excursions of temperature and/or n-hexane over zeolite M F I (Si/AI = 38 mol/mol).
54 WIELERS, VAARKAMP, AND POST

TABLE 2

Product Breakdown in Cracking of n - H e x a n e over Structurally Different Zeolites

Zeolite: FER MFI MOR FAU(VUS-Y)

Si/AI (mol/mol) 8 8 8.5 10.5

Conv. (%w) 9.4 14 7.3 10.3
W H S V (g/(g • h)) 59 550 34 16
k 0 (g/(g • h)) 5.9 83 2.6 1.7
kAi 54 747 24 19
Iog(kAi) 1.7 2.9 1.4 1.3

Selectivity (%mol)

H2 38.3 2.3 13.9 4.8

CI 4.5 0.7 0 2.3
]£C 2 22.8 6.7 5.9 5.3
C°/C~ - 3.9 0.8 0.8 1.0
~C3 26.7 59.0 59.9 38.6
C°/C~ - 2.3 2.5 3.3 14.2
~C4tot 6.8 25.3 9.7 13.6
~C42- 4.8 14.8 4.9 6.8
~n-C~- 4.8 9.9 2.0 2.3
i-C]- 0 4.9 2.9 4.5
~C4° 2.0 10.5 4.9 6.8
n-C4° 2.0 7.0 2.3 1.9
i-C ° 0 3.5 2.6 4.9
C°/C~ - 0.4 0.7 1.0 1.0
i-C°/n-C ° 0 0.5 1.1 2.5
C M R = (Cj + E C 2 ) / i - C ° ~ 2.1 2.3 1.6
~C 5 0 3.4 1.8 6.6
EC6 isomers 1 1.8 8.8 28.7

N o t e . Conditions: T = 723 K; H e / n - H = 4 (mol/mol); etot = 0.5 MPa.

run. The other zeolite structures investi- tional to the intrinsic activity (turnover fre-
gated (viz. FER, MOR, FAU), however, quency) of the strong Brensted acid sites of
deactivated severely during operation, and each particular zeolite sample. A volcano-
therefore, on account of the different rates type relation is observed between the cata-
of deactivation, the activity was assessed lytic activity and the dimensions of the
by comparing the initial rate constants (k0), pores: the medium-pore zeolite MFI exhib-
which were found by extrapolation of the its a markedly higher activity than the large-
conversion vs time-on-stream curves to pore zeolites MOR and FAU(Y) as well as
t=0. the medium-pore zeolite FER. The volcano-
In Fig. 2 the normalized rate constants type relation has also been found for n-pen-
(kA]) of the four structurally different zeo- tane (17) and n-butane (18) cracking. How-
lites are plotted as a function of the pore ever, Lombardo et al. (19) reported a differ-
dimensions of the respective zeolite. Nor- ent order for n-H cracking, viz. MOR >>
malized rate constants were calculated at FAU(Y) > MFI. The differences in activity
conversion levels of about 10% (Table 2) have been ascribed to differences in intrinsic
after correction for small differences in alu- acidity (19), to variations in the concentra-
minium content according to kAj = ko/{A1/ tion of the reactants in the pores (20), and
(A1 + Si)} and are assumed to be propor- to nest effects (21). In a forthcoming paper
 PROPERTIES AND PERFORMANCE OF ZEOLITES IN PARAFFIN CRACKING 55

4Log(kAt ) T = 723 K constant and the aluminium content in zeo-

p = 0.5 MPa lite MFI has been further investigated over
35 He/n-H = 4 mol/mol a broad range of temperatures. The apparent
MFI VARYING WHSV
:3 order in aluminium content as calculated
LE 2)
25 from these results is plotted as a function
of temperature in Fig. 4. Also included are
2
results reported in the literature. Surpris-
"15
ingly, the order increases from 1 to 2 when
1
the temperature decreases from 811 to
FAU 1"( 1
o51 623 K.
)q i i i h The effect of reaction temperature and
aluminium content of MFI on n-H cracking
CRYSTALLOGRAPHIC PORE SIZE (nm)
activity can be inferred from the results
FIG. 2. Cracking activity of various structurally dif- given in Fig. 5, showing the activation en-
ferent zeolites. ergy as a function of Ai content. Activation
energies were obtained from Arrhenius
plots. The temperature ranges studied typi-
cally spanned about 100 K and over this
we will present additional data and offer an range the relation between In k and 1/T
explanation for the observed activity order could satisfactorily be approximated by a
(22). straight line. The average temperature at
Previously, it was shown that at 703 K which the activation energy was determined
with MFI samples containing crystallites increases with decreasing aluminium con-
with dimensions between 0.1 and 5/xm the
n-H cracking rate is independent of the crys-
tallite size (23). Therefore, we conclude that Log k o
the rate constants found in the present work 20

for n-H cracking over zeolite MFI reflect T = 723 K

18
the true rate of the cracking reaction. Since p = 0.5 MPa
diffusion limitations are not important for 16
He/n--it = 4 tool/tool

the medium-pore zeolite MFI in n-H crack-

ing and since the crystaUite sizes in the vari- 14
ous zeolites are not too different, it can be
concluded that the same should be true for 12
the wide-pore zeolites MOR and FAU (Y)
IG
as well as for the medium-pore zeolite FER
(the pore dimensions of zeolite FER are only
G8
slightly smaller than those of zeolite MFI).
Using the series of MFI zeolites with dif- 0.6
ferent aluminium contents the first-order
rate constant for n-H cracking has been de- O4
termined as a function of the aluminium con-
tent. Figure 3 and Table 3 show the results 02
obtained at 723 K. It can be seen that the
0 I I I
slope of the straight line obtained upon plot- -3 -2 -1
ting log k0 vs log(Al/(A1 + Si)) is about 1.2, Log
indicating that the apparent order in the alu-
minium content is about 1.2 at this tempera- FIG. 3. Activity as a function of a l u m i n i u m content
ture. The relation between the cracking rate for a series of H - M F I catalysts.
56 W I E L E R S , V A A R K A M P , A N D POST

TABLE 3
Product Breakdown in Cracking of n-Hexane over Various MFI (ZSM-5) Zeolites containing Different
Amounts of Aluminum

Zeolite: Various MF1 (ZSM-5)

Si/AI (mol/mol) 8 40 75 200 400

Conv. (%w) 14 13.4 13.4 16.1 30.9
WHSV (g/(g • h)) 550 131 65 20 4
k0 (g/(g • h)) 83 18.8 9.3 3.5 1.4
kAi 747 772 711 706 592
log(kA0 2.9 2.9 2.9 2.8 2.8

Selectivity (%mol)

H2 2.3 1.0 6.9 9.1 9.9

CI 0.7 0.5 2.5 3.8 3.1
"~Cz 6.7 13.7 12.8 16.5 14.5
C°/C~- 0.8 0.8 1.0 1.8 1.5
~C3 59.0 52.8 47.7 47.1 45.2
C°/C~- 2.5 2.6 2.4 2.0 2.4
EC4tot 25.3 25.7 23.9 17.9 20.6
~C 2- 14.8 15.0 14.9 11.2 12.9
]£n-C42- 9.9 10.0 9.9 7.0 8.1
i-C]- 4.9 5.0 5.0 4.2 4.8
~C ° 10.5 10.7 9.0 6.7 7.7
n-C° 7.0 7.1 6.0 4.2 4.8
i-C° 3.5 3.6 3.0 2.5 2.9
C4°/C4z- 0.7 0.7 0.6 0.6 0.6
i-C°/n-C° 0.5 0.5 0.5 0.6 0.6
CMR = (Cz + ~C2)/i-C ° 2.1 3.9 5.1 8.1 6.1
~C 5 0 3.4 4.0 3.7 4.2
EC 6 isomers 1.0 2.8 3.1 1.9 2.6

Note. Conditions: T = 723 K; He/n-H = 4 (mol/mol); Ptot = 0.5 MPa.

t e n t in t h e M F I s a m p l e s a n d is i n d i c a t e d in i n t e r e s t i n g to n o t e t h a t w i t h i n c r e a s i n g p o r e
F i g . 5. T h e a c t i v a t i o n e n e r g y f o r n - h e x a n e dimensions the selectivity for C 6 isomers
cracking decreases with increasing alumin- increases. Furthermore, with increasing
ium c o n t e n t a n d / o r w i t h d e c r e a s i n g t e m p e r - p o r e d i m e n s i o n s , t h e olefinic c o n t e n t o f t h e
ature. product molecules decreases.
T h e s e l e c t i v i t y p a t t e r n s ( T a b l e 3) o f t h e
Selectivity f o r n-Hexane Cracking v a r i o u s M F I c a t a l y s t s differing in a l u m i n -
The effect of zeolite structure on product ium c o n t e n t i n d i c a t e t h a t t h e s e l e c t i v i t y f o r
s e l e c t i v i t y c a n b e i n f e r r e d f r o m the r e s u l t s the formation of hydrogen, methane, and
s h o w n in T a b l e 2. C o m p a r e d to t h e o t h e r C2 h y d r o c a r b o n s i n c r e a s e s w i t h d e c r e a s i n g
zeolites, FER exhibits a relatively low selec- a l u m i n i u m c o n t e n t in t h e l a t t i c e . M o r e o v e r ,
t i v i t y f o r t h e f o r m a t i o n o f C4 h y d r o c a r b o n s the s e l e c t i v i t y for t h e f o r m a t i o n o f olefins
a n d a high s e l e c t i v i t y f o r t h e f o r m a t i o n o f increases with decreasing aluminium
hydrogen, methane, and C 2 hydrocarbons. content.
In a g r e e m e n t w i t h t h e f o r m a t i o n o f h y d r o - T h e effect o f r e a c t i o n t e m p e r a t u r e in t h e
g e n , z e o l i t e F E R a l s o e x h i b i t s a high s e l e c - r a n g e 643 to 803 K o n t h e s e l e c t i v i t y in n - H
t i v i t y f o r t h e f o r m a t i o n o f olefins. It is a l s o c r a c k i n g has b e e n s t u d i e d in m o r e d e t a i l
 PROPERTIES AND PERFORMANCE OF ZEOLITES IN PARAFFIN CRACKING 57

ORDERIN ALUMINIUMCONTENT in order to unambiguously assess the "true"

ratio of the rates of cracking. The constraint
indices given in Fig. 7 accordingly reflect
the actual ratio of cracking rates of the two
hexane isomers and might therefore slightly
deviate from the values that would be ob-
tained using the conditions stated in the per-
tinent literature (13, 14). The results shown
in Fig. 7 indicate that the CI decreases with
I I I
600 700 800 increasing temperature and decreasing alu-
TEMPERATURE(K) minium content.
FIG. 4. Order in a l u m i n i u m content of H - M F I cata- DISCUSSION
lysts as a function of temperature. (O) M e a s u r e d u n d e r
conditions as given in Ref. (23): Ptot = 0.1 MPa; p (n- Cracking Mechanisms
H) = 0.02 MPa. (•) M e a s u r e d u n d e r conditions used
Cracking of paraffins at elevated tempera-
in this work: Ptot = 0.5 MPa; p (n-H) = 0,1 MPa. (11)
M e a s u r e d u n d e r conditions of a - t e s t (Ref. (16)): Ptot =
tures may proceed through various mecha-
0.1 M P a ; p (n-H) = 0.013 MPa. nisms. Noncatalytic, i.e., thermal cracking
can occur when hydrocarbons in the ab-
sence of a catalyst are brought to high tem-
peratures. Thermal cracking proceeds via
with H-MFI, having a Si/AI molar ratio of primary radicals, which crack at the C - C
45. It is evident from Fig. 6 that with increas-
ing temperature the selectivity for the for-
mation of C3-C 5 decreases, whereas the se-
lectivity for C1 and C 2 increases. In this A' kJ/moL(kcaL/mot)
series of experiments the conversion de-
creases from about 80% (at the highest tem-
perature) to about 30% (at the lowest tem-
126(30)I i
/

perature). The present results are in full

agreement with data previously reported by "105(25)I'k \
Haag and Dessau (4).

Constraint Index
Figure 7 shows the variation of the con- 84(20)63(.15) 753~,53
°
straint index of zeolite MFI as a function
of the aluminium content and the reaction
temperature. The majority of the results
given in Fig. 7 were obtained using a two-
component feed consisting of n-H and 3-MP 42(I O} ~3° 6 ~
as indicated in Refs. (13, 14). However, at 653
lower temperatures and with aluminium- 633
rich MFI samples isomerisation of hexanes 21(5) I I I I
5 "t0 "t5 20
is significant and, as a result, the intercon- 1000 AL205/Si02(moL/rnoLl
version of hexane isomers in the two-com-
ponent feed may severely falsify the "true" FIG. 5. The effect of alumina content o f zeolite MFI
on the apparent activation energy of cracking of n-
constraint index at these conditions. There-
hexane. Conditions: Ptot = 0.1 MPa; H e / n - H = 4 mol/
fore at lower temperatures and with alumini- mol. Note: N u m b e r s indicate the average temperature
urn-rich samples, these problems were cir- (K) of the temperature range in which E A was deter-
cumvented by using single-component feeds mined.
58 WIELERS, VAARKAMP, AND POST

SELECTIVITY (tooL % ) T (°C) SELECTIVITY (tool % ) T(°C)

530 5 0 0 470 430 400 370 530 5 0 0 4 7 0 430 400 370
a I ~ I I i I 251 h I I I I I I

50

~ n-C

i-
4

40
15

CONDITIONS: Ptot = 0.1 MPa

30
He/n--H = 4 mol/mol
10

20
I

10
9 -| I I P
~ t.2 1_3 1.4 1.5 1.~
1 I
IO00/T (K -'I)
0
12 1.3 -L4 -'1.5 t.6
I O 0 0 / T (K~)

FIG. 6. Selectivity in n-hexane cracking as a function of temperature.

bond located fl to the carbon atom having

CI
the unpaired electron. The repetition of this

~ reaction leads to the formation of large

573 K
amounts of ethene, and small amounts of
t0
methane and a-olefins (1). Laboratory ex-
periments of thermal n-hexadecane crack-
ing at 773 K established this mechanism (3).
At higher temperatures (1100-1200 K) small
o 613 K
o amounts of ethyne are produced (24). Al-
though at elevated temperatures thermal
cracking is an important pathway for the
[] 673 K conversion of hydrocarbon feedstocks, the
0 703 K contribution of the thermal cracking reac-
u 743 K tions during cracking of the relatively stable
hexane isomers at our experimental condi-
1 -- tions (temperatures up to 811 K) is negligi-
0 I I I I I ble. Experiments with both an empty reac-
0 5 10 "t S 20 25
tor and a reactor loaded with an aluminium-
1000 AL203/Si02 (mot/rnoL)
free zeolite (viz. silicalite) did not show any
FIG. 7. The constraint index (CI) of zeolite MFI: conversion of hexane isomers up to 811 K
Effect of alumina content of zeolite and reaction tem- at a space velocity of 1 g/(g • h).
perature on the ratio of the cracking rates for n-hexane Catalytic cracking of paraffins can occur
and 3-methylpentane. Conditions:/)tot = 0.1 MPa; He/
either via hydrogenolysis of hydrocarbons
(n-H + 3-MP) = 4 mol/mol. Two-component feed: He/
(n-H + 3-MP) = 4 mol/mol; n-H/3-MP = 1 mol/mol. over, e.g., Pt or Ni metal particles or via
Single-component feeds: He/n-H = 4 mol/mol; He/3- acid catalysis. Since the zeolites used in the
MP = 4 mol/mol. present work do not contain metal particles
 PROPERTIES AND PERFORMANCE OF ZEOLITES IN PARAFFIN CRACKING 59

we can confine the following discussion to However, it cannot be ruled out that the
purely acid-catalysed conversion of hydro- formation of olefins does not proceed via the
carbons proceeding via positively charged consecutive reaction (5) but occurs simulta-
carbocations, i.e., carbenium ions neously in reactions (1) to (4) according to,
(C,H~, + 1) and/or carbonium ions e.g.,
(C,H~n+3) as reaction intermediates. The
C6H14 + H - Z ~ C6H ~ + Z - ----~
strong dependence of the cracking rates on
aluminium content (see, e.g., Fig. 3) sup- C4H8 + C2H6 + H - Z (6)
ports the conclusion that we are dealing with Were cracking to proceed exclusively via
purely acid-catalysed cracking of n-hexane. reactions (1) to (6), the molar amounts of
If cracking proceeds via the protolytic C2 and C4 should be equal. However, our
monomolecular route, the formation of light results show that with all zeolites the Cz/C4
paraffins (CH4-C4Hjo) can be accounted for ratio is not unity. Therefore cracking must
by a simple cleavage of a pentacoordinated also occur via a different route. This can be
carbonium ion (C6H~) into a smaller alkane rationalized by assuming that the carbenium
(C.H2.+2) and a classical carbenium ion ions formed in reactions (1)-(4) become in-
(CmH+,,+0 with n + m = 6: volved in secondary reactions rather than in
reaction (5), namely:
C6HI4 + H - Z - - > C6H~5 + Z - ---> Isomerization to branched, tertiary carbe-
C3H ~ + C3H 8 + Z - (1) nium ions and subsequent H-transfer (7a)
followed by/3-session (7b)
C6H|4 + H - Z ~ C6HI~ + Z
C4H~ + C2H6 + Z- (2a) (i, n)-C4H ~- + n-C6Hl4 -->
C6H14 + H - Z ~ C6H(5 + Z - ---> (i, n)-C4H10 + n-C6Hl~ (7a)
CzH ~ + C4Hlo + Z - (2b) n-C6H(3---~ C3H¢ + C3H 6 (7b)
C6H14 + H - Z - - > C6H ~ + Z - ----~
Alkylation of an olefin with a small carbe-
CsHI~ + C H 4 + Z - , (3) nium ion (reaction(8a)) followed by fl-scis-
where H - Z denotes a proton site in the zeo- sion of the formed carbenium ion (8b):
lite framework.
C~H2n+l + + CmH~m---~
Since hydrogen is also observed, reaction
(4) probably also proceeds: C,,+nH2,,,+2,+f+ with (m + n) -> 6 (8a)

C6H14 + H - Z ~ C6H ~ + Z - ----> Cm+nHzm+2n+ l

C6H1~ + H 2 + Z - (4) cracked products via/3 scission. (8b)
In fact, reaction (4) describes the net forma- Isomerization (9a) followed by H-transfer
tion of a carbenium ion from a paraffin by (9b):
hydride abstraction, in agreement with ob-
servations by Kouwenhoven (25). n-C6H~3 ~ i-C6H~3 (9a)
On the basis of the present results it is
not possible to identify the structure (either i-C6HI~ + n-C6HI4----~i-C6H14 + n-C6HI ~
linear or branched) of the carbenium ions (9b)
and paraffins formed in reactions (1) to (4).
As a final secondary reaction we mention
In the next step, the carbenium ions formed
H-transfer reactions between olefins
may lose a proton and form the correspond-
(formed in reaction (5)), yielding paraffins,
ing olefin:
diolefins, cycloolefins, and ultimately aro-
C,H~+j + Z----~ CnH2n + H - Z (5) matics. Reactions (7) and (8) illustrate the
60 WIELERS, VAARKAMP, AND POST

classical cracking mechanism where/3-scis- tion energy, it is conceivable that once a

sion of a carbenium ion is the characteristic carbonium ion is formed the subsequent for-
step, which proceeds following either a H- mation of a primary carbenium ion is facili-
transfer reaction or an alkylation reaction. tated. Therefore, in addition to CI it seems
reasonable to regard both ethane and ethene
as typical products of the protolytic crack-
The Cracking Mechanism Ratio (CMR)
ing route, while isobutane is indicative of
The above discussion indicates that the the classical route.
product spectrum obtained via the proto- In order to indicate the relative contribu-
lytic route (reactions (I)-(6)) is substantiallytions of the two different cracking mecha-
different from that obtained if the classical nisms for n-hexane cracking we use a
acid-cracking mechanism prevails (reac- "cracking mechanism ratio" (CMR), which
tions (7)-(9)). The classical cracking route is defind as the ratio {(Cl + ~ C2)/i-C4°},
yields primarily butanes (especially isobu- where CI, Z Cz, and i-C ° denote the molar
tane, since the corresponding tertiary carbe- selectivities to methane, total Cz hydrocar-
nium ion is the most stable one) and pro- bons, and/-butane, respectively. We stress
pene, with little (if any) formation of that for our present series of n-hexane
methane and C2 hydrocarbons. If the proto- cracking experiments the CMR expresses
lytic mechanism is operative, cracking of n- the relative contributions of two purely acid-
hexane results in the formation of hydrogen catalysed cracking routes. A high value for
and linear C~-C4 hydrocarbons. With regard the CMR (> 1) reflects a significant contribu-
to ethene and ethane being typical products tion of the protolytic cracking route, while
of the protolytic cracking route, the follow- a low value (0 < CMR < 1) is indicative of
ing should be noted. Whereas the formation classical carbenium ion chemistry and
of ethane via protolytic cracking can be cracking through/3-scission reactions. The
readily explained on the basis of reaction CMR is considered to be a useful parameter
2a, it appears that ethene can only be formed to reveal in a qualitative manner the extent
via primary carbenium ions (i.e., reaction to which the two acid-catalysed cracking
(5): C2H5+ + Z- ~ C2H4 + H-Z). Indeed, mechanisms prevail. On the other hand, the
under conditions where protolytic cracking value of the CMR does not have an absolute
prevails (high steric constraints in FER (Ta- significance since the cracking mechanisms
ble 2) and low aluminium contents (Table are too complicated. For instance, a value
3)), relatively high C2/C2
0 2- ratios are ob- of unity for the CMR does not necessarily
served. In principle, one can correctly argue imply that the two cracking routes are
that primary carbenium ions can also be equally important.
formed via the classical cracking route.
However, despite the high C°/C~2- ratio ob-
served under the more demanding condi- Effect o f Zeolite Structure on CMR
tions, it appears that for zeolites MFI, MOR The results in Fig. 8 show that the CMR
and US-Y and in a broad compositional decreases with increasing pore dimensions,
range the C°/C~ - ratio does not strongly indicating that with decreasing pore dimen-
vary, i.e., variations in the amounts of eth- sions cracking proceeds more and more via
ane and ethene occur concomitantly. This the protolytic route. Furthermore, since es-
result suggests that the primary carbenium pecially i-C4 is a typical product of fl-scis-
ions necessary to form ethene are more sion reactions (the tertiary carbenium ion is
readily generated from pentacoordinated in- the most stable one), the increase of the i-C°~
termediates than via the classical route. n-C ° ratio with the pore dimensions supports
Since both the formation of a primary carbe- this suggestion. The i-C 6 hydrocarbons are
nium ion and the formation o f a pentacoordi- formed via isomerization reactions of the
nated carbonium ion require a high activa- intermediate carbenium ions: (again) the se-
 PROPERTIES AND PERFORMANCE OF ZEOLITES IN PARAFFIN CRACKING 61

CMR contributions of the two cracking routes

FER =0o • DATAAT LOW (10-15 %) with the pore dimensions of the zeolite in-
CONVERSIONLEVELS(TABLE2)
volved. Since the dimensions of the transi-
• DATAAT HIGH (3045 %)
tion-state complex of the intermediate in the
/3-scission route are larger than those of the
intermediate involved in the monomolecular
FE.o 53 \ I += ,23 K I cracking reaction, it can be visualized that
with zeolite FER cracking proceeds pre-
dominantly via the protolytic route, while
with MFI, MOR, and FAU (Y) cracking oc-
curs more and more via the classical (/3-

21 • I~ scission) route. Likewise, it can be ex-

plained that the occurrence of secondary
(bimolecular) reactions is also strongly de-
pendent on the dimensions of the pores. In
the large-pore sieves such as FAU and MOR

0 I
FER
I
MFI
t
MOR
I
FAU(Y)
PORE DIAMETER (ARBITRARY UNITS)
the relatively high i-C°/n-C ° ratio reflects the
involvement of tertiary C4 carbenium ions
as reaction intermediates in bimolecular hy-
drogen-transfer reactions. In the medium-
FIG. 8. Variation of cracking selectivity as a function pore zeolite MFI with smaller intracrystal-
of zeolite structure, n - H e x a n e cracking over different line space the formation of bulky bimolecu-
zeolites (Si/AI -~ 10 mol/mol).
lar reaction complexes is suppressed.
Hence, the i-C°/n-C ° ratio in the cracked
products is relatively low. Nevertheless, it
lectivity for the formation of these products can be envisaged that in the zeolites with
increases with the pore dimensions. The in- smaller pores classical cracking reactions
crease of the paraffin/olefin (C°/C ]- and CO/ via less bulky but less stable secondary car-
C~-) ratio with increasing pore dimension benium ions may still occur. Thus, the for-
can be accounted for by assuming that H- mation of C3 and linear C4 hydrocarbons
transfer reactions become more important during n-H cracking over zeolite MFI can
with increasing pore dimensions. Finally, be explained on the basis of bimolecular re-
the importance of the protolytic cracking actions proceeding via secondary carbe-
route with zeolite FER is also reflected in nium ions. We note that C3 and linear Ca can
the high selectivity of this zeolite for the also be formed via protolytic cracking (vide
formation of hydrogen, methane, and C2 hy- supra). In zeolite FER the dimensions of the
drocarbons. Other investigators have also intracrystalline channels are slightly smaller
found that the extent of protolytic cracking than in zeolite MFI and, more importantly,
is strongly affected by the zeolite structure FER has a one-dimensional 10-ring channel
(4, 26). structure and does not possess the cavities
Since the classical cracking route (pro- formed by the intersecting 10-ring channels
ceeding either via a H-transfer reaction fol- as in zeolite MFI. As a consequence, bulky
lowed by /3-scission or via alkylation be- bimolecular transition-state complexes can-
tween carbenium ions and olefins followed not be formed in the acid-catalysed cracking
by /3-scission) involves bimolecular reac- of hydrocarbons over zeolite FER and
tions, it seems fair to assume that with this cracking is most likely to proceed via mono-
reaction the transition-state complex is molecular transition-state complexes (i.e.,
more bulky than in the case of the monomo- carbonium ions) yielding significant
lecular protolytic cracking reaction. Thus, amounts of C~ and C2 hydrocarbons and hy-
it would seem justified to relate the relative drogen.
62 WlELERS, VAARKAMP, AND POST

CMR ing step in the/3-scission route (1)) requires

8- •
the presence of two adjacent acid sites
C O N D I T I O N S : T = 723 K
(formed by two neighboring lattice alumin-
Ptot = 0.5 MPa
He/n--H = 4 mol/rnol
ium ions) and that the protolytic cracking
C O N V E R S I O N B E13NEEN
route can proceed on isolated acid sites, it
can be explained that the relative contribu-
tions of the two cracking mechanisms de-
pend on the lattice aluminium content. Pre-
viously, for zeolite MFI the density of pairs
of next-nearest aluminium ions was calcu-
lated as a function of the aluminium content
and it was shown that the possibility of find-
ing two adjacent sites decreases quadrati-
cally with the number of framework alumin-
ium ions (28). Accordingly, it can be
envisaged that with increasing Si/AI ratio
0 I I I
-3 -2 -1 the relative contribution of the monomolec-
Log AL
ular protolytic cracking route as compared
AL + Si
to that of the bimolecular/3-scission route
F 1 6 . 9 . Variation of selectivity of zeolite H - M F I as increases.
a function of aluminium content. It is, however, difficult to envisage why
this bimolecular H-transfer reaction is fa-
The results shown in Fig. 8 indicate that voured by the presence of two adjacent acid
the CMR is dependent on the conversion sites. An explanation for the observed rela-
level. Since secondary cracking proceeding tion between aluminium content and the H-
via classical/3-scission becomes more im- transfer reaction has been proposed by
portant with increasing conversion levels, it Corma et al. (9, 29). These authors suggest
can be readily explained that with increasing on the basis of low-temperature adsorption
conversion level the CMR decreases. experiments that due to the increasing hy-
drophobicity of the zeolite lattice with de-
Effect o f Aluminium Content of Zeolite creasing aluminium content the concentra-
MFI on the CMR
tion of olefins (present in the zeolite pores at
Figure 9 shows that the CMR measured elevated reaction temperatures) decreases,
for zeolite MFI increases with decreasing leading to a suppression of hydrogen-trans-
aluminium content, indicating that with de- fer reactions. In fact, this explanation im-
creasing aluminium content the contribution plies that with increasing lattice aluminium
of the protolytic cracking route increases as content the concentration of carbenium ions
compared to that of the classical/3-scission in the zeolitic pores increases. It is generally
route. Since there is experimental and theo- assumed that the carbenium ions present
retical evidence in the literature (16, 27) in the zeolite pores are located at the acid
which suggests that the intrinsic acidity of centres. In the H-transfer step an incoming
the acid sites in zeolite MFI is not dependent paraffin donates a hydride ion to the ad-
on the aluminium concentration, it seems sorbed carbenium ion, yielding another par-
reasonable to conclude that the variation of affin and another carbenium ion. As is (sche-
the CMR with aluminium content cannot matically) shown in Fig. 10, it can be
be explained on the basis of differences in envisaged that compared to an isolated acid
intrinsic acidity. site the presence of two adjacent acid sites
Assuming that the hydrogen-transfer pro- (associated with lattice aluminium ions) sta-
cess (which appears to be the rate-determin- bilizes to a greater extent the transition-state
 PROPERTIES AND PERFORMANCE OF ZEOLITES IN PARAFFIN CRACKING 63

ISOLATED ACID SITE ADJACENT ACID SITES cussed above, both effects appear to influ-
At~I~o/S I AL(~o/Si AL\o/Si ence the relative contribution of the two
cracking mechanisms leading to a continu-
R~+~) H - R2 ous decrease in activation energy with in-
creasing aluminium content and decreasing
reaction temperature. Accordingly, the data
At® si Al~)o/Si At~)o/S' in Fig. 5 suggest that the activation energy
\0/
for protolytic cracking (occurring at low A1
. . . . content and/or elevated temperatures) is
higher than that of the classical route: a
® value of at least 90 kJ/mol can be inferred
AI~)o/Sl AL\o/S~ AL\o/S' from Fig. 5 for cracking at high temperature
over silica-rich MFI, while at lower temper-
atures cracking over aluminium-rich MFI
samples occurs with an activation energy as
low as about 30 kJ/mol. Thus, compared to
FIG. 10. Tentative scheme to account for the obser-
vation that adjacent acid sites in zeolite favour H-trans- the classical cracking route the protolytic
fer reaction. route proceeds with a higher activation en-
ergy and via a transition-state complex with
complex formed during the H-transfer reac- smaller dimensions (lower volume of acti-
tion, thus increasing the rate of the H-trans- vation).
fer step, particularly if space constraints in Although to the best of our knowledge
the narrow pores system do not allow an basic experimental data on the activation
optimal geometrical arrangement of the energies of the rate-determining steps in the
transition-state complex involved in the hy- two n-hexane cracking routes are not avail-
drogen-transfer reaction. It should be men- able, the data reported by Brouwer and Ho-
tioned that during the intermolecular hydro- geveen (8) may give an indication of the
gen-transfer step, a proton associated with activation energies of these two cracking
one of the acid sites will move to the adja- routes. Studying the chemistry of carboc-
cent site. Further work is necessary to sup- ations in liquid acids (such as H F - S b F 5)
port this model. these authors found for the hydrogen trans-
fer from a secondary carbon atom to a ter-
Effect of Alurninium Content and tiary carbenium ion an activation energy of
Temperature on n-Hexane Cracking about 55 kJ/mol and for the hydrogen trans-
Rate over Zeolite MF1 fer from a tertiary carbon atom to a tertiary
We have argued above that with decreas- carbenium ion a value of about 12 kJ/mol.
ing aluminium content cracking proceeds Since it is generally assumed that hydrogen
more and more via the protolytic route. This transfer is the rate-limiting step in the classi-
conclusion also offers an explanation for the cal/3-scission route (1), it can be argued that
variation in activation energy with the alu- the activation energy for/3-scission is equal
minium content of zeolite MFI (Fig. 5). to or lower than 55 kJ/mol, in agreement
Since the activation energies for the various with our observations. By contrast, it was
MFI samples differing in the aluminium con- found that protolytic cracking of neopen-
tent have been measured in different tem- tane to tert-butyl cations and methane re-
perature intervals, it appears that in Fig. quires an activation energy of about 88
5 the variation of the activation energy is kJ/mol.
caused not only by the change in the lattice Figure 11 shows that the CMR for n-H
aluminium concentration but also by the dif- cracking over zeolite MFI increases with
ferences in reaction temperatures. As dis- increasing temperature, indicating an in-
64 W I E L E R S , V A A R K A M P , A N D POST

:MR perature, the results shown in Fig. I and the

10- available literature data (16) indicate that

:- // in the entire temperature range 573-811 K

(300-538°C) the cracking rate is first-order
in n-hexane. If the H-transfer reaction be-
tween a carbenium ion and a n-hexane mol-
ecule is indeed the rate-limiting step for the
classical cracking route a second-order de-
pendence of the cracking rate on the n-hex-

i_ ane concentration would be expected. How-

ever, our results show that independent of
the mode of cracking the rate can be de-
scribed by a first-order model. With regard
to the classical route this would suggest that
7'0 for a particular zeolite the concentration of
TEMPERATURE (K) the carbenium ions (located at the lattice
aluminium ions) is virtually independent of
FIG. 11. Variation of selectivity of H-MFI (Si/Al =
21) with reaction temperature. the n-hexane pressure. Accordingly, it can
be explained that although the cracking rate
of the classical route shows a first-order de-
pendence on the n-hexane concentration,
creasing contribution of the protolytic the cracking rate exhibits a second-order
cracking route with increasing temperature. dependence on the lattice aluminium con-
This finding can be explained on the basis centration since the presence of two adja-
of the higher activation energy for protolytic cent Al-ions would favour (on the basis of
cracking as compared to the classical fl-scis- the model in Fig. 10) the H-transfer reaction.
sion route.
Our results show that with decreasing
temperature the rate constant more than The Constraint Index of Zeolite MFI
proportionally increases with the aluminium On the basis of the concept that the rela-
content (Fig. 4). In fact, the order in the tive contributions of the two cracking routes
aluminium content varies from l (at 811 K) vary with the aluminium content, an expla-
to about 2 (at 623 K), supporting the conclu- nation can be given for the variation of the
sion that the bimolecular classical route re- constraint index of zeolite MFI with alumin-
quires (as suggested above) the presence of ium content and temperature (Fig. 7). In
two neighbouring acid sites. Thus, at low zeolite MFI the difference between the
temperatures cracking mainly proceeds via cracking rates of n-H and 3-MP are related
the classical route and as a consequence the to differences in the dimensions of the tran-
cracking activity increases with the number sition-state complexes formed during crack-
of adjacent acid sites. Although usually with ing of these two compounds. It has been
silicon-rich (Si/Ai > 10) zeolites it is as- suggested that the transition-state complex
sumed that the cracking rate varies linearly formed upon 3-MP cracking is bulkier than
with aluminium content, our present results the one formed upon n-H cracking (30).
show that this assumption is only justified Since the reaction takes place in the narrow
at relatively high temperatures (at or above pores of zeolite MFI, the formation of the
811 K), where the protolytic cracking mech- bulkier 3-MP transition-state complexes ste-
anism, which requires only isolated acidic rically more hindered than the formation of
sites, dominates. the n-H transition-state complex. As a re-
Finally, we note that although the order sult, with zeolite MFI (at standard test con-
in the aluminium content varies with tern- ditions (13, 14)) the cracking rate is higher
 PROPERTIES AND PERFORMANCE OF ZEOLITES IN PARAFFIN CRACKING 65

for n-H than for 3-MP, leading to a CI above MOR, MFI, and FER, the relative contribu-
unity. Figure 7 shows that, irrespective of tion of the (monomolecular) protolytic
the reaction temperature, with decreasing cracking route increases compared to the
aluminium content the CI decreases and ul- (bimolecular) classical route. On the basis of
timately approaches 1. Our argument that, these results the variation of the Constraint
with decreasing aluminium content, crack- Index of zeolite MFI with aluminium con-
ing proceeds to an increasing extent via the tent and reaction temperature can be easily
monomolecular protolytic route gives an ex- rationalized. Furthermore, the present re-
planation for this observation. Since the sults also give an explanation for the varia-
protolytic cracking route is a monomolecu- tion of the activation energy of cracking of n-
lar reaction, it can be argued that the transi- hexane with aluminium content over zeolite
tion-state complex formed in the protolytic MFI. Finally, it is tentatively concluded that
cracking route is less bulky than the one the classical cracking route is favoured by
formed in the classical cracking route. Thus, the presence of two neighbouring acid sites
when cracking proceeds more and more via and lower reaction temperatures. As a re-
the protolytic route (which is the case with sult, the relation between the reaction rate
decreasing lattice aluminium content), it can constant and the lattice aluminium content
be easily envisaged that during cracking of changes with the reaction temperature.
n-H and 3-MP the effect of sterical con- Whereas at 811 K the cracking constant var-
straints imposed by the zeolite lattice de- ies linearly with the aluminium content, the
creases, leading to a lower CI. order in the aluminium content increases to
As has also been suggested by Haag and about 2 at 623 K.
Dessau (4), the concept that the relative
contributions of the two cracking routes ACKNOWLEDGMENTS
vary with temperature can (at least partly) TheauthorsexpresstheirappreciationtoMr.J.H.E.
explain the variation of the CI of MFI with Glezer for technical assistance in the experimental
temperature (14). With decreasing tempera- work. Furthermore, the authors are indebted to Dr.
A. L. Farragher and Dr. Ir. S. T. Sie for stimulating
ture cracking proceeds more and more via
discussions and their critical comments on the manu-
the bimolecular classical route (proceeding script.
via bulkier intermediates than in the case of
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