Journal of Porous Materials (2019) 26:1407–1425

https://doi.org/10.1007/s10934-019-00740-y

Novel hierarchical HZSM-5 zeolites prepared by combining desilication

and steaming modification for converting methanol to propylene
process
Fatemeh Gorzin1 · Jafar Towfighi Darian1 · Fereydoon Yaripour2 · Seyyed Mohammad Mousavi1

Published online: 8 March 2019

© Springer Science+Business Media, LLC, part of Springer Nature 2019

Abstract
The effect of mesoporosity formation and acidity modification have been investigated by desilication and combined desilica-
tion–dealumination treatments over highly siliceous zeolite HZSM-5 (Si/Al = 200) and its catalytic performance has been
studied in the conversion of methanol to propylene (MTP) reaction. Desilication of a conventional microporous HZSM-5
catalyst was performed using NaOH, mixtures of NaOH and tetrapropylammonium hydroxide (TPAOH), and mixtures of
NaOH and tetrabutylammonium hydroxide (TBAOH) with different ratios. Subsequent mild steaming treatment has been
used to modify acidity of the selected samples. The physicochemical properties of all samples were characterized by XRD,
FE-SEM, BET and N ­ H3-TPD methods. Textural and acidity properties confirmed that TBAOH is more effective than TPAOH
in the mesoporosity formation, micropore volume preservation, and acidity modification. Steaming treatment after desilica-
tion over the sample with TPAOH/(NaOH + TPAOH) ratio of 0.4, led to increase in selectivities to propylene from 38.4 to
41.3%, and total light olefins from 69.4 to 76.6%, while it led to decrease in ­C5+ components selectivity from 14.8 to 10.1%.
The combined alkaline-steam treatment over the sample with TBAOH/(NaOH + TBAOH) ratio of 0.2 compared to the parent
one led to considerable higher selectivities to propylene (44.8 vs. 30.7%), total light olefins (84.1 vs. 57.9%), as well as lower
­ 5+ components (7.4% vs. 27.1%). Moreover, this sample showed double lifetime (830 h) in MTP reaction
selectivities to C
compared to the conventional micropore ZSM-5 catalyst (425 h). The results showed that desilication led to a remarkable
mesoporosity development, while steaming treatment generally influenced on the HZSM-5 acidity. Therefore, the combined
alkaline-steam treatment leads to HZSM-5 zeolite formation with tailored pore architecture and surface acidic properties.

Keywords High silica ZSM-5 · Hierarchical zeolites · Desilication · Steaming modification · TPAOH · TBAOH · Methanol
to propylene (MTP)

1 Introduction

Propylene is used as a key component for the production of

polypropylene, acrylic acid, propylene oxide, acrylonitrile,
and isopropyl alcohol in petrochemical industry [1]. Due
to the growing worldwide market demand for propylene,
Electronic supplementary material The online version of this increasing oil price, and shortage of petroleum resource in
article (https​://doi.org/10.1007/s1093​4-019-00740​-y) contains
the future, the new processes with high propylene to ethyl-
supplementary material, which is available to authorized users.
ene ratio must be developed [2, 3]. Methanol can be easily
* Jafar Towfighi Darian produced from synthesis gas by using proven technologies.
towfighi@modares.ac.ir Methanol to propylene (MTP) process based on the acidic
1 catalysts is a promising way to produce light olefins with
Department of Chemical Engineering, Tarbiat Modares
University, Tehran, P.O. Box 14115‑143, Iran high propylene to ethylene ratio [4, 5]. During past decades,
2 many studies have been performed on the product distribu-
Catalysis Research Group, Petrochemical Research &
Technology Company, National Iranian Petrochemical tion and the activity of methanol conversion over ZSM-5
Company, Tehran, P.O. Box: 1493, Iran catalyst with different Si/Al molar ratios, and concluded

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that ZSM-5 zeolite with Si/Al molar ratio higher than 170
maybe a suitable catalyst for MTP process [6]. In spite of
desirable properties of ZSM-5 such as thermal stability, high
acidic activity, and excellent shape selectivity, its catalytic
activity is influenced by mass transfer limitation associated
with small micropores [7, 8]. Therefore, ZSM-5 modifi-
cation with good activity and selectivity in MTP reaction
still remains a great challenge in the catalyst and material
science.
Introducing an additional mesopore network of inter or
intracrystalline nature besides the intrinsic micropore sys-
tem, which referred to hierarchical ZSM-5, can be a prom-
ising method to overcome fast deactivation and develop a
catalyst with high stability for the MTP reaction. A wide
variety of strategies have been developed to generate the
hierarchical porous ZSM-5, such as direct synthesis in the
presence of various hard or soft templates and post treatment
approaches leading to extraction of Si (desilication) or Al
(dealumination) species from zeolite framework, which have
been presented in the reviews of Serrano et al. [9], Möller
and bein [10], and Čejka and Mintova [11].
Templating techniques involve extensive amounts of
costly templates, which must be removed by calcination at
high temperature. Calcination is always accompanied by
high energy consumption, some structural destruction, air
pollution arising from thermal decomposition, and releasing
a lot of toxic gases (mainly NOx and greenhouse gases such
as ­CO2). Moreover, mechanical strength of the hierarchical
zeolites after removing templates significantly limits their
industrial applications [12–14]. In contrast, post synthesis
treatments by using acid, base, and steam a‎ re simple ways
to produce mesoporous zeolite in industrial scales [15–17].
Among all the approaches, desilication of ZSM-5 in an
alkaline medium (typically NaOH), seems to be a promis-
ing route due to its simplicity operations, versatility, and
efficiency [18, 19]. A great attention has been concerned to
highly siliceous ZSM-5 zeolites synthesis in terms of their
higher hydrothermal stability, higher organic compounds
selectivity, and better catalytic performance compared to
aluminum rich ZSM-5 zeolites [20]. The majority of desili-
cation studies by an aqueous NaOH solution have been done
using ZSM-5 with Si/Al molar ratio in the range of 25–50,
while the desilication studies of high silica ZSM-5 have been
less frequent [21–24]. Therefore, it is necessary to find an
efficient method to introduce mesoporosity in this type of
zeolites.
Bjørgen et al. [25] studied the effect of various NaOH
concentration on the pore structure of ZSM-5 catalyst (Si/
Al = 46) and its catalytic performance in MTG reaction.
They found that the desilicated ZSM-5 shows higher selec-
tivity towards the gasoline fraction ­(C5+) and prolonger
lifetime compared to microporous one. Sadowska et al.
[26, 27] investigated the influence of alkaline treatments
13
Journal of Porous Materials (2019) 26:1407–1425
with NaOH and NaOH/TBAOH mixtures on the physico-
chemical properties and catalytic performance of two dif-
ferent ratios of ZSM-5 (Si/Al = 164 and 31.5) zeolite in
cracking reaction. The results showed that the mixture of
NaOH and TBAOH as an alkaline agent, leads to formation
of mesoporous ZSM-5 with narrower pore size distribution
compared to use NaOH alone. Ahmadpour and Taghizadeh
[18] studied the MTP reaction over desilicated ZSM-5 by
different ratio of NaOH/TPAOH mixtures. They found that
NaOH/TPAOH solution with 0.4 ratio of TPAOH in the
mixture showed higher propylene selectivity (47.2%) and
longer catalyst lifetime (80 h) compared to the parent one
(35.7% propylene selectivity and 43 h lifetime).
To date, steaming is the most common dealumination
technique which has been used to prepare industrially
important catalysts with high activity, selectivity and sta-
bility [28]. Because steaming post-treatment extracts part
of the framework aluminum species (acting as Bronsted
acid sites) and converts them into extra-framework alu-
minum, (acting as Lewis acid sites), a decrease in the num-
ber of Bronsted acid sites is expected [29]. Rostamizadeh
and Yaripour [30], investigated the effect of mild steaming
at 500 °C for 6 h on the stability of nanocatalyst ZSM-5 in
MTO reaction. The results showed that the dealuminated
catalyst represents around 43% propylene selectivity with
double lifetime (384 h) in MTO reaction compared to the
conventional micropore one. Ong et al. [31] investigated
the effect of dealumination process on the HZSM-5 cata-
lyst (Si/Al = 250) using steaming at 450 °C for different
times from 2 to 48 h. They showed steaming process for
2 h produce the highest mesoporosity (372 m2 g−1, and
0.2 cm3 g−1) than other times.
It should be noted that there are few researches on
dealumination of highly siliceous ZSM-5 catalyst, while
the high silica ZSM-5 catalysts show better catalytic per-
formance in terms of high activity and long lifetime in
MTP reaction compared to the high aluminum zeolites.
The aim of the present study is to combine the advan-
tages of desilication and steam modification. At first, we
introduced the mesoporosity into highly siliceous HZSM-5
catalyst by controlled alkaline treatment using different
ratio of NaOH/TPAOH and NaOH/TBAOH solution to
reduce the diffusion limitation. Then, the acidity of the
mesoporous HZSM-5 catalysts was modified by steam
treatment. Moreover, in this study, for the first time the
effect of combining of desilication and dealumination
modification was investigated on the catalytic performance
of highly siliceous HZSM-5 zeolite (Si/Al = 200) in MTP
reaction. Also, the physicochemical properties of these
catalysts were characterized by X-ray diffraction (XRD),
field-emission scanning electron microscopy (FE-SEM),
Brunauer–Emmett–Teller (BET) and ­NH3-TPD methods.
Journal of Porous Materials (2019) 26:1407–1425 1409

2 Experimental aqueous solution of ­NH4NO3 and stirred at 90 °C with reflux

2.1 Materials
All the chemical reagents were the analytical grade and
used without further purification. Silicic acid ­(SiO2 ­xH2O,
≥ 99 wt%), ammonium nitrate ­(NH4NO3, 99 wt%), sul-
furic acid (­H2SO4, 98 wt%), sodium hydroxide (NaOH,
99.6 wt%), tetrapropylammonium hydroxide (TPAOH,
40 wt% aqueous solution), and tetrabutylammonium hydrox-
ide (TBAOH, 40 wt% aqueous solution), were purchased
from Merck Company (Germany) while sodium aluminate
­(NaAlO2, ­Al2O3 55 wt%) was purchased from Riedel de
H ä en (Germany).
2.2 Catalysts synthesis
2.2.1 Parent zeolite synthesis
The gel composition of ­2 0SiO 2:0.05Al 2O 3:1TPAOH:
1.5Na2O:200H2O was used for synthesis of HZSM-five sam-
ples via hydrothermal method. At first, sodium aluminate
was added to NaOH aqueous solution and mixed for 30 min.
Then TPAOH was drop-wise added to the mixture for 30 min
(solution A). Simultaneously, silicic acid added slowly to
NaOH aqueous solution and mixed for 30 min (solution B).
In the next step, the solution A was added drop wise to the
solution B and stirred for 120 min, then in order to adjust
gel pH, concentrated sulfuric acid was added to the mixture.
The hydrothermal treatment was carried out in static Teflon-
lined stainless-steel autoclave at 187 °C for 48 h in an oven.
The formed powder was centrifuged, washed with deionized
water until pH reached to neutral, and then dried at 105 °C
for 12 h. Finally, in order to remove the organic template, the
sample was calcined at 530 °C for 12 h with a heating rate of
3°C min−1. In order to ion exchange of NaZSM-5–HZSM-
5, synthesized NaZSM-5 sample was soaked in 1.0 mol l−1
for 10 h. This was repeated four times, after that; the solid
products were centrifuged and washed with deionized water.
Afterward, it was dried at 105 °C, followed by calcination at
530 °C for 12 h to obtain the H-form of catalyst (HZSM-5).
This sample was denoted as parent.
2.2.2 Alkaline treatment
Desilication treatments on the parent catalyst were per-
formed in the alkaline solutions of NaOH, as well as NaOH/
TPAOH mixture, and NaOH/TBAOH mixture in differ-
ent ratios as listed in Table 1. The alkaline samples were
denoted as DeSi–NaOH–TPA-R and DeSi–NaOH–TBA-R,
which R is the molar ratio of the TPAOH/(NaOH + TPAOH)
and TBAOH/(NaOH + TBAOH) that varied from 0 to 0.6.
The concentration of each solution was 0.2 M. 300 ml of
the alkaline solution were heated to 65 °C in the flax under
reflux, after then, 30 gr of the parent catalyst were added to
the solution and stirred vigorously for 30 min. Afterwards,
the suspension was cooled down immediately in ice bath
and filtered, washed with deionized water until neutral pH.
The filtrated cake was dried at 105 °C for 12 h and converted
into the H-form following the procedure described for the
parent catalyst.
2.2.3 Steaming treatment
In order to investigate the effect of steaming treatment on
the catalytic performance of the HZSM-5 catalysts in MTP
reaction, parent and some of the desilicated samples were
selected (Table 1). For the steaming procedure, 4 g of the
samples were activated in a fixed-bed continuous flow reac-
tor to 500 °C under nitrogen gas flow of 75 ml min−1 for 2 h.
After that, nitrogen was then switched to 0.309 ml min−1
water with WHSV of 3 h−1 for 12 h which injected to the
catalyst bed with a WellChrom K-120 HPLC pump and then
cooled to the room temperature. In order to assure a constant

Table 1  Catalyst names Catalyst name TPAOH TBAOH Desilication Dealumination

R = R =
prepared with different alkaline NaOH + TBAOH NaOH + TBAOH
solutions and post treatment
Parent NA NA No No
steps
DeSi–NaOH 0 0 Yes No
DeSi–NaOH–TPA0.2 0.2 NA Yes No
DeSi–NaOH–TPA0.4 0.4 NA Yes No
DeSi–NaOH–TPA0.6 0.6 NA Yes No
DeSi–NaOH–TBA0.2 NA 0.2 Yes No
DeSi–NaOH–TBA0.4 NA 0.4 Yes No
DeSi–NaOH–TBA0.6 NA 0.6 Yes No
DeAl–parent NA NA No Yes
DeAl–DeSi–NaOH–TPA0.4 0.4 NA Yes Yes
DeAl–DeSi–NaOH–TBA0.2 NA 0.2 Yes Yes

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1410
vaporization of water flow on the catalyst bed, the entrance
of the catalyst packing of reactor was filled with the inert
quartz.
2.3 Catalyst characterization techniques
Powder XRD analysis was used to recognize the type of
crystalline phase and crystallinity of samples. Patterns
were recorded on a Philips PW1730 diffractometer (Philips
Analytical, Almelo, The Netherlands) using Cu Kα radia-
tion (λ = 1.5406 ºA) over a 2θ range of 5°–50° with a step
size of 0.05° and a step time of 1 s at the room tempera-
ture. The crystal size and morphology of HZSM-5 nano-
catalysts were determined by FE-SEM on MIRA3 TESCAN,
USA instrument, operating at 15 kV. The textural properties
of all the samples including the specific surface areas and
pore diameters were determined using N ­ 2 adsorption–des-
orption isotherms at 77 K on NOVA2000 QuantaChrome
,USA instrument. Before measurement, the samples were
evacuated at 300 °C under N ­ 2 flow for 3 h. The BET equa-
tion was used to calculate the specific surface area using
adsorption data at p·p0−1 = 0.05–0.25. Micropore volume and
micropore surface area were determined by t-plot curve at
thickness range between 3.5 and 5.4 ºA. The pore size distri-
bution was obtained from the adsorption isotherm using Bar-
rett–Joyner–Halenda (BJH) method. Mesopore volume was
calculated by the difference between the total pore volume
(p·p0−1 = 0.99) and micropore volume. The surface acidity of
the prepared catalysts was determined by temperature-pro-
grammed desorption of ammonia (­ NH3-TPD) with an online
thermal conductivity detector (TCD) using a conventional
flow apparatus (BELCAT-A, BEL Japan, instrument.). 35 mg
of the sample was preheated under helium flow at 300 °C
for 2 h with a heating rate of 10 °C min−1. After cooling to
60 °C, the sample was saturated with ­NH3 in the micro reac-
tor for 1 h. In order to remove the physically adsorbed N­ H3
on the catalyst surface, helium was passed over the sample
for 30 min. The temperature ranges of ammonia desorption
was 35–850 °C.
2.4 Catalytic performance tests
The performance of all the prepared catalysts for methanol
conversion to propylene (MTP) reaction was investigated in a
fixed-bed continuous flow reactor (L = 60 cm, I.D. = 11 mm,
S.S. 316) at 480 °C under atmospheric pressure. The reactor
was heated by a temperature-controlled three-zone furnace
and a K-type thermocouple probe was placed coaxially in
the center of the catalyst bed to measure and monitor the
reaction temperature. A schematic flow diagram of the lab
scale set-up has been shown in Fig. 1. In each run, 4 g of the
catalyst was loaded in the center section of the reactor and a
liquid mixture consisting of 50 wt% methanol in water with
13
Journal of Porous Materials (2019) 26:1407–1425
methanol WHSV of 0.9 h−1 was injected to catalyst bed with
a WellChrom K-120 HPLC pump. Prior to the MTP reaction,
the sample was activated at 300 °C for 2 h under N ­ 2 flow
with a heating rate of 3 °C min−1. Then, the ­N2 gas flow was
stopped and the mixture of methanol and water was pumped
from the feed tank to the preheater. The reactor outlet stream
was cooled to 6 °C in a refrigeration bath and then the gas
and liquid products were separated. In order to prevent heavy
components condensation, the transfer line from the reactor
outlet to the refrigeration bath was externally heated and
maintained at 170 °C. On-line analysis of the gas phase was
carried out using a micro–GC (Varian CP-4900) equipped
with a TCD detector. Four channels of this instrument were
used to separate the products [(CH4, ­C2–C5 Olefin/paraffins,
DME, ­C6-cut) and ­(H2, CO and ­CO2)]. The separated aque-
ous parts of the liquid products were analyzed using Varian
CP-3800 gas chromatograph equipped with FID and TCD
detectors in which a CP-Wax52CB column was used to sepa-
rate the components (methanol and water). The organic part
was also analyzed using Varian CP-3800 gas chromatograph
equipped with a FID detector in which a PONA column was
used to separate the components ­(C6–C16 hydrocarbons).
The methanol conversion and selectivity of products were
calculated by Eqs. 1 and 2, respectively.
N i MeOH − (N o MeOH + 2 N o DME )
Methanol Conversion = × 100
N i MeOH
(1)
x N O Cx H y
Selectivity = (2)
N i MeOH − (N o MeOH + 2 N o DME )
where N is the number of moles. Superscripts i and o repre-
sent components at the inlet and outlet of the reactor, respec-
tively. Superscript x is the number of carbon atoms.
3 Results and discussion
3.1 Characterization of desilicated catalysts
3.1.1 XRD analysis
XRD patterns of the parent zeolite along with the desili-
cated samples prepared with mixture of NaOH/TPAOH
and NaOH/TBAOH have been shown in Fig. 2. The com-
parison between the XRD patterns of the parent cata-
lyst and all desilicated samples with those of the typical
ZSM-5 framework structure (Standard JCPDS: 42–23
[32, 33]) showed two main peaks at 2θ = 7°–10° and three
peaks at 2θ = 23°–25° which assigned to the preserva-
tion of the lattice structure of MFI during alkaline treat-
ment without any additional phases formation. In order to
Journal of Porous Materials (2019) 26:1407–1425
Fig. 1  Schematic flow diagram of the experimental setup for the catalytic activity tests
determine the effect of alkaline treatment with different
base mixtures on the degree of relative crystallinity of
HZSM-5 catalysts, calculations were carried out accord-
ing to procedure A described in ASTM D5758-01 [34].
This calculation contains a comparison of the integrated
peak areas in the range of 2θ = 22.5°–25° of desilicated
HZSM-5 catalysts relative to those of a highly crystal-
line sample (parent catalyst). As can be seen in Table 2,
the relative crystallinity for the desilicated samples in the
presence of tetra alkyl ammonium cations (­ TPA+ or T ­ BA+)
in the alkaline solution is considerably higher than that of
the alkaline treated sample with only NaOH (with 88%
relative crystallinity). On the other hand, desilication with
1411
both NaOH/TPAOH and NaOH/TBAOH mixtures did not
destroy the crystallinity of the hierarchical samples.
3.1.2 Nitrogen adsorption/desorption analysis
N 2 adsorption/desorption isotherms and corresponding
BJH pore size distribution curves of the parent catalyst
along with all desilicated samples have been displayed
in Fig. 3, and their textural properties have been listed
in Table 2. As shown in Fig. 3a, the parent catalyst dis-
plays isotherm type I (IUPAC) with a plateau at high rela-
tive pressures without any distinct hysteresis loop which
only shows nitrogen uptake at p·p0−1 < 0.2. This behav-
ior is characteristic of microporous materials without
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1412 Journal of Porous Materials (2019) 26:1407–1425

(a) The comparison of pore size distribution curves for the

DeSi-NaOH-TPA0.6
samples desilicated by NaOH/TPAOH and NaOH/TBAOH
mixtures at different ratios (Fig. 3c, d, respectively) confirms
the formation of narrow and uniform mesopore size distribu-
DeSi-NaOH-TPA0.4
tion which centered at ca. 3.5 and ca. 5.5 nm, respectively,
While pore size distribution curve of the sample desilicated
Intensity (a.u.)

DeSi-NaOH-TPA0.2 by pure NaOH shows a narrow peak at around ca. 3.5 nm

and a broad peak at around ca. 14 nm. It should be noted that
DeSi-NaOH
there is no considerable difference in BJH pore size distri-
bution curves for the samples prepared with different ratios
of the NaOH and TPAOH or NaOH and TBAOH alkaline
Parent solutions.
Our results are in line with previous studies which have
Standard JCPDS: 42-23 reported similar observations on mesopore size distribution
0 10 20 30 40 50 of ZSM-5 catalyst in the presence of tetra alkyl ammonium
2Theta (degree) cations. Sadowska et al. [26] reported that alkaline treated
highly siliceous ZSM-5 catalyst with NaOH/TBAOH mix-
ture produced narrow pores with narrow pore size distribu-
(b) tion with the maximum at around 4–5 nm. Ahmadpour and
DeSi-NaOH-TBA0.6 Taghizadeh [18] showed that in case of using the mixture of
NaOH and TPAOH as a leaching agent leads to form narrow
mesopore size distribution centered at around 3.6 nm.
As listed in Table 2, for all desilicated samples, the total
Intensity (a.u.)

DeSi-NaOH-TBA0.4
DeSi-NaOH-TBA0.2
Standard JCPDS: 42-23
0 10 20 30 40
2Theta (degree)
Fig. 2  The XRD patterns of the parent, desilicated HZSM-five sam-
ples with a NaOH &TPAOH mixture b NaOH & TBAOH mixture,
and standard JCPDS: 42–23
considerable mesoporosity [35, 36]. This result was con-
firmed by BJH curve of this sample (Fig. 3c) which does
not show any obvious peak at mesoporous range
(2–50 nm). Also, as listed in Table 2, the external surface
area (30.1 m2 g−1) and mesopores volume (0.065 cm3 g−1)
of the parent catalyst are very low compared to its total
surface area and total pore volume which confirm the rela-
tively small contribution of mesoporosity in this catalyst.
As can be seen in Fig. 3a, b, nitrogen adsorption/desorp-
tion isotherms of the desilicated samples represent both
types I and VI behavior, with a pronounced hysteresis loop
type H3 at a relative pressure higher than p·p0−1 = 0.4. This
is typical for the formation of porous system coupling
micro and mesoporosity which is confirmed by the t-plot
results listed in Table 2.
BET surface areas have decreased compared to the par-
ent catalyst, which this surface reduction for DeSi–NaOH
sample is higher than other desilicated samples. It can be
explained by silicon extraction during desilication process.
It can be explained by silicon extraction during desilication
process. According to the literature [16, 37], for ZSM-5 zeo-
lite with low Si/Al ratios, aluminum acts as a pore directing
agent and prevents the framework from base attack, while
50 in high silica ZSM-5, uncontrolled excessive silicon extrac-
tion results in massive zeolite dissolution. In order to solve
the problem, the addition of tetra alkyl ammonium cations
to the NaOH extraction solution, acts as an efficient alkaline
treatment for generating mesoporosity in highly siliceous
ZSM-5 zeolite. These agents by the high adsorption affinity
towards the zeolite surface, protects zeolite against dissolu-
tion [26]. As highly siliceous zeolite (Si/Al = 200) was used
in this study, the concentration of Al extracted into solution
was negligible against strong ­OH− ions attack, and due to
­ PA+ and T
affinity of T ­ BA+ cations to the catalyst surface,
they can play as a main pore directing agent, producing nar-
row pores in zeolite [38]. Therefore, the presence of ­TPA+
or ­TBA+ in an alkaline solution, results in the generation of
narrow and uniform mesopores within the zeolite crystals
compared to the sample desilicated by pure NaOH, which
these results were verified by BJH pore size distribution
curves of these samples. All these findings indicate that the
method of producing hierarchical zeolites with both narrow
pores and narrow pore size distribution should be based on
treatment of highly siliceous zeolite with the NaOH/amine
hydroxide mixture.

13
Journal of Porous Materials (2019) 26:1407–1425 1413

Table 2  Textural properties of the parent, desilicated and dealuminated HZSM-5 samples
Sample Relative SBET ­(m2 g−1)a SMicro ­(m2 g−1)b SExt ­(m2 g−1)c VTotal ­(cm3 g−1)d VMicro ­(cm3 g−1)e VMeso ­(cm3 g−1)f HFg
crystallinity
(%)

Parent 100 398.8 368.7 30.1 0.202 0.137 0.065 0.051

DeSi–NaOH 88 361.6 266.3 95.3 0.254 0.134 0.12 0.139
DeSi–NaOH– 93 378.7 248.7 130 0.231 0.116 0.115 0.172
TPA0.2
DeSi–NaOH– 97 385.3 226.7 158.6 0.243 0.119 0.124 0.201
TPA0.4
DeSi–NaOH– 95 373.8 230.7 143.1 0.239 0.118 0.121 0.189
TPA0.6
DeSi–NaOH– 98 391.6 202.5 189.1 0.249 0.128 0.121 0.248
TBA0.2
DeSi–NaOH– 94 386.2 208.7 177.5 0.241 0.123 0.121 0.234
TBA0.4
DeSi–NaOH– 92 381.8 212.3 169.5 0.238 0.121 0.117 0.226
TBA0.6
DeAl-parent 97 370.8 327.6 43.2 0.201 0.131 0.07 0.076
DeAl–DeSi– 91 360.2 198.4 161.8 0.239 0.116 0.123 0.218
NaOH–TPA0.4
DeAl–DeSi– 94 365.4 171.7 193.7 0.243 0.121 0.122 0.264
NaOH–TBA0.2
a
Total surface areas were obtained by the BET method using adsorption data in P/P0 ranging from 0.05 to 0.25
b
Measured by t-plot method using adsorption data in P/P0 ranging from 0.19 to 0.39
c
External surface area, measured by t-plot method using adsorption data in P/P0 ranging from 0.19 to 0.39
d
Total pore volumes were estimated from the adsorbed amount at P/P0 = 0.99
e
Measured by t-plot method using adsorption data in P/P0 ranging from 0.19 to 0.39
f
Vmeso = Vads, p/po = 0.99−Vmicro
g
The hierarchical factor, defined as ­(Vmic/Vtotal) × (SExt/SBET)

The significant increase in external surface area (more
than four times) and mesopore volume with a slight drop
in micropore volume (~ max. 15%) observed for the desili-
cated samples with the NaOH/TPAOH mixtures compared
to the parent one. Among these samples with different
ratios, DeSi–NaOH–TPA0.4 (Ratio = 0.4) shows the largest
mesopore surface area (158.6 m2 g−1), and mesopore volume
(0.124 cm3 g−1).
The lower reduction in total surface area and better pres-
ervation of micropore volume were observed for the desili-
cated samples with different ratios of NaOH/TBAOH alka-
line solutions‎ compared to the NaOH/TPAOH mixtures and
the parent one. Among them, the DeSi–NaOH–TBA0.2 sam-
ple showed the largest external surface area (189.1 m2 g−1),
more than 6 times compared to the parent one (30.1 m2 g−1)
with only 10% reduction in micropore volume. Mesoporous
surface area in the range of 75–244 m2 g−1 was reported
by Caicedo-Realpe and Perez-Ramirez [39] using a two-
step path including N­ aAlO2 and acid washing treatment of
ZSM-5 zeolite.
In this study, the hierarchy factor was used to qualita-
tive comparison of the desilicated samples, in terms of
textural properties. This factor is an appropriate tool to
describe the porosity of hierarchically structured zeo-
lites, which obtains by multiplying the sample relative
micropore volume ­(Vmic/Vtotal) and the relative external
surface area ­( S Ext/S BET) [40]. As listed in the final col-
umn of the Table 2, for the desilicated samples, the value
of this factor (HF) increased from 0.051 for the parent
catalyst to its maximum value, i.e. 0.201, and 0.248 for
DeSi–NaOH–TPA0.4 and DeSi–NaOH–TBA0.2 samples,
respectively. This factor for all alkaline treated samples
with different ratios of NaOH/TBAOH is higher than in
the samples treated with NaOH/TPAOH mixtures due
to higher mesopore surface area and better preserved
micropore volume in these samples. However, the desili-
cated samples with high ratio of TPAOH or TBAOH in the
alkaline solutions have a negative effect on the mesopo-
rosity formation process in the samples. Pe´rez-Ramı´rez
et al. [40] investigated the effect of different methods on
the hierarchy factor values. They showed HF < 0.1 for
conventional microporous materials and HF > 0.15 for
hierarchically structured materials, which our results are
completely matched with these ranges.

13
1414 Journal of Porous Materials (2019) 26:1407–1425

Fig. 3  N2 adsorption/desorp- 240 240

Parent
Parent
tion isotherms of a the parent
DeSi-NaOH
(a) DeSi-NaOH (b)
and desilicated samples with DeSi-NaOH-TBA0.2
210 DeSi-NaOH-TPA0.2 210 DeSi-NaOH-TBA0.4
NaOH/TPAOH mixture in DeSi-NaOH-TPA0.4 DeSi-NaOH-TBA0.6
ratios of 0, 0.2, 0.4, and 0.6 are DeSi-NaOH-TPA0.6
vertically offset by 40, 80,120, 180 180
and 160 cm3 g−1, respectively.
b The parent and desilicated 150 150
samples with NaOH/TBAOH

Vads ( cm3STPg-1)
Vads (cm3STPg-1)
mixture in ratios of 0, 0.2, 0.4,
and 0.6 are vertically offset by 120 120
40, 80,120, and 160 cm3 g−1,
and the corresponding BJH pore 90 90
size distributions derived from
the adsorption branch of the
60 60
isotherms for c NaOH/TPAOH
mixture, d NaOH/TBAOH
mixture 30 30

0 0
0 0.2 0.4 0.6 0.8 1 0 0.2 0.4 0.6 0.8 1
Relative pressure (p.p0-1) Relative pressure (p.p0-1)

1
1
DeSi-NaOH-TPA0.6 (c) DeSi-NaOH-TBA0.6
0.9 DeSi-NaOH-TPA0.4 0.9 DeSi-NaOH-TBA0.4
(d)
DeSi-NaOH-TPA0.2 DeSi-NaOH-TBA0.2
0.8 DeSi-NaOH 0.8
DeSi-NaOH
Parent
0.7 0.7 Parent
DV(log d) (cm3.g-1)

0.6 0.6

DV(log d) (cm3.g-1)
0.5 0.5

0.4 0.4

0.3 0.3

0.2 0.2

0.1 0.1

0 0
0 50 100 150 200 0 50 100 150 200
Pore diameter (Å)
Pore diameter (Å)

3.1.3 FE‑SEM analysis surface prevent the uncontrollable dissolution of the zeo-

Figure 4 shows the surface morphology of the parent cata-
lyst and desilicated samples. As can be seen in Fig. 4a,
a relatively spherical aggregate shaped morphology was
observed for the parent catalyst. The crystal size of this
sample is large with quite clear and smooth surface that
verifies the low presence of mesopores in its structure.
This figure clearly confirms that after desilication, the
external surface of the parent catalyst becomes rough
and rugged. In addition, some ruts and voids appear on
the zeolite surface. For the sample desilicated with pure
NaOH (Fig. 4b) many broken crystals were observed on
the catalyst surface compared to the desilicated samples
in the presence of the organic base ­(TPA+ or ­TBA+). Fig-
ure 4 c and Fig. 4 d show a lot of nanoscale open holes
on the external surface of the DeSi–NaOH–TPA0.4 and
DeSi–NaOH–TBA0.2, respectively. On the other hand
these ammonium hydroxides by adhering to the zeolite
lite crystals and crystalline network destruction which
cause to generate narrow and uniform mesopores in
comparison with DeSi–NaOH [21, 40]. These results
confirmed by BJH pore size distribution curves earlier.
Moreover, these open holes facile the molecular transport
and improve the catalytic performance of these samples in
the MTP reaction which will be studied further.
Some species removed from the zeolite framework during
alkaline treatment can reinsert to the mesopore walls or cata-
lyst surface and react with TPAOH or TBAOH molecules
and produce larger crystals. It can be seen from Fig. 4c,
d that after changing the alkaline agent from TPAOH to
TBAOH, the smaller crystal size was obtained which seems
that recrystallization rate of ZSM-5 in the presence of the
TPAOH is faster than TBAOH containing solutions. This
seems to be a negative point, because the growth of crystal
size can influence on the length path of the reaction and the
catalytic performance of the catalyst in reactor test.

13
Journal of Porous Materials (2019) 26:1407–1425 1415

Fig. 4  FE-SEM images of the

a Parent, b DeSi–NaOH, c
DeSi–NaOH–TPA0.4 and d
DeSi–NaOH–TBA0.2

13
1416 Journal of Porous Materials (2019) 26:1407–1425

3.1.4 NH3‑TPD analysis have been depicted in Fig. 5. The deconvoluted curves of

Acidity plays a crucial role in the catalytic performance
of catalysts in the MTP reaction. The acidity changes
including surface concentration, strength of the acid sites
in the parent catalyst, and the desilicated samples were
studied by the ­NH3-TPD method. The TPD curves of all
samples have been displayed in Fig. 5. The ­NH3-TPD pat-
terns of the desilicated samples and the parent one were
deconvoluted into three peaks by a Gaussian-type func-
tion, which represents weak, moderate, and strong acid
sites. Also the deconvoluted curves of the parent catalyst
all the desilicated samples have been provided in the Sup-
plementary data, Fig. S1.
As depicted in this figure, all desilicated samples
exhibit similar ­NH3-TPD patterns with three desorption
peaks which the lower temperature peak ­(TP1) at around
100–300 °C and the higher temperature peak (­ T P2) at
around 300–500 °C, are related to ammonia desorption
from weak/moderate and moderate /strong acid sites,
respectively. The N ­ H3-TPD results including the amount
of acid sites (weak, moderate, and strong acidity) and
the maximum desorption temperature have been listed in

Fig. 5  NH3-TPD profiles of the

parent and desilicated HZSM-5 Total deconvoluted paek of Parent (a)
samples prepared with a NaOH/ Parent
TPAOH mixture, b NaOH/ DeSi-NaOH
TBAOH mixture
DeSi-NaOH-TPA0.2
DeSi-NaOH-TPA0.4
TCD signal(mV)

DeSi-NaOH-TPA0.6

Medium Temp.
Peak
Low Temp
Peak

High Temp
Peak

100 200 300 400 500 600 700 800 900

Temperature (°C)

Total deconvoluted paek of Parent (b)

Parent
DeSi-NaOH
DeSi-NaOH-TBA0.2
DeSi-NaOH-TBA0.4
TCD signal(mV)

DeSi-NaOH-TBA0.6

100 200 300 400 500 600 700 800 900

Temperature (°C)

13
Journal of Porous Materials (2019) 26:1407–1425 1417

Table 3  NH3-TPD data for Catalyst name Characteristic

the parent, desilicated and
dealuminated HZSM-5 samples Acidity (mmmol NH3/g) Peak temperature (°C)
Weak Medium Strong Total Low temp. High temp.
peak ­(TP1) peak ­(TP2)

Parent 0.083 0.139 0.114 0.336 191 391

DeSi–NaOH 0.101 0.176 0.118 0.395 171 358
DeSi–NaOH–TPA0.2 0.107 0.186 0.134 0.427 178 372
DeSi–NaOH–TPA0.4 0.114 0.208 0.148 0.470 190 386
DeSi–NaOH–TPA0.6 0.112 0.195 0.131 0.438 186 364
DeSi–NaOH–TBA0.2 0.119 0.241 0.153 0.513 168 353
DeSi–NaOH–TBA0.4 0.112 0.229 0.141 0.482 179 373
DeSi–NaOH–TBA0.6 0.110 0.218 0.136 0.455 161 346
DeAl–parent 0.048 0.087 0.052 0.187 187 360
DeAl–DeSi–NaOH–TPA0.4 0.050 0.094 0.091 0.235 175 360
DeAl–DeSi–NaOH–TBA0.2 0.055 0.100 0.107 0.262 154 340

Table 3 which were determined by desorption peak area
and desorption peak temperature, respectively.
In comparison with the parent catalyst, the total acid
amount increases upon desilication process with different
ratios of both NaOH/TPAOH and NaOH/TBAOH mixtures,
But for the samples desilicated in the presence of solutions
containing ­TBA+, higher increase in acid sites concentra-
tion were observed owing to higher external surface areas
in these samples compared to alkaline treated samples with
NaOH/TPAOH mixtures. On the other hand, as listed in
Table 2, higher external surface area and mesopore volume
in these samples result in more accessibility of ammonia
molecules to their acid sites.
The ­NH3-TPD profiles for the desilicated samples with
NaOH/TPAOH mixtures (Fig. 5a) and NaOH/TBAOH mix-
tures (Fig. 5b) are similar with those of the parent catalyst.
Even though, after desilication process, the both peaks of
weak and strong acid sites indicate a shift to lower tem-
peratures in comparison with the parent catalyst (see Fig. 5;
Table 3). These results indicate that desilicated samples
have the lower acidic strength than the parent catalyst, may
be assigned to the extraction of some Al atoms from the
HZSM-5 framework and more mesoporosity in these sam-
ples [41]. As listed in Table 3, the desorption peak tem-
perature for samples desilicated in the presence of TBAOH
is lower than alkaline treated samples with TPAOH owing
to higher external surface area and mesoporosity in these
samples which help the removal of ammonia at lower
temperatures.
According to easier hydrolysis of Si–OH–Si bond respect
to Si–OH–Al bond in the presence of ­OH− attack in alka-
line solution, the amount of Si–OH groups (known as weak
acid sites) on the external surface of the zeolite increase
which is expected to have a good performance in MTP reac-
tion [35, 42]. It is generally accepted that methanol to DME
conversion, alkylation and methylation reactions were car-
ried out by weak acid sites. They can also prevent many
side reactions such as hydrogen transfer reactions in MTP
process. But the strong acid sites have been known as main
acid sites for olefin production in MTH reaction [43–45].
Therefore, in order to improve catalyst stability and propyl-
ene selectivity in MTP reaction, it is necessary to adjust the
concentration amount of weak and strong acid sites.
As we expected from the textural properties of the desili-
cated samples (see Table 2), DeSi–NaOH–TPA0.4, and
DeSi–NaOH–TBA0.2 samples with higher external surface
areas show higher weak and strong acid sites. As can be seen
in Table 3, the amount of moderate acid sites in the samples
treated with different ratios of NaOH/TBAOH mixtures is
much higher than those of the other alkaline treated samples
in the presence of TPAOH. Based on the literature [46, 47],
the presence of strong acid sites on the ZSM-5 surface is the
major reason for catalyst deactivation in methanol to olefin
reaction. Hence, in order to obtain high stability and light
olefins selectivity, the modest strong acid sites are favorable
in MTP reaction. Therefore, it is expected that the desili-
cated samples with alkaline solution containing TBAOH
show better catalytic performance in MTP reaction owing
to their higher medium acid sites and lower strong acid sites.
3.2 Characterization of dealuminated catalysts
3.2.1 XRD analysis
All the steaming treated samples have a typical MFI
structure (Supplementary Fig. S2), but the peak intensity
at 2θ = 23°–25° slightly decreased compared to before
steaming treatment. The relative crystallinity values of the
steamed samples (see Table 2) confirmed that steaming pro-
cess under these mild conditions has no considerable effect

13
1418
on the ZSM-5 crystal structure. This result can be explained
by the slightly ZSM-5 framework destruction due to alu-
minum removal after steaming treatment [48].
3.2.2 FE‑SEM analysis
FE-SEM images of the parent and the optimum desili-
cated samples after steaming process have been shown in
Fig. 6. The comparison between the FE-SEM images of
the DeSi–NaOH–TPA0.4 and DeSi–NaOH–TBA0.2 before
(Fig. 4 c and Fig. 4d, respectively) and after steaming pro-
cess (Fig. 7b, c, respectively) showed that after the sec-
ond post treatment, more rough surface and defects were
appeared on the surface of the zeolite. This result can be
related to the partial break down of the zeolite crystals.
3.2.3 Nitrogen adsorption/desorption analysis
In order to investigate the effect of steaming treatment after
desilication process, the isotherm and BJH pore size distri-
bution curves of these samples have been depicted in Fig. 7.
The comparison between this figure with Fig. 3 shows that
there is no significant change in the isotherm type and pore
size distribution of the selected samples before and after
steaming treatment and these curves are very similar. As
listed in Table 2, the steaming process could not significantly
improve mesoporosity in the parent catalyst and the opti-
mum desilicated samples. These results are in line with the
results reported in the literatures for dealumination process
[28, 48–50]. After steaming process at 500 °C for 12 h on
the selected samples, the total surface area ­(SBET), micropore
surface area ­(SMicro) and micopore volume (­ VMicro) slightly
decreased (less than 10%) for all the selected samples prob-
ably due to pore blockage by extra framework aluminum
in the zeolite channels. On the other words, dealumination
process of the zeolite surface is associated with the produc-
tion of extra framework aluminum atoms which retain in
the zeolite channels and block the pores [48]. Even though
due to high relative crystallinity of the samples after steam-
ing treatment (see Table 2) and slightly framework damage
under these mild steaming conditions, these changes dose
not influence on the crystal structure, which these results are
in convince with the XRD and FE-SEM results.
3.2.4 NH3‑TPD analysis
In order to understand the effect of steaming treatment on
the acidity property of the parent and the optimum desili-
cated catalysts, ­NH3-TPD method was carried out and the
results have been listed in Table 3. Also, the ­NH3-TPD pat-
terns of the selected catalysts have been depicted in Fig. 8.
It can be seen from the Fig. 8 and Table 3 that after steaming
process, the acid strength of the samples becomes weaker
13
Journal of Porous Materials (2019) 26:1407–1425
and the amount of weak, strong, and total acid sites reduce
significantly (more than 50%) due to dealumination of
ZSM-5 framework. Rostamizadeh and Yaripour [30] showed
that after steaming process the acidity surface of the catalyst
decreased around 64% of the parent catalyst. Jin et al. [51]
reported that after dealumination by steaming treatment at
temperature above 400 °C, the strength acidity is weaken
and the surface acidity reduced around 80%.
3.3 Catalytic performance
In order to investigate the effect of mesoporosity formation
by alkaline treatment with different ratios of the NaOH/
TPAOH and NaOH/TBAOH mixtures, all the desilicated
samples and parent catalyst were tested in the conversion
of MTP reaction under the same operational conditions
(T = 480 °C, P = 1 atm, feed: 50 wt%. methanol in water,
WHSV = 0.9 h1). Table 4 represents full description of the
average product distributions in MTP reaction over the par-
ent and all the desilicated samples in steady state conditions
when methanol conversion is above 99%.
The catalytic performance of the parent catalyst in MTP
reaction shows a propylene selectivity of 30.7% with a total
light olefins ­(C2=–C4=) selectivity of 57.9%, which is along
with 13.7% selectivity to saturated hydrocarbons (­ C1–C4)
and a lot of ­C5+ heavy hydrocarbons formation (27.1%). It
can be clearly seen from the Table 4 that alkaline treated
samples in the mixtures of NaOH/TPAOH and NaOH/
TBAOH represent higher selectivities to propylene and
butylene and lower selectivity to saturated hydrocarbons
and ­C5+ heavy hydrocarbons compared to the parent catalyst
and the sample treated with pure NaOH. This can be related
to the narrow and uniform pore size distribution associated
with high external surface area and mesopore volume of
these samples compared to the alkaline treated sample with
pure NaOH.
Based on the Table 4, for the alkaline treated samples
in the presence of TPAOH, by increasing the TPAOH/
(NaOH + TPAOH) ratio from 0.2 to 0.4, the selectivities to
propylene and butylene increase from (35.8 and 19.2%) to
(38.4 and 21.3%), respectively. But a more increase in this
ratio (the DeSi–NaOH–TPA0.6 sample) leads to decrease
in propylene selectivity to 36.3% which is not beneficial. It
can be clearly seen from the different ratios of the NaOH/
TPAOH mixtures that the DeSi–NaOH–TPA0.4 sample
compared to the parent catalyst exhibits higher selectivi-
ties to propylene (38.4 vs. 30.7%) and total butylenes (21.3
vs. 16.1%), as well as total light olefins (69.4 vs. 57.9%),
while its selectivities to C
­ 1–C4 alkanes (10.6 vs. 13.7%) and
heavy hydrocarbons (14.8 vs. 27.1%) are relatively lower.
The good catalytic performance of this sample is probably
due to the formation of open cavities connected to its exter-
nal surface (Fig. 4c). Also in terms of mesoporosity and
Journal of Porous Materials (2019) 26:1407–1425 1419

Fig. 6  FE-SEM images of the parent and the selected optimum desilicated samples after steaming process

13
1420 Journal of Porous Materials (2019) 26:1407–1425

DeAl-Parent (a) increases from 12.3 to 14.2%. Moreover, all the desilicated
210
DeAl-DeSi-NaOH-TPA0.4 samples with different ratio of NaOH/TBAOH mixtures
180
DeAl-DeSi-NaOH-TBA0.2
produce less than half of heavy hydrocarbons ­(C5+) of the
parent catalyst.
150 As listed in Table 4, for the alkaline treated sam-
ples with different ratios of NaOH/TBAOH mixtures,
120 the DeSi–NaOH–TBA0.2 sample compared to the
Vads(cm3STPg-1)

DeSi–NaOH–TPA0.4 sample represents higher selec-

90 tivities to propylene (42.6 vs. 38.4%) and total butylenes
(23.9 vs. 21.3%), as well as total light olefins (76.8 vs.
60
69.4%), while its selectivities to ­C1–C4 alkanes (8.4 vs.
10.6%) and ­C5+ heavy hydrocarbons (12.3 vs. 14.8%) are
30
relatively lower. Moreover, the DeSi–NaOH–TPA0.4 and
0
DeSi–NaOH–TBA0.2 gives the maximum propylene to eth-
0 0.2 0.4 0.6 0.8 1 ylene ratios, 3.96 and 4.58, respectively, which are the most
Relative pressure (p.p0-1) important parameters in MTP reaction. This good catalytic
performance can be explained by more mesoporosity forma-
1
DeAl-DeSi-NaOH-TBA0.2 (b) tion and higher hierarchy factor associated with higher weak
0.9
DeAl-DeSi-NaOH-TPA0.4 and medium acid sites in this sample.
0.8
DeAl-Parent
According to the literature [52, 53], mesoporous ZSM-5
0.7
catalysts can accelerate the elimination of the intermedi-
ate products, especially propylene and butylene with larger
DV(log d) (cm3.g-1)

0.6
0.5
0.4
0.3
0.2
0.1
0
0 50
Pore diameter (Å)
Fig. 7  a ­N2 adsorption /desorption isotherms, and b pore size distri-
butions from the adsorption branches of the steam treated catalysts.
For clearness, in segment a the isotherms for the DeAl–DeSi–NaOH–
TPA0.4 and DeAl–DeSi–NaOH–TBA0.2 are vertically offset by 40
and 80 cm3 g−1, respectively
hierarchy factor, this sample has a higher external surface
area and mesopore volume compared to the other ratios of
NaOH/TPAOH mixtures, which leads to a shorter diffusion
path length. Therefore, a shorter residence time of heavy
hydrocarbon products in the crystal pores of this sample
before diffusing out to the gas phase results in less formation
of ­C5+ heavy hydrocarbons products in this sample.
From the point of view of high propylene and total light
olefins selectivitties and low formation of C ­ 5+ and satu-
rated hydrocarbons, the samples treated in the presence of
TBAOH are more effective than the alkaline treated sam-
ples in the presence of TPAOH. By increasing the TBAOH/
(NaOH + TBAOH) ratio from 0.2 to 0.6, the propylene
selectivity decreases from 42.6 to 37.1% and ­C5+ selectivity
molecular sizes from the reactive acid sites of the ZSM-5
catalysts due to the higher external surface area and shorter
diffusion path lengths compared to the microporous zeo-
lites. As a result, the reaction equilibrium shifts to propylene
and butylene formation, and the possibilities that these light
olefins further form higher olefins, aromatics, and heavy
hydrocarbons with secondary reactions on the acid sites of
the ZSM-5 catalyst decreased. Therefore, selectivities to pro-
100 150 200 pylene and butylene as well as propylene to ethylene ratio
over mesoporous ZSM-5 catalysts increased compared with
the microporous ZSM-5 catalyst [8]. Moreover, in conven-
tional microporous ZSM-5 catalysts, diffusion rate of the
coke precursors from the micropores to the external surface
of the ZSM-5 zeolite is relatively slow. Therefore, internal
cokes can coverage the strong acid sites of the zeolite and
block diffusion into other micropores [13].
Based on the dual cycle mechanism [46, 47], alkylation
and methylation reactions highly influence on the enhance-
ment propylene formation in the conversion of methanol to
hydrocarbons. According to the literatures [5, 32], the weak
and medium acid sites through these reactions increase pro-
pylene production while strong acid sites lead to conver-
sion of light olefins to higher olefins, heavy hydrocarbons,
aromatics, paraffins and coke. Therefore medium acid sites
have an important role in MTP reaction for more production
of propylene and light olefins, less formation of ­C5+ heavy
hydrocarbons and long catalyst lifetime. It should be noted,
weak and moderate acid sites reduce the rate of hydrogen
transfer and cyclization reactions in MTP reaction.
In this study, ­C 4 Hydrogen Transfer Index ­( C 4-HTI)
was also used to evaluate the catalytic performance of the

13
Journal of Porous Materials (2019) 26:1407–1425 1421

3000 3000
DeSi-NaOH-TPA0.4 DeAl-DeSi-NaOH-TPA0.4

2000 2000
DeSi-NaOH-TBA0.2 DeAl-DeSi-NaOH-TBA0.2
TCD signal(mV)

TCD signal(mV)

1000 1000
Parent DeAl-Parent

Low
Temp

Medium
Temp

High
Temp

0 0
100 200 300 400 500 600 700 800 900 100 200 300 400 500 600 700 800 900
Temperature (°C) Temperature (°C)

Fig. 8  NH3-TPD patterns of the parent and optimum desilicated catalysts before and after steaming treatment

parent and the desilicated samples in MTP reaction. This
parameter is defined as the ratio between the yields of
butane (n-C4 and i-C4) and the total yield of C
­ 4 hydrocar-
bons (n-C4, i-C4 and total ­C4=) which announce the pro-
gress of the hydrogen transfer reactions over the HZSM-5
catalysts. Therefore, a high value of C ­ 4-HTI indicates
extensive aromatization and cyclization reactions along
with high alkane generation [25].
As listed in the final column of the Table 4, for all the
desilicated samples C ­ 4-HTI is lower than of the parent
catalyst. This parameter for the DeSi–NaOH–TPA0.4 and
DeSi–NaOH–TBA0.2 samples is 0.173 and 0.151, respec-
tively which are less than other samples. This trend can be
expected by the ­NH3-TPD results for these samples due
to their high weak and moderate acid sites which result in
reduce the hydrogen transfer reactions over the samples in
the MTP reaction.
The average product distributions in MTP reaction over
the steam treated samples have also been listed in Table 4.
The propylene selectivity for DeAl–DeSi–NaOH–TPA0.4
and DeAl–DeSi–NaOH–TBA0.2 are 41.3 and 44.8%
respectively, which are more respect to before steam-
ing process, i.e., DeSi–NaOH–TPA0.4 (38.4%) and
DeSi–NaOH–TBA0.2 (42.6%). After steaming process, the
ethylene selectivity decreases which results in much higher
propylene to ethylene ratio in steamed samples. The simi-
lar trend for average product distribution is also observed
for DeAl-Parent. However, the samples treated by sequen-
tial desilication–steaming process represent higher selec-
tivities to propylene and butylene and lower selectivity to

13
1422 Journal of Porous Materials (2019) 26:1407–1425

Table 4  Product distribution of MTP reaction over the parent, desilicated and dealuminated HZSM-5 catalysts measured at steady state condi-
tions (Reaction condition: T = 480 °C, P = 1 atm, WHSV = 0.9 h−1, feed: 50 wt% methanol in water)
Sample Conversion (%) Selectivity (%)
C1–C4a C2= C3= Total ­C4= (C2=–C4=) C3=/C2= C5 + b C4–HTI

Parent 99.9 13.7 11.1 30.7 16.1 57.9 2.76 27.1 0.318
DeSi–NaOH 99.7 11.4 10.7 33.7 17.6 62.0 3.15 23.8 0.265
DeSi–NaOH–TPA0.2 99.8 11.2 10.2 35.8 19.2 65.2 3.51 16.2 0.225
DeSi–NaOH–TPA0.4 99.8 10.6 9.7 38.4 21.3 69.4 3.96 14.8 0.173
DeSi–NaOH–TPA0.6 99.7 11.1 10.9 36.3 19.7 66.9 3.33 16.7 0.217
DeSi–NaOH–TBA0.2 99.9 8.4 9.3 42.6 24.9 76.8 4.58 12.3 0.151
DeSi–NaOH–TBA0.4 99.8 8.9 10.9 39.8 23.1 73.8 3.65 13.5 0.183
DeSi–NaOH–TBA0.6 99.9 9.2 10.4 37.1 22.4 69.9 3.56 14.2 0.201
DeAl–parent 99.9 10.4 10.5 35.4 21.5 67.4 3.37 18.4 0.143
DeAl–DeSi–NaOH–TPA0.4 99.9 7.3 9.2 41.3 26.1 76.6 4.50 10.1 0.118
DeAl–DeSi–NaOH–TBA0.2 99.8 6.7 9.5 44.8 29.8 84.1 4.71 7.4 0.103
a
C1–C4 saturated hydrocarbons
b
C5 and higher hydrocarbons

ethylene, ­C1–C4 saturated hydrocarbons and ­C5+ heavy
hydrocarbons compared to the DeAl-Parent catalyst and
the samples treated with only desilication process. The
comparison between the MTP reactor test results over the
DeSi–NaOH–TBA0.2 sample before and after steaming pro-
cess exhibits slightly increase in propylene selectivity, while
the total ­C4= noticeably increases from 23.9 to 29.8% and
­C5+ selectivity decreases from 12.8 to 7.4%.
In comparison with DeSi–NaOH–TPA0.4 and
DeSi–NaOH–TBA0.2 samples, noticeably lower sat-
urated hydrocarbons (­C 1 –C 4 ) selectivity over both
DeAl–DeSi–NaOH–TPA0.4 and DeAl–DeSi–NaOH–TBA0.2
samples is observed, while propylene and total C ­ 4+ selec-
tivites are noticeably boosted. It can be suggested that
the reduction of saturated hydrocarbons selectivity could
enhance light olefins selectivity in the conversion of
methanol to hydrocarbons [48]. The lower acid site con-
centration on the steamed catalysts leads to the reduction
of the hydrogen transfer reactions. Moreover, the reduc-
tion of acid strength after steaming treatment is beneficial
in suppressing cyclization and hydrogen transfer reactions
[30]. The C ­ 4-HTI for DeAl–DeSi–NaOH–TPA0.4 and
DeAl–DeSi–NaOH–TBA0.2 samples is 0.118 and 0.103,
respectively which compared to before steaming decreased
considerably.
As listed in Table 4, for the parent catalyst the difference
between ­C5+ hydrocarbon selectivity before and after steam-
ing treatment is 8.5%, while this reduction in C ­ 5+ selectivity
for DeSi–NaOH–TPA0.4 and DeSi–NaOH–TBA0.2 samples
is 4.7 and 4.9%, respectively. It can be explained by this fact,
for DeAl–Parent, steaming process is the first post-treatment
process which more strong acid sites are available for the
reactants.
As presented in Table 2, the steaming process could not
significantly produce mesoporosity and mainly influence on
the surface acidity. These results showed that with changing
the surface acidity by steaming process after alkaline treat-
ment, the selectivity to propylene and butylenes enhances
and selectivity to saturated hydrocarbons ­(C1–C4) and C ­ 5+
heavy hydrocarbons reduces.
Generally, it is believed that the main drawback of MTP
catalyst is the catalyst deactivation by coke formation, which
limits the diffusion of reactants/products within zeolite cata-
lysts. These limitations lead to enhance in the contact time of
reactant/product molecules with inner active sites of the zeo-
lites, which favors for aromatic and coke formation through
side reactions [54]. According to literature [17, 55, 56],
high resistance to coke formation and shorter diffusion path
length are two important properties of mesoporous ZSM-5
catalysts. So, it is expected that alkaline or alkaline-steam
treated ZSM-5 samples represent higher activity and longer
lifetime compared to the microporous parent catalyst. For
this reason, the parent catalyst and two optimum desilicated
samples before and after steaming treatment were evaluated
in the MTP reaction under the same operation conditions
(T = 480 °C, P = 1 atm, feed: 50 wt%. methanol in water,
WHSV = 0.9 h1) until reaching to the catalyst deactivation
point. Figure 9 indicates the variations of the methanol con-
version as a function of time on stream over the selected
catalysts. From the industrial point for MTP process, the
useful catalyst lifetime is considered as the time on stream
after which the methanol/DME conversion drops below 90%
which is indicated by the dashed line in Fig. 9. As can be
seen in this figure, at the initial reaction period, all of the
mesoporous ZSM-5 catalysts and the parent one represented
nearly full methanol conversion and high activity, which is

13
Journal of Porous Materials (2019) 26:1407–1425
Fig. 9  Conversion of methanol as a function of time on stream over
the parent and optimum desilicated samples before and after steam
treatment
related to methanol’s small size [57]. However, with increas-
ing the reaction time on stream, all the samples are losing
their activity in MTP reaction with different deactivation
rates. The reactor test results over the parent catalyst showed
that the methanol/DME conversion remained approximately
100% up to 250 h on stream and then dropped slowly to 90%
after 425 h on stream. It should be noted the similar long
lifetime has been recently reported by Yaripour et al. [43].
As shown in Fig. 9, the methanol conversion over
alkaline treated samples, i.e., the DeSi–NaOH–TPA0.4
and DeSi–NaOH–TBA0.2 remains constant at full con-
version for 485 and 610 h on stream, respectively. For
these samples, the breakthrough of methanol is occurred
noticeably later than the parent catalyst, and a slower fall
in methanol conversion is observed. The methanol con-
version of the DeSi–NaOH–TBA0.2 sample falls below
90% after 770 h on stream, which is longer than 630 h
for the DeSi–NaOH–TPA0.4 sample. These results
represented high capacity for methanol conversion in
these mesoporous ZSM-5 samples. The longer lifetime
of the DeSi–NaOH–TBA0.2 sample compared to the
DeSi–NaOH–TPA0.4 sample, can be explained by its higher
external surface area and mesopore volume, which is previ-
ously discussed in the characterization section.
It should be noted that despite the higher total acidity in
these samples compared to the parent one, which is favorable
for secondary reactions, the mesoporous structure, higher
external surface area and pore volume in these samples lead
to reduce diffusion limits and accelerate reactant/products
diffuse out of the micropores of the zeolite before more con-
verting to heavy hydrocarbons and coke deposition.
1423
In addition to the mesoporosity effect, the density and
strength of the acid sites of the ZSM-5 catalyst is another
effective factor, which should be consider in the catalyst
preparation with a high activity and long lifetime [58]. It is
believed that the acid sites of the catalyst strongly influence
coke formation and catalyst lifetime in converting metha-
nol to olefins reaction [53]. Suzuki et al. [59] reported that
lowering the external aluminum content could hinder coke
formation and improve catalyst lifetime.
In order to investigate the effect of the steam
modification over catalytic lifetime of the alka-
line treated samples, catalytic reactor test have been
per for med over DeAl–DeSi–NaOH–TPA0.4 and
DeAl–DeSi–NaOH–TBA0.2, samples. As shown in Fig. 9,
after steam treatment, the lifetime of these samples increases
to 690 h and 830 h, respectively. According to literature [46,
60] the strong acid sites of ZSM-5 zeolite are responsible
for carbon–carbon bond formation and initiate methanol
reactivity, But strong acid sites can produce coke formation
through the secondary reactions in methanol conversion to
hydrocarbons reaction. On the other hand, The longer use-
ful catalytic lifetime of the alkaline-steam treated samples
can be attributed to the reduced acidity, lesser strength of
acid sites and higher external surface area compared to the
alkaline treated samples [30, 50]. Especially, the catalytic
lifetime of the DeAl–DeSi–NaOH–TBA0.2 sample due to
its appropriate acidity and good textural properties, is nearly
two times longer than that of the parent catalyst.
4 Conclusion
Mesoporosity was introduced by desilication of highly
siliceous HZSM-5 zeolite (Si/Al = 200) with pure NaOH,
mixtures of NaOH and TPAOH, mixtures of NaOH and
TBAOH. A subsequent steaming modification of the par-
ent catalyst and selected desilicated samples was performed
successfully to modify their surface acidity. The physico-
chemical properties and catalytic performance of all sam-
ples was evaluated in MTP reaction and the results have
been compared to the parent catalyst. It was found that both
TPAOH and TBAOH produce uniform and narrow pore
size distribution which centered at ca. 3.5 and ca. 5.5 nm,
respectively, in comparison with broad pore size distribution
(centered at ca. 3 nm and ca. 14 nm) produced by treatment
in pure NaOH. The results confirmed that the combining of
desilication and steaming treatments leads to mesoporosity
formation and acidity modification. Desilication by different
ratios of NaOH/TPAOH and NaOH/TBAOH increased the
mesoporosity more than four and sixfolds, respectively. Dea-
lumination by steaming treatment after desilication process,
impacts on the surface acidity of the HZSM-5 samples by
aluminum dislodgement from the zeolite framework without
13
1424
a considerable alteration of the porosity. Combining alka-
line and steaming treatment over the sample with TBAOH/
(NaOH + TBAOH) ratio of 0.2 lead to the best catalytic per-
formance in MTP reaction including the highest selectivities
to propylene (44.8%), propylene to ethylene ratio (4.71), as
well as total light olefins (84.1%), and the lowest selectivities
to ­C1–C4 alkanes (6.7%) and heavy hydrocarbons (7.4%).
Moreover, this sample showed double lifetime (830 h) in
MTP reaction in comparison with the conventional micropo-
rous HZSM-5 catalyst (425 h). The mesoporosity formation
reduces diffusion path length and steaming treatment modi-
fies surface acidity which is a key factor in the conversion of
MTP reaction. Therefore, a promising outlook of the com-
bined alkaline-steam treatment over conventional micropo-
rous HZSM-5 is expected in the conversion of methanol to
propylene reaction.
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