Modied HZSM-5 zeolites for intensifying propylene production

in the transformation of 1-butene

Eva Epelde

, Ana G. Gayubo, Martin Olazar, Javier Bilbao, Andrs T. Aguayo

Chemical Engineering Department, University of the Basque Country, P.O. Box 644, 48080 Bilbao, Spain
h i g h l i g h t s
SiO
2
/Al
2
O
3
ratio of HZSM-5 is suitable
to modulate propylene selectivity.
K and P incorporation reduce total
acidity and homogenize acid strength.
The attenuation of acid strength
disfavors HT and aromatization
reactions.
Mild in situ steaming helps to slightly
increasing 1-butene conversion.
1 wt.% K is effective for increasing
propylene yield and selectivity.
g r a p h i c a l a b s t r a c t
P
r
o
p
y
l
e
n
e
y
i
e
l
d
(
%
)

HZSM-5 zeolite
SiO
2
/Al
2
O
3
=280
1 wt.%K
0
10
20
30
40
50
60
0 50 100 150 200 250 300
0 wt.% K
1 wt.% K
Oligomerization-craking
1-butene
HTreactions; Aromatization
a r t i c l e i n f o
Article history:
Received 19 January 2014
Received in revised form 8 April 2014
Accepted 16 April 2014
Available online 24 April 2014
Keywords:
Propylene
1-Butene
HZSM-5 zeolite
Cracking
Acidity
Coke
a b s t r a c t
The transformation of 1-butene was studied in order to intensify propylene production on catalysts
prepared based on HZSM-5 zeolites of different SiO
2
/Al
2
O
3
ratio modied as follows: (i) by incorporating
K or P (15 wt.%) and (ii) subject to mild in situ steaming. The effect of zeolite modications on the cat-
alyst physical and acid properties and on their kinetic performance was analyzed, given that they are two
key factors for selectively re-routing oligomerizationcracking reactions to propylene production and for
minimizing coke formation. Experiments were carried out under the following operating conditions:
500 C; space time, up to 1.6 (g of catalyst) h (mol of CH
2
)
1
; time on stream, 5 h. The following criteria
were used for assessing catalyst performance: (i) conversion; (ii) product yield and selectivity of each
lump of reaction products (CH
4
, C
2
H
4
, C
3
H
6
, C
2
AC
3
parafns, C
4
H
10
, C
5+
aliphatics and BTX), with the
aim of maximizing propylene, and (iii) deactivation by coke deposition. Although catalytic performance
was improved by selecting a high SiO
2
/Al
2
O
3
ratio, as well as by incorporating 1 wt.% P and mild in situ
steaming, the incorporation of 1 wt.% K was the most effective treatment for maximizing propylene yield
and minimizing coke formation, which is explained by the considerable attenuation of the acid strength
of the zeolite sites. A steady propylene yield of 30% and a selectivity of 40%, for a conversion of 1-butene
higher than 70%, have been obtained with a catalyst prepared by agglomerating (with bentonite and
alumina) 1 wt.% K modied HZSM-5 zeolite with SiO
2
/Al
2
O
3
= 280.
2014 Elsevier B.V. All rights reserved.
1. Introduction
Knowledge on the transformation of light olens (ethylene,
propylene and butenes) is essential in the catalytic processes for
olen production from oil fractions by uid catalytic cracking
(FCC) and from other alternative sources and routes, such as meth-
anol by the MTO (methanol to olens) process and dimethyl ether
by the DTO (dimethyl ether to olens) process. These processes of
lower energy requirements and lower CO
2
emissions in compari-
son to steam cracking (major light olen source) [1] are subject
to continuous innovation in order to satisfy the increasing olen
http://dx.doi.org/10.1016/j.cej.2014.04.060
1385-8947/ 2014 Elsevier B.V. All rights reserved.

Corresponding author. Tel.: +34 946 015 361; fax: +34 946 013 500.
E-mail address: eva.epelde@ehu.es (E. Epelde).
Chemical Engineering Journal 251 (2014) 8091
Contents lists available at ScienceDirect
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j our nal homepage: www. el sevi er . com/ l ocat e/ cej
demand [2,3]. Moreover, new routes have been opened for olen
production by the catalytic transformation of parafnic streams
in reneries [4,5], lignocellullosic biomass (by bio-oil cracking)
[6], bioethanol [7,8] and pyrolysis/cracking of waste polyolens
[9,10]. The present demand of individual light olens is undergoing
signicant changes conditioned by their interest as raw materials,
with a current shortage in propylene production boosting its selec-
tive production according to the different processes mentioned
above [11]. Furthermore, steam cracking (the main olen produc-
tion unit, with ethylene being the major product) will be boosted
by feeding ethane (obtained from shale gas extraction) [12].
Consequently, propylene will be produced only in other catalytic
processes of low selectivity. Within this scenario, apart from the
development of ad hoc processes for the selective production of
propylene, light olen interconversion arouses great interest with
a view to adjusting its production to market prices and
requirements.
Light olen formation and their distribution in the product
stream in the catalytic processes mentioned above are explained
by a complex network based on a carbocationic mechanism for
the oligomerizationcracking of these olens [13]. This mechanism
has been widely studied since the implementation of the MOGD
(Mobil olen to gasoline and distillate) process on a HZSM-5 zeo-
lite by Mobil Research and Development Corporation. This process
takes place under low temperature conditions in which the oligo-
merization step prevails, thus obtaining middle distillates suitable
for incorporating into the diesel pool [1416]. Nevertheless, light
olen interconversion needs temperatures above 300 C to ensure
cracking of oligomers is the main step (higher activation energy
than that for their formation). Furthermore, secondary reactions
of aromatization and hydrogen transfer are also signicant [17
19].
The HZMS-5 zeolite selectively produces light olens in the
aforementioned processes thanks to its properties involving a
three-dimensional porous structure (MFI topology), a medium
severity in the shape selectivity (with channels being elipsoidal,
straight (0.53 0.56 nm) and zig-zag (0.51 0.55 nm)) and
absence of cages located at micropore intersections. In addition,
the moderate acid strength of the acid sites contributes to mini-
mizing secondary reactions of aromatization and hydrogen trans-
fer, as well as the deactivation by coke [2022].
The HZSM-5 zeolite has great possibilities for modifying its
properties (severity in the shape selectivity and acidity) in order
to improve its performance (activity, selectivity and stability) for
light olen production. Accordingly, the steps for light olen for-
mation must be promoted by attenuating those for gaseous
byproducts (parafns, aromatics, high olens) and coke formation.
Certain treatments pursue the modication of the zeolite porous
structure to generate mesopores and so reduce the contact time
of products in the zeolite crystal, by carrying out as follows: (i)
dealumination [23]; (ii) desilication [7,24], and (iii) crystal size
reduction [25,26]. In order to decrease the amount and density of
acid sites, a higher SiO
2
/Al
2
O
3
ratio is recommended, which also
enhances hydrothermal stability [27,28]. Al-Dughaiter and de Lasa
[29] studied the effect the SiO
2
/Al
2
O
3
ratio of the HZSM-5 zeolite
has on its acid properties, by using adsorption of NH
3
and FTIR
analysis of adsorbed pyridine. Different strategies have been
applied in order to control HZSM-5 acidity, as: (i) controlling calci-
nation temperature [27]; (ii) doping with different components,
such as alkali metals and alkaline earth metals [17,18,30], P [31
36], B [37], rare earth metals [38,39], or W [40]. The HZSM-5
zeolite can also be combined with other compounds by: (i)
agglomerating with a binder [4,9] and (ii) creating hybrid catalysts
by physical mixture or successive re-crystallization with other acid
catalysts, such as HSAPO-34 [41]. Most of these methods signi-
cantly affect the kinetic performance of the HZSM-5 zeolite, and
therefore provide high versatility to the zeolite.
This study explores the possibilities of the HZSM-5 for intensi-
fying propylene production, with 1-butene being the raw material.
The demand for butene stream is lower than that for ethylene and
propylene, especially due to the decrease in the production of
methyl tert-buthyl ether (MtBE) as additive for gasoline. The trans-
formation of 1-butene into other more interesting light olens is
an alternative to the oligomerization for the production of middle
distillates [16]. The literature studies on butene cracking report the
complexity of the reaction scheme and the signicant effect of
HZSM-5 zeolite properties on product distribution and stability
[4245].
HZSM-5 zeolites have been prepared based on different strate-
gies suggested in the literature as suitable for propylene intensi-
cation, as are: (i) the use of zeolites with different SiO
2
/Al
2
O
3
ratio
[8,42,46,47]; (ii) modication of the zeolite by incorporating differ-
ent amounts of P [33,48] and K [49] in order to attenuate the acid-
ity, and (iii) mild in situ steaming treatment for attenuating acidity
and generating mesopores [23]. The physical and acid properties of
the catalysts have been determined and their catalytic perfor-
mance has been evaluated, which should strike a suitable balance
between conversion and propylene selectivity. Furthermore, spe-
cial attention is paid to the stability of the catalysts in order to
attenuate deactivation by coke deposition.
2. Experimental
2.1. Catalysts preparation
The zeolites have been supplied by Zeolyst International in
ammonium form and with different SiO
2
/Al
2
O
3
molar ratios: 30,
80 and 280. The acid form of the zeolites (denoted HZ-X, where
X indicates SiO
2
/Al
2
O
3
ratio) was obtained by calcining at 570 C
for 2 h. The incorporation of K or P (nominal content in the
Nomenclature
Roman symbols
B/L Brnsted/Lewis ratio
d
p
pore diameter ()
F
i
molar ow rate of i lump in the product stream ((mol of
CH
2
) h
1
)
F
0
and F butene molar ow rate in the feed and in the outlet
stream ((mol of CH
2
) h
1
)
P
B
butene partial pressure (bar)
S
BET
BET surface area (m
2
g
1
)
S
i
selectivity of i component
t time (min)
V
N2
and V
p
volume of N
2
adsorbed at P/P
0
= 0.2 and pore volume
(cm
3
g
1
)
W catalyst mass (g)
X butene conversion
Y
i
yield of i component
Greek symbols
e
L
, e
B
molar extinction coefcients (cmlmol
1
)
E. Epelde et al. / Chemical Engineering Journal 251 (2014) 8091 81
15 wt.% range) was carried out by incipient wetness method at
70 C under vacuum, adding a suitable amount of KOH dissolution
(purity 85%, Panreac) or H
3
PO
4
(85%, Merck), respectively, in a
BCHI R-114 Rotavapor. The modied zeolites are denoted YK/
HZ-X or YP/HZ-X, where Y indicates the nominal content (1, 3
and 5 wt.%) of K or P incorporated.
Mild in situ steaming of the zeolite was carried out for partial
dealumination using only the structural water of the zeolite, with-
out adding any extra steam [23]. The zeolite was heated from 25 C
to 400 C with a ramp of 4 C min
1
, and was maintained at this
temperature for 10 h in a closed reactor. The zeolites modied with
this treatment have been denoted HZ-X-ST.
The catalysts used in the reactor were prepared mixing, by wet
extrusion, each zeolite (25 wt.%) with a binder (bentonite Exaloid,
30 wt.%) and an inert charge (alumina Martinswerk, 45 wt.%). The
solid was dried at 110 C for 24 h, then sieved to a particle diame-
ter between 0.3 and 0.15 mm and calcined at 570 C for 2 h. This
calcination temperature assures the hydrothermal stability of the
acid sites that is required for operating in reactionregeneration
cycles (with regeneration by coke combustion with air at 550 C),
with full recovery of the kinetic performance [27]. Additionally,
this agglomeration confers a suitable particle size for its use in
the reactor. Moreover, the binder and the inert charge provide a
matrix with a meso- and macroporous structure embedding the
zeolite crystals, which contributes to: (i) improving accessibility
of the reaction medium compounds to the zeolite crystals; (ii)
facilitating the deposition of coke in the mesoporous matrix, and
(iii) favoring heat dissipation in the particle during the regenera-
tion step by coke combustion, thus increasing the hydrothermal
stability [50].
2.2. Catalysts characterization
Metal contents of the catalyst samples were determined by ICP-
AES in a Jobin Yvon spectrometer (ACTIVA model). The BET surface
area and porous structure were measured by N
2
adsorption
desorption (Micromeritics ASAP 2010). The total acidity and acid
strength distribution of the catalysts have been determined by
monitoring the adsorptiondesorption of tert-butylamine (t-BA),
by combining the techniques of thermo-gravimetric analysis and
differential scanning calorimetry during the adsorption of the base
at 150 C. The total acidity is quantied as the amount of base
chemisorbed at 150 C [51], in mmol
t-BA
(g
zeolite
)
1
, whereas the
acid strength is dened as the heat released during the adsorption
of the base, kJ(mmol
t-BA
)
1
.
Catalyst saturation at 150 C is followed by temperature pro-
grammed desorption (TPD) (at 5 C min
1
up to 550 C) using a
Setaram TGDSC calorimeter connected on-line with a Thermo-
star mass spectrometer from Balzers Instruments [51]. The TPD
of the amines is based on the formation of alkylammonium ions
(from adsorbed alkyl amines protonated by Brnsted sites), which
undergo decomposition (cracking) to give ammonia and olens in
a well-dened temperature range via a reaction similar to the
Hofmann-elimination one [52]. Above 150 C (and thus in the
TPD temperature range), t-BA is cracked on the acid sites releas-
ing butene, whose signal (m/e = 56) is monitored by mass spec-
trometer, thereby identifying sites of enough acidity for
cracking t-BA [53]. Moreover, since strong acid sites are active
for cracking at lower temperature, the temperature of the peaks
for the formation of butene in the TPD indicates the acid strength
of the sites. Thus, the lower the temperature of the peak in the
TPD, the higher the acid strength of the sites, which is the oppo-
site effect to that observed in the TPD analysis of commonly used
NH
3
[29]. Besides, a small fraction of t-BA is desorbed without
cracking. This desorption of t-BA (signal at m/e = 58) corresponds
to the base physisorbed on weak acid sites, which are inactive for
the cracking of t-BA, and consequently also for the reactions
involved in the transformation of 1-butene.
Moreover, the interest of using this base is noteworthy, since
t-BA allows a greater sensitivity in the thermo-gravimetric
measurement than NH
3
(due to its higher molecular weight).
This sensitivity is required for determining rigorously the dif-
ferential adsorption heat of the base, especially for catalysts
of moderate acid strength as some of the samples studied in
this work.
The Brnsted/Lewis (B/L) acid site ratio has been determined by
FTIR spectrum (14001700 cm
1
region) of pyridine adsorbed at
150 C, by using a Specac catalytic chamber connected on-line with
a Nicolet 6700 FTIR spectrometer. The results have been deter-
mined from the ratio between the intensity of pyridine adsorption
bands at 1545 and 1450 cm
1
and taking into account the molar
extinction coefcients of both adsorption bands (e
B
= 1.67 cm
lmol
1
and e
L
= 2.22 cmlmol
1
) [54].
The coke content deposited on the catalyst was determined
by temperature-programmed oxidation (TPO) in a TGA Q5000
thermobalance (TA Instruments). After stabilization of the sam-
ple at 250 C for 30 min in a He stream, the oxidant mixture
(25% O
2
in He) was introduced and the combustion took place
by following a heating ramp of 8 C min
1
up to 600 C, and this
temperature was maintained for 1 h to complete coke
combustion.
2.3. Reaction equipment and product analysis
The runs have been carried out under atmospheric pressure
in automated reaction equipment (Microactivity of PID Technol.,
Madrid, Spain) (Fig. 1). The reactor is made of 316 stainless steel
with an internal diameter of 9 mm and 10 cm of effective length.
It is located inside a ceramic covered stainless steel cylindrical
chamber, which is heated by an electric resistance and can
operate up to 700 C with a catalyst mass of up to 5 g. The
bed consists of a mixture of catalyst and inert solid (carborun-
dum with an average particle diameter of 0.105 mm) to ensure
bed isothermality and attain sufcient height under low space
time conditions. The temperature is controlled by a digital
TTM-125 Series controller and measured by a thermocouple (K
type) situated in the catalyst bed. There are two more tempera-
ture controllers: one for the furnace chamber and the other for
the transfer line between the reactor and the micro-GC. At the
end of each run, the temperature is kept constant and catalyst
sweeping is carried out with a He ow of 30 cm
3
min
1
for
30 min, stabilizing and homogenizing the coke deposited on
the catalyst for further analysis. The operating variables are con-
trolled by bespoke software (Process@ from PID Eng&Tech,
Madrid, Spain).
A small fraction of the reaction products (diluted in a He
stream of 17 cm
3
min
1
) is continuously sent to a gas chromato-
graph (Agilent micro-GC 3000A) for its analysis, and the remain-
ing stream of reaction products passes through a Peltier cell at
0 C. The amount of liquid condensate is controlled by a level sen-
sor and the non-condensable gas ow is vented. The micro-GC
(with Soprane software) is provided with 4 analytical modules
and the following columns: a molecular sieve (MS-5A) (10 m)
for analysis of CH
4
; Porapak Q (PPQ) (8 m), for C
2
AC
3
light olens;
Alumina (10 m), for C
2
AC
5
light parafns and olens, and OV-1,
for C
5
AC
10
fraction and aromatics BTX. Product stream is ana-
lyzed every 4 min. The quantication and identication of the
compounds is carried out based on calibration standards of
known concentration. The balance of atoms (C, H) is closed in
all runs above 99.5%.
82 E. Epelde et al. / Chemical Engineering Journal 251 (2014) 8091
3. Results and discussion
3.1. Catalysts properties
Table 1 sets out the chemical and physical properties of the syn-
thesized zeolites (prior to agglomeration). ICP-AES analysis reveals
that real K and P metallic content is close to the nominal one,
which indicates that impregnation has been carried out correctly.
The different modications (K and P incorporation and mild
in situ steaming) entail a drop in the adsorbed volumes of N
2
(and consequently in the BET area and pore volume) at a relative
pressure of P/P
0
= 0.2, with this effect being more signicant for
high metallic contents, which is attributed to the partial blockage
of the micropores as also observed in literature for these treat-
ments [33,36,52,55,56]. It should also be noted that the micropore
volume corresponds exclusively to the zeolite, whereas the matrix
(bentonite and alumina) provides most of the mesopores and mac-
ropores (results not shown) [50].
Table 2 summarizes the results of total acidity, average acid
strength, temperature of the peaks in t-BA-TPD proles and Brn-
sted/Lewis (B/L) ratio at 150 C for unmodied and modied zeo-
lites (without agglomeration in all the cases). It has been proven
that agglomeration with bentonite and alumina does not provide
signicant acidity (0.013 mmol
base
(g)
1
) to the nal catalyst. Con-
sequently, the total acidity per catalyst mass unit is approximately
a quarter of the corresponding zeolite.
As an example of the results of acidity measurement, Fig. 2
shows the t-BA-TPD proles (graph a) and acid strength distribu-
tion (graph b) for HZSM-5 zeolites (without agglomeration) with
different SiO
2
/Al
2
O
3
ratio (solid lines), as well as modied by
1 wt.% K (dashed lines). The TPD proles of the unmodied zeolites
show a main peak at low temperature (180 to 200 C) related to
strong acid sites and whose position differs slightly for HZ-30
(SiO
2
/Al
2
O
3
= 30) and HZ-80 zeolites (SiO
2
/Al
2
O
3
= 80). For the
HZ-280 zeolite this peak shifts towards higher temperatures,
which correspond to a lower acid strength of the acid sites. The
second peak identied at higher temperatures (250300 C), corre-
sponds to weak acid sites that require higher temperature for
cracking t-BA. Furthermore, the area of the peaks corresponding
to strong and weak acid sites notably decreases when SiO
2
/Al
2
O
3
is increased, which evidences a signicant reduction in total acid-
ity. This effect of the SiO
2
/Al
2
O
3
ratio is consistent with that
observed by Al-Dughaither and de Lasa [29] for the measurement
of acidity, which has been determined by TPD-NH
3
analysis.
The TPD proles for 1 wt.% K modied zeolites (dotted lines in
Fig. 2a) reveal a signicant decrease in the amount of weak acid
sites and an increase in strong acid sites compared to the unmod-
ied zeolites, as well as a clear shift of the peak corresponding to
strong acid sites towards higher temperatures, which evidences a
reduction in the acid strength of these sites that is consistent with
the results of acid strength distribution (Fig. 2b). These effects of K
modication become more important as SiO
2
/Al
2
O
3
ratio is
increased, and therefore a sole peak corresponding to an interme-
diate level of acid strength is observed in the TPD proles for
1K/HZ-80 and 1K/HZ-280. Moreover, the average acid strength of
K modied zeolites is considerably lower in the zeolites with high
SiO
2
/Al
2
O
3
ratio.
Furthermore, the addition of K contents above 1 wt.% to the HZ-
280 zeolite signicantly decrease the amount of total acid sites,
and for 3 and 5 wt.% K contents the zeolite has a very low acidity.
These results have also been reported in the literature, with an
AE
2-20 C
VENT
HOT BOX
AE
PIC
TIC
LIQ
M
FIC2
FIC1
FIC3
AIR
M
LIC
FT1
FT2
FT3
BYPASS
He
Micro-GC
AGILENT
3000 1-butene
Air
He
FIC4 FT4
Fig. 1. Reaction equipment.
Table 1
Chemical composition and physical properties of the fresh zeolites.
Zeolite Metal content
a
(wt.%)
S
BET
(m
2
g
1
)
V
N2
b
(cm
3
STP
g
1
)
V
p
c
(cm
3
g
1
)
HZ-30 448 137 0.151
HZ-30-ST 447 136 0.150
1K/HZ-30 0.92 434 132 0.147
1P/HZ-30 0.98 413 126 0.151
HZ-80 556 168 0.110
HZ-80-ST 495 150 0.121
1K/HZ-80 0.93 456 140 0.100
1P/HZ-80 0.95 464 142 0.109
HZ-280 512 144 0.101
HZ-280-ST 480 132 0.062
1K/HZ-280 0.81 415 121 0.068
3K/HZ-280 2.75 235 70 0.059
5K/HZ-280 4.79 211 63 0.064
1P/HZ-280 0.97 423 126 0.089
3P/HZ-280 3.21 322 95 0.069
5P/HZ-280 4.84 298 93 0.048
a
As determined by ICP-AES. The error associated with the average values is
below 5%.
b
Volume of N
2
adsorbed at P/P
0
= 0.2.
c
Pore volume, 17 < d
p
< 3000 .
E. Epelde et al. / Chemical Engineering Journal 251 (2014) 8091 83
excessive deterioration of acid structure being observed for K
contents higher than 1 wt.% [49,57,58].
The general low values of Brnsted/Lewis ratio are consequence
of the high calcination temperature (570 C) required for the
equilibration of the acid structure in order to attain reproducible
performance in successive reactionregeneration cycles [27,59].
Furthermore, the B/L ratio decreases with an increase in the SiO
2
/
Al
2
O
3
molar ratio, due to the decrease in the amount of Brnsted
sites and an increase in Lewis sites, as reported in the literature
[42]. It is noteworthy that the incorporation of 1 wt.% K entails a
decrease in the B/L ratio, as also reported in the literature
[49,60], which conrms that KOH treatment affects more signi-
cantly to Brnsted acid sites than to Lewis sites and, moreover,
entails a transformation of Brnsted into Lewis sites. These results
complement those obtained in the TPD of t-BA, and conrm the
capability of creating Lewis sites when the HZSM-5 zeolite is mod-
ied with K. These new sites have an intermediate acid strength
(determined by TPD of t-BA) of those corresponding to the Brn-
sted and Lewis sites of unmodied zeolites.
Mild in situ steaming at 400 C of the HZ-30 (the one with the
highest total acidity and acid strength determined by TPD of
t-BA) causes a decrease in total acidity, with the weak acid sites
being mainly affected and no signicant effect on strong acid sites.
This result is consistent with that reported by Jin et al. [23] for a
similar treatment of a HZSM-5 zeolite (SiO
2
/Al
2
O
3
= 38). Lower
attenuation of total acidity is observed as the SiO
2
/Al
2
O
3
ratio
increases due to the following: (i) lower steam pressure in the
treatment due to a lower amount of structural water, and (ii)
increase in hydrothermal stability of the HZSM-5 by the increase
in this ratio [61,62].
Mild in situ steaming treatment at 400 C has a moderate effect
on acidity, given that although the amount of Brnsted sites
decreases, the average acid strength is slightly affected. Moreover,
the temperature values corresponding to the two peaks identied
are similar, with only a slight deviation towards lower tempera-
tures in the case of HZ-30-ST and HZ-80-ST zeolites, for which an
increase of the acid strength is observed. These results reveal the
heterogeneity of the steaming treatment depending on its severity
and on the zeolite structure. It is well established that water may
hydrolytically remove Al atoms fromtheir tetrahedral coordination
in the lattice of the HZSM-5 zeolite, but the nature of the resulting
extra-framework Al species is not unequivocally accepted [63].
Despite all discrepancy in the literature concerning the effect of
mild steaming on acid strength, Niwa et al. [64] determined that
mild steaming of the HZSM-5 zeolite causes a decrease in the B/L
ratio, with the dislodged Al remaining in the extra framework con-
tributing to maintaining a high level of acid strength in the zeolite.
The incorporation of 1 wt.% P in the HZ-80 zeolite (TPD proles
not shown) cause a similar qualitative effect as the aforementioned
for 1 wt.% K incorporation, given that weak acid site concentration
also decreases and strong acid site concentration increases, but the
peak shifts towards higher temperatures, thus evidencing a lower
acid strength than the parent zeolite.
A decrease in strong acidity determined by TPD of t-BA,
especially in the sites with higher acid strength, has been observed
for the zeolite modied with P, which is consistent with the stabi-
lizing effect of P reported in literature, which is explained by its
interaction with the Brnsted acid sites in the HZSM-5 zeolite
[31,33,55,6568], and so a more signicant decrease in the Brn-
sted/Lewis ratio is observed. Blasco et al. [31] conrm that the
acidity of P modied zeolites corresponds to structural Al atoms
(TFAL) non neutralized by P, which is consistent with the higher
stabilizing effect of P in the zeolites with high Al content, as
observed by [69,70] and also in this work, in which the highest
attenuation of acidity is achieved for HZ-30 (SiO
2
/Al
2
O
3
= 30).
3.2. Catalytic results
The operating conditions are as follows: pressure, 1.5 bar; feed,
35 cm
3
min
1
of 1-butene diluted in He (10% v/v); 500 C; mass of
Table 2
Total acidity, average acid strength, temperature of the peaks in t-BA-TPD and B/L
ratio for unmodied and modied HZSM-5 zeolites.
Zeolite Total acidity
(mmol of
t-BA) g
1
Average acid
strength
(kJ mol
1
)
T (C) peak
in the TPD
B/L ratio
at 150 C
First
peak
Second
peak
HZ-30 0.67 150 197 277 0.70
HZ-30-ST 0.57 153 195 274 0.58
1K/HZ-30 0.59 110 217 269 0.20
1P/HZ-30 0.58 145 200 275 0.57
HZ-80 0.42 145 194 272 0.32
HZ-80-ST 0.36 146 190 273 0.29
1K/HZ-80 0.38 85 232
b
0.05
1P/HZ-80 0.41 140 206 276 0.27
HZ-280 0.15 120 204 260
a
HZ-280-ST 0.15 120 205 265
a
1K/HZ-280 0.13 75 241
b a
3K/HZ-280 0.06
a
235
b a
5K/HZ-280
a a
240
b a
1P/HZ-280 0.15 120 215 273
a
3P/HZ-280 0.14 120 227
b a
5P/HZ-280 0.14 118 241
b a
a
Undetectable.
b
The sole peak identied.
0.0
0.4
0.8
1.2
1.6
2.0
150 200 250 300 350 400 450
T
P
D

t
-
B
A
,

m
o
l
t
-
B
A
(
s

g
z
e
o
l
i
t
e
)
-
1
T (C)
0wt.%1 wt.%
HZ-30
HZ-80
HZ-280
Kcontent
0
50
100
150
200
0.0 0.2 0.4 0.6 0.8 1.0
A
c
i
d

s
t
r
e
n
g
t
h
,

k
J

(
m
o
l

t
-
B
A
)
-
1
mmol t-BA (g
zeolite
)
-1
a
b
Fig. 2. t-BA-TPD proles (a) and acid strength distribution (b) for parent zeolites of
different SiO
2
/Al
2
O
3
ratio (solid lines) and modied with 1 wt.% K (dotted lines).
84 E. Epelde et al. / Chemical Engineering Journal 251 (2014) 8091
catalyst, up to 0.55 g; space time, up to 1.6 (g of catalyst) h (mol of
CH
2
in the feed)
1
; time on stream, 5 h. Blank runs (without
catalyst) were carried out to conrm that thermal cracking is insig-
nicant below 550 C.
The product lumps considered are as follows: CH
4
, C
2
H
4
, C
3
H
6
,
C
2
AC
3
parafns, C
4
H
10
, C
5+
aliphatics, and aromatics (BTX). These
lumps were established according to their similar kinetic behavior.
The reaction indices studied are as follows (i) butene conversion;
(ii) yield (Y
i
), and (iii) selectivity (S
i
) of lumps.
Conversion has been dened as:
X
F
0
F
F
0
100 1
where F
0
is the molar ow rate of 1-butene in the feed and F is the
ow rate of butenes (in thermodynamic equilibrium) in the reactor
outlet stream.
The yield of each i lump is dened as follows:
Y
i

F
i
F
0
100 2
where F
i
is the molar ow rate of the i lump in the product stream
expressed in CH
2
equivalent units.
Selectivity is dened as:
S
i

F
i
F
0
F
100 3
3.2.1. Effect of modifying HZSM-5 zeolites on the kinetic results at zero
time on stream
3.2.1.1. Zeolites with different SiO
2
/Al
2
O
3
ratio and modied with
K. Fig. 3 shows the effect of SiO
2
/Al
2
O
3
molar ratio and the incor-
poration of 1 wt.% K on butene conversion and propylene and eth-
ylene yields (Fig. 3a) and on the selectivity of product lumps
(Fig. 3b and 3c) at zero time on stream. The reaction indices at zero
time on stream have been obtained by extrapolating the results of
evolution of each reaction index (conversion and yield) to zero
time on stream.
Butene conversion decreases with an increase in SiO
2
/Al
2
O
3
molar ratio of unmodied (solid lines) and 1 wt.% K modied (dot-
ted lines) zeolites due to the lower acidity of the catalysts. Propyl-
ene and ethylene yields (Fig. 3a) increase with this ratio, with the
latter to a lower extent, and therefore propylene/ethylene (P/E)
ratio increasing from 1.8 (HZ-30 catalyst) to 3.1 (HZ-280 catalyst).
An increase in the SiO
2
/Al
2
O
3
ratio enhances ethylene and propyl-
ene selectivity as well as that of the non-aromatic C
5+
fraction
(mainly composed of pentenes) (Fig. 3b) due to the attenuation
of hydrogen transfer and aromatization reactions that give way
to the formation of C
2
AC
3
parafns and BTX. The lower acid
strength of the sites as well as the lower acid site density will con-
tribute to attenuating the intensity of hydrogen transfer reactions.
The selectivity of butanes (Fig. 3c) peaks slightly for a moderate
SiO
2
/Al
2
O
3
ratio, given that an increase in this ratio, on the one
hand, hinders butene conversion to higher hydrocarbons (boosting
the indirect transformation of butenes to butanes) and, on the
other hand, suppresses hydrogen transfer reactions to some extent
[39,57]. A low formation of methane is noted under these operat-
ing conditions, and is insignicant for SiO
2
/Al
2
O
3
= 280.
The aforementioned results on the effect of SiO
2
/Al
2
O
3
ratio of
the HZSM-5 zeolite on product distribution are consistent with
those obtained in the literature for 1-butene [42] and n-octane
cracking [28] and for the MTP (methanol to propylene) process
[46], and they are a consequence of the attenuation of hydrogen
transfer reactions when SiO
2
/Al
2
O
3
is increased, which also occurs
with other zeolites, such as with H-beta zeolites in naphtha
cracking [71].
The severe modication of acidity caused by K incorporation
has a great impact on the kinetic performance of the HZSM-5.
The incorporation of 1 wt.% K (Fig. 3a, dotted lines) entails a
0
20
40
60
80
100
0 40 80 120 160 200 240 280
Y
i
,

X
(
%
)
SiO
2
/Al
2
O
3
molar ratio
a
0 wt.%1 wt.%
x
Y
C2H4
Y
C3H6
K content
0
10
20
30
40
50
60
0 40 80 120 160 200 240 280
S
i

(
%
)
SiO
2
/Al
2
O
3
molar ratio
b
C
2
H
4
C
3
H
6
C
5+
0 wt.%1 wt.%
K content
0
10
20
30
40
50
60
0 40 80 120 160 200 240 280
S
i

(
%
)
SiO
2
/Al
2
O
3
molar ratio
CH
4
C
2
-C
3
C
4
H
10
BTX
c
0 wt.%1 wt.%
K content
Fig. 3. Effect of SiO
2
/Al
2
O
3
ratio and K incorporation in HZSM-5 zeolites on the
values at zero time on stream of butene conversion and ethylene and propylene
yield (graph a), and product selectivity (graph b for ethylene, propylene and non-
aromatic C
5+
hydrocarbons, and graph c for methane, C
2
AC
3
parafns, butanes and
BTX). Reaction conditions: 500 C, W/F
B0
= 1.6 g
catalyst
h (mol
CH2
)
1
, P
B
= 1.35 bar.
Solid lines, parent zeolite catalysts. Dashed lines, 1 wt.% K modied zeolite
catalysts.
E. Epelde et al. / Chemical Engineering Journal 251 (2014) 8091 85
decrease in conversion, which is more pronounced by increasing
SiO
2
/Al
2
O
3
ratio due to the higher attenuation of acidity (especially
the acid strength). However, it is remarkable that propylene selec-
tivity increases with the incorporation of 1 wt.% K (Fig. 3b), as the
moderation of the acid strength hinders undesired hydrogen trans-
fer and aromatization reactions, with this effect being more signif-
icant by increasing SiO
2
/Al
2
O
3
ratio. Thus, propylene selectivity
increases from 26% for HZ-280 catalyst to 40% for 1K/HZ-280 cat-
alyst. The great increase in propylene selectivity compensates the
decrease in conversion, so that propylene yield is higher for all K
modied zeolites, with a value of 30% for 1K/HZ-280.
Ethylene yield (Fig. 3a) and selectivity (Fig. 3b) are slightly
modied by the incorporation of 1 wt.% K, and both of them
decrease for high SiO
2
/Al
2
O
3
ratio. This difference between the
effects of incorporating K on propylene and ethylene selectivities
has been reported by Jung et al. [28], who explained it by the
different impact of the reaction extent attenuation on olens of
different reactivity. Propylene is more reactive than ethylene and
consequently its selectivity is higher at lower conversion levels.
Moreover, based on the effect of K incorporation on the zeolite
physical properties (Table 1), the signicant decrease in micropore
volume contributes at the same time as the decrease in acidity to
the results (decrease in conversion and change in product
distribution). Although the effect of the physical properties will
presumably be lower than the effect of acidity, the decrease in
micropore volume by incorporating K will contribute to attenuat-
ing hydrogen transfer bimolecular reactions, thus favoring an
increase in the selectivity of propylene (potentially active for these
reactions).
Fig. 4 shows the effect of incorporating different K contents in
the HZ-280 zeolite on butene conversion and propylene and ethyl-
ene yields (graph a) and on the selectivity of product lumps (graph
b). These results correspond to zero time on stream, which have
been calculated by extrapolating the results of evolution with time
to zero time on stream. Butene conversion signicantly decreases
with an increase in K content (Fig. 4a), whereas propylene selectiv-
ity peaks at 3 wt.% K. Consequently, propylene yield peaks (30%)
between 1 and 3 wt.% K (Fig. 4a). Ethylene selectivity remains con-
stant for K contents up to 1 wt.% and decreases for higher contents,
being insignicant for 5 wt.% K. These results are explained by the
attenuation in acidity. By increasing K content to moderate values,
the rate of the reactions giving undesired products (aromatization
and hydrogen transfer) is attenuated, because they require high
acid strength sites [57,72]. However, K contents higher than
3 wt.% signicantly deteriorate acidity and the catalyst is inactive
for the cracking of [C
n
]
+
carbenium ions to propylene and ethylene,
and their desorption as olens (mainly pentene) is favored [49].
Therefore, an increase in K content above 3 wt.%, the selectivity
of C
5+
fraction (mainly composed of pentenes) increases, whereas
propylene selectivity decreases. Zhu et al. [49] obtained similar
qualitative results for a HZSM-5 zeolite with lower SiO
2
/Al
2
O
3
ratio, concluding that the suitable K content for maximizing
propylene yield and selectivity is in the 0.71 wt.% range.
3.2.1.2. Zeolites modied by incorporating P and by mild in situ
steaming. Table 3 summarizes the results of reaction indices at
zero time on stream for HZSM-5 zeolites with different SiO
2
/
Al
2
O
3
ratio and modied by incorporating 1 wt.% P and by mild
in situ steaming. These results correspond to a lower value of space
time (0.4 g
catalyst
h (mol
CH2
)
1
) than those in Fig. 3 (1.6 g
catalyst
h
(mol
CH2
)
1
), which allows extending the information to conditions
under which the deactivation is faster.
Comparing the results of Table 3 for unmodied zeolites, with
those shown in Fig. 3 corresponding to a higher space time
(1.6 g
catalyst
h (mol
CH2
)
1
), it is observed that butene conversion
and ethylene selectivity decrease with a decrease in space time,
whereas propylene selectivity increases, with this effect being
more pronounced as the SiO
2
/Al
2
O
3
ratio is increased. Thus, for
the HZ-280 catalyst a decrease in space time from 1.6 down to
0.4 g
catalyst
h (mol
CH2
)
1
results in a drop in zero time conversion
from 80% to 73% and an increase in propylene selectivity from
26% to 42%. This result conrms the aforementioned different evo-
lution of propylene and ethylene selectivity with the reaction
extension.
The zeolites with a SiO
2
/Al
2
O
3
ratio of 30 and 80 subjected to
in situ steaming give way to a slight increase in butene conversion.
This result seems to be in contradiction with the decrease in total
acidity observed for this treatment, but it is explained by the mod-
ication of the acid strength distribution caused by an increase in
the average acid strength in these zeolites. However, this redistri-
bution of the acid strength after this treatment is not effective for
increasing propylene selectivity.
The zeolites modied with 1 wt.% P give way to slightly lower
butene conversion than the parent zeolite due to the decrease in
total acidity and acid strength, and therefore propylene selectivity
and yield increase by partially hindering secondary reactions.
Fig. 5 shows the effect of incorporating different P contents into
HZ-280 zeolites on the reaction indices at zero time on stream.
Butene conversion decreases by increasing P content (Fig. 5a),
due to the decrease in total acidity and acid strength, although this
0
20
40
60
80
100
0 1 2 3 4 5
Y
i
,

X

(
%
)
K content (wt.%)
X
Y
C2H4
Y
C3H6
a
0
20
40
60
80
0 1 2 3 4 5
S
i
(
%
)
K content (wt.%)
CH
4
C
2
-C
3
C
4
H
10
BTX
C
2
H
4
C
3
H
6
C
5+
b
Fig. 4. Effect of K content incorporated into HZ-280 zeolite on butene conversion
and ethylene and propylene yield (a) and on the selectivity of product lumps (b), at
zero time on stream. Reaction conditions: 500 C, W/F
B0
= 1.6 (g
catalyst
h) (mol
CH2
)
1
,
P
B
= 1.35 bar.
86 E. Epelde et al. / Chemical Engineering Journal 251 (2014) 8091
decrease is hardly noticed for contents lower than 3 wt.%. This
effect is lower than that reported in the literature, given that other
authors modied HZSM-5 zeolites of higher acidity than the HZ-
280 (lower SiO
2
/Al
2
O
3
ratio) [33,34,36,55]. Furthermore, all the
catalysts used in this study have been equilibrated by calcination
at 570 C, which has a considerable attenuating effect on the acid
site strength.
Propylene selectivity (Fig. 5b) increases from 27% for the
unmodied zeolite to 37% for a P content of 5 wt.%. The selectivity
of C
5+
aliphatic hydrocarbons and ethylene lumps remain almost
constant, and the selectivity of the remaining products decreases
due to the suppression of hydrogen transfer and aromatization
reactions that give way to aromatics and light parafns.
It should be mentioned that the effect of modifying HZSM-5
zeolite by P incorporation (Fig. 5) is lower than the aforementioned
for K incorporation (Fig. 4), since K incorporation is very effective
for attenuating acid strength, with the favorable effect of increas-
ing propylene selectivity.
Table 3
Effect of modifying the HZSM-5 zeolite (with different SiO
2
/Al
2
O
3
ratios) with 1 wt.% of P and by mild in situ steaming on the values at zero time of butene conversion, ethylene
and propylene yield and selectivity of product lumps. Reaction conditions: 500 C, W/F
B0
= 0.4 g
catalyst
h (mol
CH2
)
1
, P
B
= 1.35 bar.
Catalyst X (%) Y
C2H4
(%) Y
C3H6
(%) Selectivity (%)
CH
4
C
2
H
4
C
3
H
6
C
2
AC
3
C
4
H
10
C
5+
BTX
HZ-30 90.0 5.5 14 0.4 6.1 15.6 19.3 25.2 16.2 17.2
HZ-80 84.0 7.2 19.2 0.1 8.6 22.9 9.7 18.4 29.8 10.5
HZ-280 73.4 4.3 31.4 0.1 5.8 41.8 3.3 9.1 37.7 2.2
1P/HZ-30 88.7 5.1 13.1 0.3 5.8 14.8 18.7 26 20.4 14.0
1P/HZ-80 81.8 6.2 23.6 0.1 7.6 28.9 6.5 16.7 34.5 5.7
1P/HZ-280 70.1 4.1 33.6 0.1 5.8 46.9 2.2 4.3 40.1 0.6
HZ-30-ST 90.9 3.6 12.1 0.4 6.2 13.3 22.1 26.7 13.3 18.0
HZ-80-ST 86.6 6.2 17.4 0.1 6.5 20.1 11.8 21.8 27.5 12.2
HZ-280-ST 71.9 3.8 32.2 0.1 5.4 44.8 3.1 8.2 38 0.4
0
20
40
60
80
100
0 1 2 3 4 5
Y
i
,

X

(
%
)
P content (wt.%)
X
Y
C2H4
Y
C3H6
a
0
10
20
30
40
50
60
0 1 2 3 4 5
S
i

(
%
)
P content (wt.%)
CH
4
C
2
-C
3
C
4
H
10
BTX
C
2
H
4
C
3
H
6
C
5+
b
Fig. 5. Effect of P content in the HZ-280 zeolite on the values at zero time on stream
of butene conversion and ethylene and propylene yield (a) and selectivity of
product lumps (b). Reaction conditions: 500 C, W/F
B0
= 1.6 (g
catalyst
h) (mol
CH2
)
1
,
P
B
= 1.35 bar.
40
50
60
70
80
90
100
0 50 100 150 200 250 300
X

(
%
)
t (min)
HZ-30
HZ-280
HZ-80
a
0 wt.%1 wt.%
K content
0
10
20
30
40
50
60
0 50 100 150 200 250 300
P
r
o
p
y
l
e
n
e

y
i
e
l
d

(
%
)
t (min)
HZ-30
HZ-280
HZ-80
b
0 wt.%1 wt.%
K content
Fig. 6. Evolution with time on stream of butene conversion (a) and propylene yield
(b), for HZSM-5 catalysts with different SiO
2
/Al
2
O
3
ratio, unmodied (empty points)
and modied with 1 wt.% K (lled points). Reaction conditions: 500 C, W/
F
B0
= 1.6 (g
catalyst
h) (mol
CH2
)
1
, P
B
= 1.35 bar.
E. Epelde et al. / Chemical Engineering Journal 251 (2014) 8091 87
3.2.2. Catalyst stability
3.2.2.1. Zeolites with different SiO
2
/Al
2
O
3
ratio and modied with
K. Fig. 6 shows the evolution with time on stream of butene
conversion (graph a) and propylene yield (graph b), for the cata-
lysts prepared with zeolites of different SiO
2
/Al
2
O
3
ratio (lled
points) and modied with 1 wt.% K (empty points). The coke con-
tents of the spent catalysts are also summarized in Fig. 6. The sta-
bility of unmodied zeolites increases with an increase in SiO
2
/
Al
2
O
3
ratio, so that the conversion of HZ-280 catalyst only
decreases 2.8% after 5 h on stream. This result is explained by the
attenuation of coke deposition with an increase in SiO
2
/Al
2
O
3
ratio
(with coke amounts values of 3.7 and 1.3 wt.% for spent HZ-30 and
HZ-280 catalysts, respectively) due to a lower acid strength of the
zeolite. In fact, it is well established in the literature that high acid
strength sites activate the condensation reactions of coke precur-
sors [20,21,50,56].
The decrease in conversion with time on streamof 1 wt.% K mod-
ied zeolites follows a similar trend to that observed with unmodi-
ed zeolites. This result seems to be in contradiction with the
attenuation of acid site strength obtained with the incorporation
of K (Table 2), i.e., a less pronounced deactivation for catalysts pre-
pared with modied zeolites due to the attenuation of the coke
deposition rate. Nevertheless, the incorporation of K has an unfavor-
able effect on the micropore partial blockage, giving way to a minor
volume of micropores (Table 1), and therefore a lower coke content
causes a similar decrease in conversion with time on stream.
It should be noted that propylene yield increases with time on
stream due to catalyst deactivation (Fig. 6b). This increase is signif-
icant and almost the same to the decrease in butene conversion,
which evidences that deactivation affects selectively to the trans-
formation of light olens into parafns and aromatics by aromati-
zation and hydrogen transfer reactions that are activated by strong
acid sites, which are preferentially blocked by coke [20,21,50,56].
The effect of K content on the stability of different catalysts is
shown in Fig. 7, where the evolution with time on stream of butene
conversion (graph a) and propylene yield (graph b) for unmodied
and modied HZ-280 catalysts has been plotted. Catalysts with HZ-
280 unmodied and modied with 1 wt.% K are very stable for 5 h,
with a decrease in conversion of 1.6% and 2.6%, respectively. It
should be noted that a steady propylene yield higher than 30% is
obtained using 1K/HZ-280 catalyst. However, the deactivation is
more pronounced when K contents higher than 1 wt.% are added.
The results of coke content, determined by temperature pro-
gramme oxidation (TPO) are as follows: 1K/HZ-280
(1.1 wt.%) > 3K/HZ-280 (0.9 wt.%) > 5K/HZ-280 (0.6 wt.%), which
are consistent with the attenuation of acid strength for high K con-
tents and so being a key factor for coke deposition. Despite the
lower coke content, the deactivation (decrease in conversion and
increase in propylene yield throughout time) is faster as K content
is increased due to the lower total acidity (Table 2) and so the
lower initial activity of the catalysts, and therefore it is faster
0
20
40
60
80
100
0 50 100 150 200 250 300
X

(
%
)
t (min)
HZ-280
1K/HZ-280
3K/HZ-280
5K/HZ-280
a
0
10
20
30
40
50
60
0 50 100 150 200 250 300
P
r
o
p
y
l
e
n
e

y
i
e
l
d

(
%
)
t (min)
HZ-280
1K/HZ-280
3K/HZ-280
5K/HZ-280
b
Fig. 7. Effect of K content added to the HZ-280 zeolite on the evolution with time
on stream of butene conversion (a) and propylene yield (b). Reaction conditions:
500 C, W/F
B0
= 1.6 (g
catalyst
h) (mol
CH2
)
1
, P
B
= 1.35 bar.
0
20
40
60
80
100
0 50 100 150 200 250 300
X

(
%
)
t (min)
HZ-30
HZ-280
HZ-80
a
0 wt.%1 wt.%
P content
0
10
20
30
40
50
60
0 50 100 150 200 250 300
P
r
o
p
y
l
e
n
e

y
i
e
l
d

(
%
)
t (min)
HZ-30
HZ-280
HZ-80
b
0 wt.%1 wt.%
P content
Fig. 8. Evolution with time on stream of butene conversion (a) and propylene yield
(b) for HZSM-5 zeolite catalysts with different SiO
2
/Al
2
O
3
ratio, unmodied (lled
points) and modied with 1 wt.% of P (empty points). Reaction conditions: 500 C,
W/F
B0
= 0.4 (g
catalyst
h) (mol
CH2
)
1
, P
B
= 1.35 bar.
88 E. Epelde et al. / Chemical Engineering Journal 251 (2014) 8091
due to the decrease in the volume of micropores (which is signi-
cant for K contents higher than 1 wt.%, Table 1), with these pores
being more susceptible to blockage by coke.
The stability of the catalysts studied is higher than that
observed in previous studies [42,49]. This may be attributed to
the agglomeration of the zeolite with bentonite and alumina,
which generates a mesoporous matrix that enhances the growth
of coke on the outside of the zeolite crystals, thus reducing the
blockage of micropore mouths, and therefore contributing to the
stability of the catalysts studied and to the efciency of K incorpo-
ration [50].
3.2.2.2. Zeolites modied by incorporating P and mild in situ steam-
ing. Fig. 8 shows the effect of adding 1 wt.% P on the evolution with
time on stream of butene conversion (graph a) and propylene yield
(graph b). Although there are no signicant differences in the reac-
tion indices at zero time on stream for the catalysts prepared with
parent zeolites and with zeolites modied with 1 wt.% P, the
results in Fig. 8 evidence a higher stability of P modied catalysts,
due to the signicant attenuation of the acid strength of the sites,
(Table 2) thus hindering the bimolecular reactions involved in the
formation of coke [33]. Consequently, modied catalysts have
lower coke contents than unmodied catalysts, with the order
being: HZ-30 (4.0 wt.%), 1P/HZ-30 (3.1 wt.%), HZ-80 (3.0 wt.%),
1P/HZ-80 (1.7 wt.%), HZ-280 (1.7 wt.%), and 1P/HZ-280 (1.2 wt.%).
This improvement on stability is lower as the acid strength of
the unmodied zeolite decreases. Therefore, this effect is very
important for the catalyst with the zeolite of low SiO
2
/Al
2
O
3
ratio
modied with P (1P/HZ-30), which is stable for 5 h runs, thus
avoiding the rapid deactivation of the catalyst. The improvement
on stability is less signicant for zeolites of high SiO
2
/Al
2
O
3
ratio,
which are very stable even without modication.
These results concerning the attenuation of deactivation by the
modication of HZSM-5 with P are consistent with those obtained
in literature for the cracking of C
4+
olens. The stability of the mod-
ied zeolite is due to the fact that structural Al (TFAL) is trans-
formed into disordered Al species (DTAL) or pentacoordinated
aluminum(PAL), which are still active for the production of propyl-
ene [32,33].
Fig. 9 shows the evolution with time on stream of butene con-
version (graph a) and propylene yield (graph b), for the catalysts
prepared with HZSM-5 zeolites, unmodied (lled points) and
modied by in situ steaming (empty points). It is observed that this
treatment increases conversion at zero time on stream, particularly
for HZ-30 and HZ-80 catalysts, and the deactivation slightly atten-
uates for the catalysts with the lowest SiO
2
/Al
2
O
3
ratio (HZ-30 cat-
alyst), with butene conversion remaining constant for 2 h of time
on stream and subsequently decreasing. In addition, the propylene
yield obtained is slightly lower than that corresponding to the
unmodied zeolite catalysts, which evidences that in situ steaming
treatment is not suitable for increasing propylene yield in the
transformation of 1-butene (Fig. 9b).
4. Conclusions
Due to its inuence on the density of the acid sites and on their
strength, the selection of the SiO
2
/Al
2
O
3
ratio of HZSM-5 zeolite is a
suitable tool to modulate olen selectivity (and propylene selectiv-
ity) in the transformation of 1-butene at 500 C. An increase in the
SiO
2
/Al
2
O
3
ratio increases propylene selectivity by hindering
hydrogen transfer and aromatization reactions (catalyzed by
strong acid sites), although this increase also entails a decrease
in conversion. Catalyst deactivation is also considerably attenuated
because a decrease in the acid strength attenuates acid site activity
for the condensation reactions of coke precursors.
The modications carried out on HZSM-5 zeolites by incorpo-
rating K and P and dealumination by mild in situ steaming are
effective for reducing total acidity and for homogenizing acid
strength by decreasing the amount of strong Brnsted-type acid
sites and increasing the number of moderate acidity sites. The
incorporation of K is the most severe treatment, which mainly
affects the acid strength distribution. 1 wt.% K incorporation is
effective for signicantly increasing propylene yield and selectiv-
ity, as well as for decreasing coke deposition. This effect is more
noticeable in the zeolites with a high SiO
2
/Al
2
O
3
ratio, and the
1K/HZ-280 catalyst (with a zeolite of SiO
2
/Al
2
O
3
ratio = 280) is sta-
ble for 5 h time on stream, with a propylene yield of 30% and a
selectivity of 40%.
The results evidence that the attenuation of acid strength is a
key factor in the enhancement of propylene selectivity as the sec-
ondary reactions of hydrogen transfer and aromatization decrease.
Additionally, this attenuation of acid strength favors catalyst sta-
bility, as coke condensation reactions (which also require high acid
strength) are partially suppressed. However, the modication of
the porous structure is not generally desired, and requires a rigor-
ous control of treatment conditions in order to avoid an excessive
deterioration of micropores and their ensuing blockage by coke.
The incorporation of 1 wt.% P increases propylene yield at zero
time on stream and has a considerable stabilizing effect by attenu-
ating acid site strength.
0
20
40
60
80
100
0 50 100 150 200 250 300
X

(
%
)
t (min)
ref. ST
HZ-30
HZ-280
HZ-80
a
0
10
20
30
40
50
60
0 50 100 150 200 250 300
P
r
o
p
y
l
e
n
e

y
i
e
l
d

(
%
)
t (min)
ref. ST
HZ-30
HZ-280
HZ-80
b
Fig. 9. Evolution with time on stream of butene conversion (a) and propylene yield
(b) for HZSM-5 zeolite catalysts with different SiO
2
/Al
2
O
3
ratio, unmodied (lled
points) and modied by in situ steaming at 400 C (empty points). Reaction
conditions: 500 C, W/F
B0
= 0.4 (g
catalyst
h) (mol
CH2
)
1
, P
B
= 1.35 bar.
E. Epelde et al. / Chemical Engineering Journal 251 (2014) 8091 89
Mild in situ steaming treatment helps to slightly increase
butene conversion, without any perceptible effect on stability,
but with a decrease in propylene yield. This treatment is not there-
fore suitable for the selective production of propylene.
This papers results allow establishing alternative routes for
adjusting HZSM-5 properties for the selective production of pro-
pylene. Nevertheless, the reaction extension also has a signicant
effect on selectivity, which requires a broader study of the effect
of operating conditions in order to determine the suitable condi-
tions for the process (especially of temperature and space time).
Acknowledgements
This work was carried out with the nancial support from the
Ministry of Economy and Competitiveness (MINECO) of the Span-
ish Government (Project CTQ2010-19188), from the Basque Gov-
ernment (Project IT748-13) and from the University of the
Basque Country (UFI 11/39). Eva Epelde is grateful for the Ph.D.
grant from the Department of Education, University and Research
of the Basque Country (BFI08.122) and for the University of the
Basque Country. Technical and human support provided by SGIKer
(UPV/EHU) is gratefully acknowledged.
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