Synthesis and characterization of

hierarchical ZSM-5 zeolite using various

templates as cracking catalysts
Cite as: AIP Conference Proceedings 2023, 020088 (2018); https://doi.org/10.1063/1.5064085
Published Online: 23 October 2018

Z. Zahara, Y. K. Krisnandi, W. Wibowo, D. A Nurani, D. U. C. Rahayu, and H. Haerudin

ARTICLES YOU MAY BE INTERESTED IN

Synthesis of ZSM−5 zeolite using Bayat natural zeolite as silica and alumina source
AIP Conference Proceedings 1862, 030094 (2017); https://doi.org/10.1063/1.4991198

Synthesis and characterization hierarchical HY zeolite using template and non template
methods
AIP Conference Proceedings 2023, 020094 (2018); https://doi.org/10.1063/1.5064091

Three-step crystallization in synthesis of ZSM-5 without organic template

AIP Conference Proceedings 1718, 060002 (2016); https://doi.org/10.1063/1.4943324

AIP Conference Proceedings 2023, 020088 (2018); https://doi.org/10.1063/1.5064085 2023, 020088

© 2018 Author(s).
 Synthesis and Characterization of Hierarchical ZSM-5
Zeolite Using Various Templates as Cracking Catalysts
Z. Zahara1, Y. K. Krisnandi1, W. Wibowo1, D. A Nurani1,
D. U. C. Rahayu1, and H. Haerudin2
1
Department of Chemistry, Faculty of Mathematics and Natural Sciences (FMIPA),
Universitas Indonesia, Depok 16424, Indonesia
2
Research and Development, PT. Pertamina (Persero), Jalan Raya Bekasi, Jakarta 13920, Indonesia

Corresponding author’s e-mail: yuni.krisnandi@sci.ui.ac.id

Abstract. Attempt to hydrothermally synthesize hierarchical ZSM-5 zeolites (ZSM-5_h) through double template
method has been carried out. In order to develop the structure of microporous ZSM-5 zeolite (ZSM-5_m), three different
structure directing agents were used, i.e. TPAOH (t), ethylenediamine (en), and triethylenetetramine (teta), followed by
dimethyl dialyl ammonium chloride acrylamide copolymer as mesopore directing agent. All samples were characterized
using XRD, BET Surface Area Analyzer, and SEM. XRD pattern of ZSM-5_h/t showed the characteristic peaks of ZSM-
5 at position 2θ of 7-9° and 22-25°. Otherwise, the XRD pattern of ZSM-5_h/en and ZSM-5_h/teta showed very weak
peaks, indicating that ZSM-5 were not well formed. Nitrogen adsorption of ZSM-5_h/t exhibited hysteresis loop at P/Po
0.7-0.9 indicating the presence of hierarchical mesoporous. SEM images of ZSM-5_h/t showed the characteristic of
ZSM-5 which was hexagonal shape. Afterward, H/ZSM-5_h/t zeolite was prepared through ion exchange-treatment using
1 M ammonium nitrate solution, followed by calcination at 823 K to remove all ammonia and produced H/ZSM-5_h/t.
This sample was further characterized using XRD and FTIR to observe its acidity. Preliminary test on H/ZSM-5_h/t as
catalyst in cracking of n-hexadecane was conducted. As comparison, microporous ZSM-5_m was synthesized and tested
under the same conditions to study the effect of different pore size on its activity in catalytic cracking of n-hexadecane.
The result showed that ZSM-5_h/t delivered higher conversion than ZSM-5_m, 37.23 and 17.9 in % moles, respectively.
It can be concluded that ZSM-5_h was more effective to be used in catalytic cracking of n-hexadecane.

INTRODUCTION
ZSM-5 zeolites have been widely known as potential catalyst additive in catalytic cracking reaction of n-paraffin
[1, 2]. Their properties which is thermally stable, shape selective, and strong acidity make these materials are used in
many industrial mainly as catalyst, adsorbent, and molecular sieves [3]. Many researches have been carried out to
understand the effect of ZSM-5 additive in total yield of catalytic cracking. Hollander et al. [4] reported that ZSM-5
zeolites can increase the total product of olefin yield from gasoline conversion. Furthermore, Adewuyi et al. [1]
reported that addition of 25 %wt ZSM-5 zeolite into FCC catalyst can affect the C2- and butadiene product that did
not observed in lower ZSM-5 addition [1].
In order to improve their activity as catalyst, many researches have been modified the pore size of ZSM-5 zeolite
to be larger [5, 6] and the acidity properties through ion exchange-treatments. Besides, many studies also reported
the various organic directing agent in order to diminish the production cost in synthesis of ZSM-5 zeolites [7]. This
present work focused on synthesis and characterization of hierarchical ZSM-5 zeolites using different organic
templates and their application as catalyst in catalytic cracking reaction of n-hexadecane.

Proceedings of the 3rd International Symposium on Current Progress in Mathematics and Sciences 2017 (ISCPMS2017)
AIP Conf. Proc. 2023, 020088-1–020088-6; https://doi.org/10.1063/1.5064085
Published by AIP Publishing. 978-0-7354-1741-0/$30.00

020088-1
 MATERIALS AND METHODS

Materials
All materials used in this experiment were analytical grade and used without further purification i.e. sodium
aluminate, TPAOH 1M, TEOS 98%, triethylenetetramine, ethylenediamine, PDD-AM 35%, and deionized water.
All materials were purchased from Sigma Aldrich. Deionized water was provided from MilliQ devices.

Synthesis of ZSM-5 Zeolite

Sodium aluminate, deionized water, TPAOH, and TEOS were mixed at 373 K under vigorous stirring and aged
for 3 hours. Molar ratio of the materials were 1Al2O3 : 64.35SiO2 : 10.08(TPA)2O : 3571.66 deionized water [8]. For
two other materials, (TPA)2O was replaced with 10.08TETA or 100en [7]. Then, PDD-AM solution was added into
the mixture at room temperature and stirred for 48 hours [8]. The mixture was transferred into Teflon-line stainless
steel autoclave for further crystallization at 443 K for 144 hours. The product was collected by filtration, washed,
and dried. ZSM-5 zeolite was calcined until 823 K and characterized using XRD, FTIR, Surface Area Analyzer, and
SEM-EDS. The ZSM-5 zeolites then denoted as ZSM-5_h/t, ZSM-5_h/teta, ZSM-5_h/en. As comparison,
microporous ZSM-5 zeolite (ZSM-5_m) was synthesized at the same condition without PDD-AM solution as
secondary template.

Preparation of H/ZSM-5
H/ZSM-5 zeolites were prepared through ion exchange-treatment using 1 M ammonium nitrate solution with
ratio 1:50. The mixture was heated at 333 K for 6 hours. The products were filtered, dried, and calcined at 823 K to
remove all ammonia and produced H/ZSM-5.

Catalytic Cracking Test

The catalytic activity of H/ZSM-5 zeolites was tested using micro activity test (MAT) reactor at 773 K using n-
hexadecane as feed. The catalyst was weighed for about 0.5 g and put into silica reactor. Catalyst was purged with
N2 gas to remove all impurities at temperature of 573 K for 30 min. Then, feed n-hexadecane was weighed about
1.35 grams and injected into reactor for 80 s. Liquid and gas products were collected in a liquid receiver and in
Teddlar bag for gases. After injected feed, nitrogen gas was purged into reactor to pull out all feed in syringe pump.

RESULTS AND DISCUSSION

Catalyst Characterization

Figure 1 and Fig. 2 showed the XRD pattern of the as-synthesized ZSM-5 zeolites and their modification into
H/ZSM-5. Figure 1 showed that the as-synthesized ZSM-5_h/en and ZSM-5_h/teta showed weak intensity at those
position 2θ indicating that ZSM-5 zeolites did not well formed. Therefore, further characterization were not
employed on both materials. The XRD powder pattern of ZSM-5_h/t and ZSM-5_m showed the strong intensity of
ZSM-5 characteristic peak in position 2θ of 7-9° and 22-25° [9]. According to Fig. 1, ZSM-5_h/t had lower intensity
than ZSM-5_m indicating that the presence of secondary template can decrease the crystallinity of ZSM-5.
Therefore, only those last materials that subjected to ammonium ion exchange treatment to obtain H/ZSM-5. For
H/ZSM-5_m and H/ZSM-5_h/t zeolites showed the same powder pattern to ZSM-5_m and ZSM-5_h/t, indicating
that the modification did not destroy their primary structure.
The result of surface area analysis was showed in Table 1. The surface area and the average of pore diameter for
ZSM-5_h/t were larger than ZSM-5_m. This data was supported by isotherm adsorption – desorption curve that for
ZSM-5_h/t showed in Fig. 3. The broad hysterical loop at 0.7 to 0.9 P/P˚ only appeared in ZSM-5_h/t, indicating the
presence of mesoporous in this sample. Furthermore, according to Table 1, ZSM-5_h/t has lower surface area than
ZSM-5_m. This result indicated that the adding of secondary template could cause more amorphous ZSM-5 zeolite,
as match as XRD result.

020088-2
 TABLE 1. Surface area analysis of the as-synthesized ZSM-5 zeolites
Sample SBET Smikro Smeso Total pore Vmikro Vmeso Average Pore
(m2/g) (m2/g) (m2/g) volume (cc/g) (cc/g) (cc/g) Diameter
(nm)
ZSM-5_m 334.02 334.02 - 0.2 0.2 - 1.729
ZSM-5_h/t 293.885 118.382 175.503 0.2115 0.062 0.1495 2.878

(a) (b)
FIGURE 1. Diffraction pattern of the FIGURE 2. Diffraction pattern of
as-synthesized ZSM-5 zeolites H/ZSM-5 zeolites

FIGURE 3. Isotherm adsorption – desorption of ZSM-5 zeolites

Figure 4 explained that the presence of PDDAM as secondary template successfully developed hierarchical pores
in the as synthesized of ZSM-5_h/t, giving pore size distribution of 2.10 (microporous), 3.98 and 37.63 nm
(mesoporous). This mesoporosity is not observed in ZSM-5_m. Furthermore, SEM analysis had been carried out to
observe the morphology of the as-synthesized zeolites and the result showed in Fig. 5. The SEM images that all of
the as-synthesized ZSM-5 zeolites have hexagonal shape that were specific characteristic of ZSM-5 zeolites [10].
ZSM-5_h/t showed more rough morphological than ZSM-5_m, indicating the presence mesoporous in this sample
[8]. Besides, the smaller shape in ZSM-5_h/t showed that this sample has larger surface area than ZSM-5_m. This
data was appropriate with surface area analysis.
EDS analysis (Table 2) showed the decrement of Na composition before and after modification to H/ZSM-5
zeolites in both the as-synthesized ZSM-5 zeolite, indicating that ion exchange-treatment had been successfully
carried out. The decrement of percent weight of Na in correlation with the increasing acidity in all samples. Molar
ratio Si/Al of ZSM-5 zeolites and their modification did not changed significantly; indicating that the modification

020088-3
 (a) (b)
FIGURE 4. Pore distribution of (a) ZSM-5_m and (b) ZSM-5_h/t

(a) (b)
FIGURE 5. SEM images of (a) ZSM-5_m and (b) ZSM-5_h/t

TABLE 2. EDS analysis of ZSM-5 and H/ZSM-5 zeolites

Sample Element ( % wt ) Molar Ratio
Si Al O Na of Si/Al
ZSM-5_m 32.65 0.895 60.845 0.44 35.18
H/ZSM-5_m 28.04 0.765 59.000 0.085 35.34
ZSM-5_h/t 34.32 1.245 57.490 0.735 26.58
H/ZSM-5_h/t 36.515 1.105 58.165 N/A 31.86

did not extracted many atoms in the framework. EDS analysis also showed that H/ZSM-5_h/t has higher acidity that
H/ZSM-5_m because its lower Si/Al molar ratio.
Analysis using FTIR instrument was conducted to observe the change of acidity after modification into H/ZSM-
5 zeolite. In this experiment, ammonia gases were used as a probe molecule to observe their acidity. Based on FTIR
result (Fig. 6), all H/ZSM-5 samples showed peak at 960, 1600-1650, and 3300 cm-1. Those appearance peaks were
specific for N-H vibration from ammonia gases adsorbed in ZSM-5 zeolites [11]. Those peaks did not appear in as-
synthesized ZSM-5, indicating that the acidity properties had increase after modification [3].

Catalytic Cracking Test

The preliminary catalytic activities of H/ZSM-5 zeolites were tested in micro activity test (MAT) reactor to
measure their activity in cracking of heavy crude oil. As a model, n-hexadecane was chosen because it had boiling
point in the range of boiling point of heavy crude oil.

020088-4
 FIGURE 6. FTIR spectra of H/ZSM-5 zeolites before
and after ammonia adsorption

FIGURE 7. Percent conversion of n-hexadecane

using various H/ZSM-5 catalyst

Figure 7 showed the percent conversion of n-hexadecane cracking. According to Fig. 7, H/ZSM-5_h/t showed
higher conversion of n-hexadecane than H/ZSM-5_m. This data confirmed that the appearance of mesoporous will
facilitate the mass transportation of reactant into active site of catalyst easier than in microporous catalyst.

CONCLUSIONS
Both microporous and hierarchical ZSM-5 zeolites, ZSM-5_m and ZSM-5_h/t, had been successfully
synthesized using TPAOH as directing agent. Meanwhile, ZSM-5 zeolites that was synthesized using
ethylenediamine and triethylenetetramine as template were not well formed. H/ZSM-5_h/t zeolites had been
successfully prepared through ion exchange-treatments and their catalytic activity was tested in cracking of n-
hexadecane. The result showed that ZSM-5_h/t delivered higher conversion than ZSM-5_m, with 37.23 and 17.9 in
% moles, respectively, as it provided the larger average pore diameter and higher acidity properties. It can be
suggested that H/ZSM-5_h/t is promising catalyst additive in heavy crude oil cracking reaction.

ACKNOWLEDGMENTS
This work was funded from collaboration research project between PT. Pertamina (Persero) and Universitas
Indonesia year 2016 – 2017 number 004/E20400/2016-S0.

020088-5
 REFERENCES
1. Y. G. Adewuyi, D. Klocke, and J. S. Buchanan, Appl. Catal. A: Gen. 131, 121 (1995).
2. J. S. Buchanan and Y. G. Adewuyi, Appl. Catal. A: Gen. 134, 247 (1996)
3. J. C. Groen, J. A. Moulijn, and J. Pérez-Ramírez, Micropor. Mesopor. Mater. 87, 153 (2005)
4. M. A den Hollander, M. Wissink, M. Makkee, and J. A. Moulijn, Appl. Catal. A: Gen. 223, 85 (2002).
5. L. Wang et al., Colloids Surf. A Physicochem. Eng. Asp. 340, 126 (2009).
6. S. Abelló, A. Bonilla, and J. Pérez-Ramírez, Appl. Catal. A: Gen. 364, 126 (2009)
7. S. Sang et al., Catal. Today 93, 729 (2004)
8. L. Wang, Z. Zhang, C. Yin, Z. Shan, F. S. Xiao, Micropor. Mesopor. Mater. 131, 58 (2010)
9. N. Mohan and L. Cindrella, Mat. Sci. Semicon. Proc. 40, 361 (2015)
10. Y. K. Krisnandi et al., Procedia Chem. 14, 508 (2015)
11. F. Yin, A. L. Blumenfeld, V. Gruver, and J. J. Fripiat, J. Phys. Chem. B 101, 1824

020088-6